A corrosão por processos eletroquímicos se manifesta através do cenário de haver um Anodo de Sacrifício e um Catodo mencionados na Aula 6, onde em um fluxo de elétrons e com eles , íons transitando em um meio eletrolítico , levam a perda e desgaste da massa do eletrodo eleito como Anodo, resultando na sua destruição. O mecanismo é sempre idêntico tanto em Folha-de-Flandres bimetálico, quanto em Alumínio multimetálico com todas as suas ligas . No geral chamamos genericamente a este processo de perda de elétrons, com fluxo iônico Anodo→Catodo , de Corrosão Galvânica ou Eletro-Química.
É importante mencionar que “Agua Livre” bem reativa, tem comportamento diferente da “Agua Ligada” menos reativa. Complexar a agua é uma maneira de a manter “ocupada” na relação com outras substâncias que não sejam os materiais de embalagem e se prevenir a Corrosão.
A Corrosão pode se manifestar de diferentes maneiras , e para ajudar a se reconhecer o fenômeno, descreveremos abaixo os Tipos e Formas de Corrosão mais comuns em embalagens Aerossol:
Tipos de Corrosão:
Corrosão geral, generalizada ou de ataque uniforme;
É a corrosão que se manifesta por toda a superfície de uma chapa , causando perda uniforme de espessura, sem contudo apresentar pontos ou crateras (pites) . Também conhecida como corrosão generalizada, contudo tal termo não é muito usado por carecer de especificidade e precisão na descrição do fenômeno, ou até para explicar alguma coisa, quando não se sabe o que aconteceu.
O termo de corrosão generalizada é mais aplicável em ataque químico , quando se forma um filme de ferrugem por toda a extensão da superfície corroída, sem formar pontos ou furos isolados.
A taxa de corrosão pode ser facilmente determinada a partir da mediação da perda de massa ou da quantidade de Hidrogênio ou de outro gás , que é gerada. Tais gases por vezes induzem a embalagem de Aerossol a sobrepressão e até estufamento.
Corrosão por Cavidades ou Pites;
Segundo vários autores, é a corrosão interna mais comum em embalagens de Aerossol.
Não ocorre de maneira generalizada como descrito anteriormente, mas sim em áreas específicas onde por algum motivo houve um ponto de vulnerabilidade do material.
O Mecanismo provável é de que ocorre uma sequência de rompimento da camada interna do verniz , da película de passivação , acidificação do ponto (pite) e de sua proximidade e uma vez exposta esta pequena área debilitada (frente a grande área catódica circunvizinha), o metal exposto assume a situação de Anodo de Sacrifício , iniciando-se implacavelmente a corrosão localizada.
Tal tipo de Corrosão é caracterizada pela formação de cavidades ou pontos de deterioração do metal através de corrosão alveolar resultante da perda de átomos de metal e consequente perda de massa , e no caso específico de Aerossol , com o aprofundamento da degradação ocorre a redução da espessura da parede que acaba por não resistir a pressão interna e isto leva fatalmente a vazamentos.
Segue abaixo imagem de Corrosão alveolar de uma chapa de FL , com escavação e perda de átomos formando uma “cratera”, eternizada foto de Microscópio Eletrônico de energia dispersiva por raio X, como cortesia do laboratório de Metalografia da CSN – Volta Redonda – RJ
É de se considerar que um fator importante para o mecanismo da formação de cavidades (pites) seja a existência de pontos de maior fragilidade da película de passivação (com possíveis defeitos em sua formação), fazendo com que o pH no interior do pite se altere substancialmente para o espectro ácido dificultando a restituição da camada passiva inicial. Resultando disto que a pequena área ativa anódica formada diante de uma grande área catódica provoca a intensa corrosão localizada , citada.
