Polymers in concrete have received considerable attention over the past 30 years. Superplasticizers are one of the admixtures which have polymeric structure. In this study, polycarboxylate type slump-releasing dispersant, which is a copolymer of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and methacrylic acid (MAA), was synthesized in different feed compositions. The synthesis procedure of this copolymer was retrieved from literature. The derivatives of this water-soluble copolymer (AMPS-MAA) were synthesized by a macromonomer which was synthesized by the esterification of poly(ethylene glycol) methyl ether (PEG) with MAA (PEGMA) and then copolymerizing this macromonomer with AMPS monomer, the resulting copolymer is AMPS-PEGMA. In order to study the methyl group effect on fluidity, the other type of macromonomer (PEGA), composed of PEG and acrylic acid (AA), was synthesized and copolymerized with AMPS monomer, giving AMPS-PEGA. The structures of synthesized polymers were verified by NMR and FT-IR analysis. The slump-releasing effect of the synthesized copolymers was studied in terms of reaction pH, composition, molecular weight, amount of PEG side chains, and molecular weight of PEG side chains. The AMPS-MAA copolymer with 40% AMPS content was the most effective in promoting the fluidity of cement pastes. In scope of reaction pH, the AMPS-MAA copolymer, synthesized at a pH of 11, gave the most effective result on fluidity of the cement pastes. In copolymers of PEG acrylate macromonomers and AMPS monomers, copolymers with 5% PEG acrylate content showed the highest fluidity both in copolymers of PEGA and PEGMA. In copolymers with PEG side chains, the 15% AMPS-PEGA copolymer synthesized at pH of 6 gave the most effective result on fluidity of cement pastes. In the study of mechanical properties of the mortar samples prepared by the copolymers selected, AMPS-PEGA copolymer with 25% PEG content showed the highest flexural strength, and AMPS-MAA copolymer with 60% AMPS content and a reaction pH of 11 gave the highest compressive strength. In this study, zeta potential measurements were also performed to analyze the fluidity behavior of the copolymers.

As propriedades requeridas em relação à resistência e à durabilidade de um concreto no estado endurecido estão diretamente ligadas às suas condições no estado fresco, sendo assim, etapas como processo de mistura, transporte, lançamento e adensamento do concreto devem ser adequadamente monitoradas e controladas ao longo do tempo, durante seu estado fresco. A norma brasileira NBR 7212 (ABNT, 2012), para execução de concreto dosado em central, estipula o tempo máximo para que o concreto seja completamente descarregado (aplicado) em 150 minutos. No entanto, em diversas situações práticas observam-se contratempos relacionados com atrasos na execução da obra ou no transporte para entrega do concreto, fazendo com que no momento de lançamento este concreto seja rejeitado em função do tempo decorrido entre o início da mistura dos materiais e a aplicação do concreto no canteiro de obra, além de apresentar considerável perda em sua trabalhabilidade. Porém, principalmente, em função de cronogramas de obras, de custo e da preocupação ambiental, fica clara a necessidade de alternativas que viabilizem sua utilização, garantindo as condições adequadas para lançamento e adensamento, sem que haja impactos negativos em suas propriedades finais. O objetivo desta pesquisa consiste na avaliação das propriedades mecânicas e de durabilidade do concreto, quando mantido em mistura prolongada e utilizado após esse tempo máximo de mistura e transporte especificado pela norma, a partir do primeiro contato do cimento com a água. Os concretos foram produzidos com dois tipos de cimento, CPIV e CPII, e seu abatimento foi mantido ao longo de 6 horas de mistura com a incorporação de aditivo superplastificante à base policarboxilato. Nesse estudo adotaram-se três relações a/c e a produção dos concretos foi realizada em laboratório e em condição real numa central dosadora de concreto. Os resultados obtidos, para os materiais e procedimento utilizados, avaliando o comportamento do concreto em relação ao módulo de deformação, calor de hidratação gerado, carbonatação e penetração de cloretos pela exposição à condição natural, mostram que não há perda no seu desempenho final, quando utilizado acima do tempo especificado por norma, adotando o procedimento de manutenção do abatimento com a incorporação de aditivo superplastificante à base de policarboxilato, conforme proposta deste estudo. Análises do comportamento reológico e microestruturais em pastas de cimento, com as mesmas características utilizadas na produção dos concretos, corroboram com os resultados obtidos. / The required properties in relation to the concrete strength and durability in the hardened state are directly linked to its fresh state conditions, thus, steps such as concrete mixing, transporting, launching and compacting must be properly monitored and controlled during this material production. The Brazilian Standard (NBR 7212/2012) for central mixed concrete stipulates as 150 minutes the maximum time for completely concrete discharging (applying). However, there are setbacks related to execution or transportation delays, resulting in workability loss, often causing this concrete rejection in building plants. Therefore, due to work schedules, cost and environmental concern, it is clear the need for alternatives that make feasible this concrete use, guaranteeing the appropriate launching conditions and densification, without negative impacts on its hardened properties. In this context, this research subject is to evaluate the concrete mechanical properties and durability, when kept in prolonged mixing conditions and used after the maximum mixing and transport time specified by the Brazilian standard. The concretes were produced with two kinds of Portland Brazilian cement, called CP IV e CP II, with fixed consistency and with polycarboxylate superplasticizer addition. Additionally, three water/cement ratios were analyzed in concretes mixed in the laboratory and central mixed conditions. In this research, where analyzed concretes with an overpass time of application, maintaining the consistency with superplasticizer addition. With the materials and procedures utilized, it was not observed loss on concrete performance related to the modulus of elasticity, hydration heat, carbonation and chloride penetration under natural exposure. The rheological and microstructural analysis in cement pastes, reproducing the concrete proprieties, corroborates with this conclusion.

