FEDERAL UNIVERSITY OF SANTA CATARINA GRADUATION COURSE IN MATERIALS ENGINEERING

WALTER DALMAZ SILVA

INTERACTION OF 1,1-BIPHENYL WITH AN AR/O2 MICROWAVE PLASMA POST-DISCHARGE WITH AND WITHOUT N2 ADDITONS

FLORIANPOLIS 2011

FEDERAL UNIVERSITY OF SANTA CATARINA GRADUATION COURSE IN MATERIALS ENGINEERING

WALTER DALMAZ SILVA

INTERACTION OF 1,1-BIPHENYL WITH AN AR/O2 MICROWAVE PLASMA POST-DISCHARGE WITH AND WITHOUT N2 ADDITONS

Thesis presented to the Graduation Course of Materials Engineering from the Federal University of Santa Catarina as partial requirement for the attainment of Materials Engineer degree. Supervisor: Prof. Dr. Ana Maria Maliska. Co-supervisor: Dr. Thierry Belmonte

FLORIANPOLIS 2011

FEDERAL UNIVERSITY OF SANTA CATARINA GRADUATION COURSE IN MATERIALS ENGINEERING

WALTER DALMAZ SILVA

INTERACTION OF 1,1-BIPHENYL WITH AN AR/O2 MICROWAVE PLASMA POST-DISCHARGE WITH AND WITHOUT N2 ADDITONS

This work was assessed adequate to the attainment of the title Engenheiro de Materiais and approved by the Graduation Course of Materials Engineering from the Federal University of Santa Catarina.

Professor Fernando Cabral Course Coordinator

Dylton do Vale Pereira Filho Subject Professor

Professora Ana Maria Maliska, Dr. Eng. (orientadora) Universidade Federal de Santa Catarina

Professor Guilherme Mariz de Oliveira Barra, Dr. Eng. Universidade Federal de Santa Catarina

Professor Euclides Alexandre Bernardelli, Dr. Eng. Instituto Federal de Santa Catarina

Professor Dylton do Valle Pereira Filho, M. Eng. Universidade Federal de Santa Catarina

Silva, Walter DalMaz, 1989Interaction of 1,1-biphenyl with a microwave plasma post-discharge / Walter DalMaz Silva. 2011. 58 fl. : il. color. 30 cm Orientadora: Dra. Eng. Ana Maria Maliska Co-orientador: Dr. Thierry Belmonte Trabalho de Concluso de Curso (graduao) Universidade Federal de Santa Catarina, Curso de Graduao em Engenharia de Materiais, 2011. 1. 1,1-biphenyl. 2. Plasma Post-discharge. 3. Reaction mechanisms. I. Maliska, Ana Maria. II. Universidade Federal de Santa Catarina, Curso de Graduao em Engenharia de Materiais. III. Interaction of 1,1-biphenyl with an Ar/O2 microwave plasma post-discharge with and without N2 addtions.

To my parents: Deise and Walter.

Lexistence prcde lessence (Jean-Paul Sartre)

ACKNOWLEDGEMENTS

First of all, to my parents, responsible to my life, who afforded my formation during all these years and gave me the moral basis for living in this society.

To Prof. Ana Maliska, who conducted and oriented me in several works, including this, during college.

To Dr. Thierry Belmonte, who made this work possible in France, always clarifying my observations and teaching me so much about plasmas.

To everybody in LCM, including Misleine, Patrcia, Thiago, Daniel, Bruno, Fred, Keila and Euclides . To everbody in LSGS, including Cdric, Thierry Czerwiec, Tony, Gregory and Grard.

To all my friends, mainly Bruno Borges, Jefferson Rosrio, Lenise Knner, Mirella Leite, Guilherme Wagner and Jlio Correa.

To the examining board of this thesis, comprehending Prof. M. Eng. Dylton Pereira, Dr. Guilherme Barra and Dr. Euclides Bernardelli, for accepting the invitation and all the given advices.

To everybody involved in my formation who I did not explicitly mention here.

RESUMO

O presente trabalho apresenta o comportamento reacional bsico do composto 1,1bifenil com uma ps-descagar de um plasma microondas de argnio-oxignio em condies de baixa presso. Foi demonstrado que o 1,1-bifenil pode ser transformado em diversos produtos, principalmente compostos hidroxilados. O fracionamento contnuo destes promove a formao de compostos volteis, levando a limpeza superficial. O estudo destas reaes tambm pode fornecer informaes importantes para o tratamento superficial de polmeros e a degradao de ligantes na tecnologia de moldagem de ps por injeo. A temperatura e perda de massa do material foram estudadas em funo do tempo. A perda de massa apresentou um comportamento exponencial de primeira ordem e a temperatura atingiu um patamar constante em todas as condies de filme espesso. Interao da presso e fluxo aparentemente suprimem a reao por efeitos hidrodinmicos, modificam o tempo de interao das espcies excitadas e superfcie das amostras, levando a uma diferente temperatura superficial e portanto, uma diferente cintica de reao. O estado excitado do oxignio a1g foi considerado responsvel pela degradao do material. Demonstrou-se por ambas cromatografia em fase gs e espectroscopia de massa que molculas polissubstitudas relacionadas aos produtos reacionais so do tipo hidroxibifenil. Alguns mecanismos so propostos e relacionados a observaes prvias na literatura.

Palavras-chave: ps-descarga, microondas, bifenil.

ABSTRACT

The present work provides the basic reaction behavior of 1,1-biphenyl with an argonoxygen microwave plasma post-discharge under low pressure conditions. It has been shown that 1,1-biphenyl can efficiently be transformed in several by-products, mainly hydroxylate compounds. Continuous cracking of these promotes formation of volatile products leading to surface cleaning. Studying such reactions may also provide useful data for polymer surface treatments as well as degradation of binders in powder injection molding technology. Material temperature and mass loss were studied as function of time, as well as applied power and pressure. Mass loss has shown to present a first order exponential decrease and temperature has stabilized in all thick layer conditions. Interaction of pressure and flux seems to suppress reaction due to hydrodynamic effects, which modify the interaction time of the excited species and sample surface, leading to a different surface temperature and thus surface kinetics. Oxygen excited state a1g was related to material degradation. It has been shown by both gas chromatography and mass spectroscopy techniques that poly-substituted molecules concerning to the main by-products are hydroxybiphenyl-type. Several mechanisms are proposed and referred to previous observations found in the literature.

Keywords: post-discharge, microwave, biphenyl.

LIST OF FIGURES
FIGURE 1 ATOMIC OXYGEN CONCENTRATION AS A FUNCTION OF PRESSURE ADAPTED FROM MAFRA, (2008)........................................................................................................................................... 20 FIGURE 2 CHROMATOGRAPHIC BASIC SCHEMA, AS PRESENTED BY ROUESSAC, (2007). ........... 21 FIGURE 3 GAS CHROMATOGRAPHIC BASIC SCHEMA, AS PRESENTED BY ROUESSAC, (2007). .. 22 FIGURE 4 EXPERIMENTAL SETUP AS PRESENTED BY BERNARDELLI, (2011). ................................ 26 FIGURE 5 A SCHEMATIC VIEW OF REACTIVE PROCESS IN STEADY STATE. .................................. 31 FIGURE 6 TEMPERATURE EVOLUTION ALONG THE PROCESSING FOR THE THREE DESCRIBED CONDITIONS. ............................................................................................................................................ 33 FIGURE 7 WEIGHT LOSS FOR ALL CONDITIONS AS FUNCTION OF TIME......................................... 34 FIGURE 8 GRAFTING RATES FOR ALL CONDITIONS. ............................................................................ 35 FIGURE 9 ARRHENIUS PLOT FOR DETERMINATION OF TEMPERATURE DEPENDENCE OF EFFECTIVE REACTION COEFFICIENT. ................................................................................................ 36 FIGURE 10 GRAFTING RATE AS FUNCTION OF TIME FOR THREE DIFFERENT PRESSURES......... 38 FIGURE 11 GRAFTING RATE AS FUNCTION OF APPLIED POWER FOR THREE DIFFERENT PRESSURES. .............................................................................................................................................. 39 FIGURE 12 WEIGHT LOSS AS FUNCTION OF THE THERMAL CYCLE IMPOSED TO THE SAMPLES. ..................................................................................................................................................................... 40 FIGURE 13 DIFFRACTION PATTERN AS FUNCTION OF THE THERMAL CYCLE IMPOSED TO THE SAMPLES. .................................................................................................................................................. 41 FIGURE 14 OPTICAL MICROGRAPH OF SAMPLE IN THE CONDITION FC0 AT A MAGNIFICATION OF 50X. ....................................................................................................................................................... 42 FIGURE 15 XPS ANALYSES FROM THIN FILMS BEFORE AND AFTER TREATMENT. ...................... 43 FIGURE 16 BLUE LAYER EMISSION SCHEMA. ......................................................................................... 46 FIGURE 17 GC/MS OF SOLUTIONS #1, #2 AND #3, AT THE TOP IS PRESENTED THE EXPERIMENTAL AND NIST DATABASE SPECTRA FOR BIPHENYL.............................................. 54 FIGURE 18 GC/MS OF SOLUTIONS #1, #2 AND #3, AT THE TOP IS PRESENTED THE MASS SPECTRA FOR SIM EQUAL TO 170 M/Z. .............................................................................................. 54 FIGURE 19 GC/MS OF SOLUTIONS #1, #2 AND #3, AT THE TOP IS PRESENTED THE MASS SPECTRA FOR SIM EQUAL TO 186 M/Z. .............................................................................................. 55 FIGURE 20 COMPOUNDS USED IN CHEMICAL DERIVATIZATION ...................................................... 55 FIGURE 21 GC/MS OF COMPOUNDS TMS-DERIVED FROM SOLUTIONS #2 AND #3, SIM OF IONS AT M/Z EQUAL TO 211, 227 AND 242. ................................................................................................... 56 FIGURE 22 GC/MS OF COMPOUNDS TMS-DERIVED FROM SOLUTIONS #2 AND #3, SIM OF IONS AT M/Z EQUAL TO 299, 315 AND 330. ................................................................................................... 56 FIGURE 23 GC/MS OF COMPOUNDS TMS-DERIVED FROM SOLUTIONS #2 AND #3, SIM OF IONS AT M/Z EQUAL TO 418. ........................................................................................................................... 57 FIGURE 24 GC/MS OF COMPOUNDS TMS-DERIVED FROM SOLUTIONS #2 AND #3, SIM OF IONS AT M/Z EQUAL TO 105 AND 179 SHOWING DERIVATES CORRESPONDING TO BENZOIC ACID............................................................................................................................................................ 57 FIGURE 25 POSITIVE IONS LDI (266 NM) MASS SPECTRA OBTAINED FROM SOLUTIONS #1 #2 AND #3 BEFORE CHEMICAL DERIVATIZATION. .............................................................................. 58 FIGURE 26 POSITIVE IONS LDI (266 NM) MASS SPECTRA OBTAINED FROM SOLUTIONS #1 #2 AND #3 BEFORE CHEMICAL DERIVATIZATION FOR HIGH ATOMIC MASSES........................... 58

