Table of contents

This book aims to give a cross section from a wide range of phenomena that, to different degrees, fall under the heading of non-equilibrium phenomenology. The selection is, of course, biased by the interests of the members of the scientific committee and of the FP6 Project 026328 IPB-CNP Reinforcing Experimental Centre for Non-equilibrium Studies with Application in Nano-technologies, Etching of Integrated Circuits and Environmental Research. Some of the papers included here are texts based on selected lectures presented at the Second International Workshop on Non-equilibrium Processes in Plasmas and Environmental Science. However, this volume is not just the proceedings of that conference as it contains a number of papers from authors that did not attend the conference. The goal was to put together a volume that would cover the interests of the project and support further work. It is published in the Institute of Physics journal Journal of Physics: Conference Series to ensure a wide accessibility of the articles.

The texts presented here range from in-depth reviews of the current status and past achievements to progress reports of currently developed experimental devices and recently obtained still unpublished results. All papers have been refereed twice, first when speakers were selected based on their reputation and recently published results, and second after the paper was submitted both by the editorial board and individual assigned referees according to the standards of the conference and of the journal. Nevertheless, we still leave the responsibility (and honours) for the contents of the papers to the authors. The papers in this book are review articles that give a summary of the already published work or present the work in progress that will be published in full at a later date (or both).

In the introduction to the first volume, in order to show how far reaching, ubiquitous and important non-equilibrium phenomena are, we claimed that ever since the early cosmos collapsed from the uniform plasma stage into stars and empty space, practically nothing is in real equilibrium only in local equilibrium. How wrong we were. As our focus turned to anti particles, positrons and positronium, we realized that even in those early stages there was major non-equilibrium between matter and anti matter originating from the earliest stages of the Big Bang. Thus it is safe to correct the famous quote by the renowned natural philosopher Sheldon Cooper into: 'If you know the laws of [non-equilibrium] physics anything is possible'. From the matter–anti-matter ratio in the universe to life itself. But do we really need such farfetched introductory remarks to justify our scientific choices? It suffices to focus on non-equilibrium plasmas and transport of pollutants in the air and see how many new methods for diagnostics and treatment have been proposed for medicine in the past 10 years. So in addition to the past major achievements such as plasma etching for integrated circuit production, the field is full of possibilities and truly, almost anything is possible. We hope that some of the papers presented here summarize well how we learn about the laws of non-equilibrium physics in the given context of plasmas and air pollution and how we open new possibilities for further understanding and further applications.

A wide range of topics is covered in this volume. This time we start with elementary collisional processes and a review of the data for excitation of polyatomic molecules obtained by the binary collision experiments carried out at the Institute of Physics in Belgrade by the group of Bratislav Marinković. A wide range of activities on the foundation of gaseous positronics ranging from new measurements in the binary regime to the simulation of collective transport in dense gases is presented by James Sullivan and coworkers. This work encompasses three continents, half a dozen groups and several lectures at the workshops while also covering a lot of material that was not presented as a lecture at the workshop. Michael Charlton has written a major review of the past work on the transport of positrons in gases. This review is a thorough summary of the field which more importantly looks at the future and invites a continuation of activities while providing an excellent foundation for the new experiments and modeling.

The next paper submitted by Jasmina Jovanović covers the ongoing activities in the Gaseous Electronics Laboratory in Belgrade to prepare sets of data for ions that are required for modeling of gas discharges based on cross sections rather than interaction potentials. In many situations direct application of swarm physics modeling is possible, one such example is in the upper layers of the atmosphere – how this is done in the case of NO production and emissions from NO is shown in a paper by Laurence Campbell from Flinders University. Self-consistent coupling of electron kinetics as described by the solution to the Boltzmann equation and chemical and excited state kinetics in gases is described by Nuno Pinhao.

From swarms to gas discharges the transition is made through gas breakdown. Studies of the development of the anatomy of a hollow cathode discharge obtained in collaboration between groups from Bulgaria and Serbia are presented by Dragana Marić. Remote treatment by plasmas is an option in biomedical applications and one such example is given by Kinga Kutasi, presenting results of a modeling of a well established plasma sterilizer. Another interesting application of plasmas is for the propulsion of satellites in vacuum where intelligent design (of plasma geometry and operating conditions) proves to be the most efficient method of controlling the orbits. Some new results combining experiments and modeling of plasma propulsion devices from Ecole Polytechnique in Paris are presented here by Ane Aanesland.

