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Atividade - Caracterização de matérias primas para processamento

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Prévia do material em texto

Item 1. Plote os gráficos de TGA das matérias primas e do produto final produzido. Apresente as informações que podem ser retiradas do gráfico.
Gráfico I: Taxa de degradação do EMA-GMA puro – 10°C/min em N2
Fonte: Autores (2020)
Gráfico II: Taxa de degradação da borracha natural pura – 10°C/min em N2
	
Fonte: Autores (2020)
Gráfico III: Taxa de degradação do Poli(ácido lático) – 10°C/min em N2
Fonte: Autores (2020)
Gráfico IV: Taxa de degradação do compósito (PLA/NR/EMA-GMA) – 10°C/min em N2
Fonte: Autores (2020)
A partir dos gráficos de Análise Termogravimétrica (TGA) é possível identificar se há a presença de substâncias voláteis, realizar a análise da composição e a temperatura inicial de degradação dos materiais, além de identificar se há presença de substâncias inorgânicas (materiais refratários). Tendo isso em vista e após a análise dos gráficos, é possível verificar que não há presença de voláteis na matéria prima, nem no produto, já que foi necessário uma elevada temperatura de ignição para a ocorrência das reações.
Através da análise dos gráficos pode-se concluir que a decomposição das substâncias em questão ocorre em um único estágio, sendo possível utilizar a curva para definir os limites de estabilidade da amostra, determinar a estequiometria da reação e investigar a cinética da reação. Verifica-se também que a degradação térmica ocorreu na faixa de temperatura de 300 a 500 ºC, durante a qual ocorreu a perda de praticamente 100% de massa, ou seja, há baixa resistência térmica envolvida nas quatro situações.
Tabela I: Perda de Massa e intervalo de temperatura do processo de degradação
Fonte: Os autores (2020)
Item 2. Plote os gráficos de DSC do PLA puro. Apresente as informações que podem ser retiradas do gráfico.
A Calorimetria Exploratória Diferencial (DSC - do inglês "Differential Scanning Calorimetry"), é a análise na qual se acompanha a variação da energia entre a amostra e a referência (Cláudia Bernal, Andréa Boldarini, SuseteTrazzi e Eder Tadeu, 2002). Em um experimento de Calorimetria Exploratória Diferencial, mede-se a variação de entalpia que ocorre entre a amostra e a referência durante o processo de aquecimento/resfriamento, e eles ainda pontuam que para um processo endotérmico, com absorção de calor, observa-se a diminuição na temperatura da amostra e a inflexão na curva.
Gráfico V- Análise DSC para PLA puro- 1º corrida de aquecimento
Fonte: Os autores (2020)
Os dados de DSC foram obtidos em atmosfera inerte (N2) com taxa de aquecimento a 10ºC por minuto. O círculo em laranja no gráfico apresenta um ponto onde há mudança de linha de base sem pico, os círculos na cor verde apresentam picos endotérmicos (onde há absorção de calor) e os círculos de cor vermelha mostram picos exotérmicos (onde há liberação de calor). Esses picos representados estão associados também a eventos físico-químicos dos materiais. Quando se tem picos “para baixo” normalmente estão relacionados à fusão e ebulição do material com característica endotérmica por exemplo. Esse segundo pico inferior demonstra uma cristalização que ocorre antes da fusão.
	