Corrosão Intergranular ou Intercristalina;
Mesmo não sendo considerado por alguns autores como caso comum de ocorrência em embalagens de Aerossol, vale ressaltar de que uma vez feita a exposição do metal, aos Graneis funcionando como eletrólitos , e a nivel granular , os metais constituintes do contenedor , particularmente de Alumínio e suas diversas ligas ou mesmo com falhas de sua estrutura microcristalina, tais componentes de eletronegatividade diferente podem reagir de forma galvânica bimetálica entre si e induzir a Corrosão.
Muitas vezes ocorre que não conseguimos entender o porque dos aspectos teóricos científicos de tais fenômenos, contudo não se pode deixar de reconhecer que as consequências dos mesmos existem.
“Todo mundo sabe que acontece, poucos sabem explicar porque”.
Este autor não descarta nenhuma forma de interação dos metais com o meio e por isso existe a intenção de listar todos as possibilidades conhecidas e tentar contextualizar em Aerossol, cabendo a nós pesquisadores o uso de dialética Aristotélica de Tese versus Antítese, em forma de Sim/Não/Porque?
- Porque Sim?
- Porque Não?
Servindo a Filosofía ao propósito prático de investigar os fenômenos de estabilidade de embalagens de Aerossóis.
Corrosão Transgranular ou Transcristalina;
Ocorre por exemplo em tubos de ALU , quando da propagação em forma de trincas , que avançam dentro da estrutura macrocristalina ,difundindo-se entre os grãos do metal, levando a perfurações e vazamentos. É uma versão cujo desfecho poderia ser caracterizado como puntiforme ou Pite, intensificado pelo fato da embalagem estar premida em kg/cm² e com esta relação de Força/Area muito pequena e pontual, forçar os eletrólitos para dentro do material. É visível em pequenos pontos do lado exterior de tubos de Alumínio, onde o verniz forma uma bolha que se rompe deixando o furo visível, e por onde vaza o conteúdo da embalagem.
Corrosão por concentração diferencial ( Iônica e/ou por Aeração);
Ocorre em Aerossóis que formam múltiplas fases dentro do contenedor (ou seja, além das duas normais formadas pelo granel e pela fase vapor) . A variação de concentração de determinados componentes (íons) de cada fase da formulação , imersos em distintas fases líquidas e consequentemente suas diferentes alturas, dentro do contenedor no qual o granel está envasado ou mesmo eventualmente imerso (quando estocado deitado) provoca potencial de ação corrosiva, também nominada Corrosão por concentração Iônica diferencial.
Seu mecanismo se dá pela formação de pilhas de corrosão devido ao diferencial da concentração iónica e seu potencial eletroquímico em cada fase , em áreas de maior ou menor concentração dos mesmos , resultando invariavelmente , em Anodo e Catodo.
Existe também e não pode ser subestimado o potencial de formação de pilhas de corrosão por aeração ou presença de Oxigênio na câmara de expamsão ou de íons na fase gasosa , ou seja, nem a fase vapor que contém Ar (entenda-se Oxigênio), que misturado ao propelente, fica imune. Tal tipo de ocorrência na fase vapor se chama de Corrosão por Aeração diferencial. Alguns envases especiais de Aerossol são feitos a vácuo afim de minimizar o risco de se ter Oxigênio como oxidante reativo potencial.
Existem casos onde além de não se retirar o Oxigênio a vácuo, se faz sobrepressão de ar na embalagem afim de estabilizar na emulsão , a fase liquefeita dos gases , ou seja, muitas referencias de Aerossol , ficariam horrorizadas com tal sobrepressão, que pouca ou nenhuma ação tem sobre a estabilidade. Cada caso é um caso.
Tal extratificação pode ser observada em ensaios de estabilidade quando da abertura do contenedor , na forma de faixas de corrosão , com boa definição das Interfaces entre cada uma delas, incluso da Líquido-Vapor.
Para antecipar uma leitura preliminar de tal fenômeno, e “Ver” as fases bastaria fazer o teste de envase de Aerossol “inVitro”. O formulador precisa “Querer” fazer o teste para poder “Ver”.
