Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: An instrument, named solution crystallization analysis by laser light scattering (SCALLS), that measures the solution melting and crystallization of polymers in solution was developed further in this study. The instrument was tested in a theoretical study to evaluate the Flory-Huggins relationship of melting point depression in solution of copolymers. It was found that the solvent interaction parameter for propylene/higher 1-alkene copolymers, with low comonomer content is dependent on the comonomer type. It was also showed that the melting point depression is dependent on both the type and amount of comonomer included in the copolymer. The instrument was further developed to include a total of three lasers with different wavelengths. Initial problems with laser interference was rectified by the introduction of dichroic mirrors to direct the laser light to the relevant detectors and broad pass filters in front of the the detectors to ensure that only the relevant laser light passes through. For homogenous polypropylene samples it was found that even though a slower cooling rate increases the relative peak temperatures as well as the relative temperature differences between the peaks, detail in the peak profiles is the same for the faster cooling rate. The subsequent heating analysis does show that there is a definite dependence on the cooling rate. The ZNPP-4 sample shows that the appearance of a shoulder in the heating analysis becomes more defined as a peak if the preceding cooling analysis is slower. Complex impact-polypropylene samples, differing only in the amount of ethylene were analysed and even small differences between samples were detected. The possible application of the SCALLS instrument was investigated. It was proven that the instrument can be used as a screening method for prep-TREF to determine the fractionation temperatures. / AFRIKAANSE OPSOMMING: 'n Instrument, genoem oplossing kristallisasie-analise deur laser lig verstrooiing (SCALLS), wat die smeltpunt asook die kristallisasie temperatuur in oplossing kan meet is verder ontwikkel in hierdie studie. Die Flory-Huggins verhouding oor die smeltpunt depressie in oplossing van ko-polimere is ondersoek in ‘n teoretiese studie. Daar is bevind dat die oplossing interaksie parameter vir propileen/hoër 1-alkeen kopolimere, met lae ko-monomeer inhoud is afhanklik op die ko-monomeer tipe. Dit is ook getoon dat die smeltpunt depressie afhanklik is van beide die tipe en hoeveelheid ko-monomeer in die ko-polimeer. Die instrument is verder ontwikkel om 'n totaal van drie lasers met verskillende golflengtes in te sluit. Aanvanklike probleme met laser inmenging is reggestel deur die bekendstelling van dichromatiese spieëls wat die laser lig na die regte ooreenstemmende detektor rig en filters voor die detektors verseker dat net die relevante laser lig die detektor bereik. Vir homogene polipropileen monsters is dit bevind dat selfs al is die analises gedoen teen ‘n stadiger afkoelings tempo wat lei tot ‘n verhoging in die piek kristallisasie temperatuur asook die relatiewe temperatuur verskille tussen die lasers, bly die detail in die piek profiele dieselfde as wat gesien word met ‘n vinniger afkoelings tempo. Die daaropvolgende verhitting analise toon dat die analise definitief afhanklik is op die voorafgaande afkoelings analise. Die ZNPP-4 monster toon dat die voorkoms van 'n skouer in die verwarming-analise word meer gedefinieerd en ‘n piek word gevorm soos die voorafgaande afkoelings tempo verlaag. Komplekse impak-polipropileen monsters, wat net verskil in die hoeveelheid etileen inhoud is geanaliseer en verskille is bepaal. Moontlike toepassings van die SCALLS instrument is ondersoek. Dit is bewys dat die instrument gebruik kan word om die fraksionering temperature vooraf te bepaal vir prep-TREF.

The impact strength of Nylon 6 was improved by adding Ethylene- n-Butyl acrylate- maleic anhydride (E-nBA-MAH) terpolymer with various concentrations from 0% (w/w) to 15% (w/w). The bare interaction energy between two polymers was investigated by using melting point depression approach utilizing both the Flory-Huggins (FH) theory and the Sanchez-Lacombe Equation of State (SL EOS). The solution of the mixture was electrospun, and the effects of process parameters on the expected radii of nanofibers were investigated. The effects of process parameters such as polymer concentration in solution, electrical field, diameter of syringe needle, feed rate, and collector geometry on nanofibers were studied. The statistical analysis to relate these parameters on the diameter of nanofibers was carried out by using Johnson SB distribution. The ratio of elastic modulus to viscosity coefficient of nanofibers was worked out by using AFM and combined viscoelastic models. The experiments were carried out on single fiber. The ratio came out to be a function of nanofiber diameter and terpolymer concentration. Isothermal crystallization kinetics and WAXS diffraction patterns of blends revealed and also SEM images supported that after 5% addition of elastomeric terpolymer, the interaction between the components of the blend gets weaker. The elastic modulus of the blend with 5% of terpoymer was greater than that of the neat Nylon 6, but the elastic modulus decreased for the blends containing more than 5% terpolymer.