LIST OF TABLES
TABLE 1 INITIAL CONDITIONS FOR TEMPERATURE AND MASS CHANGE EVOLUTION. ............. 26 TABLE 2 INITIAL CONDITIONS FOR THE STUDY OF THE COUPLING BETWEEN PROCESS DURATION AND APPLIED PRESSURE........................................................................................................... 27 TABLE 3 INITIAL CONDITIONS FOR THE STUDY OF COUPLING BETWEEN PROCESS PRESSURE AND APPLIED POWER. ..................................................................................................................................... 27 TABLE 4 ADOPTED NOMENCLATURE FOR THE STUDY OF HEAT TREATMENT INFLUENCES. .. 28 TABLE 5 EQUIVALENT REACTION RATE COEFFICIENT FOR CONDITIONS C1, C2, C3 AND C4. .. 36

TABLE OF CONTENTS 1 1.1 2 2.1 2.2 INTRODUCTION .......................................................................................................... 14 Objectives .................................................................................................................... 15 LITERATURE REVIEW .............................................................................................. 16 Plasma Technologies .................................................................................................. 16 Interaction of Organic Compounds with Plasma .................................................... 18

2.3 Analytical Techniques ................................................................................................ 20 2.3.1 Gas Phase Chromatography ..................................................................................... 20 2.3.2 Laser Ionization Mass Spectroscopy ........................................................................ 22 2.3.3 X Ray Photoelectron Spectroscopy .......................................................................... 23 3 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 4 4.1 4.2 4.3 4.4 4.5 5 MATERIALS AND EXPERIMENTAL PROCEEDS ................................................ 25 Materials ...................................................................................................................... 25 Time evolution of the reactive process ...................................................................... 25 Effects of applied power and pressure...................................................................... 26 Heat treatment influences .......................................................................................... 27 Thin Film Analysis ..................................................................................................... 28 Gas Phase Chromatography coupled to Mass Spectroscopy GC/MS ................... 29 LDI-ToF-MS ............................................................................................................... 29 XPS Analysis ............................................................................................................... 30 RESULTS AND DISCUSSION ..................................................................................... 31 Time evolution of the reactive process ...................................................................... 31 Effects of applied power and pressure...................................................................... 37 Heat treatment influences .......................................................................................... 39 Chemical Analysis and Reaction Mechanics Investigation .................................... 42 Effects of Addition of Nitrogen and Hydrodynamics .............................................. 46 CONCLUSIONS ............................................................................................................. 48

REFERENCES ....................................................................................................................... 49 ANNEX A PHYSICAL AND CHEMICAL ANALYSIS ................................................. 54

14

INTRODUCTION
Plasma processes have been used in the last few decades due to their higher efficiency

and better environmental suitability. Low pressure plasma processes lead to lower effluent production and energy consumption, typically producing high level results. The present study deals with the interaction of an aromatic organic molecule, named 1,1-biphenyl, with an argon-oxygen microwave plasma post-discharge. Reactive oxygen species can be produced by using electrical discharges. They can be transported to an uncharged region by the gas flow in the so-called afterglows that are being intensively studied (PINTASSILGO, 2007; PINHEIRO, 1998; KUTASI, 2008; KUTASI, 2010; GUERRA, 2010; KUTASI, 2009). These species are well known to modify polymers (VESEL, 2009), to have bactericidal effects (YASUDA, 1982; FRIDMAN, 2008) but interaction mechanisms that occur between them with living microorganisms are still misunderstood (MOISIN, 2002; LEROUGE, 2001). Model molecules, i.e. molecules with a limited number of chemical bonds, were chosen (LEROUGE, 2001; BERNARDELLI, 2011) to allow the comprehension of interaction mechanisms between each type of specific bonds with these oxygen species. Previous studies employed hexatriacontane (C36H74, here named HTC) (HODY, 2006; MAFRA, 2008) and stearic acid (C18H36O2, here named SA) (NOL, 2009; BERNARDELLI, 2011) as model molecules. In HTC only sp3 bonds are found, being the material a model molecule for polyethylene. For SA an additional acid group is present, which is not modified. The present work introduces aromatic sp2 hybridized carbon, containing resonant bonds. Gonzales, (2009), proposed that atomic oxygen was responsible to ring opening in various polymers (polyetheretherketone, polyphenylsulfone, polyethersulfone and

polysulfone), while studying the interaction of remote atmospheric plasma with them. The model molecule here studied was chosen because it helps the study of aromatic bonds and because its melting point is 342 K, close to HTC (348 K) and SA (342,7 K). Aiming the comprehension of these interactions two different approaches are done: a macroscopic phenomenological explanation of the reactions, followed by physical-chemical analysis. In the first approach a general description of phenomena is presented and then physical features are explained according to a point of view of thermodynamics. The second

15

one gives a general view of molecular reactions, allowing identification of reaction byproducts, completing the thermodynamic explanation. The study is then condensed in a set of interface phenomena. Due to this characteristic it makes necessary to present a formal definition of an interface. From Gibbs definition, a heterogeneous system is that one which contains at least one interface. This interface is the matter zone separating two contiguous phases, each one characterized by an atomic and chemical structure. Absence of autonomy and its low extension in the perpendicular direction makes its characterization very delicate. According to the above given definition, the gas phase and the solid 1,1-biphenyl are a heterogeneous system, comprehending the gas-solid and solid-solid (grain boundaries) interfaces. Due to chemical homogeneity of solid state, focus is given in reactions occurring in gas-solid interface in a first approach. As it will be seen, liquid is formed in this region, producing two further interfaces, being these the real focus of the study. Other important features for the comprehension of the present work are presented in Section 2 (Literature Review), which is followed by experimental detailed description, results and discussion and finally the conclusion of the work. This work is a first step in the comprehension of oxidation of solid 1,1-biphenyl in low pressure post-discharge conditions. Its major contribution is the elucidation of some reaction mechanisms and mechanics of post-discharge and interface interactions.

1.1 Objectives
The present work has as main objective the comprehension of the basic mechanisms of the interaction of aromatic bonds with an argon-oxygen and argon-oxygen-nitrogen postdischarges. Specific objectives may be listed as: Description of reaction pathways of 1,1-biphenyl with oxygen; Identification of reactive species in the post-discharge zone; Experimental identification of reaction by-products; Consolidate a basis for comprehension of aromatic polymers treatments.

16

LITERATURE REVIEW
As a first step in the comprehension of the degradation mechanisms of organic

compounds in microwave plasma post-discharge, a literature review is presented preparing the basis for the understanding of the present study. Basic plasma concepts, electrodynamics, an overview on plasma cleaning and the applied analysis are presented in this section.