Corrosão em Fendas ou Frestas , ou ataque por depósito
Muito comum em embalagens de Aerossol , o potencial de ocorrerem células de Corrosão diferencial aumenta na presença de fendas ou frestas nas juntas de materiais de embalagens metálicas , mais especificamente FL , tais como a junção de chapas sobrepostas soldadas e Recraves de embalagens de 3peças. Lembrar de que pode haver Oxigênio enclausurado na recravação da válvula e também nas dobras de recravação ou Agrafagem do contenedor, e este acelera os processos de corrosão. Alguns fabricantes já estudam estampar o domo e corpo da embalagem de FL, para fabricar-la em duas peças, afim de minimizar a vulnerabilidade e potenciais pontos de corrosão além de baratear seu processo e seu contenedor.
Em relação ao mecanismo eletro-químico de corrosão, as bordas da chapa de FL ficam expostas e durante o processos de fabricação de solda e de recravação , os metais predominantes Ferro e Estanho entram em contato direto, ou seja , sem necessidade de meio eletrolítico condutivo e praticamente unidos sem necessitar de meio de transferência iônica, eles tem FEM em E(V) integral , entrando literalmente e na prática em:
CURTO CIRCUITO !!!
Isto explica do porque a corrosão em latas FL de Aerossol tem tendência a aumentar nas juntas e soldas, bem ilustrado na figura abaixo;
Alumínio é Monobloco e só tem a única junta e as possíveis frestas na virola (interna ou externa), são aquela geradas no momento do acoplamento e recravação com a válvula , sob responsabilidade do Envasador.
É importante mencionar de que metais diferentes ,muito frequentemente podem , na prática são e devem ser unidos de forma segura e condições controladas , mesmo que existam eletrólitos de baixa condutividade ou mesmo umidade, que sob condições controladas de exposição aos meios adversos das diversas formulações possíveis em Aerossol , acabam por manter os processos de Corrosão dentro da validade normal dos acabados.
Uma previsão teórica usando cálculos ou tabelas de eletronegatividade e de todos as causas e efeitos possíveis é muito difícil , pois o numero de variáveis complexas ultrapassa a nossa capacidade humana , de prever todas as combinações possíveis de tais fatores. A relevância deste trabalho consiste em não tentar dar todas as respostas, mas induzir às perguntas.
Finalizando nesta questão, as frestas e espaços vazios disponíveis para o Oxigênio são inerentes ao projeto e tecnologia que cada um dos fabricantes de material de embalagem , dispõe em seus processos de fabricação de materiais de embalagem para Aerossol , e eles devem levar em conta todos estes riscos e variáveis , com a finalidade sincera de mitigar o potencial de risco de Corrosão em suas embalagens.
Corrosão de Entorno da Solda;
È um tipo de corrosão que surge na área de reserva de solda onde uma vez submetido o metal ao processo de soldagem elétrica e suas altas temperaturas , ocorre alteração de algumas características da chapa como a tempera e diminuição de sua resistência química. Para tal os fabricantes aplicam um filete de verniz protetor logo após a soldagem , para evitar os processos de oxidação, principalmente da parte externa da lata de FL. Com as novas tecnologias a área de reserva tem ficado cada vez mais fina e menos exposta. Se com o passar do tempo tal verniz acompanhar a cor geral da impressão, o aspecto ficará impecável, e não será mais motivo de pontuação dos fabricantes de contenedores de Alumínio.
Corrosão Química;
É a mais fácil de se explicar e está relacionada a reações químicas extremas principalmente de ácidos , um tanto menos de bases fortes, com os materiais metálicos de embalagem , e com dezenas de reações disponíveis, de tal magnitude que não cabe neste trabalho listar.
Fora destes casos extremos é sabido que o Alumínio pode ser corroído na presença de graneis de base aquosa e também , embora menos em graneis de base solvente, tal como o Alcool Anidro.