Tabela 2- Caráter Exotérmico e Endotérmico dos picos DTA, de acordo com sua origem física ou química 
Fonte: Revista virtual Quimica Nova, vol 25, São Paulo (Set/Out 2002)
Gráfico VI- Análise DSC para PLA puro – 1º corrida de resfriamento
Fonte: Os autores (2020)
Durante a 1º corrida em fase de resfriamento observa-se que a curva do gráfico se mostra de certa forma constante, isso acontece pois quando a amostra atinge a temperatura de Fusão ou de Ebulição por exemplo, ele mantém sua temperatura “estacionada” por um período, o que significa que essa amostra está absorvendo energia para fazer a mudança de estado físico. Durante esse momento não há nenhum pico de cristalização a quente. 
Segundo Klein (2009), quando é realizado o resfriamento de um polímero semicristalino a partir de seu estado fundido, isto é, acima da temperatura de fusão, o mesmo atinge uma temperatura na qual um grande número de cadeias poliméricas inicia uma ordenação espacial formando uma estrutura cristalina. Isto se reflete em toda a massa polimérica produzindo-se a cristalização da massa fundida. A cristalização pode correr de duas maneiras, de forma isotérmica, quando a temperatura é abaixada rapidamente até um dado valor de Tc, estabilizada e mantida constante até que toda a cristalização ocorra, ou de forma dinâmica quando a temperatura é reduzida a uma taxa constante. A cristalização neste caso ocorrerá dentro de uma aixa de temperatura, onde se tem a máxima taxa de conversão da cristalização. A cristalização isotérmica é a mais estudada, mas a dinâmica é a que está mais próxima dos sistemas industriais de solidificação
Gráfico VII- Gráfico de análise DSC para PLA puro- 2º corrida de aquecimento
Fonte: Os autores (2020)
Na segunda corrida o material foi fundido e cristalizado novamente, por esse motivo apagam-se memórias das propriedades dos materiais e ele se comporta de maneira mais regular, sem tensões residuais do processo, pode-se observar que os picos não estão “tão acentuados.
	Através da análise dos gráficos é possível se identificar a temperatura de transição vítrea (Tg), temperatura de fusão (Tm) e a cristalização a frio (Tcc), sendo:
Tabela 3 – Resultados das análises de DSC para primeiro e segundo aquecimento
	 