2.1 Plasma Technologies

A brief introduction to plasma physics and technology needs at least a simple definition of this medium. According to Moisin, (2006), plasma is a medium composed by electrons and ions free to move in any direction. It differentiates from a classical neutral gas by the strong interactions between charged particles. Considering columbic forces in a plasma volume, it is given a collective response to any perturbation inside it. In other words, one may conclude that plasma is a collective behavior medium. Still considering charge equilibrium, plasma is macroscopically neutral if its dimensions are greater than a quantity known as Debye length, defined in terms of the maximum average displacement that a perturbation can induce in a given plasma (MOISIN, 2006; CHAPMAN, 1980). The two main characteristic quantities of a plasma, from the point of view of its particles, are its electron density and temperature. In general, electron density of a laboratory discharge is of the magnitude of 1010 to 1015 electrons per cubic centimeter. In comparison, a nuclear explosion may present density in the order of 1020 electrons per cubic centimeter (MOISIN, 2006). From its definition, temperature is a quantity that allows characterizing thermal agitation energy of the particles in a system, once it is related to its mean value (MOISIN, 2006). Plasmas can be classified in two main groups: cold plasmas and plasmas in thermodynamic equilibrium. The first group is characterized by non-equilibrium between electron and ions temperatures. The second one is assumed to present thermal equilibrium between different species, leading to a so-called hot plasma, with known applications in nuclear fusion (MOISIN, 2006; FRIDMAN, 2008). Plasmas hereafter treated are classified as cold discharges. Plasma applications and research domains are encountered in most diverse science areas. Some examples presented by Moisin, (2006), comprehend controlled thermonuclear fusion, astrophysics, gaseous lasers, chemical transformations and effluent treatments,

17

medical objects sterilization, elemental analysis, illumination, plasma screens, ion sources and surface treatments. Chemical transformations and surface treatments are the focus of the present work. In general, surface treatments comprehend deposition process, chemical reactions, physical-chemical process or erosion (sputtering). It is fundamental to investigate pretreatment conditions of surfaces, aiming a better adherence of deposits, greater efficiency of physical, chemical or erosive processes, and also avoid formation of undesirable products. For instance, in production of microelectronic components, following a general tendency of miniaturization, plasma applications has gained functions in elemental operations, mentioning surface cleaning, etching, deposition, ionic implantation, lithography, oxidation, and heat treatments. Also with great importance one can mention the production of polycrystalline diamond films of great interest of electronic industry (MOISIN, 2006). Research and industry have applied several types of laboratory discharges. The main techniques can be listed as: Low frequency AC or DC discharges; High frequency discharges; Laser induced discharges. In applications employing AC or DC sources electrodes need to be in direct contact with discharge. Discharge breakdown is given by acceleration of free electrons in the electrical field with a subsequent production of electrons and ions by successive collisions (MOISIN, 2006). High frequency plasmas are divided in two main ranges of frequencies complaining RF (radiofrequency, between 1 MHz and 300 MHz) and MW (microwave, from 300 MHz to 300 GHz). RF electrodes may be positioned or not in contact with discharge, depending on application requirements. Microwave discharges are in general produced by an external field source, without contact with the discharge (waveguide) (MOISIN, 2006). Laser induced plasmas are based in the nature of interaction of photons with gas atoms. It is basically divided in processes applying low or high photonic intensity (MOISIN, 2006). According to Mora et al. (MORA, 2010), it is expected that the introduction of a molecular compound in pure argon shall induce important changes in plasma kinetics. This is done to the lower energy transfer from electrons to argon species due to losses in vibration excitation in molecular species. Moreover, ionization/excitation of argon will be changed, once part of the free energy in the discharge is applied in dissociation/excitation of molecules.

18

2.2 Interaction of Organic Compounds with Plasma

This item has the aim to present the brief explanation about the current state of art of low pressure plasma cleaning processes. Several works already known in literature, concerning to decomposition and modification of organic compounds in low pressure discharge or post-discharge, are presented. Mafra, (2008), highlights the works by Holland, (1958), as being the pioneers in plasma cleaning, even before 1960. However in that time the applied technique, as mentioned by the first author, was more likely to be art as to be science. Still in 1970s, a study presented by OKane, (1974), showed higher efficiency in Ar and He+3%O2 plasmas cleaning in comparison with organic solvents. It was clear, however, that re-contamination was faster when of the employment of plasma cleaning. Due to prohibition of CFCs in 1997 by Montreal Protocol, a drastic revision in cleaning processes was begun. Petasch, (1997), mention that a direct impact of the interdiction is that aqueous or solvent processes are applied with final plasma cleaning to better finishing. The authors emphasize that plasma processes lead to completely dry components after cleaning, suppressing further drying processes. In the same work, it is still presented, in an aircraft industry approach, the processing applying a microwave discharge of 2,45 GHz containing oxygen and CF4, allowing ideal painting of metallic components, filling the acceptable erosion tolerances and without hydrogen embrittlement. Ricard, (2003), obtained by analytical means the production of atomic oxygen in Ar-O2 and N2-O2 discharges. Their objective was to determine post-discharge characterization, applying NO titration and the FOCP (Fiber Optic Catalytic Probe) technique. In applied conditions it was determined a saturation in atomic oxygen production for effective power over 120 W in Ar-O2 discharges. This result is particularly important once it provides information to process optimization, avoiding energy losses. According to Pinheiro, (2002), low pressure discharges in oxygen (in the present study containing oxygen) are of special interest as sources of atomic oxygen for materials treatment or O2 (a1) metastables for biochemical depolution of liquids. In order to justify the sequence of experiments carried in the present work focus has been given in the works from Mafra, (2008), and Bernardelli, (2011), since this one is taken as a third part of a sequence of those studies. Previous experiences by Mafra, (2008), showed that the sample holder should not be greater than about 20 mm, once homogeneity is expected from material treatment. The author has also shown that initial temperature has great

19

influence over treatment kinetics and reaction sequence and by-products. Initially heating has been linked to heated gases coming from discharge region, which was proved to be wrong since sample cooling was observed after several minutes of treatment and simulation of rotational temperature of the gas has shown that its temperature was well below that measured in the samples. In the case of HTC, atomic oxygen was related to material modification. Mafra, (2008), divides material behavior in three different parts: an initial heating, followed by constant temperature and a final decrease in temperature. The rate of mass variation presents a high increase and then the samples increase weight. After about 120 minutes the sample mass remains almost the same from initial condition. The behavior of HTC follows a sequence of melting, formation of a thin solid film, stabilization of the film followed by stabilization of the surface. Evidences of structural chemical modifications are given by a change of color, which goes from white to light yellow. Bernardelli, (2011), has observed different behavior for SA from that observed by Mafra, (2008), to HTC. Stearic acid seems to present a very different behavior depending on initial temperature, while HTC seems to present the same behavior retarded to the lower treatment temperature. As presented by Mafra, (2008), the author also divides the mass variation in three regions. Mass increases in the first part until 45 minutes independently from initial temperature. In the second one, for treatments with initial temperature of 313 K, decreases rapidly until 60 minutes and remaining constant up to 90 minutes of treatment, loosing mass up to 120 minutes. Treatments with initial temperature of 333 K only present a constant gain of mass during the whole process. The same change in color mentioned by Mafra, (2008), is observed by Bernardelli, (2011), as well as the formation of a liquid puddle. As presented by Mafra, (2008), an increase in pressure leads to increase in atomic oxygen population, as depicted in Figure 1. This observation will be used in justification of some of the experimental results hereafter presented.

20

Figure 1 Atomic oxygen concentration as a function of pressure adapted from Mafra, (2008).

Both thesis from these authors (MAFRA, 2008; BERNARDELLI, 2011) formed the basis for the description and conduction of the experiments hereafter presented.

2.3 Analytical Techniques

This section has the aim to provide basic information about the hereafter employed experimental techniques. Gas phase chromatography, laser desorption mass spectroscopy and x ray photoelectron spectroscopy are presented, as a basis for the comprehension of the experimental results and discussion.

2.3.1 Gas Phase Chromatography

In the middle of 19th century Schnbein and Goppelsrder made the first step to the technique which became shortly after 1900, by Tswett, the modern chromatography. The process has been one of the primary analytical methods for identification and quantification of compounds in fluids, i.e. gases or liquids. Its principle is based on the concentration equilibrium of the components of interest, between two immiscible phases, being one named stationary phase and the other the mobile phase. Since the different compounds in a mixture have different mobility in these phases, differential migration of compounds leads to their separation. In Figure 2 it is presented a basic schema for the process which may be described as follows:

21

a) The column is filled with suitable finely powder, the stationary phase (SP); b) At the top of the column a small volume of the sample is placed; c) Elution is carried by continuous addition of the mobile phase (MP), which carries the various constituents of the mixture along the column; d) Recovery of the constituents.

Figure 2 Chromatographic basic schema, as presented by Rouessac, (2007).

An evolution of the process has been developed in the 1940s by taking account in the retention times of specific compounds, which was then compared to pattern samples to perform the identification of the compound. Nowadays chromatographic techniques are piloted by computers, achieving high definition (ROUESSAC, 2007). Identification of a molecular compound only by its retention time is somewhat arbitrary. The association of a chromatograph with a second technique, such as mass spectrometry or infrared spectrometry, allows the determination of composition and concentration of samples with a few nanograms without ambiguity (ROUESSAC, 2007). Gas chromatography is a process by which a mixture is separated into its components by a moving gas phase passing over a stationary sorbent. It is divided in to major categories: gas-liquid and gas-solid chromatography. Gas-liquid process occurs by partitioning a sample between a mobile gas and a thin layer of a non-volatile liquid coated on an inert support (JEFFERY, 1989). It was Martin and Synge who, in 1941, suggested the replacement of the liquid mobile phase by a gas in order to improve the separations. From this era comes the true beginnings of the development of analytical chromatography. In gas-solid chromatography a solid of large surface area is employed as the stationary phase. In this process, the separations can be so complex that it can be difficult to determine in advance whether the temperature

22

should be increased or decreased. The choice of column, its length, its diameter, the stationary phase composition and the phase ratio (VM/VS) as well as the parameters of separation (temperature and flow rate), are amongst the factors which interact with each other (ROUESSAC, 2007). Figure 3 presents a schema for gas chromatographic systems.

Figure 3 Gas Chromatographic basic schema, as presented by Rouessac, (2007).