Block copolymers, long chain molecules of two distinct chemical species joined covalently to one another, have long been known to form organized structures on the nanoscopic level. For example, if the two chains are the same length a lamellar structure results . In this work we show how this internal structure causes distinct deviation from 'normal' fluid behavior. We begin with the observation of block copolymer droplets with atomic force microscopy. We note the droplets form nearly conical shapes in stark contrast to the usual spherical cap. These droplets are found t o spread at an incredibly slow speed, and to have interesting instabilities in their wetting layer. We move on to studies of completely wet substrates (i.e. thin films) near the order-disorder transition of the material. Here we directly observe, with optical microscopy, a change in the fundamental spacing of the diblock's internal structure. This represents a superior method of measurement of the Flory-Huggins interaction parameter, which we verify in several ways. We also use the change in lamellar thickness to drive diffusion from one layer to another, and by similar measurements we can determine the kinetics of diffusion between the lamellar layers. In the last study we measure the lamellar edges on a gradient thickness sample with optical microscopy. In so doing we can directly observe surface induced ordering, and for the first time, can precisely resolve the near surface ordering dynamics. / Thesis / Doctor of Philosophy (PhD)

No description available.

Thesis (MScEng)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: When a sailing ship passes a moored ship the moored ship experiences forces and moments. These forces and moments cause the moored ship to move. The resulting ship motions due to the passing ship can sometimes be more severe than the ship motions due to ocean waves and can cause serious accidents at moorings such as the failing of mooring lines or even the total break away of the ship from the berth. Since bulk carriers and tankers were traditionally the largest seafaring ships, passing ship studies have focused mainly on these vessels, but recently container ships have grown to a comparable size. In this study an existing numerical model “Passcat” is validated with physical model measurements for a Post Panamax container ship passing a Panamax bulk carrier. Other existing mathematical formulae are also evaluated by comparison with these model tests. In the physical model tests the passing speed (V), passing distance (G), depth draft ratio (d/D) and the presence of walls and channels were varied. It was found that the passing ship forces are proportional to the passing speed to the power of 2.32. This is slightly higher than the generally accepted quadratic relationship for passing ship induced forces. Similar relationships were found for the other variables. The numerical model results were compared to the physical model measurements by determining agreement ratios. A perfect agreement between the numerical and physical models would result in an agreement ratio of 1. Agreement ratio boundaries, wherein agreement would be regarded as good, were drawn between 0.7 and 1.3. The numerical model, Passcat, was found to under predict the passing ship forces. It was found that Passcat is valid for a wide range of sensitivities and remains within the agreement ratio limits as long as passing speed is limited to 10 knots (kt), depth draft ratio to more than 1.164, passing distance to less than four times the moored ship beam (Bm) for surge and sway estimation and passing distance to less than three times the moored ship beam for yaw estimations. These limits are true for no structures in the water. For structures in the water only the passing speed limits are different. When quay walls are present, the surge and sway forces will only provide acceptable answers at passing speeds below 9kt. When 9Bm or 12Bm channels are present, the sway force will only provide acceptable answers at passing speeds below 7kt. When a 6Bm channel is present, the yaw moments will only provide acceptable