Le but de cette thèse est d'évaluer le rôle de la solvatation des PCP (copolymère greffé utilisé en tant qu'additif du béton) sur la fluidité et la viscosité des bétons. Pour répondre à cette problématique, des copolymères greffés différant par la nature chimique des chaînes latérales sont synthétisés. L'état de solvatation des PCP est évalué à l'aide du paramètre de Flory-Huggins χ. Ce dernier est calculé à partir du 2nd coefficient du viriel A2, déterminé par diffusion de la lumière. Des valeurs du paramètre χ de 0,37 ; 0,43 ; 0,47 et 0,48 ont été obtenues pour des PCP comportant des chaînes latérales à base d'éthylène glycol (EG), de 2-méthyloxazoline (MOx), de N-vinylpyrrolidone (NVP) et de N-acryloylmorpholine (NAM), respectivement. Le pouvoir couvrant des PCP et leur épaisseur de couche peuvent être calculés par l'intermédiaire d'une formule proposée par Flatt. L'introduction des PCP à différents dosages (donc différents taux de recouvrement) à des suspensions de calcite a permis de montrer qu'à même taux de recouvrement de surface, tous les PCP induisaient la même fluidité, alors que l'épaisseur de couche de PCP diffère de plus de 50% dans les cas les plus extrêmes. Le taux de recouvrement de surface joue un rôle tout aussi important en ce qui concerne la viscosité des suspensions. Appliquer ces conclusions sur un mortier s'avère délicat car les PCP pourraient entrainer des retards d'hydratation différents en fonction de la nature des chaînes latérales / The objective of this PhD work is the evaluation of the role of the solvation of PCP (grafted copolymer used in concrete as additive) on the concrete fluidity and viscosity. Grafted copolymers with different side-chains were synthesized. The solvation state of the PCP was estimated by mean of the χ Flory-Huggins parameter. The latter was calculated from the 2nd virial coefficient A2, itself determined by light scattering measurements. χ -parameter values of 0,37 ; 0,43 ; 0,47 and 0,48 are obtained for PCP respectively possessing ethylene glycol (EG), 2-methyloxazoline, N-vinylpyrrolidone and N-acryloylmorpholine-based side-chains. The surface coverage of the PCPs and their layer thickness can be calculated with Flatt’s formula. The introduction of the PCPs at different contents (therefore different surface coverage ratio) to calcite suspensions showed that at same surface coverage ratio, all PCPs induce the same fluidity, although the adsorbed PCP layer thickness differed up to 50% in the certain cases. The surface coverage played also a keyrole in the suspensions viscosity. The transposition of these results to a mortar seemed however risky since PCPs might lead to hydration delays depending on the chemical nature of the side-chains

