The degree of cure and temperature are consistent variables used in models to describe the state of material behaviour development for a thermoset during cure. Therefore, the validity of a cure kinetics model is an underlying concern when combining several material models to describe a part forming process, as is the case for process modeling. The goals of this work are to identify sources of uncertainty in the decision-making process from cure measurement by differential scanning calorimeter (DSC) to cure kinetics modeling, and to recommend practices for reducing uncertainty. Variability of cure kinetics model predictions based on DSC measurements are investigated in this work by a study on the carbon-fiber-reinforced-plastic (CFRP) T800H/3900-2, an interlaboratory Round Robin comparison of cure studies on T800H/3900-2, and a literature review of cure models for Hexcel 8552. It is shown that variability between model predictions can be as large as 50% for some process conditions when uncertainty goes unchecked for decisions of instrument quality, material consistency, measurement quality, data reduction and modeling practices. The variability decreases to 10% when all of the above decisions are identical except for the data reduction and modeling practices. In this work, recommendations are offered for the following practices: baseline selection, balancing heats of reaction, comparing data over an extensive temperature range (300 K), choosing appropriate models to describe a wide range of behaviour, testing model reliability, and visualization techniques for cure cycle selection. Specific insight is offered to the data reduction and analysis of thermoplastic-toughened systems which undergo phase separation during cure, as is the case for T800H/3900-2. The evidence of phase separation is a history-dependent Tg-α relationship. In the absence of a concise outline of best practices for cure measurement by DSC and modeling of complex materials, a list of guidelines based on the literature and the studies herein is proposed.

The degree of cure and temperature are consistent variables used in models to describe the state of material behaviour development for a thermoset during cure. Therefore, the validity of a cure kinetics model is an underlying concern when combining several material models to describe a part forming process, as is the case for process modeling. The goals of this work are to identify sources of uncertainty in the decision-making process from cure measurement by differential scanning calorimeter (DSC) to cure kinetics modeling, and to recommend practices for reducing uncertainty. Variability of cure kinetics model predictions based on DSC measurements are investigated in this work by a study on the carbon-fiber-reinforced-plastic (CFRP) T800H/3900-2, an interlaboratory Round Robin comparison of cure studies on T800H/3900-2, and a literature review of cure models for Hexcel 8552. It is shown that variability between model predictions can be as large as 50% for some process conditions when uncertainty goes unchecked for decisions of instrument quality, material consistency, measurement quality, data reduction and modeling practices. The variability decreases to 10% when all of the above decisions are identical except for the data reduction and modeling practices. In this work, recommendations are offered for the following practices: baseline selection, balancing heats of reaction, comparing data over an extensive temperature range (300 K), choosing appropriate models to describe a wide range of behaviour, testing model reliability, and visualization techniques for cure cycle selection. Specific insight is offered to the data reduction and analysis of thermoplastic-toughened systems which undergo phase separation during cure, as is the case for T800H/3900-2. The evidence of phase separation is a history-dependent Tg-α relationship. In the absence of a concise outline of best practices for cure measurement by DSC and modeling of complex materials, a list of guidelines based on the literature and the studies herein is proposed.

