Effect of additives, precursors and process conditions on particle morphology

The objective of the thesis was to develop methods to manufacture and control calcium carbonate crystal nucleation and growth in precipitation process. The work consists of experimental part and literature part that addresses theory of nucleation, crystallization and precipitation. In the experimental part calcium carbonate was precipitated using carbonization reaction. Precipitation was carried out in presence of known morphology controlling agents (anionic polymers and sodium silicate) and by using different operation conditions. Formed material was characterized using SEM images, and its thermal stability was assessed. This work demonstrates that carbon dioxide feeding rate and concentrations of calcium hydroxide and additives can be used to control size, shape and amount of precipitating calcium carbonate.

Photophysical studies of zinc phthalocyanine and chloroaluminum phthalocyanine incorporated into liposomes in the presence of additives

The photophysical properties of zinc phthalocyanine (ZnPC) and chloroaluminum phthalocyanine (AlPHCl) incorporated into liposomes of dimyristoyl phosphatidylcholine in the presence and absence of additives such as cholesterol or cardiolipin were studied by time-resolved fluorescence, laser flash photolysis and steady-state techniques. The absorbance of the drugs changed linearly with drug concentration, at least up to 5.0 µM in homogeneous and heterogeneous media, indicating that aggregation did not occur in these media within this concentration range. The incorporation of the drugs into liposomes increases the dimerization constant by one order of magnitude (for ZnPC, 3.6 x 10(4) to 1.0 x 10(5) M-1 and for AlPHCl, 3.7 x 10(4) to 1.5 x 10(5) M-1), but this feature dose does not rule out the use of this carrier, since the incorporation of these hydrophobic drugs into liposomes permits their systemic administration. Probe location in biological membranes and predominant positions of the phthalocyanines in liposomes were inferred on the basis of their fluorescence and triplet state properties. Both phthalocyanines are preferentially distributed in the internal regions of the liposome bilayer. The additives affect the distribution of these drugs within the liposomes, a fact that controls their delivery when both are used in a biological medium, retarding their release. The addition of the additives to the liposomes increases the internalization of phthalocyanines. The interaction of the drugs with a plasma protein, bovine serum albumin, was examined quantitatively by the fluorescence technique. The results show that when the drugs were incorporated into small unilamellar liposomes, the association with albumin was enhanced when compared with organic media, a fact that should increase the selectivity of tumor targeting by these phthalocyanines (for ZnPC, 0.71 x 10(6) to 1.30 x 10(7) M-1 and for AlPHCl, 4.86 x 10(7) to 3.10 x 10(8) M-1).

Microstructural changes of frozen strawberries submitted to pre-treatments with additives and vacuum impregnation

Strawberries were submitted to freezing after pre-treatments with hydrocolloid and calcium salts (pectin and calcium chloride) at different concentrations, in the attempt to establish a correlation of the effects of these substances and their processing, on the physical and microstructural characteristics of fruits after thawing. Strawberry halves were submitted to impregnation with controlled vacuum pressure of 84.4, 50.5 and 16.6 kPa; comprising pectin at concentrations of 0, 1.5 and 3%; with the addition of calcium chloride at concentrations of 0, 3 and 6%; and glucose at 20%, for 4 hours. Measurements were made of the total soluble solid contents, cellular fluid loss, texture and viscosity of the solution, before and after the freezing/thawing. Images of the tissue cuts during the freezing, in function of time, were taken in an optic microscope coupled to a cold-stage and controlled temperature system, where the reduction of the cellular area was quantified using an image analyzing software. The pectin concentration had an influence on and demonstrated a potential for protection of the frozen tissue samples. The photomicrographs showed that the loss of cellular fluid occurs during the growth of ice formed in the intercellular spaces and it is retarded through treatments with high pectin concentrations.