Because separation of compound mixtures on the column occurs while they are in the gaseous state, solid and liquid samples must first be vaporized. This represents, without hesitation, the greatest constraint of gas phase chromatography and weighs against it, since its use is limited to the study of thermostable and sufficiently volatile compounds. The mobile phase that transports the analytes through the column is a gas referred to as the carrier gas. The carrier gas flow, which is precisely controlled, enables reproducibility of the retention times. Further information on equipments, columns, control parameters may be found in literature.

2.3.2 Laser Ionization Mass Spectroscopy

Laser Ionization Mass Spectroscopy (LIMS) is an analytical technique employed in measurement and detection of trace-level elemental or molecular contaminants or dopants on surfaces, in thin films or bulk materials. LIMS is similar to SIMS technique, except that a laser beam is used instead of an ion beam. The laser beam is focused in a small area of sample surface (1 to 5 m in diameter) to remove and ionize some material. Using low intensity laser pulses permits the removal of organic compounds or molecules fragments. LIMS spectra can be quantified using standards in certain cases, but LIMS data are usually qualitative only (BRUNDLE, 1992).

23

The basic principle is high-power short pulse laser desorption/ionization followed by a time-of-flight mass spectrometer analysis. This technique is considerably more sensitive than other survey microanalytical techniques, such as Auger Electron Spectroscopy (AES) or Electron Probe Microanalysis (EPMA). Additionally, LIMS can be used to analyze insulating samples and has the ability to sometimes provide basic molecular information about inorganic as well organic surface contaminations, as required in this research (BRUNDLE, 1992). When the energy radiated into the material significantly exceeds its heat of vaporization, a small plasma cloud is formed near the sample surface. The further interaction of the laser with the plasma cloud provides formation of various ionic fragments, typically single charged (BRUNDLE, 1992). The laser irradiation of a material can produce molecular ionsif the power density of each pulse is sufficiently low. The analysis of such molecular species includes the study of organic materials ranging from polymers to biological specimens, as well as the analysis of known or suspected organic surface contaminants. LIMS is applied primarily to identify a number of fragment ions in a spectrum that are diagnostic for a given class of organic species (BRUNDLE, 1992). A general requirement for LIMS analysis is that the material must be vacuum compatible and able to absorb UV laser radiation. Irregular samples are often analyzed. This is possible because ions are produced and extracted from pm-sized regions of the sample, without much influence from nearby topography. However, excessive sample relief is likely to result in reduced ion signal intensity (BRUNDLE, 1992). In the present work this technique will be referred as LDI-ToF-MS.

2.3.3 X Ray Photoelectron Spectroscopy

The photoelectric process, discovered in the early 1900 was developed for analytical use in the 1960s, largely due to the pioneering work of Kai Siegbahn's group. Surface sensitivity, combined with quantitative and chemical state analysis capabilities have made XPS the most broadly applicable general surface analysis technique today. It is applicable to biological, organic, and polymeric materials through metals, ceramics, and semiconductors (BRUNDLE, 1992). A photon of sufficiently short wavelength (i.e., high energy) can ionize an atom, producing an ejected free electron. The kinetic energy KE of the electron (the photoelectron) depends on the energy of the photon E=hv expressed by the Einstein photoelectric law: the

24

kinetic energy of the photoelectron is equal to the balance of energy between the incident electron and the binding energy (BE) of the particular electron to the atom concerned (BRUNDLE, 1992). The energy levels of each orbital are discrete and are different for the same orbital in different atoms because the electrostatic attraction to the different nuclei is different. To a first approximation, the BE of an electron, as determined by the amount of energy required to remove it from the atom, is equal to the E value (this would be exactly true if, when removing an electron, all the other electrons did not respond in any way). So, by experimentally determining a BE, one is approximately determining an E value, which is specific to the atom concerned, thereby identifying that atom (BRUNDLE, 1992). The number of peaks in the spectrum corresponds to the number of occupied energy levels in the atoms whose BEs are lower than the X-ray energy hv; the position of the peaks directly measures the BEs of the electrons in the orbitals and identifies the atom concerned; the intensities of the peaks depend on the number of atoms present and on the Q values for the orbital concerned. All these statements depend on the idea that electrons behave independently of each other. This is only an approximation. When the approximation breaks down, additional features can be created in the spectrum, owing to the involvement of some of the passive electrons (those not being photoejected). More about XPS may be found in Brundle, (1992).

25

MATERIALS AND EXPERIMENTAL PROCEEDS

This item has the aim to describe the applied materials, process parameters and the

analysis employed in the present work.

3.1 Materials
The basic materials employed in the present study were 1,1-biphenyl, silicon wafers used in thin film analysis and gases. Biphenyl was supplied by Merck Schuchardt OHG in degree of purity over 99%. According to the supplier the material presents melting point in the range from 341 K to 343 K and molar mass of 154.21 g.mol-1. Silicon wafers were supplied by Siltronix, single side polished and with orientation (100). Industrial oxygen and nitrogen were applied with purity over 99,5%, being the maximum water contamination of 200 ppmv. Argon with purity over 99,995% was used.

3.2 Time evolution of the reactive process

As a first step in the research of the reaction mechanisms of biphenyl with the plasma post-discharge it was carried a study involving the measurement of mass change and temperature evolution as functions of process duration. Biphenyl was molten by means of a resistance heater in a glass recipient and then cast in a PTFE sample holder and touching the reaction material, which was covered by another PTFE part in turn to allow slow cooling and solidification, forming a 4 mm thick film. After this procedure, each sample had its weight measured, which was repeated after each cycle, in order to follow mass change as function of process duration. Temperature evolution was followed by means of a thermocouple connected directly to the sample holder. Mass and temperature evolution were registered in the range of 1 minute to 60 minutes. After 1 hour hydrodynamic effects take place due to sample holder geometry and no reliable data can be obtained. It was impossible to carry experiments with duration over 90 minutes for the basis condition of 400 Pa and 150 W. Samples were placed at a distance of 900 mm from the wave-guide (discharge generation) with a PTFE cover, avoiding contact of post-discharge with the biphenyl before pre-heating and discharge stabilization. The process chamber was then evacuated by means of a vacuum pump, which allowed final pressures of less than 200 Pa. An argon flux of 900 sccm was inserted in the reactor and pressure was set to be 400 Pa. Power of 150 W was

26

applied to discharge, which was lightened by an electrical arc. The microwave source has a frequency of 2,45 GHz.

Figure 4 Experimental setup as presented by Bernardelli, (2011).

A set of three different initial conditions were carried in the present study, combining initial heating and process pressure. Oxygen flux of 100 sccm was inserted in the chamber only after pre-heating, allowing pressure to be set according one of the three initial conditions. Sample cover was removed, allowing reaction to take place on the sample exposed surface. Process duration was considered only after the removal of this sample cover. Table 1 presents parameters and identification of the three applied initial conditions.

Table 1 Initial conditions for temperature and mass change evolution. Condition Pressure (Pa) Initial Temperature (K) C1 400 313 C2 600 313 C3 400 333

3.3 Effects of applied power and pressure

In a second plan, the interactions between couples of variables time, pressure and applied power were investigated. Sample preparation was carried in the same way as before described to temperature evolution. Total flux and atmosphere composition were the same as

27

for section 3.2. Initial temperature was set to be 313 K in all cases. The practice of covering the sample and measuring the sample mass before and after processing were still employed here in order to allow process control and determine grafting rate, respectively. For the study of coupling between time and pressure, processing times of 20, 40 and 60 minutes were used. Specific conditions and process identification (some of which coincide with those from section 3.2) are presented in Table 2. Previous experiments showed that weight loss for pressures over 800 Pa was negligible in the first 60 minutes of process.

Table 2 Initial conditions for the study of the coupling between process duration and applied pressure. Condition Pressure (Pa) C1 400 C2 600 C4 800

Coupling between pressure and applied power was studied in fixed process duration of 60 minutes. Applied power in the range from 150 to 450 W was employed. By intersection of columns and lines, specific conditions are identified by Table 3. As it has been observed in previous experiments, increasing power over 450 W has little effect over grafting process when compared with this limiting power.

Table 3 Initial conditions for the study of coupling between process pressure and applied power. Pressure (Pa) 400 Power (W) 150 300 450 C1 C11 C12 C2 C21 C22 C4 C41 C42 600 800

3.4 Heat treatment influences

It has been observed in previous experiments that weight loss was not reliable since the pre-heating time of the samples in the reactor was changed due to external conditions. Due to these observations, it was proposed that thermal cycling of the material could promote changes in its reactivity and on the grafting rate. In the aim to explain this phenomenon, four different thermal cycles were applied to samples, which were submitted to post-discharge treatments and optical microscopy, which allowed observation of microstructure of the

28

samples before processing. As an additional method, x ray diffraction was employed to verify if any preferential crystal orientation is observed. Sample preparation as well as process configuration were carried almost in the same manner as described in section 3.2. The main difference in this case was that in some configurations no cover was used on the samples during solidification, allowing fast cooling. Samples may be divided in two groups: Samples covered during cooling (slow cooling); Samples without cover during cooling (fast cooling).

Both groups were then divided in two further groups: Samples in the solidified condition; Samples annealed.

These divisions promoted four different kinds of samples, which were then submitted to treatments at same total flux, atmosphere composition and applied power as section 3.2. Processing was carried in durations from 30 to 60 minutes with an initial temperature of 313 K and pressure of 400 Pa. Annealing was carried in the range of 323-333 K with duration of 60 minutes in argon atmosphere in pressure over 1000 Pa. Previous tests with 30-minuteannealing showed no reliability. Table 4 presents the adopted nomenclature for sample conditions.

