No description available.

Cocoa butter is a highly complex system of triacyglycerides which has been shown to crystallize in a markedly different fashion under the application of shear. A rheometer insert was developed to enable the intact extraction of sheared samples for study of melting properties, crystal orientation and breaking stress. Samples were created by ramping from 50°C at three different cooling rates (0.5, 1 and 2°C/min) to three different end point temperatures (16, 18 and 20°C), creating nine different temperature sets. Viscosities of the cocoa butter samples under shear were recorded during sample creation and large jumps in viscosity were identified as form II and form V crystallization. Comparison of crystallization times for the nine different temperature profiles allowed for the conclusion that over a shear range of 90 – 1000 s^-1 there was no further appreciable shear acceleration of the form V transformation for the 16 and 18°C temperatures and only a slight increase up to 500 s^-1 for the 20°C temperature. Sheared samples were also examined with differential scanning calorimetry. Samples were examined for peak melting temperature on each of day 0, day 1, day 7 and day 28. Six of the nine different temperature conditions examined yielded a critical shear rate, above which the melting points of the samples were dramatically different than for low shear and no shear samples. For the day 0 and day 1 samples, above 500 s^-1 the melting temperatures were ~2°C higher than for 360 s-1 and below. For the day 7 and day 28 samples, above 500 s^-1 the peak melting temperatures were ~2°C lower than for the lower shear and no shear samples. The orientation of sheared samples was also examined using x-ray diffraction. In all of the nine temperature sets, orientation was present for shear rates of 360 s^-1 and higher. Breaking stress measurements were performed on sheared and non-sheared samples. These tests showed results remarkably similar to those seen in the DSC tests, with a critical shear rate existing in six of the nine temperature sets, above which an increase in the breaking strength occurs. Examination of samples on either side of the critical shear rate with x-ray diffraction yielded two distinct x-ray patterns leading to speculation that the application of high shear rates causes a change in the crystallization of cocoa butter leading to selective crystallization and the formation of a compositionally different form V crystal with fewer defects than its lower/no shear counterparts.

Cocoa butter is a highly complex system of triacyglycerides which has been shown to crystallize in a markedly different fashion under the application of shear. A rheometer insert was developed to enable the intact extraction of sheared samples for study of melting properties, crystal orientation and breaking stress. Samples were created by ramping from 50°C at three different cooling rates (0.5, 1 and 2°C/min) to three different end point temperatures (16, 18 and 20°C), creating nine different temperature sets. Viscosities of the cocoa butter samples under shear were recorded during sample creation and large jumps in viscosity were identified as form II and form V crystallization. Comparison of crystallization times for the nine different temperature profiles allowed for the conclusion that over a shear range of 90 – 1000 s^-1 there was no further appreciable shear acceleration of the form V transformation for the 16 and 18°C temperatures and only a slight increase up to 500 s^-1 for the 20°C temperature. Sheared samples were also examined with differential scanning calorimetry. Samples were examined for peak melting temperature on each of day 0, day 1, day 7 and day 28. Six of the nine different temperature conditions examined yielded a critical shear rate, above which the melting points of the samples were dramatically different than for low shear and no shear samples. For the day 0 and day 1 samples, above 500 s^-1 the melting temperatures were ~2°C higher than for 360 s-1 and below. For the day 7 and day 28 samples, above 500 s^-1 the peak melting temperatures were ~2°C lower than for the lower shear and no shear samples. The orientation of sheared samples was also examined using x-ray diffraction. In all of the nine temperature sets, orientation was present for shear rates of 360 s^-1 and higher. Breaking stress measurements were performed on sheared and non-sheared samples. These tests showed results remarkably similar to those seen in the DSC tests, with a critical shear rate existing in six of the nine temperature sets, above which an increase in the breaking strength occurs. Examination of samples on either side of the critical shear rate with x-ray diffraction yielded two distinct x-ray patterns leading to speculation that the application of high shear rates causes a change in the crystallization of cocoa butter leading to selective crystallization and the formation of a compositionally different form V crystal with fewer defects than its lower/no shear counterparts.