Mesmo envasando tais graneis agressivos em sistemas de Aerossol (não-convencional) do tipo bi ou tri-compartimentais onde os materiais estariam confinados isolados em bolsas laminadas de plástico, estes casos são exceções tais como mousse de Peróxido de Hidrogênio (Agua Oxigenada H2O2) para tinturas capilares, ou Espuma de Barbear a quente.
Alguns autores mencionam este tipo de corrosão (de teoria Ácida) como que relacionada aos fatores externos aos quais embalagens de Aerossóis são expostos ,tais como Dióxido de Carbono(CO2) e Oxigênio atmosférico (O2) e sais minerais (Na+Cl-)que se dissociam na presença de muito pouca umidade tal como ocorre na Maresia e provocam ataque direto chamada por vezes de Corrosão Seca , ou seja na ausência de umidade.
Em geral tal tipo e Corrosão Química não ocorre comumente em Aerossol pelo simples fato de que há pouca utilidade prática ou serventia para produtos de consumo envasados com Acido Sulfúrico concentrado ou Solução de Soda Cáustica 50% entre outros produtos químicos similares altamente reativos. Os materiais de embalagem de Aço FL ou Alumínio ALU, simplesmente se dissolvem nestas condições em poucos minutos e em reações por vezes muito Exotérmicas, ou seja, não envase nada assim , nem mesmo por “diversão” no laboratório.
Corrosão Galvânica ou Eletro-Química, já foi descrita como o mecanismo genérico bimetálico sempre em atuação em Corrosão Anodico-Catodica e diferem apenas na forma em que se manifestam.
Corrosão Seletiva;
Dentre as várias ocorrências no campo de tubulações das redes hidráulicas de abastecimento de agua industrial, segmentando uma aplicação em nosso setor de Aerossol , a Corrosão seletiva poderia ser caracterizada por um processo eletrolítico de condução iônica, onde algum elemento do material de embalagem é influenciado por algum elemento da formulação e este mecanismo facilita a formação do par galvânico entre o elemento do material de embalagem como Anodo , e do outro elemento Catodo , oriundo da formulação. Envases de Grafíte em Aerossol apresentam tal fenômeno.
É sabido que o Grafite é um excelente condutor de energia elétrica , e tanto é verdade que as escovas dos motores elétricos são feitas deste material.
Em um Aerossol nestas condições , com alguma falha no revestimento do verniz interno, o Grafite é muito mais catódico que o Estanho e por sua vez mais do que o Ferro, e estando este concentrado no granel e nas frestas dentro do contenedor , acaba de forma seletiva assumindo sua natureza de Catodo enquanto que o Ferro novamente assume como Anodo de Sacrifício, potencializando os processos de corrosão. A presença de contaminantes e umidade pode desencadear e até mesmo acelerar tais processos de Corrosão.
Corrosão Microbiológica;
Se manifesta como uma Corrosão Pontual ou por Pites, mas a sua causa é uma atividade microbial anormal , em que bactérias , algas ou fungos, reduzem o metal da embalagem a sulfatos férricos , em meios aeróbicos (com presença de Ar) e funciona também em meios anaeróbicos (sem a presença de Oxigênio). Em Aerossóis dado que a pressão interna é 3 a 4 vezes maior do que a pressão atmosférica , esta condição extrema rompe a membrana plasmática do micro-organismo , eliminando a sua atividade.
Corrosão associada a Erosão;
Este tipo de corrosão está relacionado ao escoamento e impactos causados por sólidos ou fluidos cavitando dentro de tubulações metálicas e não teria nenhuma relação com o aplicador Aerossol, se não fosse o fato de que por vezes adicionamos na estrutura do Sistema Aerossol um elemento sólido móvel e solto tal como uma esfera de Vidro inerte (a Bolinha de Gude) ou esfera metálica de Aço.