Just how much can the studies inspired by the practical needs of plasma technologies lead to new fundamental understanding is illustrated well in the paper by Uwe Czarnetzki which describes a new method for separate control of flux and energy of ions reaching the surface of electrodes. Deborah O'Connell from Belfast has shown space and phase resolved mode transitions in rf inductively coupled plasmas obtained by optical emission measurements. At the same time an application of a similar rf discharge for the treatment of paper was presented by Irina Filatova from Belarus.

Many applications of non-equilibrium plasmas depend on the development of plasma sources operating at atmospheric pressure and one such source that promises to be prominent in medicine is described by Timo Gans. In a similar way, practical considerations require studies of the injection of liquids into plasmas and progress on the development of one such source is described by Mathew Goeckner and his colleagues from Dallas. From the Institute Jožef Štefan in Slovenia and the group of Miran Mozetič we have a detailed review of their work on functionalization of organic materials by oxygen plasmas.

Even higher density plasmas, where the collective phenomena dominate, show different degrees of non-equilibrium and one example presented here by Zoltan Donko deals with two dimensional plasma dust crystals and liquids, while the lecture by Jovo Vranješ from Belgium deals with the treatment of collisions in multicomponent plasmas.

Finally we have papers on the transport of pollutants. The association of the two fields started initially through joint interest in some of the methods for removal of NO_x and SO_x, from electrostatic precipitation of industrial dust to dielectric barrier discharges. The joint work continued on the application of flowing afterglow plasma combined with a hollow cathode discharge in order to achieve a proton transfer mass analysis of organic volatile compounds and also on the possibilities of applying similar methods for solving transport equations. In this volume we have the presentation of monitoring of the deposition of airborne particles by the group from Belgrade led by Mirjana Tasić, and a study of such particles by elemental analysis by van Grieken and his colleagues from Belgium.

We hope that the continuation of our workshops and the publication of our books will contribute to finding a common thread that connects different topics, even different fields, that share some aspects of the phenomena associated with non-equilibrium. As Anton Chekhov once stated 'Only entropy comes easy' so any work aimed at bringing order into the field is difficult. Organization of the workshop and publication of the book are of course not as hard as the pursuit of knowledge itself but we hope that it is, to some degree, a minor contribution to the everlasting human struggle against the entropy. And while we, of course, agree with scientists that are much better than we are that thermodynamics will never be overthrown, it is only human to try to cheat it. Doing the related science is allowing us to achieve exactly that and it is a source of numerous practical applications.

The editors are grateful to all the members of the Gaseous Electronics Laboratory for organization of the workshop, in particular the members of the organizing committee and the staff of the Academy of Science and Institute of Physics. Finally and above all we acknowledge great efforts of all the participants who have invested a lot of funds, their time and effort to join us, sometimes travelling from distant continents. This book exists, however, mainly thanks to the efforts of all the authors who have invested their time and experience to write the papers. We also acknowledge the contribution by Professor Rastko Ćirić whose rendering of Maxwell's demon remains as symbol of our meeting and our publications.

Perhaps the most chaotic aspect of human society, as our current experience teaches us, is the flow of funds and several agencies helped us get the needed funds to continue. The conference and this book were primarily supported by the COE Centre for Non-equilibrium processes and the Ministry of Science of the Republic of Serbia. Additional funding and facilities were provided by the Academy of Sciences and Arts of Serbia, Institute of Physics Belgrade (project No 141025) and Hiden Analytical.

The editors Zoran Petrovic, Dragana Maric and Gordana Malovic

Studies of higher excited states of some polyatomic molecules relevant for plasma physics and environment have been presented. Spectra of chlorofluorocarbons are discussed together with their influence on ozone layer depletion and global warming. Tetrahydrofuran molecule was studied by photoabsorption and electron energy loss spectroscopy while the states are assigned following extensive ab initio calculations. Nitrous oxide and hydrogen sulphide spectra are discussed in terms of identifying valence and Rydberg character of excited states.

Recent experiments, theory and modelling of positron interactions with atoms and molecules are discussed. The first half of the paper is devoted to binary collisions between positrons and crossed beams of atoms or molecules (in this case neon) and the second half deals with ensembles of non-interacting positrons, otherwise known as swarms which are transported through the background gas. We review the recent results on measurements of the cross sections based on obtained from collisional positron traps and subsequent calculations of transport properties of positron swarms that may be used to model thermalization experiments, collisional traps and possible applications of positrons in materials science and biomedicine. It was found that kinetic phenomena occur in positron transport that are mainly the result of the positronium (Ps) formation which has a larger cross section than elastic scattering in most gases and at the same time is a non-conservative process. Most importantly negative differential conductivity (NDC) occurs only for the bulk drift velocity while it does not exist for the flux property, a phenomenon that has not been observed for electrons.