answers at passing speeds below 6kt. From the mathematical model evaluation study it was found that empirical or semi empirical methods can not provide answers with good agreement to the physical model when walls or channels are present. For the open water case, it is only the Flory method that can provide answers with good agreement to the physical model for surge, sway and yaw forces. The Flory method can provide answers with acceptable agreement within narrow boundaries of passing distance (1 to 2 times the beam of the moored ship), passing speed (4 kt to 14 kt) and depth draft ratio (less than 1.7). The numerical model, Passcat can be used with little effort to provide answers with better agreement to the physical model for a larger range of variables. / AFRIKAANSE OPSOMMING: Wanneer ’n skip verby ‘n vasgemeerde skip vaar, ondervind die vasgemeerde skip kragte en momente. Hierdie kragte induseer beweging van die vasgemeerde skip. Die beweging kan soms groter wees as die effek van wind of golwe. Indien die bewegings groot genoeg is kan dit van die vasmeer lyne van die skip laat breek, of al die lyne laat breek sodat die skip vry in die hawe ronddryf. Aangesien erts skepe en tenk skepe vir jare die grootste skepe in the wêreld was, het die meeste van die skip interaksie studies op daardie skepe gefokus. Die grootte van behouering skepe het egter in die onlangse tye gegroei om dimensies soortgelyk aan die van erts en tenk skepe te hê. In hierdie studie word ’n bestaande numeriese model “Passcat” gestaaf met fisiese model metings op ’n Post Panamax behoueringskip wat verby ‘n Panamax erts skip vaar. Bestaande wiskundige formules is ook getoets deur dit met dieselfde fisiese model metings te vergelyk. In die fisiese model studie is die spoed van die skip (V), tussenafstand (G), diepte diepgang verhouding (d/D) en die teenwoordigheid van kaai mure en kanale in die water getoets. Daar is gevind dat die kragte op die vasgemeerde skip direk eweredig is aan die spoed van die skip tot die mag 2.32. Dit is effens meer as die algemeen aanvaarde kwadratiese verhouding tussen vloeistof sleurkrag en vloeisnelheid asook tussen skip interaksie kragte en vaar snelheid. Soortgelyke verhoudings is vir al die veranderlikes bereken. Numeriese model resultate is vergelyk met die fisiese model om die verhouding van ooreenstemming te bepaal. ’n Perfekte ooreenstemming word voorgestel deur ’n verhouding van ooreenstemming van 1. Grense waarbinne die verhouding van ooreenstemming as goed beskou word is getrek tussen 0.7 en 1.3. Daar is gevind dat die numeriese model, Passcat, kragte oor die algemeen onderskat. Passcat is geldig vir 'n breë reeks van veranderlikes en sal geldig bly solank die skip spoed tot 10 knope, diepte diepgang verhouding tot meer as 1.164, tussenafstand tot minder as vier skipwydtes (Bm) vir 'surge' en 'sway' kragte en tot minder as drie skipwydtes vir 'yaw' momente beperk word. Hierdie grense is opgestel vir geen strukture in die water. Vir strukture in die water word slegs die skip spoed aangepas. Wanneer daar mure in die water is sal 'surge' en 'sway' slegs geskikte antwoorde gee as die skip spoed tot 9 knope beperk word. Vir 9Bm of 12Bm kanale sal geskikte antwoorde vir 'sway' kragte slegs voorkom met 'n skip spoed minder as 7 knope. Vir 6Bm kanale sal geskikte antwoorde vir 'yaw' momente slegs voorkom met 'n skip spoed van minder as 6 knope. Van die wiskundige model evaluasie studie is gevind dat empiriese of semi empiriese metodes nie resultate met goeie ooreenstemming tot the fisiese model metings kan gee, wanneer daar kaai of kanaal mure in die water is nie. Vir die oopwater geval is dit slegs die Flory metode wat antwoorde kan voorsien wat goed ooreenstem met die fisiese model vir 'surge', 'sway', en 'yaw' kragte. Die Flory metode voorsien hierdie resultate binne noue grense vir tussenafstand (1 tot 2 wydtes van die vasgemeerde skip), verbyvaar spoed (4 knope tot 14 knope) en diepte diepgang verhouding (minder as 1.7). Die numeriese model, Passcat, kan met min moeite antwoorde bereken wat beter ooreenstemming vir 'n groter reeks veranderlikes gee.