Two novel methods for the sulphur vulcanisation of NR, BR and EPDM rubbers using N-tert-butyl-2-benzothiazole sulphenamide (TBBS) accelerator and zinc oxide (ZnO) activator have been developed. In one method, the optimum loading of TBBS and ZnO were measured for some sulphur-filled NR, BR and EPDM rubbers. The cure systems for the NR were (S/TBBS/ZnO), (1/1.5/0.2), (2/1.5/0.3), (3/1.5/0.25), and (4/3.5/0.2), for the BR, (0.5/1.75/0.2) and (1/3/0.2), and for the EPDM, (1/1/0.075). The cure was very efficient in spite of reducing the amount of TBBS and ZnO chemicals. In another method which used a single additive component in the form of a powder (TBBS/ZnO: 350mg/1g), the loading of the powder in NR was raised increasingly from 0.63 to 5.63 phr, the scorch time was unchanged and the optimum cure time reduced at 1.25 phr powder. The rate of cure accelerated at 1.25 phr powder. The crosslink density reached its maximum value at 5.63 phr powder. This method reduced the TBBS and ZnO requirement in the cure system by 85wt%. Solid kaolin filler pre-treated with a sulphur-bearing mercaptosilane was used to reinforce NR, BR and EPDM rubbers. For NR, to react the sulphur in the silane on the kaolin surface with the rubber chains and optimise the reaction between the two, 16 phr TBBS and 0.2 phr ZnO were added to the kaolin-filled rubber. The hardness and Young s modulus increased and compression set decreased when up to 3 phr elemental sulphur was included in the kaolin-filled rubber with 16 phr TBBS and 0.2 phr ZnO. The tensile strength, elongation at break, stored energy density at break, and tear energy of the rubber vulcanisate reduced when elemental sulphur was added. Notably, the inclusion of elemental sulphur was the key factor in controlling the rubber properties. In an extended work, 60 phr silane pre-treated kaolin was mixed with NR, BR and EPDM and the rubbers were cured using the novel cure systems developed earlier. The effect of 140 phr kaolin on the properties of NR was also investigated. For NR, the hardness increased by 64% when 60 phr kaolin was added and the trend continued rising by another 28% when the loading of kaolin reached 140 phr. Similarly, the Young s modulus rose by 170% with 60 phr kaolin and then by an extra 148% when the full amount of kaolin, i.e. 140 phr, was reached. The tensile strength and tear energy were unchanged and the elongation at break and stored energy density at break deteriorated by a total of 65% and 34%, respectively with 140 phr kaolin. The compression set of the unfilled rubber was 41%, and it then rose to 64% and 71%, when 60 and 140 phr kaolin was added, respectively. For BR, the hardness increased by 23% and for EPDM, by 34%, respectively when 60 phr kaolin was incorporated in the rubbers. For BR, the tensile strength, elongation at break and Young s modulus rose by 759%, 256% and 114%, respectively. The compression set of the unfilled BR was 9.4%, and subsequently rose to 26% when 60 phr kaolin was mixed with the rubber. For EPDM, the tensile strength, elongation at break and Young s modulus improved by 964%, 332% and 71%, respectively. For BR, the stored energy density at break and tear energy were increased by 2442% and 536%, respectively and for EPDM, by 3133% and 1479%, respectively. The compression set of the unfilled EPDM was 39%, and afterward increased to 48% with 60 phr kaolin. Kaolin was found to be extending or non-reinforcing filler for the strain-induced crystallising NR and highly reinforcing for the non-crystallising BR and EPDM.

Made available in DSpace on 2013-01-07T15:59:32Z (GMT). No. of bitstreams: 2 license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) 8.pdf: 4242312 bytes, checksum: 8b278d24e6e04c5009da68aa07091d51 (MD5) Previous issue date: 2007 / Fundação Oswaldo Cruz. Casa de Oswaldo Cruz, Rio de Janeiro, RJ, Brasil. / Tem por fim refletir sobre o início do processo de institucionalização da farmácia, através de duas associações de cunho científico-profissional, que se formaram em meados do século XIX na capital do Império: Sociedade Farmacêutica Brasileira (1851) e o Instituto Famacêutico do Rio de Janeiro (1858). O período entre 1851-1887 correspondeu ao tempo de vida das sociedades, preenchido pela circulação de seus periódicos e pela existência de seus respectivos gestores. / The study aims to think about the beginning of the process of institutionalization of pharmacy through the analysis of two professional-scientific societies, that were created in the middle of the XIX century in the capital of the Empire: the Sociedade Farmacêutica Brasileira (1851) and the Instituto Farmacêutico do Rio de Janeiro (1858). These institutions presented some proposals designed to give the status of science to pharmacy: the improvement of pharmacy education, the control of the illegal practice of pharmacy and the creation of a brazilian pharmaceutical code. The 1851-1887 period corresponded to the lifetime of those societies, the circulation of their periodicals and the existence of the respective directors. The relations established between those societies and the Sociedade Farmacêutica Lusitana, created in 1834, in the city of Lisbon, reveal that the history of the two countries remained intertwined, even after the independence of Brazil, allowing some common points to be identified: the inferiority stigma regarding medicine and the nations considered as civilized; the structuring of pharmacy education linked to medical education; the sanitary legislation; the political regime among others. The relation between art, science and politics is shown by the reconstitution of the life of the main pharmacy founders on the two sides of the Atlantic. Drugs stand out as the main object of this science. Tensions between pharmacists and chemists, and/ or homeopaths, and/ or doctors in medicine, the last representing health institutions of the imperial government, are analyzed through drug uses and meanings/ These tensions are characterized by the contrasts between the scientific and commercial natures of its activities, besides the magical and/or sacred meaning of drugs, wich remains latent in the daily life of the imperial society. Actions related to education, expressed by the inclusion of the Sociedade Farmacêutica Brasileira in the Faculdade de Medicina do Rio de Janeiro, and the creation of a college by the Instituto Farmacêutico do Rio de Janeiro, reveal the search for a scientific nature for its activities, intending to enlarge its scope of action beyond the preparation and conservation of drugs. For developing this study, dialogs have been established between a varied documentary material and the literature available on the subject, or related to it. Among the main documentary material, periodicals of the Brazilian societies and of the Sociedade Farmacêutica Lusitana, reports of the Minister of the Empire and of the Central Board of Public Hygiene, historical memories of the Faculdade de Medicina do Rio de Janeiro and the sanitary legislation of the period have been used. Consulted bibliography includes works in the areas of History of Pharmacy, Medicine and Drugs; History and History of Science; History of Brazil and History of Portugal, besides some literary and dramaturgic works.