Orientadores: Lireny Aparecida Guaraldo Gonçalves, Renato Grimaldi / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-27T17:41:44Z (GMT). No. of bitstreams: 1 Silva_ThaisLomonacoTeodoroda_M.pdf: 4781686 bytes, checksum: 71da04b9cf4bdf2b971bd669e6c631c5 (MD5) Previous issue date: 2015 / Resumo: A manteiga de cacau (MC) é uma gordura natural extremamente importante para formulação de chocolate, mas devido à dificuldade em seu acesso e volatilidade de seus preços outras gorduras alternativas têm sido estudadas e produzidas a fim de substituí-las, como as gorduras equivalentes (Cocoa Butter Equivalent-CBE) e as substitutas (Cocoa Butter Substitutes-CBS). Entretanto as características de cristalização e sensoriais da MC promovidas no chocolate são muito peculiares, além disto, pode ocorrer uma incompatibilidade entre as gorduras sucedâneas o que ocasionará defeitos no chocolate como o fat bloom. O objetivo desse trabalho foi estudar a cristalização da MC, CBE, CBS, bem como entre estas misturas, a fim de se obter uma fração o mais semelhante possível à MC pura para elaboração de chocolates amargos, e a partir da avaliação destes chocolates, estudar a influência dessas gorduras na formação do fat bloom. As misturas elaboradas foram baseadas no teor total de MC presente no chocolate (MC adicionada e do liquor) e as concentrações estudadas variaram de 5%, 10%, 15%, 20% e 37,5% da CBE ou CBS na MC. As matérias-primas e as misturas foram caracterizadas mediante composição em ácidos graxos, composição triacilglicerólica, isotermas de cristalização, teor de sólidos, microestrutura, comportamento térmico, polimorfismo, consistência e ponto de fusão. Para verificar o efeito da adição dessas gorduras na qualidade do chocolate e resistência ao fat bloom amostras produzidas foram armazenados sob duas condições, 100 dias por 20°C e seis ciclos de 48h com 24h a 20°C e 24h a 33°C, sendo periodicamente avaliados quanto ao, índice de brancura, tensão de ruptura, configuração visual, polimorfismo e comportamento térmico. As misturas entre CBS e MC apresentaram grandes alterações na cristalização e plasticidade à medida que se aumentou o teor de CBS, e o principal efeito desta foi a formação de uma mistura eutética entre as duas gorduras. Já misturas entre CBE e MC são completamente compatíveis e poucas alterações são encontradas para estas misturas mesmo em altas concentrações de CBE. Por isso foi possível utilizar concentrações de até 20% de CBE e 10% de CBS, na produção dos chocolates. Os chocolates armazenados a 20°C apresentaram ótima resistência ao fat bloom e nenhum apresentou sinais da ocorrência deste defeito após 100 dias. Dentre os chocolates submetidos a flutuações de temperatura, após 3 ciclos o chocolate padrão apresentou alterações polimórficas e visuais características de fat bloom que foram intensificadas à medida que os ciclos foram prosseguindo. Os demais chocolates não sofreram influência da variação de temperatura, principalmente o chocolate com CBE que não apresentou nenhuma alteração visual ou estrutural característica de fat bloom, e o com CBS apenas após o sexto ciclo apresentou os primeiros sinais deste fenômeno. Através destes resultados foi possível concluir que apesar da incompatibilidade entre CBS e MC observada pelo estudo da cristalização destas misturas, esta incompatibilidade não foi determinante para acelerar a formação de fat bloom nos chocolates com esta gordura, sendo estes mais resistentes do que o chocolate padrão. A utilização de CBE em chocolates além de não ocasionar alterações de cristalização significativas ainda aumenta a resistência do chocolate ao fat bloom / Abstract: Cocoa butter (CB) is an extremely important natural fat for chocolate formulation, but due to the difficulty access and volatility of its price, alternative fats have been studied and produced to replace them as the Cocoa Butter Equivalent (CBE) and Cocoa Butter Substitutes (CBS). However, the crystallization and sensory characteristics that CB promoted in chocolate are very singular. Moreover, there may be an incompatibility between the alternative fats and CB which will cause defects in chocolate as fat bloom. The aim of this work was study the crystallization of CB, CBE, CBS, and their mixtures, in order to obtain a fraction as similar as possible to the pure CB for the preparation of dark chocolates, and study the influence of these fats on fat bloom formation. The mixtures were prepared based on the total content of CB on chocolate (CB added and CB inside the liquor), and the studied concentrations ranging from 5%, 10%, 15%, 20% and 37.5% of the CBE or CBS on CB. Raw materials and mixtures were characterized by fatty acid composition, triacylglycerol composition, isothermal crystallization, solid fat content, microstructure, thermal behavior, polymorphism, consistency and melting point. To check the effect of the addition of these fats in chocolate quality and resistance to fat bloom, the samples were produced and stored under two conditions, 100 days at 20° C and by temperature cycling for six cycles of 48h, 24h at 20°C and 24h at 33°C, periodically evaluated for, whiteness index, snap, microstructure, polymorphism and thermal behavior. The mixtures between CBS and CB showed large changes in the crystallization and plasticity as the CBS content was increased and the main effect is the formation of an eutectic mixture between the two fats. CBE and CB mixtures are fully compatible and little changes on crystallization of these mixtures are found even at high concentrations of CBE. Therefore it was possible to use 20% of CBE and 10% of CBS in chocolate production. All chocolates stored at 20°C showed excellent resistance to fat bloom and showed no signs occurrence of this defect during the 100 days. Nevertheless, the chocolate standard under temperature cycling, after 3 cycles showed modifications polymorphic and visual characteristics of fat bloom, and these characteristics were enhanced as the cycles were proceeding. Other chocolates were not so influenced by the variation of temperature, especially chocolate with CBE that showed no visual change or structural feature of fat bloom, and with CBS only showed after the sixth cycle the first small signs of this phenomenon. Through these results was concluded that despite the incompatibility between CBS and MC observed in the study of crystallization of these mixtures, this incompatibility was not decisive to accelerate the formation of fat bloom in chocolates with this fat, which are more resistant than standard chocolate. The addition of CBE on chocolates did not result on significant crystallization changes and also increased the resistance of chocolate to fat bloom / Mestrado / Tecnologia de Alimentos / Mestra em Tecnologia de Alimentos