Viscosity of egg white from hens of different strains fed with commercial and natural additives

Yolk color and egg white (albumen) cleanliness and viscosity are important parameters by which consumers judge the quality of eggs. This study aimed to investigate changes in albumen viscosity during storage of eggs for up to 36 days from two different commercial laying hen strains (Carijo Barbada and Isa Brown) fed a diet containing annatto (1.5 and 2.0%) or a synthetic additive without synthetic colorants (control). Analyses of humidity, albumen height, pH, viscosity, foam formation, and stability were carried out on eggs. Carijo Barbada strain had smaller albumen, lower humidity and higher egg white viscosity than Isa Brown strain; however, with storage, viscosity lowered significantly on both strains. Initially, the addition of 2.0% of annatto or a synthetic additive increased viscosity in both strains, but with storage only the control maintained longer viscosity. Lower viscosity did not change foam density and stability.

Représentation d'un polynôme par un circuit arithmétique et chaînes additives

Un circuit arithmétique dont les entrées sont des entiers ou une variable x et dont les portes calculent la somme ou le produit représente un polynôme univarié. On assimile la complexité de représentation d'un polynôme par un circuit arithmétique au nombre de portes multiplicatives minimal requis pour cette modélisation. Et l'on cherche à obtenir une borne inférieure à cette complexité, et cela en fonction du degré d du polynôme. A une chaîne additive pour d, correspond un circuit arithmétique pour le monôme de degré d. La conjecture de Strassen prétend que le nombre minimal de portes multiplicatives requis pour représenter un polynôme de degré d est au moins la longueur minimale d'une chaîne additive pour d. La conjecture de Strassen généralisée correspondrait à la même proposition lorsque les portes du circuit arithmétique ont degré entrant g au lieu de 2. Le mémoire consiste d'une part en une généralisation du concept de chaînes additives, et une étude approfondie de leur construction. On s'y intéresse d'autre part aux polynômes qui peuvent être représentés avec très peu de portes multiplicatives (les d-gems). On combine enfin les deux études en lien avec la conjecture de Strassen. On obtient en particulier de nouveaux cas de circuits vérifiant la conjecture.

The effects of additives and chemical modification on the solution properties of thermo-sensitive polymers

Cette thèse concerne l’étude de phase de séparation de deux polymères thermosensibles connus-poly(N-isopropylacylamide) (PNIPAM) et poly(2-isopropyl-2-oxazoline) (PIPOZ). Parmi des études variées sur ces deux polymères, il y a encore deux parties de leurs propriétés thermiques inexplicites à être étudiées. Une partie concerne l’effet de consolvant de PNIPAM dans l’eau et un autre solvant hydromiscible. L’autre est l’effet de propriétés de groupes terminaux de chaînes sur la séparation de phase de PIPOZ. Pour ce faire, nous avons d’abord étudié l’effet de l’architecture de chaînes sur l’effet de cosolvant de PNIPAMs dans le mélange de méthanol/eau en utilisant un PNIPAM en étoile avec 4 branches et un PNIPAM cyclique comme modèles. Avec PNIPAM en étoile, l’adhérence de branches PNIPAM de à un cœur hydrophobique provoque une réduction de Tc (la température du point de turbidité) et une enthalpie plus faible de la transition de phase. En revanche, la Tc de PNIPAM en étoile dépend de la masse molaire de polymère. La coopérativité de déhydratation diminue pour PNIPAM en étoile et PNIPAM cyclique à cause de la limite topologique. Une étude sur l’influence de concentration en polymère sur l’effet de cosolvant de PNIPAM dans le mélange méthanol/eau a montré qu’une séparation de phase liquide-liquide macroscopique (MLLPS) a lieu pour une solution de PNIPAM dans le mélange méthanol/eau avec la fraction molaire de méthanol entre 0.127 et 0.421 et la concentration en PNIPAM est constante à 10 g.L-1. Après deux jours d’équilibration à température ambiante, la suspension turbide de PNIPAM dans le mélange méthanol/eau se sépare en deux phases dont une phase possède beaucoup plus de PNIPAM que l’autre. Un diagramme de phase qui montre la MLLPS pour le mélange PNIPAM/eau/méthanol a été établi à base de données expérimentales. La taille et la morphologie de gouttelettes dans la phase riche en polymère condensée dépendent de la fraction molaire de méthanol. Parce que la présence de méthanol influence la tension de surface des gouttelettes liquides, un équilibre lent de la séparation de phase pour PNIPAM/eau/méthanol système a été accéléré et une séparation de phase liquide-liquide macroscopique apparait. Afin d’étudier l’effet de groupes terminaux sur les propriétés de solution de PIPOZ, deux PIPOZs téléchéliques avec groupe perfluorodécanyle (FPIPOZ) ou groupe octadécyle (C18PIPOZ) comme extrémités de chaîne ont été synthétisés. Les valeurs de Tc des polymères téléchéliques ont beaucoup diminué par rapport à celle de PIPOZ. Des micelles stables se forment dans des solutions aqueuses de polymères téléchéliques. La micellization et la séparation de phase de ces polymères dans l’eau ont été étudiées. La séparation de phase de PIPOZs téléchéliques suit le mécanisme de MLLPS. Des différences en tailles de gouttelettes formées à l’intérieur de solutions de deux polymères ont été observées. Pour étudier profondément les différences dans le comportement d’association entre deux polymères téléchéliques, les intensités des signaux de polymères correspondants et les temps de relaxation T1, T2 ont été mesurés. Des valeurs de T2 de protons correspondants aux IPOZs sont plus hautes.