The degree of cure and temperature are consistent variables used in models to describe the state of material behaviour development for a thermoset during cure. Therefore, the validity of a cure kinetics model is an underlying concern when combining several material models to describe a part forming process, as is the case for process modeling. The goals of this work are to identify sources of uncertainty in the decision-making process from cure measurement by differential scanning calorimeter (DSC) to cure kinetics modeling, and to recommend practices for reducing uncertainty. Variability of cure kinetics model predictions based on DSC measurements are investigated in this work by a study on the carbon-fiber-reinforced-plastic (CFRP) T800H/3900-2, an interlaboratory Round Robin comparison of cure studies on T800H/3900-2, and a literature review of cure models for Hexcel 8552. It is shown that variability between model predictions can be as large as 50% for some process conditions when uncertainty goes unchecked for decisions of instrument quality, material consistency, measurement quality, data reduction and modeling practices. The variability decreases to 10% when all of the above decisions are identical except for the data reduction and modeling practices. In this work, recommendations are offered for the following practices: baseline selection, balancing heats of reaction, comparing data over an extensive temperature range (300 K), choosing appropriate models to describe a wide range of behaviour, testing model reliability, and visualization techniques for cure cycle selection. Specific insight is offered to the data reduction and analysis of thermoplastic-toughened systems which undergo phase separation during cure, as is the case for T800H/3900-2. The evidence of phase separation is a history-dependent Tg-α relationship. In the absence of a concise outline of best practices for cure measurement by DSC and modeling of complex materials, a list of guidelines based on the literature and the studies herein is proposed. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

No description available.

Cure rate models are widely used to model time-to-event data in the presence of long-term survivors. Cure rate models, since introduced by Boag (1949), have gained significance over time due to remarkable advancements in the drug industry resulting in cures for a number of diseases. In this thesis, cure rate models are considered under a competing risk scenario wherein the initial number of competing causes is described by a Conway-Maxwell (COM) Poisson distribution, under the assumption of proportional hazards (PH) lifetime for the susceptibles. This provides a natural extension of the work of Balakrishnan & Pal (2013) who had considered independently and identically distributed (i.i.d.) lifetimes in this setup. By linking covariates to the lifetime through PH assumption, we obtain a flexible cure rate model. First, the baseline hazard is assumed to be of the Weibull form. Parameter estimation is carried out using EM algorithm and the standard errors are estimated using Louis' method. The performance of estimation is assessed through a simulation study. A model discrimination study is performed using Likelihood-based and Information-based criteria since the COM-Poisson model includes geometric, Poisson and Bernoulli as special cases. The details are covered in Chapter 2. As a natural extension of this work, we next approximate the baseline hazard with a piecewise linear functions (PLA) and estimated it non-parametrically for the COM-Poisson cure rate model under PH setup. The corresponding simulation study and model discrimination results are presented in Chapter 3. Lastly, we consider a destructive cure rate model, introduced by Rodrigues et. al (2011), and study it under the PH assumption for the lifetimes of susceptibles. In this, the initial number of competing causes are modeled by a weighted Poisson distribution. We then focus mainly on three special cases, viz., destructive exponentially weighted Poisson, destructive length-biased Poisson and destructive negative binomial cure rate models, and all corresponding results are presented in Chapter 4. / Thesis / Doctor of Philosophy (PhD)