La presente tesis realizó el estudio de la dosificación del concreto utilizando agregados de la cantera Figueroa en Huánuco con aditivo superplastificante Sika Viscocrete 3330 tercera generación. El objetivo principal fue el de determinar la dosificación del concreto de mediana resistencia para optimizar la calidad del concreto, y así tener un concreto en condiciones óptimas y resistencias a la compresión considerables. Para lo cual se basó en investigaciones pasadas referidas a concretos utilizando superplastificante, también se utilizó como fuente una investigación parecida perteneciente a la misma región del presente estudio. Todo ello aporto a dar opciones de solución en concretos de mediana resistencia utilizando aditivos superplastificantes, ya que el problema para esta región es la poca información en cuanto al uso de aditivos en concretos de mediana resistencia. El tipo de investigación es un análisis mixto, el nivel de investigación es descriptivo correlacional, porque especifica propiedades y características del concreto de mediana resistencia, asocia variables mediante un patrón para una determinada población. Concluida la investigación se obtuvieron resultados favorables del concreto de mediana resistencia, ya que el diseño patrón de menor relación agua/cemento presento una mejor resistencia a la compresión obteniendo un incremento del 21.13% de resistencia a la compresión, los demás diseños también tuvieron un incremento significativo de resistencia a la compresión los cuales se mencionaran en las conclusiones de esta investigación. This thesis conducted the study using dosage of concrete aggregates quarry in Huanuco Figueroa with Sika ViscoCrete superplasticizer additive 3330 third generation. The main objective was to determine the dosage of the particular medium strength to optimize the quality of the concrete, and thus have a particular under optimal conditions and considerable resistance to compression. For which it relies on past investigations into concrete using superplasticizer, also used a similar research as a source belonging to the same region of the study. I bring all this to give possible solutions in medium strength concrete using superplasticizers, because the problem in this region is the lack of information on the use of additives in concrete of medium strength. The research is a joint analysis, the level of research is descriptive correlational, for specific properties and characteristics of the particular medium strength, variables associated with a pattern for a given population. The investigation favorable results of the specific medium strength, since the design pattern of lower water / cement ratio is obtained I present a better compressive strength obtaining an increase of 21.13% of compressive strength, other designs also had an increase significant compressive strength which were mentioned in the conclusions of this investigation.

Dix molécules organiques modèles simulant les fonctions chimiques des superplastifiants utilisés dans la formulation des bétons ont été intercalées dans les hydrates cimentiers lamellaires conduisant à la formation de phases AFm hybrides. Les interfaces entre les deux sous-réseaux organiques et inorganiques de ces composés hybrides ont été étudiées afin de caractériser les interactions entre hydrates cimentiers et adjuvants organiques lors de la prise du béton. Les affinités de ces molécules vis-à-vis du feuillet minéral ont pu être comparées et il en ressort les deux séries suivantes : -PO32- > -SO3- > -CO2- pour les parties hydrophiles et C7-R > Φ-R > C5-R > C2-R pour les parties hydrophobes. L’interface organique-inorganique i.e. le mode d’accrochage et l’orientation de la molécule organique au sein de l’espace interlamellaire ont principalement été caractérisés par DRX sur poudre et spectroscopie infrarouge. Différents modes de connexion ont pu être identifiés par intercalation et par greffage. Les molécules organiques examinées sont ainsi orientées soit perpendiculairement, soit parallèlement aux feuillets associés à différents mode d’accroche. Différents taux d’hydratation de ces hydrants hybrides ont ensuite été identifiés et un travail de résolution structurale sur la phase insérant l’anion C6H5SO3- a permis de préciser l’organisation structurale de l’espace interlamellaire. Finalement, une étude sur l’intercalation de quelques superplastifiants commerciaux a mis en évidence un phénomène d’exfoliation de ces hydrates lamellaires. L’étude préalablement réalisée sur des molécules modèles permet alors de mieux comprendre les interactions se produisant au sein du milieu complexe que constitue un béton frais. / Ten organic molecules models simulating the chemical functions of superplasticizers used in concretes formulation were intercalated into lamellar cement hydrates to synthesize hybrid AFm phases. The interfaces between the organic and inorganic networks of these hybrid compounds have been studied to characterize the interactions between cementitious hydrates and organic additives in concrete. The affinities of these molecules toward the mineral layers have been compared and display the following tendencies : -PO32- > -SO3- > -CO2- for the hydrophilic parts and C7-R > Φ-R > C5-R > C2-R for the hydrophobic parts. The organic-inorganic interface (connection mode and orientation of the organic molecule) of the hybrid AFm phases was characterized by powder WRD and infrared spectroscopy. Organic molecules are oriented either perpendicular or parallel to the sheets resulting from different connection modes mainly intercalation and also grafting. The various hydration levels of these hybrids hydrates were then determined, and a structural resolution was attempted on AFm inserting C6H5SO3- anion allowing a description of its interlayer structure. Finally, a study on the intercalation of some commercial superplasticizers highlighted the exfoliation phenomenon for these lamellar hydrates.The present study on model molecules leads to a better understanding of the interactions occuring in complex fresh concrete environment.