Made available in DSpace on 2014-12-17T15:01:22Z (GMT). No. of bitstreams: 1 AlessandroALA_DISSERT.pdf: 1662616 bytes, checksum: c000a859b64ca5e0d06f0ed970192748 (MD5) Previous issue date: 2010-08-05 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The nonionic surfactants are composed of substances whose molecules in solution, does not ionize. The solubility of these surfactants in water due to the presence of functional groups that have strong affinity for water. When these surfactants are heated is the formation of two liquid phases, evidenced by the phenomenon of turbidity. This study was aimed to determine the experimental temperature and turbidity nonilfenolpoliethoxyled subsequently perform a thermodynamic modeling, considering the models of Flory-Huggins and the empirical solid-liquid equilibrium (SLE). The method used for determining the turbidity point was the visual method (Inoue et al., 2008). The experimental methodology consisted of preparing synthetic solutions of 0,25%, 0,5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12,5%, 15%, 17% and 20% by weight of surfactant. The nonionic surfactants used according to their degree of ethoxylation (9.5, 10, 11, 12 and 13). During the experiments the solutions were homogenized and the bath temperature was gradually increased while the turbidity of the solution temperature was checked visually Inoue et al. (2003). These temperature data of turbidity were used to feed the models evaluated and obtain thermodynamic parameters for systems of surfactants nonilfenolpoliethoxyled. Then the models can be used in phase separation processes, facilitating the extraction of organic solvents, therefore serve as quantitative and qualitative parameters. It was observed that the solidliquid equilibrium model (ESL) was best represented the experimental data. / Os tensoativos n?o-i?nicos s?o constitu?dos por subst?ncias cujas mol?culas, em solu??o aquosa, n?o se ionizam. A solubilidade destes tensoativos em ?gua deve-se ? presen?a de grupamentos funcionais que possuem forte afinidade pela ?gua. Quando esses tensoativos s?o aquecidos ocorre ? forma??o de duas fases l?quidas, evidenciada pelo fen?meno da turbidez. Este trabalho teve como intuito determinar os dados experimentais da temperatura de turbidez do nonilfenolpolietoxilado e posteriormente realizar uma modelagem termodin?mica, considerando os modelos de Flory-Huggins e o emp?rico de equil?brio s?lido-l?quido (ESL). O m?todo empregado para determina??o do ponto de turbidez foi o m?todo visual (Inoue et al., 2008). A metodologia experimental consistiu na prepara??o de solu??es sint?ticas de: 0,25%, 0,5%,1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12,5%, 15%, 17% e 20% em massa de tensoativo . Os tensoativos n?o-i?nicos utilizados de acordo com seu grau de etoxila??o (9,5, 10, 11, 12 e 13). No decorrer dos experimentos as solu??es foram homogeneizadas e a temperatura do banho foi aumentada gradativamente ao passo que a temperatura de turbidez da solu??o foi verificada visualmente Inoue et al. (2003). Esses dados da temperatura de turbidez foram utilizados para alimentar os modelos avaliados e obter par?metros termodin?micos para sistemas de tensoativos nonifenolpolietoxilados. Em seguida os modelos poder?o ser utilizados em processos de separa??o de fases, facilitando a extra??o de solventes org?nicos, pois servir?o como par?metros quantitativos e qualitativos. Foi observado que o modelo de equil?brio s?lido l?quido (ESL) foi o que melhor representou os dados experimentais obtidos

Selon l’hypothèse d’idéalité de Flory, les chaînes de polymères flexibles à l’état fondu se présentent sous la forme de marches aléatoires à trois dimensions, aussi appelées pelotes gaussiennes. Cette hypothèse suppose que toute information relative à la conformation locale subit une décroissance exponentielle le long de la chaîne principale et, par conséquent, n’a aucune influence sur la conformation à grande échelle. De plus, il est avancé que l’écrantage du volume exclu par les chaînes voisines compense tout effet de gonflement. Des expériences de diffusion neutronique (DN) effectuées il y a une trentaine d’années confirment que les polymères adoptent bien des configurations gaussiennes. S’ensuit l’un des piliers de la théorie des polymères : En solution ”suffisamment dense” tout polymère flexible peut être décrit comme une marche aléatoire à trois dimensions, indépendamment de sa structure chimique, et ce, après un rééchelonnage adéquat. Les progrès réalisés dans les domaines des techniques de simulation et de la puissance informatique ont rendu possible l’étude de chaînes très longues. Ceci a permis d’observer de plus près la structure des chaînes de polymère à l’état fondu et révélé une déviation par rapport à la chaîne idéale. Jusqu’à présent, la déviation par rapport à la structure gaussienne a uniquement été étudiée dans le cas de modèles à gros grains, par simulation et calcul analytique. La présente thèse cherche à vérifier si ces déviations peuvent également être mesurées à l’aide de simulations atomistiques réalistes et d’expériences de DN modernes. / The Flory ideality hypothesis states that flexible polymer chains in a melt assume the shape of three-dimensional random walks leading to so called Gaussian coils. The basis of this hypothesis is that any local conformational information decays exponentially along the chain backbone and thus has no influence on the long range conformation. Additionally it is argued that the excluded volume shielding of neigbor chains cancels out any swelling effects. Neutron scattering (NS) experiments dating back 30 years confirm the postulated Gaussian coil shape of polymers. This leads to a pillar of polymer theory: Any flexible polymer can be described as a three-dimensional random walk. Advances in simulation technics and computing power have opened the door to the possibility of studing very long chains. This allowed for a closer look at the chain structure of polymer melts and revealed deviations from ideality. This deviation is very slight and thus great care must be taken to distinguish it from noise. So far the deviation from the Gaussian coil structure was only studied for coarse-grained models. The scope of this thesis is to explore if these deviations are also measurable in atomistically realistic simulations and modern day NS experiments.