We review the field of positron transport physics in gases, starting with a historical overview. In particular, experiments which have measured positron drift velocities and mobilities in specially constructed cells are highlighted. The relevance of understanding positron transport in current efforts to manipulate trapped clouds of positrons is emphasised. We suggest some ways in which the output of a positron accumulator might be used to develop a new and versatile technique to study positron drift.

We have used a combination of a simple semi-analytic theory - Momentum Transfer Theory (MTT) and exact Monte Carlo (MC) simulations to develop momentum transfer cross sections of negative ions in collisions with noble gases based on the available data for reduced mobility at 300K as a function of E/N. At very low energies, we extrapolated obtained cross sections using Langevin's cross section and supplemented it by the total detachment cross section that was used from the threshold around 6 eV up to 100 eV. Other possible reactive processes have not been taken into account. A good agreement for the mean energy and diffusion coefficients is an independent proof of the validity of the cross sections that were derived for the negative ion mobility data.

We review our recent work on nonequilibrium modelling of the density of nitric oxide and its infrared emissions in the Earth's upper atmosphere. The aim of these studies was to investigate the contribution of electron impact excitation to the NO density and the sensitivity of this process to the electron impact cross sections. The results are compared with satellite measurements of NO densities in equatorial and auroral high-latitude conditions and with rocket measurements of infrared emissions in auroral conditions. Particular findings are that electron impact excitation of N₂ makes a significant contribution to the NO density at altitudes around 105 km and to auroral infrared emissions for the (1 → 0) ground-state emission from NO. The sensitivity of the NO fundamental emissions to various measured and theoretical integral cross sections is investigated and found to be significant.

PLASMAKIN is a user-friendly software package to handle physical and chemical data used in plasma physics modeling and to compute the production and destruction terms in fluid models equations. These terms account for the particle or energy production and loss rates due to gas-phase and gas-surface reactions. The package has been restructured and expanded to (a) allow the simulation of atomic emission spectra taking into account line broadening processes and radiation trapping; (b) include a library to compute the electron kinetics; (c) include a database of species properties and reactions and, (d) include a Python interface to allow access from scripts and integration with other scientific software tools.

We report measurements of electrical properties and spatial emission profiles of hollow cathode discharge, both for steady state and transient phases during formation of the discharge. A commercial hollow cathode tube filled with neon at 3.5 Torr has been studied. Our aim was to relate discharge anatomy to the voltage-current characteristics in a wide range of the operating conditions. It was particularly interesting to track down in time formation of the discharge structure, which is typical for "hollow cathode effect".

We present the modeling of a low pressure post-discharge system used for plasma sterilization, which consists of a flowing microwave discharge, an early-afterglow region developed downstream of the discharge in the same tube, and a large post-discharge reactor. The kinetic model valid for the discharge and early-afterglow region is based on the Boltzmann and rate balance equations, while in the post-discharge reactor a 3-D hydrodynamic model is used. The calculations are conducted in an N₂-O₂ mixture, which has seen to constitute an efficient system for sterilization purpose. The possibilities offered by modeling is presented through a discussion of the effects on relevant species densities and distributions caused by varying: (i) the initial gas mixture composition; (ii) the length of early-afterglow zone; (iii) the gas flow rate and gas pressure.

Recently, we have proposed to use both positive and negative ions for thrust in an electromagnetic space propulsion system. This concept is called PEGASES for Plasma Propulsion with Electronegative GASES and has been patented by the Ecole Polytechnique in France in 2007. The basic idea is to create a stratified plasma with an electron free (ion-ion plasma) region at the periphery of a highly ionized plasma core such that both positive and negative ions can be extracted and accelerated to provide thrust. As the extracted beam is globally neutral there is no need for a downstream neutralizer. The recombination of positive and negative ions is very efficient and will result in a fast recombination downstream of the thruster and hence there is no creation of a plasma plume downstream. The first PEGASES prototype, designed in 2007, has recently been installed in a small vacuum chamber for preliminary tests in our laboratory and the first results have been presented in several conferences. This paper reviews important work that has been used in the process of designing the first PEGASES prototype.