L'objectif de ce travail est d'étudier le phénomène de ségrégation des coulis cimentaires sous cisaillement et de déterminer un critère rhéométrique quantitatif capable d'évaluer leur ségrégabilité pendant les essais de caractérisation rhéologique.Pour répondre à cet objectif, un protocole expérimental spécifique a été développé permettant, d'une part, la caractérisation rhéologique des coulis cimentaires sous cisaillement et, d'autre part, le suivi de leur état de stabilité au cours de la caractérisation. Un rhéomètre à cylindres coaxiaux de type Couette a été employé pour la mise en œuvre d'un essai rhéométrique composé de deux cycles et de différents paliers de taux de cisaillement, permettant la caractérisation rhéologique des coulis. L'essai rhéométrique a été effectué systématiquement deux fois en faisant varier le rapport du volume cisaillé – volume non cisaillé dans le rhéomètre. La caractérisation rhéologique des coulis a été associée à plusieurs mesures de masse volumique dans les différentes parties du rhéomètre à des moments caractéristiques de l'essai rhéométrique permettant le suivi de sa stabilité et l'évaluation quantitative d'une éventuelle ségrégation.Les relations possibles entre le comportement rhéologique spécifique des coulis ségrégatifs et l'évolution de la fraction solide du coulis dans le volume cisaillé du rhéomètre ont été recherchées. L'influence des différents paramètres de formulation tels que le rapport E/C, la nature et le dosage en adjuvant fluidifiant, le dosage en agent de viscosité et l'introduction d'additions calcaires en substitution du ciment sur la ségrégation dynamique des coulis cimentaires a été étudiée de manière détaillée. L'ensemble des résultats a permis, en premier lieu, de déterminer la spécificité du comportement rhéologique des coulis ségrégatifs et, en deuxième lieu, de définir un nouveau critère basé uniquement sur les mesures rhéométriques permettant de quantifier la ségrégabilité des coulis cimentaires pendant la caractérisation rhéologique à cause du cisaillement. Ce critère rhéométrique est très fortement corrélé à la diminution de la fraction volumique dans la partie haute du volume cisaillé dans le rhéomètre pendant l'essai rhéométrique indépendamment des paramètres de composition du coulis. / This work aims to study the phenomenon of segregation of cement grout under shearing and determine a quantitative rheometric criterion which can evaluate their segregability during the rheological characterization tests.To meet this objective, a specific experimental protocol was developed, firstly, for the rheological characterization of cement grout under shearing and secondly, for the flowing-up of their state of stability during the characterization. A rotational rheometer with coaxial-cylinder geometry (Couette type) was used for the implementation of a rheometric test composed of two shearing cycles with various steps of shear rate allowing the rheological characterization of the grout. The rheometric test was systematically performed twice by varying the ratio of the sheared volume and un-sheared volume in the rheometer. The rheological characterization of the grout has been associated with several density measurements in different parts of the grout in the rheometer at the characteristic times during the rheometric test allowing the monitoring of its stability and/or quantitative segregability.The possible relationship between the specific rheological behavior of segregative grout and the evolution of solid fraction in the sheared volume in the rheometer was studied. The influence of different mix designs such as the W/C, nature and dosage of superplasticizer, dosage of viscosity modifying admixture and the introduction of limestone additions on the dynamic segregation of cement grouts was researched in detail. The overall results allowed, firstly, determining the specificity of the rheological behavior of segregative grout and, secondly, defining a new criterion based only on the rheometric measurements to quantify the segregability of the cement grout during the characterization rheology and resulting from shearing. This rheometric criterion is strongly correlated with the decrease in the volume fraction in the upper part of the sheared volume in the rheometer during the rheometric test, and independent of the mix design of the grout.

Preparation of geopolymers with main components of slug and metakaolin. After being alcali activated the raw materials are complemented by superplasticizers of different kind and concentracion.