Plusieurs indices suggèrent que le repliement du chromosome et la régulation de l’expression génétique sont étroitement liés. Par exemple, la co-expression d’un grand nombre de gènes est favorisée par leur rapprochement dans l’espace cellulaire. En outre, le repliement du chromosome permet de faire émerger des structures fonctionnelles. Celles-ci peuvent être des amas condensés et fibrillaires, interdisant l’accès à l’ADN, ou au contraire des configurations plus ouvertes de l’ADN avec quelques amas globulaires, comme c’est le cas avec les usines de transcription. Bien que dissemblables au premier abord, de telles structures sont rendues possibles par l’existence de protéines bivalentes, capable d’apparier des régions parfois très éloignées sur la séquence d’ADN. Le système physique ainsi constitué du chromosome et de protéines bivalentes peut être très complexe. C’est pourquoi les mécanismes régissant le repliement du chromosome sont restés majoritairement incompris.Nous avons étudié des modèles d’architecture du chromosome en utilisant le formalisme de la physique statistique. Notre point de départ est la représentation du chromosome sous la forme d’un polymère rigide, pouvant interagir avec une solution de protéines liantes. Les structures résultant de ces interactions ont été caractérisées à l’équilibre thermodynamique. De plus, nous avons utilisé des simulations de dynamique Brownienne en complément des méthodes théoriques, car elles permettent de prendre en considération une plus grande complexité dans les phénomènes biologiques étudiés.Les principaux aboutissements de cette thèse ont été : (i) de fournir un modèle pour l’existence des usines de transcriptions caractérisées in vivo à l’aide de microscopie par fluorescence ; (ii) de proposer une explication physique pour une conjecture portant sur un mécanisme de régulation de la transcription impliquant la formation de boucles d’ADN en tête d’épingle sous l’effet de la protéine H-NS, qui a été émise suite à l’observation de ces boucles au microscope à force atomique ; (iii) de proposer un modèle du chromosome qui reproduise les contacts mesurés à l’aide des techniques Hi-C. Les conséquences de ces mécanismes sur la régulation de la transcription ont été systématiquement discutées. / Increasing evidences suggest that chromosome folding and genetic expression are intimately connected. For example, the co-expression of a large number of genes can benefit from their spatial co-localization in the cellular space. Furthermore, functional structures can result from the particular folding of the chromosome. These can be rather compact bundle-like aggregates that prevent the access to DNA, or in contrast, open coil configurations with several (presumably) globular clusters like transcription factories. Such phenomena have in common to result from the binding of divalent proteins that can bridge regions sometimes far away on the DNA sequence. The physical system consisting of the chromosome interacting with divalent proteins can be very complex. As such, most of the mechanisms responsible for chromosome folding and for the formation of functional structures have remained elusive.Using methods from statistical physics, we investigated models of chromosome architecture. A common denominator of our approach has been to represent the chromosome as a polymer with bending rigidity and consider its interaction with a solution of DNA-binding proteins. Structures entailed by the binding of such proteins were then characterized at the thermodynamical equilibrium. Furthermore, we complemented theoretical results with Brownian dynamics simulations, allowing to reproduce more of the biological complexity.The main contributions of this thesis have been: (i) to provide a model for the existence of transcrip- tion factories characterized in vivo with fluorescence microscopy; (ii) to propose a physical basis for a conjectured regulatory mechanism of the transcription involving the formation of DNA hairpin loops by the H-NS protein as characterized with atomic-force microscopy experiments; (iii) to propose a physical model of the chromosome that reproduces contacts measured in chromosome conformation capture (CCC) experiments. Consequences on the regulation of transcription are discussed in each of these studies.