	1ª corrida
	2ª corrida
	Tc (°C)
	59,4
	63,4
	Tcc (°C)
	92,4
	96,1
	Tm (°C)
	169,8
	168,6
Fonte: Os autores (2020)
Segundo Ana Cristina Malheiros (2012), a temperatura de transição vítrea revela a mudança de um comportamento rígido para um comportamento de amolecimento do material. Os polímeros termoendurecíveis não apresentam fusão, eles apenas se degradam a elevadas temperaturas de forma irreversível. Por isto, a sua temperatura de transição vítrea é controlada pelo grau de reticulação da estrutura, e surgem, geralmente, alterações muito menos acentuadas quando comparados com os termoplásticos.
Nos polímeros as propriedades mecânicas são extremamente dependentes da temperatura e do tempo de exposição. Os polímeros são viscoelásticos, ou seja, apresentam algumas propriedades dos líquidos viscosos e dos sólidos elásticos. A temperaturas baixas, a mobilidade das cadeias é muito pequena e o estado amorfo permanece. No caso de temperaturas altas, o polímero comporta-se como uma borracha, as cadeias poliméricas podem adquirir mobilidade suficiente para dar início ao processo de cristalização. Nesta região, e durante um arrefecimento lento, o polímero exibe grandes alongamentos quando lhe é aplicada carga e pode resistir a grandes extensões da ordem dos 100% ou mais sem deformações permanentes (Bower 2002).
Segundo Tammann (1933), a temperatura de transição vítrea é a temperatura em que a fragilidade desaparece, ou seja, uma temperatura na qual a propensão a surgirem fendas é menor. Várias propriedades se alteram bruscamente na Tg. Acima da temperatura de transição vítrea, os polímeros têm comportamento do tipo borracha, facilmente deformáveis, tornando-se dúcteis. Quando a temperatura de um polímero cai abaixo da Tg, os átomos das cadeias poliméricas estão como congelados numa dada posição, ou seja, não se dá o movimento rotacional ou translacional, e o polímero comporta-se de maneira cada vez mais frágil. Muitos fatores podem alterar a Tg de um polímero, entre eles estão a estrutura química, o grau de cura e a massa molar. (da Silva et al. 2007).
Quanto a Cristalização a frio, Marcelo Silveira Rabello, diz que esse fenômeno é originado do rearranjo das regiões amorfas numa fase cristalina, e ocorre quando temperaturas inadequadas são utilizadas durante a etapa de aquecimento das pré-formas ou quando o material utilizado apresenta alta tendência para cristalização. Embora a cristalização a frio seja indesejável durante o reaquecimento da pré-forma e antes do sopro, sua ocorrência durante a fase de soproestiramento é importante, pois o material semicristalino possui melhores propriedades mecânicas e de barreira. Da mesma forma, durantea termoformagem do PET a cristalização a frio pode ser desejável para a obtenção de produtos mais rígidos e mais resistentes ao calor por exemplo.
A temperatura de fusão (Tm) é a temperatura na quais as cadeias poliméricas saem de sua estrutura cristalina se tornando um líquido sem ordem estabelecida. Neste ponto, a energia do sistema atinge o nível necessário para vencer as forças intermoleculares secundárias entre as cadeias da fase cristalina, destruindo a estrutura regular de empacotamento, mudando do estado de borracha para o estado viscoso (Spadetti et all, 2017).
Segundo Klein (2009), este evento térmico só ocorre em materiais com um mínimo de cristalinidade. Em materiais totalmente amorfos este evento não ocorre, mas um outro evento chamado amolecimento. Trata-se de uma mudança termodinâmica de primeira ordem, afetando variáveis como volume específico e entalpia.
A temperatura de fusão de materiais semicristalinos é um parâmetro muito importante tanto na aplicação quanto no processamento do material, também para se estabelecer os parâmetros do processo e prever as condições de temperatura na qual este material pode ser aplicado.
Item 3) De acordo com os dados retirados de ambas análises (TGA e DSC), defina a faixa de temperatura para configurar os parâmetros de processamento e quais os cuidados que devem ser tomados com as matérias primas antes e durante o processamento
Ao transferir os dados das análises termogravimétricas, pode se observar que a faixa de temperatura tem relação direta com a configuração elementar das amostras. No ensaio de TGA, a faixa de temperatura tem relação com a quantidade de elementos voláteis, umidade e de materiais orgânicos, que são queimados antes de chegar em 500ºC. Nos ensaios que necessitam eliminar a amostra para sua análise, é importante se atentar que a amostra não possua elementos voláteis em sua composição, também será necessário fazer a secagem do material, pode ser por meio de estufa em mais ou menos 110ºC, para que a presença de umidade seja totalmente eliminada.
Em análises de DSC, para a definição da faixa de temperatura em relação à entalpia, é observado onde ocorre à temperatura de fusão cristalina do PLA, os picos de entalpia podem ocorrer em diversos pontos, então se deve adotar a análise das reações desde a temperatura inicial desejada, e a presença de líquidos e voláteis também interferem no diagrama. Então por isso também é importante secagem e eliminação de partículas heterogêneas.
REFERÊNCIAS BIBLIOGRÁFICAS
Bernal, Cláudia. Boldarini, Andréa Couto. Breviglieri, Trazzi. Cavalheiro, Éder Tadeu. Departamento de Química, Universidade Federal de São Carlos. INFLUÊNCIA DE ALGUNS PARÂMETROS EXPERIMENTAIS NOS RESULTADOS DE ANÁLISES CALORIMÉTRICAS DIFERENCIAIS – DSC. Quimica Nova, volume 25, nº 5. São Paulo, Setembro/outubro, 2002. Disponível em:< https://www.scielo.br/scielo.php?pid=S0100-40422002000500023&script=sci_arttext>. Acesso em 26/05/2020 às 22h15min.
Carbolite Gero. Loss on ignition (LOI)/Loss on dry (LOD) Thermogravimetric analysis (TGA). Disponível em: <https://www.carbolite-gero.com/applications/heating-applications/loss-on-drying-ignition/> Acesso em 01/06/2020 ás 09:40
Klein, Catia. Síntese e caracterização de poliésteres termoplásticos. Disponivel em: http://tede2.pucrs.br/tede2/bitstream/tede/3148/1/418870.pdf. Acesso em 30/05/2020 às 10h42.
Malheiro, Ana Cristina. Efeito da temperatura de cura na temperatura de transição vítrea de um adesivo estrutural. Dissertação do MIEM. Faculdade de Engenharia da Universidade do Porto, Mestrado Integrado em Engenharia Mecânica. Janeiro de 2012. Disponível em:< https://repositorio-aberto.up.pt/bitstream/10216/63347/1/000151156.pdf. Acesso em 27/05/2020 às 13h02min.
Rabello, Marcelo Silveira. Wellen, Renate Maria. Estudo da cristalização a frio do poli (tereftalato de etileno) (PET) para produção de embalagens. Revista Eletrônica de Materiais e Processos, Vol. 3, No 2 (2008). Disponível em:< http://www2.ufcg.edu.br/revista-remap/index.php/REMAP/article/viewArticle/71>. Acesso em: 26/05/2020 às 22h40min.
Spadetti, Carolini. Filho, Eloi. Sena, Geovane. Melo, Carlos. Propriedades térmicas e mecânicas dos compósitos de Polipropileno pós-consumo reforçados com fibras de celulose. Disponível em: https://www.scielo.br/pdf/po/v27nspe/0104-1428-po-0104-14282320.pdf. Acesso em 30/05/2020 às 10h18. 
Poli(ácido lático)
Temperatura 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