If a temporally symmetric voltage waveform is applied to a capacitively coupled radio frequency (CCRF) discharge, that contains one or more even harmonics of the fundamental frequency, the sheaths in front of the two electrodes will necessarily be asymmetric even in a geometrically symmetric discharge. Optimally this is achieved with a dual-frequency discharge driven at a phase locked fundamental frequency and its second harmonic, e.g. 13.56 MHz and 27.12 MHz. An analytical model, a hybrid fluid/Monte-Carlo kinetic model as well as a Particle in Cell (PIC) simulation show that this Electrical Asymmetry Effect (EAE) leads to the generation of a DC self bias as a function of the phase between the applied voltage harmonics in geometrically symmetric as well as asymmetric discharges. The DC self bias depends almost linearly on the phase angle and the role of the electrodes (powered and grounded) can be reversed. At low pressures the EAE is self-amplifying due to the conservation of ion flux in the sheaths. By tuning the phase, precise and convenient control of the ion energy at the electrodes can be achieved, while the ion flux remains constant. The maximum ion energy can typically be changed by a factor of about three at both electrodes. At the same time the ion flux is constant within ±5%.

Inductively coupled radio-frequency plasmas can be operated in two distinct modes. At low power and comparatively low plasma densities the plasma is sustained in capacitive mode (E-mode). As the plasma density increases a transition to inductive mode (H-mode) is observed. This transition region is of particular interest and governed by non-linear dynamics, which under certain conditions results in structure formation with strong spatial gradients in light emission. These modes show pronounced differences is various measureable quantities e.g. electron densities, electron energy distribution functions, ion energy distribution functions, dynamics of optical light emission. Here the transition from E- to H- mode in an oxygen containing inductively coupled plasma (ICP) is investigated using space and phase resolved optical emission spectroscopy (PROES). The emission, measured phase resolved, allows investigation of the electron dynamics within the rf cycle, important for understanding the power coupling and ionization mechanisms in the discharge. The temporal variation of the emission reflects the dynamics of relatively high-energy electrons. It is possible to distinguish between E- and H-mode from the intensity and temporal behaviour of the emission.

A paper for offset printing was exposed to radio frequency discharge plasma and radio frequency electromagnetic field. Optical response and structural features of paper before and after the treatment have been investigated by several techniques: digital laser speckle photography, laser Stokes polarimetry and attenuated total reflectance (ATR). The changes of statistical distributions of speckle patterns has been observed for plasma treated paper as a result of increase of correlative dimensions of structural heterogeneity of modified paper. It is shown also that the radio wave treatment leads to anisotropy reduction in the paper structure that is more apparent if the magnetic field lines are oriented transversely to the plane of a paper sheet.

The complex dynamics of radio-frequency driven atmospheric pressure plasma jets is investigated using various optical diagnostic techniques and numerical simulations. Absolute number densities of ground state atomic oxygen radicals in the plasma effluent are measured by two-photon absorption laser induced fluorescence spectroscopy (TALIF). Spatial profiles are compared with (vacuum) ultra-violet radiation from excited states of atomic oxygen and molecular oxygen, respectively. The excitation and ionization dynamics in the plasma core are dominated by electron impact and observed by space and phase resolved optical emission spectroscopy (PROES). The electron dynamics is governed through the motion of the plasma boundary sheaths in front of the electrodes as illustrated in numerical simulations using a hybrid code based on fluid equations and kinetic treatment of electrons.

While laboratory based plasmas are always in contact with solid surfaces (often vacuum chambers) they have historically been formed in gas environments. In more recent times, the use of plasmas has grown to include plasma contact with liquids including biological items. Inevitably the plasmas in contact with liquids had been at or near atmospheric pressures. This need not be the case. We have developed a novel method for injecting liquids directly into low-pressure discharges. As such, this technique opens new areas of possible industrial use for plasmas. For example, we have injected inorganic nano-particles into argon plasma by suspending them in hexane (or ethanol) as a high vapor pressure liquid carrier. As a result, we believe that metals, dielectrics, superconductors, aromatics, proteins, viruses, etc. could all potentially be injected into low-pressure plasma environments using this technique. The resulting films indicate the ability to synthesize nano-structured composites. Here we examine some of the basic phenomenon that are observed both experimentally and theoretically.