<p>A new kind of lipid/polymer composite particle, consisting of a biodegradable polymer matrix with well-defined lipid domains, has been created. The lipid used is the water-swelling lipid monoolein (MO), which forms a reversed bicontinuous cubic diamond structure in aqueous solutions. The polymer is poly(d,l-lactide-co-glycolide) (PLG), which degrades into water-soluble monomers through hydrolysis. This new particle might be a good alternative for encapsulation of active substances intended to be released over a longer period of time, i.e. sustained/retained/controlled release.</p><p>To prepare such particles can be difficult. Suitable phase behaviour and a solvent with the right properties are needed. For this reason, the phase behaviours of several different lipid/polymer/solvent/water systems have been explored. From the phase behaviour of a suitable system (i.e. MO/PLG/ethyl acetate/water), a route for formation of lipid/polymer composite particles has been deduced. Particles have been formed and distinct, water-swelling, lipid domains have been confirmed by characterization by means of confocal laser scanning probe microscopy (CLSM). </p><p>The sample preparation process has been automated and a method based on using a robotic liquid handler has been developed. Phase diagrams have been determined by examination of macroscopic behaviours and the microstructures of the phases have been studied by small- and wide-angle X-ray scattering (L₃, V₂, L_α, L), nuclear magnetic resonance self-diffusion (L, L₃), viscosimetry (L) and rheology (L). Several different theoretical models have been applied for interpretation of the results. For example, the swelling of the reversed bicontinuous cubic phases and the sponge phase have been modelled by applying the theory of infinite periodical minimal surfaces, the sponge phase has been shown to be bicontinuous according to the theory of interconnected rods and the phase behaviour of the polymer has been described by the Flory-Huggins theory. The main focus of this work (4/5) concerns phase studies in multicomponent systems from a physical-chemical point of view.</p>

A new kind of lipid/polymer composite particle, consisting of a biodegradable polymer matrix with well-defined lipid domains, has been created. The lipid used is the water-swelling lipid monoolein (MO), which forms a reversed bicontinuous cubic diamond structure in aqueous solutions. The polymer is poly(d,l-lactide-co-glycolide) (PLG), which degrades into water-soluble monomers through hydrolysis. This new particle might be a good alternative for encapsulation of active substances intended to be released over a longer period of time, i.e. sustained/retained/controlled release. To prepare such particles can be difficult. Suitable phase behaviour and a solvent with the right properties are needed. For this reason, the phase behaviours of several different lipid/polymer/solvent/water systems have been explored. From the phase behaviour of a suitable system (i.e. MO/PLG/ethyl acetate/water), a route for formation of lipid/polymer composite particles has been deduced. Particles have been formed and distinct, water-swelling, lipid domains have been confirmed by characterization by means of confocal laser scanning probe microscopy (CLSM). The sample preparation process has been automated and a method based on using a robotic liquid handler has been developed. Phase diagrams have been determined by examination of macroscopic behaviours and the microstructures of the phases have been studied by small- and wide-angle X-ray scattering (L3, V2, Lα, L), nuclear magnetic resonance self-diffusion (L, L3), viscosimetry (L) and rheology (L). Several different theoretical models have been applied for interpretation of the results. For example, the swelling of the reversed bicontinuous cubic phases and the sponge phase have been modelled by applying the theory of infinite periodical minimal surfaces, the sponge phase has been shown to be bicontinuous according to the theory of interconnected rods and the phase behaviour of the polymer has been described by the Flory-Huggins theory. The main focus of this work (4/5) concerns phase studies in multicomponent systems from a physical-chemical point of view.