Orientador: Lireny Aparecida Guaraldo Gonçalves / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-21T23:51:40Z (GMT). No. of bitstreams: 1 Oliveira_IngridFrancode_M.pdf: 12512639 bytes, checksum: 63474efdec388007cba17547f09ce8c9 (MD5) Previous issue date: 2013 / Resumo: Gorduras equivalentes de manteiga de cacau (CBEs) são utilizadas nas formulações de chocolates, substituindo parte da manteiga de cacau (MC). Embora as CBEs sejam compatíveis com a MC é importante um estudo detalhado a fim de se conhecer as propriedades de cristalização, fusão e estabilidade dos cristais, uma vez que as mesmas alteram a qualidade dos chocolates. Este estudo objetivou aumentar o conhecimento sobre CBEs e propor alteração do comportamento de fusão e cristalização de uma CBE escolhida. Sendo assim, foram caracterizadas quatro CBEs, com base em uma MC usada como padrão. As análises utilizadas para a caracterização foram índices de qualidade e de identidade, composição em ácidos graxos, índice de iodo, índice de saponificação, ponto de fusão, teor de sólidos por Ressonância Magnética Nuclear (RMN), isoterma de cristalização a 17,5°C por RMN, eventos de cristalização por Calorimetria Diferencial de Varredura (DSC), eventos de fusão por DSC em quatro tempos de armazenamento a 25°C (0, 4, 8 e 24 horas) e análise por difração de Raios-X. Adicionou-se 0,3% de triestearato de sorbitana (STS) às CBEs e o efeito do STS foi avaliado por meio de isotermas a 17,5°C, eventos de fusão por DSC em quatro tempos de armazenamento a 25°C (0, 4, 8 e 24 horas) e análise por difração de Raios-X. Ao final do estudo, foram elaboradas três formulações de chocolate: chocolate com 12% de MC, chocolate com 12% de CBE e chocolate com 12% de CBE com adição de 0,3% STS. Os chocolates foram avaliados quanto à viscosidade plástica, limite de fluidez, evento de fusão, tensão de ruptura (snap test) e microscopia eletrônica de varredura (MEV). A MC e as CBEs estudadas apresentaram-se dentro dos padrões de qualidade e identidade e os teores de ácidos graxos e triacilgliceróis analisados individualmente diferiram, destacando que as CBEs apresentaram maiores discrepâncias nos teores de POP (1, 3 palmitoil oleoil glicerol) e SOS (1,3 estearoil oleoil glicerol). As amostras apresentaram diferentes comportamentos de fusão, cristalização, estabilização e polimorfismo. O uso de STS promoveu elevação das curvas de cristalização a 17,5°C acarretando em perfis mais similares ao da MC em duas CBEs, embora não tenha alterado o polimorfo final das amostras após a estabilização. O uso de 0,3% STS em chocolate promoveu elevação do snap, embora não tenha sido verificada alteração na viscosidade plástica e no limite de fluidez dos chocolates. Diferentes estruturas foram visualizadas nas imagens realizadas em MVE / Abstract: Cocoa butter equivalent (CBEs) are used in chocolate formulations, replacing part of the cocoa butter (CB). Although there is compatibility between CBEs and cocoa butter, it is important a detail study that aims to know the properties of crystallization, melting and stability of the crystals, once it modifies the quality of the chocolate. This study intends to increase knowledge of CBEs and modify the melting and crystallization behavior of a selected CBE. Present study characterized and differentiated four CBEs and a standard CB. Analyzes used for the characterization and differentiation were free fatty acids, peroxide value, fatty acid composition, iodine value, saponification value, melting point, solid fat content by Nuclear Magnetic Resonance (NMR), isothermal crystallization at 17.5 ° C by NMR, crystallization events by Differential Scanning Calorimetry (DSC), fusion events by DSC during storage in four times at 25 ° C (T0 ¿ 0 hour, T1 ¿ 4 hours, T2 - T3 and 8 hours - 24 hours) and analysis by X-rays diffraction. It was added to CBE 0.3% tristearate sorbitan (STS) and the effect of STS addiction was evaluated by isotherms at 17.5 ° C, fusion events by DSC at four times of storage at 25 °C (T0 ¿ 0 hour, T1 ¿ 4 hours, T2 - 8 hours and T3 - 24 hours ) and analysis by X-rays diffraction. At the end of the study, three formulations of chocolates were prepared: chocolate with 12% CB, chocolate with 12% CBE and chocolate with 12% CBE and 0.3% STS. Chocolates were evaluated by plastic viscosity, shear stress, fusion event, texture (snap test) and scanning electron microscopy (SEM). The CB and CBEs studied were within the standards of quality and identity and fatty acids and triacylglycerols analyzed individually differed, emphasizing that the CBEs had differences in the levels of POP (palmitoil oleoil glycerol) and SOS (stearoyl oleoyl glycerol). The samples showed different behaviors melting, crystallization, stabilization and polymorphism. The use of STS caused increase of the crystallization curves at 17.5 ° C resulting in profiles most similar to the CB in two CBEs, although not changed polymorph end of the samples after equilibration. The use of 0.3% STS in chocolate increased the snap, though not verified change in plastic viscosity and fluidity limit of chocolates. Different structures were visualized in the images of SEM / Mestrado / Tecnologia de Alimentos / Mestra em Tecnologia de Alimentos