Table 4 Adopted nomenclature for the study of heat treatment influences. Nomenclature SC0 SCA FC0 FCA Condition Slow cooled, as solidified Slow cooled and annealed Fast cooled, as solidified Fast cooled and annealed

3.5 Thin Film Analysis

Thin films of biphenyl were produced by spin coating over silicon wafers in the aim to investigate, by means of advanced techniques, the reaction products of the post-discharge with the compound.

29

The molten material was cast over a silicon substrate (~1cm2) rotating at 150 Hz. This procedure allowed obtaining films in the range of 30 to 70 m. This kind of sample served as base for ion bombardment spectroscopy, XPS and gas phase chromatography. Wafers were placed in a sample holder adapted to them, allowing the practice of covering the samples before discharge stabilization. All treatments of thin films were carried at 313 K and pressure of 400 Pa for 5 minutes. For Ar-O2 mixtures, total flux, atmosphere composition and applied power were the same as section 3.2.

3.6 Gas Phase Chromatography coupled to Mass Spectroscopy GC/MS

In gas phase chromatography and mass spectroscopy it was employed a chromatograph Varian GC-3800 coupled with a mass spectrometer Varian Saturn 2000 in full scan mode, operating from 50 to 650 amu with an ionization energy of 70 eV. The temperature varies from 323 to 593 K for 18 minutes. Different solutions were obtained in function of residues colors, as presented below: Solution #1: 0,5 mg of white crystals in 200 l of dichloromethane; Solution #2: 0,5 mg of yellow crystals in 200 l of dichloromethane; Solution #3: 0,6 mg of brown crystals in 200 l of dichloromethane. Solutions were analyzed directly or after chemical derivatization (trimethoxysilylation of eventual acid functions, amines, alcohols) in the aim of make polar compounds compatible with GC/MS. Injection volume of 0,5 l was employed, with split ratio of 50, with a total of about 25 ng.

3.7 LDI-ToF-MS
The same solutions described in section 3.6 were employed here. In this case, the solutions were deposed over a metallic sample holder and analyzed in a Brucker MALDITOF-MS, type Reflex IV. It is equipped with a nitrogen laser (337 nm) classically used for protein analysis in MALDI mode. In this case an alternative laser (266 nm) was employed, without necessity of MALDI matrix, allowing analysis of compounds with a high absorption in this wavelength. This shows particularly efficient in aromatic compounds analysis.

30

3.8 XPS Analysis

XPS measurements are performed with a Thermo VG Microlab350 spectrometer using a non-monochromated Al Ka and Mg Ka dual anode as X-ray source operated at 300 W and a Spherical Sector Analyser. Survey spectra to identify elements on the surface were recorded in steps of 1 eV at a 100 eV pass energy. High resolution spectra of separate photoelectron lines (C 1s, O 1s, Si 2p and N 1s) were taken by steps of 0.05 eV at a constant pass energy of 20 eV. The normal operation pressure was 5x107 Pa. The photoelectron take-off angle (TOA) was normal to the surface of the samples. The sample surface covered by the analysis is 2x5 mm. Spectra processing (atomic concentrations, curve fitting, etc.) was done after the removal of a Shirley type background with the CasaXPS software. The atomic concentrations were calculated using the Scofield relative sensitivity factor provided by the CasaXPS library. Samples are introduced in the spectrometer readily after plasma treatment in order to limit contamination from ambient air storage.

31

RESULTS AND DISCUSSION

Hereafter are presented the results obtained from the experiments. Firstly, the main

features of the measurements are presented and then a general discussion is given.

4.1 Time evolution of the reactive process

As a first step for the comprehension of the reactive processes involving biphenyl and the post-discharge, it makes necessary to describe the macroscopic related phenomena. For condition C1 (313 K, 400 Pa) the first change observed was the surface color, which turned into light brown after a few seconds exposed to post-discharge. As it will be explained in section 4.4, this was related to formation of oxidized biphenyl. Heating is observed and melting of a light brown compound occurs, which was linked to mass loss. In this point the first interface, concerning contact of solid with gas is replaced by two further interfaces: solidliquid and liquid-gas. These both interfaces represent the process steady state and govern reaction mechanics. Reactions by-products are formed mainly in liquid-gas interface, retrodiffusing into the liquid puddle, and possibly carrying further reactions. Biphenyl is supposed to be soluble in the puddle, diffusing to the liquid-gas interface to feed further reactions. Figure 5 presents a schematic view of the reactive process.

Figure 5 A schematic view of reactive process in steady state.

In great part of the cycles of processing, solid bubbles apparently with the same color were observed. After the formation of these bubbles no further grafting in these areas is observed, indicating process termination. It is important to emphasize that no melting of the bulk material occurs. Another point is that the measured surface temperature is just qualitative in process beginning. Due to high energies dissipated in the liquid-gas interface by chemical reactions the temperature is significantly higher in this region until temperature steady state.

32

Higher pressure is applied in condition C2 (313 K, 600 Pa), in which the same general features were observed. In this case a lower final temperature is achieved as well as lower grafting rates were observed. After formation of a liquid film competition between diffusion flux and surface reaction rate take part and diffusion governs the process in the steady state. These phenomena are related to gas phase consumption of the reactive species responsible to surface reactions with biphenyl. Under the present experimental conditions used to create the post-discharge, the most concentrated species are O2 (~2.4 x 1018 cm-3), O2 (a1g) (~2.4 x 1018 cm-3) and O (~1015 cm-3) (PINTASSILGO, 2007; PINHEIRO, 1998; KUTASI, 2008; KUTASI, 2010; GUERRA, 2010; KUTASI, 2009). Ozone was shown to be negligible (MAFRA, 2008) and other excited states of O and O2, at low concentrations (<1013 cm-3) will not be considered. As presented by Mafra, (2008), an increase in pressure leads to increase in atomic oxygen population in the experimental conditions very close to those here employed, which is shown in Figure 1. The insertion of a tungsten sheet inside the post-discharge tube with the aim to decrease atomic oxygen density has shown no effect over grafting kinetics. Since no reaction was observed only with oxygen and heat (3382 K), one may argue that molecular excited oxygen O2 (a1g) is the main responsible for reaction with biphenyl, and its decomposition in atomic oxygen due to increase in pressure decreases the reaction rate. In other way, condition C3 (333 K, 400 Pa) shows melting of the bulk material in the first minutes of process with a subsequent decrease of temperature. After this decrease of temperature the same change of color, as bubbles formation are observed. Initial heating is due to high energy supply in the interface solid-gas, which is soon substituted by a liquid one, limiting the reaction mechanism by liquid diffusion of biphenyl in direction of the interface liquid-gas. The peak temperature is determined by the high availability/activity of biphenyl in the first minutes. As the non-reacted biphenyl in the liquid puddle is consumed, reaction rate is governed by liquid diffusion of solid biphenyl in the puddle, giving rise to a steady state condition after approximately five minutes. The decrease in temperature is easily explained by the fact that no external heating device is sustaining temperature over the initial setup. It is important to emphasize that temperature stabilization is given in a higher value than that observed for condition C1. Two basic approaches may be done: reaction mechanisms are changed with the higher temperature and so a different final temperature is observed, or diffusion kinetics of non-reacted biphenyl in the thin solid film is changed and so a higher temperature is sustained. It will be considered that the same mechanisms (and so reaction kinetics) occur for condition C3, and so hereafter the diffusion controlled approach is accepted, as it has been inferred by mass spectroscopy of laser desorpted thin films.

33

The solid-gas interface in the beginning has only reactive biphenyl, which turns into a liquid film rich in non-reacted material. So, in the first moments, i.e. initial five minutes of process, mass loss is also due to direct evaporation. In the other hand, liquid has only a certain quantity of non-reacted biphenyl. As one may point, the higher free-energy compound in this series of oxidized biphenyls in the non-reacted biphenyl, being the most reactive compound in the liquid puddles. This explains the rapid heating in the first three minutes of process and the non-sustainability of temperature by diffusion-limited reactivity during long term processes. For condition C3 final temperature is higher than that observed for condition C1 due to the higher diffusion coefficient in the limiting liquid phase. Heating curves are presented for the conditions described in section 3.2 are presented in Figure 6.

Temperature Evolution as Funtion of Time

340

335

Temperature (K)

330

325

320

315 0 5 10 15 20 25

C1 C2 C3
30

Time (minutes)

Figure 6 Temperature Evolution along the processing for the three described conditions.

In all cases, heating rate is high in three first minutes of processing due to direct solidgas contact. Depending on the initial temperature, the behavior is separated in thermal equilibrium between energy due reaction mechanisms with loss to walls (conduction) and to post-discharge flux (convection). If melting is observed, a maximum temperature is achieved and then heat dissipation is carried by evaporation (association of low pressures, flux and high vapor pressure) and several reactions, leading to thermal equilibrium after a temperature decrease and the same reactions as in others conditions before described occur.

34

Weight change is negative in conditions C1, C2 and C3. Actually, mass loss is observed in this whole study. Different mechanisms were identified for these three conditions. Weight change measurements for these conditions are presented in Figure 7.
Weight Loss as Funtion of Time
0,0

Weight Loss, -dm, (g)

-0,2

-0,4

-0,6

C1 C2 C3
0 10 20 30 40 50 60

-0,8

Time (minutes)

Figure 7 Weight loss for all conditions as function of time.