Como os dizeres de rotulagem frequentemente nos orientam :“Agite bem antes de usar”; com a finalidade de suspender algum sólido que por diversos motivos se decanta por ação inevitável das forças gravitacionais , tal esfera acabam por chocar-se com as paredes da embalagem, produzindo riscos , danificando/esfoliando os revestimentos internos desde os vernizes , rompendo passivação e até mesmo o Estanho expondo a área anódica, e pazmem, tal “martelamento” pode induzir a pontos de Corrosão. Agite bem uma lata de tinta em FL ou maquiagem corporal em ALU, com tais esferas e observe os pontos de impacto e deformação no seu fundo. Dá até para imaginar o que ocorre com os vernizes internos que não são feitos para suportar tais impactos . Existem maneiras mais elegantes , por vezes mais caras, de se manter suspensos os sólidos dispersos nestas formulações de Aerossol.
Corrosão por Estresse;
Em fontes de referência tal Corrosão é chamada de Corrosão por Tensão , que ocorre sob ação de estresse de tensão mecânica , combinado a um meio corrosivo.
Contextualizando para o caso de Aerossol, o termo mais adequado de se chamar tal tipo de seria Corrosão por Estresse.
Em Aerossol existe o fato ligado a Lei de Charles-GayLussac de que com o aumento da temperatura , ocorre aumento no volume de gases. Como o Sistema Aerossol é fechado, não existe aumento do volume fixo da embalagem e daí decorre um aumento de Pressão. Tal aumento da pressão interna que é um dos fatores de Estresse da embalagem, que pode ocasionar trincas e fraturas microscópicas , induzindo a pontos de Corrosão.
De fato ocorrem algumas formas predominantes de tensões nos materiais de embalagens, gerando fraturas e aumento da capacidade de reação com o eletrólito sob condições de Pressão, sendo fato em cinética química de que as velocidades de Reação aumentam com o aumento da Temperatura e da Pressão;
Seguem abaixo variáveis a verificar e controlar as tensões envolvidas;
- Durante o recrave da válvula e seu canal de deformação que faz o contato mecânico da virola da lata ou do tubo , o excesso de abertura da pinça pode-se gerar estresse mecânico em ambas as partes metálicas e romper o verniz,com exposição do metal.
- Nos processos de dobra em recravação do domo e fundo da lata de FL;
- No processo de conificação dos tubos de ALU, que podem inclusive gerar estrias;
- Na passagem do banho-maria de teste de resistência da embalagem, o aumento de pressão interna em Kg/cm² , pode gerar estresse nos materiais dos contenedores;
- Tal aumento de temperatura do banho de teste, do forno de Schrink, das condições de transporte e estocagem, em todas as circunstâncias em que se faça a energia interna da embalagem subir, também geram tensões internas no contenedor de Aerossol.
- Se com o aumento da temperatura e por conseguinte da tensão , o meio em forma de formulação acabar por aumentar a velocidade de reação.
- Se tal reação gerar hidrólise ou outras reações de acidificação , com produção de gases podendo resultar em sobrepressão ou aumento dos processos de Corrosão,
- Se o aumento de pressão intensificar a penetração do eletrólito pelas cavidades e frestas ,trincas e fraturas, poderá aumentar a corrosão, causando perfurações,
Ou seja, um certo controle das condições de processo, podem auxiliar a evitar a ocorrência de Corrosão por Tensão, contudo é provável de que uma vez fora de nossas fabricas , se torna impossível controlar tantas variáveis desconhecidas, que independem de nossas melhores intenções no dimensional de projeto, de nosso zelo em desenvolver, de testar e fabricar bons produtos , que uma vez no mundo afora, deverão sobreviver por sí mesmos dentro da validade estabelecida e gravada no corpo do Acabado.
Todos os Direitos autorais deste trabalho são protegidos por lei. É autorizada reprodução parcial de trechos, desde que sempre seja citada a fonte. As considerações filosóficas refletem apenas a opinião do autor ,que não está nem aí, com a hipocrisia do politicamente correto.
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