The Effect of Glass Additives on the Microwave Dielectric Properties of Ba(Mg 1 /3Ta2/3)03 Ceramics

The effect of glass additives on the densification , phase evolution, microstructure and microwave dielectric properties of Ba(Mg1;3 Ta2i3)03 (BMT) was investigated . Different weight percentages of quenched glass such as B203 , Si02, B203-SiO2, ZnO-B203, 5ZnO-2B2O3, Al203-SiO2, Na20-2B203.10H20, BaO-B203-SiO2, MgO-B203-SiO2, PbO-B203-SiO2 , ZnO-B203-SiO2 and 2MgO-Al203-5SiO2 were added to calcined BMT precursor . The sintering temperature of the glass -added BMT samples were lowered down to 1300 °C compared to solid-state sintering where the temperature was 1650 °C. The formation of high temperature satellite phases such as Ba5Ta4O15 and Ba7Ta6O22 were found to be suppressed by the glass addition . Addition of glass systems such as B203, ZnO-B203, 5ZnO-2B203 and ZnO-B203-SiO2 improved the densification and microwave dielectric properties. Other glasses were found to react with BMT to form low-Q phases which prevented densification . The microwave dielectric properties of undoped BMT with a densification of 93 . 1 % of the theoretical density were Cr = 24 . 8, Tr = 8 ppm/°C and Q„ x f= 80,000 GHz. The BMT doped with 1.0 wt% of B203 has Q„ x f = 124,700GHz, Cr = 24.2, and T f = -1.3 ppm /°C. The unloaded Q factor of 0.2 wt% ZnO-B203-doped BMT was 136,500 GHz while that of 1.0 wt% of 5ZnO-2B203 added ceramic was Q„ x f= 141,800 GHz . The best microwave quality factor was observed for ZnO -B203-SiO2 (ZBS) glass-added ceramics which can act as a perfect liquid-phase medium for the sintering of BMT. The microwave dielectric properties of 0.2wt% ZBS-added BMT dielectric was Q„ x f= 152,800 GHz, F,= 25.5, and Tr = - 1.5 ppm/°C

Influence of additives on the charactaristics of stone matrix asphalt

The increase in traffic growth and maintenance expenditures demands the urgent need for building better, long-lasting, and more efficient roads preventing or minimizing bituminous pavement distresses. Many of the principal distresses in pavements initiate or increase in severity due to the presence of water. In Kerala highways, where traditional dense graded mixtures are used for the surface courses, major distress is due to moisture induced damages. The Stone Matrix Asphalt (SMA) mixtures provide a durable surface course. Proven field performance of test track at Delhi recommends Stone Matrix Asphalt as a right choice to sustain severe climatic and heavy traffic conditions. But the concept of SMA in India is not so popularized and its application is very limited mainly due to the lack of proper specifications. This research is an attempt to study the influence of additives on the characteristics of SMA mixtures and to propose an ideal surface course for the pavements. The additives used for this investigation are coir, sisal, banana fibres (natural fibres), waste plastics (waste material) and polypropylene (polymer). A preliminary investigation is conducted to characterize the materials used in this study. Marshall test is conducted for optimizing the SMA mixtures (Control mixture-without additives and Stabilized mixtures with additives). Indirect tensile strength tests, compression strength tests, triaxial strength tests and drain down sensitivity tests are conducted to study the engineering properties of stabilized mixtures. The comparison of the performance of all stabilized mixtures with the control mixture and among themselves are carried out. A statistical analysis (SPSS package Ver.16) is performed to establish the findings of this study