A review on surface modification of different polymers by treatment in oxygen plasma is presented. Plasma is created in a high frequency inductively coupled gaseous discharge at the power of about 200 W. In such discharge created in pure oxygen, plasma with the following parameters is obtained: the electron temperature of about 50.000 K, the charged particle density around 1x10¹⁶ m^-3, and the neutral oxygen atom density of the order of 10²¹ m^-3. A huge flux of neutral oxygen atoms on the surface of samples exposed to plasma assures for rapid interaction with polymer materials. The modification of surface properties of the following polymers was studied: polyethyleneterephthalate (PET), polyethersulphone (PES), polyphenylenesulfide (PPS), Nylon 6 polyamide (PA6), polytetrafluoroethylene (PTFE), polystyrene (PS), polypropylene (PP) and cellulose (ink-jet paper and textile). The polymer samples were treated for 3 s in oxygen plasma at a pressure of 75 Pa where the O-atom density was the largest at 4x10²¹ m^-3. The appearance of the functional groups on the surface of the samples was monitored by high resolution X-ray photoelectron spectroscopy (XPS). The results show that oxygen plasma treatment is an effective tool for surface modification. On all polymer surfaces increased concentration of oxygen is detected. The high resolution C1s peaks indicate formation of several new oxygen-containing functional groups. On all polymers groups like C-O, C=O and O=C-O are observed. The concentration of these groups depends on the type of polymer. The highest uptake of oxygen by the polymer was found for cellulose and the lowest for polypropylene. The only exception was polymer PTFE where practically no chemical changes were observed after plasma treatment.

Strongly coupled plasmas - in which the average potential energy per particle dominates over the average kinetic energy - appear in a wide variety of physical systems. Among these systems, dust plasma crystals and liquids realized in low-pressure gas discharges by dispersing mesoscopic grains into the plasma have attracted a lot of attention during the past years. We describe the experimental realization of the quasi-two-dimensional dust system, summarize the basics of the computer simulation and theoretical approaches capable of their description in the liquid and solid phases. We discuss the properties of the dynamical density and current correlation spectra, generated by molecular dynamics simulations, and address the issues associated with the existence of different phases and transport coefficients (e.g. superdiffusive behavior) in the low-dimensional systems under study.

The friction in multi-component plasmas is discussed, and its effects on ion acoustic (IA) and drift waves. In the case of the IA wave it is shown that the friction between the two species has no effect on the mode in a quasi-neutral plasma. Using the Poisson equation instead of the quasi-neutrality reveals the possibility for an instability driven by the collisional energy transfer. However, the different starting temperatures of the two species imply an evolving background. It is shown that the relaxation time of the background electron-ion plasma is, in fact, always shorter than the growth rate time. Therefore the instability is unlikely to develop. The drift wave instability is also reexamined taking into account the ion response in the direction parallel to the magnetic field lines, which appears due to friction with electrons and which can not be omitted in view of the momentum conservation. A modified instability threshold is obtained. In plasmas with dominant electron collisions with neutrals, the instability threshold is shifted towards higher frequencies, compared to the case of dominant electron collisions with ions. The difference between the two cases vanishes when the ion sound response is negligible, i.e., when the instability threshold disappears, and both ions and neutrals react to the electron friction in the same manner. The results obtained here should contribute to the definite clarification of some contradictory results obtained in the past.

The primary objective of the present study was to assess anthropogenic impacts of heavy metals to the environment by determination of total atmospheric deposition of heavy metals. Atmospheric depositions (wet + dry) were collected monthly, from June 2002 to December 2006, at three urban locations in Belgrade, using bulk deposition samplers. Concentrations of Fe, Al, Pb, Zn, Cu, Ni, Mn, Cr, V, As and Cd were analyzed using atomic absorption spectrometry. Based upon these results, the study attempted to examine elemental associations in atmospheric deposition and to elucidate the potential sources of heavy metal contaminants in the region by the use of multivariate receptor model Positive Matrix Factorization (PMF).

The strategies for sampling and analysis by SEM/EDX and micro-Raman spectrometry for individual airborne particles analysis as applied at the University of Antwerp (Belgium) by the MITAC group have been reviewed. Microbeam techniques provide detailed information concerning the origin, formation, transport, reactivity, transformation reactions and environmental impact of particulate matter. Moreover, some particles of certain chemical properties have been recognized as a threat for human health and cultural heritage objects. However, the small sizes of particles result in specific problems with respect to single particle analysis. Development of equipment and software for improvement of analysis and quantification are reported.