In those cases in which no melting of the bulk material is observed (C1 and C2), grafting rates are kept constant during all treatment, indicating a possible single mass lost mechanism during the hole cycle. In the other side, when melting is observed, as a first step both evaporation of liquid phase and volatile compounds formation are competitive. After this initial step, grafting rate approaches to the case in which same pressure but lower temperature is applied. This comparison may be done between conditions C1 and C3, which sustains the possibility of same reaction mechanisms for both initial temperatures, even if the steady state temperature is different. Grafting rates, as determined from Figure 7 are presented in Figure 8.

35

2,5

Grafting Rate as Function of Time, =() C1 C2 C3

2,0

Grafting Rate, - (g.m .s )

-2

-1

1,5

1,0

0,5

0,0 0 10 20 30 40 50 60

Time (minutes)

Figure 8 Grafting rates for all conditions.

Disregarding the initial melting observed in condition C3, which was related to larger mass loss, etching rates follow always the same trend, a first order exponential decay, at least in the accuracy of the raw data. Assuming constant temperature and oxygen precursor concentration versus time we deduce that the etching process is a first order process with respect to biphenyl: and are the concentrations of biphenyl and the reactive oxygen species impinged on biphenyl surface. Kinetics may be described as: where is the constant of the etching process. Since mass is proportional to concentration of

biphenyl, the solution of the kinetic equation leads to: 1

36

is the equivalent etching constant, since we have considered constant where concentration of reactive oxygen species. Fitting curves applied to this model mod employing the software Origin 8.1 were obtained and are present with raw data in Figure 7. Table 5 presents the obtained values for while Figure 9 presents its determination from an Arrhenius plot. plot

Arrhenius Plot for ke

-7

ln(ke)

-8

ln(ke)
-9 -10 2,96 2,98 3,00 3,02
-1

3,04

3,06

3,08

1000/T (K )

Figure 9 Arrhenius nius plot for determination of temperature dependence of effective reaction coefficient.

Table 5 Equivalent reaction rate coefficient for conditions C1, C2, C3 and C4. Condition C1 C2 C3 C4* (x10-4 s-1) 2,91 0,69 6,32 0,10 Relative 1,00 0,24 2,17 0,04 *calculated

Since discharge conditions for conditions C1 and C3 were the same, it is assumed that both conditions present the same reactive species in post-discharge. post discharge. With this assumption of constant one can point that the reaction rate coefficient is multiplied mu by a factor of

2,17 with an increase of 5 K in this range of temperatures, as observed for both conditions. Assuming an exponential behavior for temperature dependence of the rate coefficient:

37

and so an Arrhenius plot can be obtained by: ln ln This procedure lead to the determination of the effective reaction rate coefficient as function of the temperature, for R expressed in J.mol-1.K-1. 1,314 10 exp 144,4 10

The importance of this procedure will be presented in the following section, justifying and approximate constancy in the concentration of the reactive specie responsible for biphenyl degradation. Parallel experiments were carried in the aim to understand post-discharge dissolution effects over temperature and mass loss. It was observed that both argon and oxygen addition had no measurable changes in these variables. This confirmed the rule of excited molecular oxygen and atomic oxygen as main reactive species.

4.2 Effects of applied power and pressure

After an overview of the general features of biphenyl decomposition, plasma control variables were studied in the aim to comprehend their influence over formation of reactive species in post discharge. For a constant power, it was identified that mass loss from condition C2 is in the range from 25% to 30% of that observed from C1, with no dependence of process duration until 60 minutes. For condition C4 this constant is about 4 to 5% from condition C1 in the same range of process duration. Pressures over 1000 Pa lead to no mass loss in the studied time scale. In previous section the effective reaction rate coefficient was determined as a function of temperature. Comparing the experimental values obtained of 400 and 600 Pa (conditions C1

38

and C2) it is possible to identify the same ratio between their reaction rate coefficients. Using the maximum temperature achieved for the sample processed at 800 Pa (C4) to calculate its effective reaction rate coefficient at this pressure the same pattern is observed. At this stage one may point that the concentration of has remained constant in this range of

pressures and the degradation is limited only by the maximum temperature achieved in sample surface (mainly due to hydrodynamic effects). This comparison can be made since the time for which mass loss is compared is considerably greater than heating time (due to the supposition of constant temperature). The grafting rate as a function of time for the three applied pressures is presented in Figure 10. The small decrease in grafting rate from 40 to 60 minutes is mainly due to hydrodynamic effects (turbulence over the sample holder after large grafting), since no polymerization is observed.
Grafting Rate as Function of Time
0,0

-0,1

dm/(A*t) (g.m .t )

-0,2

-2 -1

-0,3

-0,4

-0,5

400 Pa 600 Pa 800 Pa

20 40 60

-0,6

Time (minutes)

Figure 10 Grafting rate as function of time for three different pressures.

It was observed that higher pressures lead to a decrease in the region of the postdischarge with light emission. This cannot be related to mass loss as a function of pressure since it was demonstrated a good agreement between the calculate values for effective reaction rate coefficient and the measured mass loss, as presented above. Interaction of power and pressure showed that the process has a limit of efficiency with increasing power. This is done by saturation in the excitation cross section for

39

production of molecular state O2 (a1g), with increasing efficiency in atomic oxygen production. Pressure dependence was the same as for this variable treated isolated. In Figure 11 grafting rate is presented in function of applied powers for three different pressures. As it can be seen, at 800 Pa no considerable mass change may be observed.
Grafting Rate as Function of Applied Power
0,0

-0,2

dm/(A*t) (g.m .s )

-1 -2

-0,4

-0,6

-0,8

400 Pa 600 Pa 800 Pa

150 300 450

-1,0

Power (W)

Figure 11 Grafting rate as function of applied power for three different pressures.

4.3 Heat treatment influences

As previously mentioned, heat treatment (i.e. thermal cycle) seemed to have influence over grafting rate. Heat treatment effects are presented in Figure 12. For the same solid state heat treatment, samples slowly solidified present smaller weight loss than samples rapidly solidified. For both conditions of solidification, annealing improves grafting, implying in a mechanism dependent on preferential crystal orientation or different surface energy state promoted by the heat treatment. Conditions FC0 and SCA are statistically identical.

40

Mass Variation as function of the Thermal Cycles

0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0,0 SC0 FC0 SCA FCA

-dm (g)

Thermal Cycle

Figure 12 Weight loss as function of the thermal cycle imposed to the samples.

In order to identify preferential crystal orientation, x ray diffraction patterns were obtained. According to Gller, (2000), 1,1-biphenyl is a compound with monoclinic structure, space group P21/a, resulting from the great oscillation in the single bonding between rings. As it is shown in Figure 13, differences can be observed between powder and other conditions. No difference was observed when comparing samples only solidified in analogy with themselves annealed. The hypothesis that crystal orientation was responsible to larger grafting rates is then excluded. It was assumed that fast cooling promoted formation of a crystal structure highly populated by lattice defects and consequently higher surface energy. Annealing probably generated micro-cracks, which lead to higher grafting rates. These phenomena imply in an increase in grafting rates.

41

Diffraction Patterns
200000

Powder SC0 SCA

150000

Intensity (counts)

100000

50000

0 20 40 60

Diffraction Angle (2)

Figure 13 Diffraction pattern as function of the thermal cycle imposed to the samples.

Optical microscopy showed the influences from cooling rate and heat treatment in samples before post-discharge processing. It can be pointed that: The material presents a lamellar structure in all cooling and thermal cycling applied in the present study; the lamellar structure is mainly nucleated in sample holder and is due to molecule geometry; Fast cooling makes heterogeneous nucleation more important and gives a clear solidification direction; Step discontinuities are observed in both fast/slow cooling conditions, been more visible in fast cooling; after annealing these discontinuities become more easily identified. These points serve as a basis to explanation of the higher reaction rate observe in fast cooled and annealed samples. As it has been mentioned step discontinuities lead to an increase in surface area, also increasing grafting rate. Figure 14 presents a typical micrograph obtained in FC0 condition, observe directional solidification.

42

Figure 14 Optical micrograph of sample in the condition FC0 at a magnification of 50x.

4.4 Chemical Analysis and Reaction Mechanics Investigation

To clarify the etching processes, thin films of biphenyl were analyzed after treatment by various characterization techniques. In Figure 15, we show typical spectra of O(1s) and C(1s) peaks. We clearly observe a grafting of oxygen on the O(1s) spectrum. On the C(1s) spectrum, we notice a decrease of the C-C bonds and an increase of the peak component at 286,9 eV, which can be attributed to C-O bond in ring structures. We also find, but to lesser extent, ketone groups and carbonates at higher energy. These latter groups are present in the untreated biphenyl and are likely due to air contamination.

43

Figure 15 XPS analyses from thin films before and after treatment.