Influence Of Additives On The Drain Down Characteristics Of Stone Matrix Asphalt Mixtures

In Kerala highways, where traditional dense graded mixtures are used for the surface courses, major distress is due to moisture induced damages. Development of stabilized Stone Matrix Asphalt (SMA) mixtures for improved pavement performance has been the focus of research all over the world for the past few decades. Many successful attempts are made to stabilize SMA mixtures with synthetic fibres and polymers. India, being an agricultural economy produces fairly huge quantity of natural fibres such as coconut, sisal, banana, sugar cane, jute etc.. Now- a -days the disposal of waste plastics is a major concern for an eco- friendly sustainable environment. This paper focuses on the influence of additives like coir, sisal, banana fibres (natural fibres), waste plastics (waste material) and polypropylene (polymer) on the drain down characteristics of SMA mixtures. A preliminary investigation is conducted to characterize the materials used in this study. Drain down sensitivity tests are conducted to study the bleeding phenomena and drain down of SMA mixtures. Based on the drain down characteristics of the various stabilized mixtures it is inferred that the optimum fibre content is 0.3% by weight of mixture for all fibre mixtures irrespective of the type of fibre. For waste plastics and polypropylene stabilized SMA mixtures, the optimum additive contents are respectively 7% and 5% by weight of mixture. Due to the absorptive nature of fibres, fibre stabilizers are found to be more effective in reducing the drain down of the SMA mixture. The drain values for the waste plastics mix is within the required specification range. The coir fibre additive is the best among the fibres investigated. Sisal and banana fibre mixtures showed almost the same characteristics on stabilization.

A structural investigation relating to the pozzolanic activity of rice husk ashes

Various factors determine the applicability of rice husk ash (RHA) as a pozzolanic material. The amount and accessibility of reactive sites is thought to be a key factor. A structural study of RHA samples in relation to their reactivity has been performed; Silica in RHA formed by burning rice husk in a laboratory furnace under continuous supply of air have been characterized as a function of incineration temperature, time and cooling regime. The characterization methods included chemical analyses, conductivity measurements, microscopic analysis, X-ray diffraction (XRD) and 29Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR). In line with earlier observations, the analyses show that the highest amounts of amorphous silica occur in samples burnt in the range of 500 °C–700 °C. The 29Si NMR data allow direct identification of the reactive silanol sites in the RHA samples. De-convolution of the NMR spectra clearly shows that the quickly cooled RHA resulting from burning rice husk for 12 h at 500 °C has the highest amount of silanol groups. This sample also induced the largest drop in conductivity when added to a saturated calcium hydroxide solution giving an indication of its reactivity towards lime. Therefore, this RHA is the favorable sample to be used as pozzolanic cement additive

Novel Electrochemical and Fluorescence Sensors for Food Additives and Neurotransmitters

There is an enormous demand for chemical sensors in many areas and disciplines including chemistry, biology, clinical analysis, environmental science. Chemical sensing refers to the continuous monitoring of the presence of chemical species and is a rapidly developing field of science and technology. They are analytical devices which transform chemical information generating from a reaction of the analyte into an measurable signal. Due to their high selectivity, sensitivity, fast response and low cost, electrochemical and fluorescent sensors have attracted great interest among the researchers in various fields. Development of four electrochemical sensors and three fluorescent sensors for food additives and neurotransmitters are presented in the thesis. Based on the excellent properties of multi walled carbon nanotube (MWCNT), poly (L-cysteine) and gold nanoparticles (AuNP) four voltammetric sensors were developed for various food additives like propyl gallate, allura red and sunset yellow. Nanosized fluorescent probes including gold nanoclusters (AuNCs) and CdS quantum dots (QDs) were used for the fluorescent sensing of butylated hydroxyanisole, dopamine and norepinephrine. A total of seven sensors including four electrochemical sensors and three fluorescence sensors have been developed for food additives and neurotransmitters.