The thesis provides a background on crystallisation, the effects of applied fields and summarises the techniques used for characterisation and analysis. The study of applied magnetic fields was carried out on three crystallising systems (a) sucrose, (b) lactose and (c) cocoa butter. Both sucrose and lactose were crystallised from aqueous solutions in incubators at 50°C in applied magnetic fields and the resulting crystals compared to the those obtained under zero field conditions. The results for the sucrose study where the magnetic treatment was carried out under static, dynamic pumped and dynamic syphoned conditions domonstrated that changes in phase, crystallinity, morphology and microcrystallinity were a result of the applied magnetic fields and additional strongly bound water was found to be present within the sucrose crystals most likely to be sucrose hydrates. The resulting sucrose crystals were dependant on the type of field applied, the purity of the sucrose solution and the residence time within the applied field. The lactose study under static conditions provided similar results concluding that applied fields resulted in a more controlled crystallisation resulting in increased crystal size, increased crystallinity and changes in morphology. Crystallisation of cocoa butter from the melt, under normal production conditions in applied fields, resulted in changes in morphology and the time taken to reach optimum tempering which were dependant on the type of applied field and the residence time in the applied field.

No description available.

O desenvolvimento de formulações cosméticas multifuncionais tem sido cada vez mais crescente na indústria cosmética. A elaboração de uma formulação que contém diferentes ativos com propósitos diferentes podendo agir sinergicamente, muitas vezes, confere resultados cosméticos eficazes e até mesmo terapêuticos ao usuário. Nesta pesquisa foram desenvolvidas emulsões cosméticas apresentando formação de fases líquido cristalinas à base de manteiga de cupuaçu (Theobroma grandiflorum), manteiga de cacau (Theobroma cacau), o agente hidratante Hidraskin? e aditivos estabilizantes tais como álcool cetoestearílico, lanolina polietoxilada e carbômero. O desenvolvimento das formulações deu-se pelo método de inversão de fases. Estas foram caracterizadas quanto à formação de mesofases líquido cristalinas e avaliadas quanto à estabilidade física. Foram selecionadas quatro emulsões, duas com manteiga de cupuaçu (com e sem Hidraskin?) e duas com manteiga de cacau (com e sem Hidraskin?) que apresentaram maior estabilidade física e formação de fases líquido-cristalinas mais abundante. A adição do ativo hidratante (Hidraskin?) não alterou as características morfológicas das fases líquido cristalinas, identificadas como fase lamelar e a adição de lanolina polietoxilada como aditivo estabilizante promoveu maior estabilidade fisico-química das emulsões, principalmente quando submetidas à temperaturas em torno de 40ºC também sem alteração das fases líquido cristalinas. / Development of multifunctional cosmetic formulations has been growing each day in cosmetic industry. Elaboration of formulations, which presents many actives with different purposes acting together, many times give good and therapeutic results to customers. In this research cosmetic emulsions with liquid crystals were developed based on cupuaçu (Theobroma grandiflorum) or (Theobroma cacau) butter, Hidraskin? as a moisturizer active and actives for stabilization such as cetostearil alcohol, poliethoxilated lanolin and carbomer. Formulations were prepared by the Emulsion Phase Inversion method and characterized on the liquid crystal assembly and evaluated for physical stability. Four emulsions were chosen, two formulated with cupuaçu butter (one with and the other without Hidraskin?) and two with cocoa butter (one with and the other without Hidraskin?), which presented the highest amount of liquid crystals. Addition of Hidraskin? did not change the morphological aspects of liquid crystals, identified as lamellas. Also addition of polyethoxilatted lanolin increased the physical stability of all emulsions prepared, especially when they were submitted to increase of temperature (40ºC).