As a first step of the study, biphenyl was submitted to an argon/oxygen flux with the sample heated to a temperature of about 338 K. Therefore, O2 alone, without any excited state or in the atomic form, does not induce any modifications in the material. After post-discharge treatments it has been shown by both gas chromatography and mass spectroscopy that the main solid residues of biphenyl degradation are hydroxybiphenyls. In major intensity, monohydroxibiphenyl is observed, followed by di- and tri- hydroxybiphenyl. From solutions #1, #2 and #3, GC/MS has shown that biphenyl signal is weaker for colored solutions. Figure 17 in Annex A presents both GC and MS from these solutions. Single Ion Monitoring (SIM) at 170 m/z showed the formation of hydroxylated compounds

44

from biphenyl. In this monitoring it was demonstrated demonstrated that solution #1 (white crystals) does not contain these compounds, being related to pure biphenyl. As the color turns darker into brown an increase intensity of such compounds is observed. The compounds relative to the peaks identified in Figure 18 are the following: 1 ortho-hydroxybiphenyl; hydroxybiphenyl; 2 meta-hydroxybiphenyl; hydroxybiphenyl; 3 para-hydroxybiphenyl. hydroxybiphenyl. The order of elution of the compounds 2 and 3 was confirmed confirmed by the analysis of the reference compounds. It was also shown that hydroxylation of biphenyl could promote the formation of dihydroxylated compounds. SIM analysis performed at 186 m/z confirmed this. Figure 19 presents these results. It is possible to conclude that the darker de compounds are, the more hydroxylated they are. The analysis of hydroxylated compounds by GC/MS is better conducted after afte chemical derivatization. This is done with the aid of reactants of combined BSTFA (N,O(N,O bis(trimethylsilyl)trifluoroacetamide) and TMCS (trimethylchlorosilane). These compounds are presented in Figure 20. . The method here employed consists in the formation of compounds with trimethoxysilyl radicals from polar functions according to the following reaction:

Two new solutions were prepared from yellow and and brown crystals in acetonitrile (known to accelerate this reaction). The reaction was conducted at 343 K for 2 hours. Under these conditions, for hydroxybiphenyl it is expected to obtain trimethoxysilyloxibiphenylene (MW= 242 amu).

The analysis by GC/MS confirmed the formation of these derivates with an identification by correspondence with NIST spectra libraries (match probability > 92,5%). Isomers ortho- and meta- TMS derived are easily separated that these isomers before chemical

45

derivatization, which implies in higher resolution in GC. Chemical derivatization reaction may be considered complete once no hydroxylated compound is detected. In an analogous way, compound di and trihydroxylated conduct to the formation of compounds with three TMS (MW=330 amu). These results are, respectively, presented in Figure 21, Figure 22 and Figure 23 in ANNEX A PHYSICAL AND CHEMICAL ANALYSIS.

There are many isomers from dihydroxybiphenyl which lead to each of these retention times. Due to the fact their structure are too similar, certain isomers are very difficult to separate with the method here employed. A temperature programming in the range of 45 to 50 minutes would be necessary to improve their chromatographic separation. The mass spectrum from trihydroxybiphenyl has many ion fragments common to dihydroxybiphenyl. Chromatograms of ions extracted from these both groups may contain overlap from they. Any amine ion is observed, but the TMS-derivate from benzoic acid is detected. Its detection demonstrates that the mechanism of post-discharge degradation of biphenyl leads to ring opening by means of the formation of an acid group. Analyses were also conducted with aid of a LDI-TOF-MS system. The analysis of positive ions formed by laser desorption/ionization (266 nm) provided the mass spectra are presented in Figure 25 and Figure 26 after solutions #1, #2 and #3, confirming results already obtained by GC/MS (before chemical derivatization). It is possible to identify potassium, biphenyl and mono-hydroxybiphenyl in all cases. For darker crystals it is observed an intense signal for compounds derivate from biphenyl containing several groups OH, as well as high molecular weight compounds, probably due to dimerization. It has been observed, for solutions #2 and #3, ions characteristics of products of biphenyl degradation, implying in a mechanism of ring opening (C7H7+ at m/z = 91 and C7H5O+ at m/z = 105). Negative ion analyses confirmed the identification of formulas observed in positive polarity (C12H10On- with n between 1 and 4). However, the intense detection of such ions may be understood as carboxylate ions, for those in which negative mode is favored. These ions may be the contribution of different hydroxylate and carboxylate isomers. In this manner, the ion at m/z=217 may be identified as to possible isomers:

46

Exact Mass : 217.051 Formula : C12 H9 O4

The right side isomer (carboxylate) is formed following the oxidation of a vicinal diol. Its oxidation could produce benzoic acid detected by GC/MS.

4.5 Effects of Addition of Nitrogen and Hydrodynamics

Several experiments have been carried to identify influence of nitrogen in discharge over degradation of 1,1-biphenyl. Starting with small quantities of nitrogen, it has been shown that at least 150 sccm of nitrogen per 1000 sccm of argon is necessary to promote sample heating. The observed effects are limited to sample surface, achieving steady state after a few minutes with following decrease in temperature. Mixtures containing several ratios of O2/N2 were also employed with pressure of 200 Pa and applied power of 300 W. Since both gases as molecular, lower degree of ionization/excitation in such species is achieved. In accordance with this supposition, no reaction is observed when employing such mixtures in any ratio and sample temperature only decreases. Aiming the determination of the minimum conditions to promote sample degradation, several conditions of flux were employed. Beginning with a total flux of 100 sccm, composed of 40 sccm of argon and 60 sccm of oxygen, no reaction is observed in sample surface. Under this condition an inhomogeneous post-discharge emission is observed.

Figure 16 Blue layer emission schema.

47

Oxygen flux was increased up to 100 sccm and argon content was slowly increased until reaction between post-discharge and samples surface becomes visible. At 420 sccm of argon the blue emission over the sample becomes intense indicating this minimum flux of 520 sccm to be necessary to promote degradation of the organic compound. A schema of the blue layer is presented in Figure 16. A further increase in argon flux up to 840 sccm has shown an increase in the blue emission layer and temperature has achieved 303 K, indicating that the increase in flux has promote a better transport condition of excited oxygen species responsible to surface reactions. Small additions of nitrogen, in the order of 5 sccm lead to complete suppression of the blue layer.

48

CONCLUSIONS
It has been shown that 1,1-biphenyl can efficiently be decomposed in several by-

products. Continuous cracking of these promotes formation of volatile products leading to surface cleaning. Mass loss has shown to present a first order exponential decrease and temperature has stabilized in all thick layer conditions. The main specie responsible for reacting with biphenyl is probably the molecular state O2 (a1g). Interaction of pressure and flux seems to suppress reaction due to hydrodynamic effects, which modify the interaction time of the excited species and sample surface, leading to a different surface temperature and thus surface kinetics. Power has shown to be limited at a certain value over 450 W, once excitation of molecular state O2 (a1g) is supposed to be limited. From a chemical point of view, the present study showed that reaction of aromatic compounds with oxygen may lead mainly to hydroxylation and formation of low molecular weight volatile products. Both gas chromatography and mass spectroscopy techniques allowed the observation of poly-substituted molecules. Thus, the present data may show applicability to polymer surface modifications with previous knowledge of possible by-products and finally leading to reaction engineering of such desired modifications.

49

REFERENCES
BELMONTE, T.; PINTASSILGO, C.; CZERWIEC, T.; HENRION, G.; HODY, V.; THIBAUT, J.M.; Loureiro, J. Oxygen plasma surface interaction in treatments of polyolefines Surface Coatings Technology, vol. 200, pp. 2630, 2005.

BERNARDELLI, E.A. Estudo dos mecanismos de interao de plasma de O2, Ar e Ar-O2 com cido esterico - Tese de Doutorado apresentada ao Programa de Ps-graduao em Cincia e Engenharia de Materiais, PGMAT - UFSC. Florianpolis, 2008.

BERNARDELLI, E. ; BELMONTE, T. ; DUDAY, D.; FRACHE, G. ; PONCINEPAILLARD, F.; MALISKA, A. Interaction Mechanisms Between ArO2 Post-Discharge and Stearic Acid I: Behaviour of Thin Films. Plasma Chemistry and Plasma Processes, vol. 31, pp. 189-203, 2011.

BERNARDELLI, E. ; BELMONTE, T. ; DUDAY, D.; FRACHE, G. ; PONCINEPAILLARD, F. ; MALISKA, A. Interaction Mechanisms Between ArO2 PostDischarge and Stearic Acid I: Behaviour of Thick Films. Plasma Chemistry and Plasma Processes, vol. 31, pp. 205-215, 2011.

BERNARDELLI, E.; RICARD, A.; BELMONTE, T. Production of N and O atoms in flowing Ar-N2-O2 microwave discharges with separated N2 and O2 pulsed gases, Accepted in Plasma Sources Science and Technology

BRUNDLE, C. R.; EVANS Jr, C. A.; WILSON, S. Encyclopedia of Materials Characterization. Butterworth-Heinemann, Stoneham, 1992.

CHAPMAN, B. Glow Discharge Process: Sputtering and Plasma Etching. New York: J. Wiley & Sons, 1980.

FRIDMAN, A. Plasma Chemistry. Cambridge University Press, 2008.

50

FRIDMAN, G.; FRIEDMAN, G.; GUTSOL, A.; SHEKHTER, A.B.; VASILETS, V. N.; FRIDMAN, A. Applied Plasma Medicine. Plasma Processes and Polymers, vol.5, pp. 503 533, 2008.

GOLLER, A., GRUMMT, U-W. Torsional barriers in biphenyl, 2,2X-bipyridine and 2-phenylpyridine. Chemical Physics Letters, v. 321, pp. 399-405, 2000.