This study focuses on the development of a multi-objective optimisation methodology for the vacuum assisted resin transfer moulding composite processing route. Simulations of the cure and filling stages of the process have been implemented and the corresponding heat transfer and flow through porous media problems solved by means of finite element analysis. The simulations involved material sub-models to describe thermal properties, cure kinetics and viscosity evolution. A Genetic algorithm which constitutes the foundation for the development of the optimisation has been adapted, implemented and tested in terms of its effectiveness using four benchmark problems. Two methodologies suitable for multi-objective optimisation of the cure and filling stages have been specified and successfully implemented. In the case of the curing stage the optimisation aims at finding a cure profile minimising both process time and temperature overshoot within the part. In the case of the filling stage the thermal profile during filling, gate locations and initial resin temperature are optimised to minimise filling time and final degree of cure at the end of the filling stage. Investigations of the design landscape for both curing and filling stage have indicated the complex nature of the problems under investigation justifying the choice for using a Genetic algorithm. Application of the two methodologies showed that they are highly efficient in identifying appropriate process designs and significant improvements compared to standard conditions are feasible. In the cure process an overshoot temperature reduction up to 75% in the case of thick component can be achieved whilst for a thin part a 60% reduction in process time can be accomplished. In the filling process a 42% filling time reduction and 14% reduction of degree of cure at the end of the filling can be achieved using the optimisation methodology. Stability analysis of the set of solutions for the curing stage has shown that different degrees of robustness are present among the individuals in the Pareto front. The optimisation methodology has also been integrated with an existing cost model that allowed consideration of process cost in the optimisation of the cure stage. The optimisation resulted in process designs that involve 500 € reduction in process cost. An inverse scheme has been developed based on the optimisation methodology aiming at combining simulation and monitoring of the filling stage for the identification of on-line permeability during an infusion. The methodology was tested using artificial data and it was demonstrated that the methodology is able to handle levels of noise from the measurements up to 5 s per sensor without affecting the quality of the outcome.

Photopolymerizations offer many advantages (such as temporal and spatial control of initiation, cost efficiency, and solvent-free systems) over traditional thermopolymerization. While they are now well-established as the preferred option for a variety of films and coating applications, they are limited from many applications due to problems such as oxygen inhibition, light attenuation, additive interference, or the creation of shadow regions and oxygen pockets due to complex shapes. These problems can be solved by using an underutilized form of photopolymerization--cationic photopolymerization. Cationic photopolymerizations have unique active centers which are essentially non-terminating causing extremely long active center lifetimes. In this contribution, the unique characteristics of cationic active centers are explored for their ability to be used in many new applications where previous photopolymerization techniques failed. It was found that the long lifetimes of the active centers permitted them to be very mobile, allowing them to migrate into and polymerize regions that were never illuminated in a process termed shadow cure. The mobility of cationic active centers provides a very efficient means of photopolymerizing of thick and pigmented systems. The long lifetimes of the cationic active centers can be used in the creation of a sequential stage curable polymer system and in the development of novel methods to cure complex shapes, two applications previously unattainable by photopolymerization. The termination of the cationic active centers was found to be reversible and can be used as a technique for external temporal control of the photopolymerization after the illumination has ceased. These abilities have great potential and will allow cationic photopolymerization to be used in many new applications where previous photopolymerization techniques failed, expanding their influence and benefits.

La formation des analystes, articulant le problème thérapeutique des modes de résolution de la cure aux questions collectives de garantie et d’enseignement, pose avec acuité la question des conditions de transmission et de formation propres au champ de la psychopathologie. La thèse s’attache d'une part à expliciter les fondements de la question et les conséquences Cliniques et institutionnelles des options à cet endroit; d'autre part, à rendre compte de la cohérence interne et spécifique des modes de transmission de la psychanalyse, dans la voie épistémologique ouverte par Lacan, dont la « Proposition d’Octobre sur le psychanalyste de ’Ecole » est ici le texte de référence. / The training of the psychoanalysts, articulating the therapeutic problem of the modes of resolution of the cure in the collective questions of guarantee and teaching, pose with acuteness the question of the conditions of transmission and training appropriate to the psychopathology. The thesis attempts on one hand to clarify the foundations of the questionand the clinical and institutional consequences of the options ; on the other hand, to report the internal and specific coherence of the modes of transmission of the psychoanalysis, in the epistemological way opened by Lacan, Whose is here the reference text. In the epistemological way opened by Lacan, whose « Proposition d’Octobre sur le psychanalyste de l’Ecole » is here the reference text.