The effects of temperature, reaction time, and substrate concentration on the incorporation of decanoic acid (DA) and alpha-linolenic acid (ALA), into cocoa butter, were compared, using an immobilized enzyme derived from Rhizomucor miehei. All variables had an effect on incorporation of DA and ALA into cocoa butter but effects were not equivalent for the two fatty acids. Thus, DA was not an adequate model fatty acid for the incorporation of ALA into cocoa butter. The highest ALA incorporation achieved was 77.3±1.3. Samples with ALA incorporated were prepared as “pure” and “blends”, and these exceeded the milk and dark chocolate Canadian Food and Drug Regulation guidelines for products making omega-3 fatty acid content claims. The highest %TAG content, 97.3±1.0%, was achieved for the 11.9wt% “blend” sample. Differential scanning calorimetry suggested that both “pure” and “blend” samples contained mainly form IV and V, with much smaller quantities of form II polymorphs.

O desenvolvimento de formulações cosméticas multifuncionais tem sido cada vez mais crescente na indústria cosmética. A elaboração de uma formulação que contém diferentes ativos com propósitos diferentes podendo agir sinergicamente, muitas vezes, confere resultados cosméticos eficazes e até mesmo terapêuticos ao usuário. Nesta pesquisa foram desenvolvidas emulsões cosméticas apresentando formação de fases líquido cristalinas à base de manteiga de cupuaçu (Theobroma grandiflorum), manteiga de cacau (Theobroma cacau), o agente hidratante Hidraskin? e aditivos estabilizantes tais como álcool cetoestearílico, lanolina polietoxilada e carbômero. O desenvolvimento das formulações deu-se pelo método de inversão de fases. Estas foram caracterizadas quanto à formação de mesofases líquido cristalinas e avaliadas quanto à estabilidade física. Foram selecionadas quatro emulsões, duas com manteiga de cupuaçu (com e sem Hidraskin?) e duas com manteiga de cacau (com e sem Hidraskin?) que apresentaram maior estabilidade física e formação de fases líquido-cristalinas mais abundante. A adição do ativo hidratante (Hidraskin?) não alterou as características morfológicas das fases líquido cristalinas, identificadas como fase lamelar e a adição de lanolina polietoxilada como aditivo estabilizante promoveu maior estabilidade fisico-química das emulsões, principalmente quando submetidas à temperaturas em torno de 40ºC também sem alteração das fases líquido cristalinas. / Development of multifunctional cosmetic formulations has been growing each day in cosmetic industry. Elaboration of formulations, which presents many actives with different purposes acting together, many times give good and therapeutic results to customers. In this research cosmetic emulsions with liquid crystals were developed based on cupuaçu (Theobroma grandiflorum) or (Theobroma cacau) butter, Hidraskin? as a moisturizer active and actives for stabilization such as cetostearil alcohol, poliethoxilated lanolin and carbomer. Formulations were prepared by the Emulsion Phase Inversion method and characterized on the liquid crystal assembly and evaluated for physical stability. Four emulsions were chosen, two formulated with cupuaçu butter (one with and the other without Hidraskin?) and two with cocoa butter (one with and the other without Hidraskin?), which presented the highest amount of liquid crystals. Addition of Hidraskin? did not change the morphological aspects of liquid crystals, identified as lamellas. Also addition of polyethoxilatted lanolin increased the physical stability of all emulsions prepared, especially when they were submitted to increase of temperature (40ºC).