Concrete in Sweden has traditionally been manufactured with natural aggregate from glaciofluvial eskers. There is a need to preserve the remaining eskers because of their cultural value and importance for water filtration, thus natural aggregate has to be replaced. The most realistic alternative is to use crushed rocks. The major problem with crushed rocks in concrete production is the workability. This is because crushed rocks have less favorable properties. The fragments are flakier and have a rougher surface than natural aggregates that have been rounded in water. Without any amelioration of the crushed rock, to reach a certain workability and strength, the amount of cement in the mix has to be increased. Cement production requires large amounts of energy and the decarbonation of limestone releases large amounts of CO2. Combined, the release of CO2, due to burning and decarbonation of limestone, accounts for about 5% of the global CO2 emissions. An increase in cement consumptions is less desirable. Thus to replace natural aggregates, the use of crushed rocks has to be optimized as regard cement consumption. Several crushed aggregates, most from granitic rocks, from all over Sweden were analysed in this study. These crushed rocks were characterized according to their grading, specific surface, shape and petrography and compared to natural sand. Rheological tests that reveals the workability in detail was performed on mortars. The tests showed that as regard workability the 0-2 mm fraction is the most important factor. Further, the maximum aggregate size was gradually increased up to 16 mm, to have a more realistic approach to the concrete produced by the building industry. The results showed that with grading optimization and superplasticizer, some crushed rocks can be used for concrete production without increasing, and even decreasing, the cement consumption. This research also contemplated the use of filler. As a mineral admixture it can improve the compressive strength. It can also be used to replace cement; a replacement up to 20 kg/m3 of cement by filler can be done without significant effect on compressive strength.

Cemented paste backfill (CPB) technology is widely used in the mining industry as an effective means of tailings disposal. CPB is a mixture of tailings, binder, water, and additional admixtures when required. It is prepared in a mixing plant on the ground surface and then transported into the mine cavities through pipelines either by gravity and/or using pumps. To ensure efficiency during transportation and avoid pipe clogging (which can cause unnecessary delays and loss of productivity), fresh CPB must have sufficient flowability. To achieve that, high-range water reducing admixtures, also known as superplasticizers, are usually added to the CPB during mixing. These admixtures are widely used in the construction industry due to their ability to improve flowability without undermining other important engineering properties. However, their influence on the rheology, mechanical strength and environmental performance (reactivity and permeability) of CPB is not fully understood. Thus, experimental studies were conducted to investigate the effects of superplasticizers on the performance properties of cemented paste backfill at different curing temperatures. Yield stress and viscosity of fresh CPB cured for 0, 1, 2, and 4 hours were measured using a vane shear device and a Brookfield Viscometer respectively. Unconfined compressive strength (UCS) of samples cured for 1, 3, 7, and 28 days was determined in accordance with ASTM - C39. Superplasticizer contents were varied as 0%, 0.125%, and 0.25% of the total weight of the CPB. Preparations and curing of the specimens were performed at controlled conditions of 2, 20, and 35 °C to investigate the effect of ambient or curing temperatures. To have a better understanding of the environmental performance of CPB containing superplasticizer, reactivity, and hydraulic conductivity up to 90 days of curing were also investigated. The reactivity was measured using oxygen consumption test while hydraulic conductivity was measured using flexible wall permeability test. Microstructural analyses (thermogravimetric analyses, X-Ray diffraction, and mercury intrusion porosimetry) and monitoring tests (pH, zeta potential, electrical conductivity, and matric suction) were carried out to understand the principles behind the changes of the observed properties. The obtained results show that superplasticizer dosage and temperature variation have significant effects on the rheology, strength development, hydraulic conductivity and reactivity of the CPB. The polycarboxylic ether-based superplasticizer significantly reduces the yield stress and viscosity by creating strong electrostatic repulsion between the solid particles in the CPB and by steric hinderance. The CPB containing the superplasticizer remains fluid for longer period (as compared with the CPB without superplasticizer) due to the retardation of binder hydration. However, high curing temperature induces faster cement hydration, which thickens the fresh CPB. The unconfined compressive strength (UCS) of the CPB containing superplasticizer was observed to be lower in the early age (up to 7 days), which is also attributed to retardation of the binder hydration. At later ages, the superplasticizer improves the mechanical strength as the binder hydration accelerates and the solid particles self-consolidate. Coupled THMC processes in the CPB showed the role played by the changes in electrical conductivity, volumetric water content, matric suction, and temperature on the development of mechanical strength of the CPB containing superplasticizer. Similarly, addition of the superplasticizer in the CPB decreases both the hydraulic conductivity and reactivity of CPB, thus improving its environmental performance. The improvement is largely attributed to enhanced binder hydration and self-consolidation which decrease the porosity of the CPB. Increasing the curing temperature was found to magnify the improvement of the CPB properties by inducing faster binder hydration. The findings from this study will undoubtedly inform the design of CPB structure with better mechanical stability and environmental performance.

No description available.