GONZALEZ, E.; BARANKIN, M.D.; GUSCHL, P.C.; HICKS, R.F. Ring Opening of Aromatic Polymers by Remote Atmospheric-Pressure Plasma Science, vol. 37, pp. 823 831, 2009. IEEE Trans. Plasma

GUERRA, V.; KUTASI K.; SA, P.A. Active species downstream of an ArO2 surface-wave microwave discharge for biomedicine, surface treatment and

nanostructuring. Applied Physical. Letters, vol. 96, 2010. HODY, V.; BELMONTE, T.; CZERWIEC, T.; HENRION, G.; THIBAUT, J.M. Oxygen grafting and etching of hexatriacontane in late N2O2 post-discharges. Thin Solid Films, vol. 506507, pp. 212216, 2006.

HODY, V.; BELMONTE, T.; PINTASSILGO, C.; PONCIN-EPAILLARD, F.; CZERWIEC, T.; HENRION, G.; SEGUI, Y.; LOUREIRO, J. Modification of Hexatriacontane by O2N2 Microwave Post-Discharges. Plasma Chemistry and Plasma Processes, vol. 26, pp. 251266, 2006.

HOLLAND, L. The cleaning of glass in a glow discharge. British Journal of Applied Physics, vol. 9, p. 410-415, 1958.

JEFFERY, G.H.; BASSET, J.; MENDHAN, J.; DENNEY, R.C. Quantitative Chemical Analysis. Longman Scientific & Technical, 5th ed, 1989

JUNKAR, I.; CVELBAR, U.; VESEL, A.; HAUPTMAN, N.; MOZETI, M. The Role of Crystallinity on Polymer Interaction with Oxygen Plasma. Plasma Processes and Polymers, vol. 6, 667675, 2009.

51

KUTASI, K.; GUERRA, V.; SA, P.A. Theoretical insight into ArO2 surface-wave microwave discharges Journal of Physics. D: Applied Physics, vol. 43, pp. 175-201, 2010.

KUTASI, K.; GUERRA, V.; S, P.A.; LOUREIRO, J. Active species in Ar-O2 and ArO2-N2 flowing microwave discharges and post-discharges. Proceeds of 19th International Symposium on Plasma Chemistry, Bochum, Germany, 2009.

KUTASI, K.; SAOUDI, B.; PINTASSILGO, C.D.;

LOUREIRO, J.; MOISAN, M.

Modelling the Low-Pressure N2O2 Plasma Afterglow to Determine the Kinetic Mechanisms Controlling the UV Emission Intensity and Its Spatial Distribution for Achieving an Efcient Sterilization Process. Plasma Process and Polymers vol. 5, pp. 840852, 2008.

LARRIEU, J.; HELD, B.; CLMENT F.; HIORNS, R.C. DC pulsed plasma surface treatment of atactic and isotactic polystyrene thin films with oxygen, oxygen-nitrogen mixture and nitrogen: study of wettability. European Physics Journal of Applied Physics, vol. 22, pp. 6167, 2003.

LEFVRE, L.; BELMONTE, T.; CZERWIEC, T.; RICARD, A.; MICHEL, H. Study of late argonnitrogen post-discharge interactions with oxidized iron surfaces. Applied Surface Science, vol. 153, pp. 8595, 2000.

LAROUSSI, M. Low temperature plasma-based sterilization: Overview and state-ofthe-art. Plasma Processes and Polymers, vol. 2, pp. 391400, 2005.

LEROUGE, S.; WERTHEIMER, M. R.; YAHIA, L'H. Plasma Sterilization: A Review of Parameters, Mechanisms and Limitations. Plasmas and Polymers, vol. 6, pp. 175-188, 2001.

MAFRA, M. Estudo dos mecanismos de limpeza por plasma: interao ps-descarga Ar-O2 e hexatriacontano - Tese de Doutorado apresentada ao Programa de Ps-graduao em Cincia e Engenharia de Materiais, PGMAT - UFSC. Florianpolis, 2008.

52

MAFRA, M.; BELMONTE, T.; F. PONCIN-EPAILLARD; DA SILVA SOBRINHO, A. S.; MALISKA, A. Role of the Temperature on the Interaction Mechanisms Between ArgonOxygen Post-Discharge and Hexatriacontane. Plasma Chemistry and Plasma Processes, vol. 28, pp. 495509, 2008.

MAFRA, M.; BELMONTE, T.; MALISKA, A.; DA SILVA SOBRINHO, A. S.; CVELBAR, U.; PONCIN-EPAILLARD, F. Argon Oxygen post-discharge treatment of hexatriacontane: heat transfer between gas phase and sample. Key Engineering Materials, vol. 373-374, pp. 421425, 2008.

MOISAN, M. ; BARBEAU, J.; CREVIER, M.-C. ; PELLETIER, J.; PHILIP, N.; SAOUDI, B. Plasma sterilization. Methods and mechanisms. Pure and Applied Chemistry, vol.74, pp. 349358, 2002.

MOISIN, M.; PELLETIER, J.; Physique des Plasmas Collisionnels: Application aux Dcharges Haute Frquence. EDP Sciences, 2006.

MORA, M. GARCA, M.C.;JIMNEZ-SANCHIDRIN,C.; ROMERO-SALGUERO, F.J. Transformation of light paraffins in a microwave-induced plasma-based reactor at reduced pressure. International Journal of Hydrogen Energy, v.35, pp. 4111-4122, 2010.

NOL, C.; DUDAY, D.; VERDIER, S.; CHOQUET, P.; BELMONTE, T.; MIGEON, H.-N. Interaction of Stearic Acid Deposited on Silicon Samples With Ar/N2 and Ar/O2 Atmospheric Pressure Microwave Post-discharges. Plasma Processes and Polymers, vol. 6, pp. S187S192, 2009.

OKANE, D. F., MITTAL, K.L. Plasma cleaning of metal surfaces. Journal of Vacuum. Science and Technology, vol. 11, pp. 587-589, 1974.

PETASCH, W.; KEGEL, B.; SCHMID, H.; LENDENMANN, K.; KELLER, H.U. Low pressure plasma cleaning: a process for precision cleaning applications. Surface and Coatings Technology. v.97, pp. 176-181, 1997.

53

PINHEIRO, M.J.; GOUSSET, G.; GRANIER, A.; FERREIRA, C.M. Modeling of a low-pressure surface wave discharges in flowing oxygen: I. electrical properties and species concentrations. Plasma Sources Science and Technology, vol. 7, pp. 524-536, 1998.

PINTASSILGO, C.D.; KUTASI, K.; LOUREIRO, J. Modeling of a Low-Pressure N2O2 discharge and post-discharge reactor for plasma sterilization. Plasma Sources Science and Technology, vol. 16, pp. S115-S122, 2007.

RICARD, A.; MONNA, V.; MOZETIC, M. Production of O atoms in Ar-O2 and N2O2 microwave flowing post discharges. Surface and Coatings Technology, v. 174-175, p. 905-908, 2003.

ROUESSAC, F.; ROUESSAC, A. Chemical Analysis: Modern instrumentation methods and Techniques. Wiley, 2nd ed, 2007.

VESEL, A.; MOZETI, M. Surface Functionalization of Organic Materials by Weakly Ionized Highly Dissociated Oxygen Plasma. Journal of Physics: Conference Series, vol. 162, 2009.

YASUDA, H.; GAZICKI, M. Biomedical applications of plasma polymerization and plasma treatment of polymer surfaces. Biomaterials, vol. 3, pp. 6877, 1982.

54

ANNEX A PHYSICAL AND CHEMICAL ANALYSIS

Figure 17 GC/MS of solutions #1, #2 and #3, at the top is presented the experimental and NIST database spectra for biphenyl.

Figure 18 GC/MS of solutions #1, #2 and #3, at the top is presented the mass spectra for SIM equal to 170 m/z.

55

Figure 19 GC/MS of solutions #1, #2 and #3, at the top is presented the mass spectra for SIM equal to 186 m/z.

Figure 20 Compounds used in chemical derivatization

56

Figure 21 GC/MS of compounds TMS-derived from solutions #2 and #3, SIM of ions at m/z equal to 211, 227 and 242.

Figure 22 GC/MS of compounds TMS-derived from solutions #2 and #3, SIM of ions at m/z equal to 299, 315 and 330.

57

Figure 23 GC/MS of compounds TMS-derived from solutions #2 and #3, SIM of ions at m/z equal to 418.

Figure 24 GC/MS of compounds TMS-derived from solutions #2 and #3, SIM of ions at m/z equal to 105 and 179 showing derivates corresponding to benzoic acid.

58

Intens.

7_1\1: +MS

2500

170.07

Solution #1

2000

38.96
1500

1000

154.08
500

74.10

0 x10 4

7_2\1: +MS

170.07
3

Solution #2

105.03 38.96 91.05 143.07

186.07 154.08 202.07

7_3\1: +MS

0 x10 4 3.0

170.07

Solution #3

2.5

2.0

1.5

38.97
1.0

186.07 154.08 105.03 91.05

25 50 75 100 125

0.5

143.08
150 175

0.0

202.07
200 225 m/z

Figure 25 Positive ions LDI (266 nm) mass spectra obtained from solutions #1 #2 and #3 before chemical derivatization.
Intens. 7_1\1: +MS

10

Solution #1

0 7_2\1: +MS

500

306.28

Solution #2

400

300

200

325.33 311.32 327.34

100

0 300 7_3\1: +MS

306.25
250

Solution #3

200

150

100

308.27

50

0 280 300 320 340 360 m/z

Figure 26 Positive ions LDI (266 nm) mass spectra obtained from solutions #1 #2 and #3 before chemical derivatization for high atomic masses.