Surface modification of nylon 6,6 using a carbene insertion approach

The diazirine functionalised fluorenone, 3-[3-(trifluoromethyl)diazirin-3-yl]phenyl-9-oxo-9H-fluorene-2-carboxyla te was synthesised to act as a model compound capable of modifying a wide variety of polymeric substrates. Photochemical activation of the diazirine moiety of the fluorenone derivative was utilised to afford highly reactive carbenes capable of insertion into or addition to a wide variety of functionalities. In this paper the photoinduced attachment of a fluorenone derivative to nylon 6,6 has been studied using UV-visible spectroscopic analysis. Incorporation of the fluorenone chromophore onto the backbone of nylon at different loading levels and after different coating cycles has been investigated and is detailed in this paper.

An investigation into the mechanics of cutting using data from orthogonally cutting Nylon 66

Cutting force data for Nylon 66 has been examined in terms of various different models of cutting. Theory that includes significant work of separation at the tool tip was found to give the best correlation with experimental data over a wide range of rake angles for derived primary shear plane angle. A fracture toughness parameter was used as the measure of the specific work of separation. Variation in toughness with rake angle determined from cutting is postulated to be caused by mixed mode separation at the tool tip. A rule of mixtures using independently determined values of toughness in tension (mode 1) and shear (mode 11) is found to describe well the variation with rake angle. The ratio of modes varies with rake angle and, in turn, with the primary shear plane angle. Previous suggestions that cutting is a means of experimentally determining fracture toughness are now seen to be extended to identify the mode of fracture toughness as well.

Conducting nylon, cotton and wool yarns by continuous vapor polymerization of pyrrole

Conductive textile yarns were prepared by a continuous vapor polymerization method; the application of polypyrrole by the continuous vapor polymerization method used is designed for the easy adaptation into industrial procedures. The resultant conductive yarns were examined by longitudinal and cross-sectional views, clearly showing the varying levels of penetration of the polymer into the yarn structure. It was found that for wool the optimum specific resistance was achieved by using the 400 TPM yarn with a FeCl3 solution concentration of 80 g/L FeCl3 to produce 1.69 Ω g/cm2. For cotton yarn, the optimum specific resistance of 1.53 Ω g/cm2 was obtained with 80 g/L of a FeCl3 solution.

Silver sulfide as a staining agent for scanning electron microscopy of nylon 6/MXD6 blends

BACKGROUND: In transmission and scanning electron microscopy imaging, the ability to obtain sufficient contrast between the components of a blend when they are both of a similar chemical structure still remains problematic. This paper investigates the domain morphology of a polymer blend containing two polyamides, nylon 6 and the semi-aromatic polyamide poly(m-xylene adipamide) (MXD6), using scanning electron microscopy in backscattered electron imaging mode. The efficiency of three staining agents, ruthenium tetroxide, phosphotungstic acid and silver sulfide, in obtaining optimum phase contrast between the two polymers is discussed.
RESULTS: The use of silver sulfide as a staining agent was found to be a fast and reliable approach which required basic sample preparation and provided excellent compositional contrast between the phases present in the nylon 6/MXD6 blends compared to the other staining agents.
CONCLUSIONS: The technique described in this paper is believed to be a novel and versatile method that has the potential to further improve the ability to study complex polymer blends where one polymer contains an aromatic ring.

Structure-property relationships of nylon 6, MXD6, their blends and nanocomposites

This research project aimed to develop an understanding of the structure-property relationships of nanocomposite materials (injection moulded and fibres) based on nylon 6, MXD6 and their blends, with a layered silicate in combination with polyhedral oligomeric silsesquioxane nanoparticles and SEBS rubber particles.

Biofunctionalization of 3D nylon 6,6 scaffolds using a two-step surface modification

Nylon is a relatively inert polymer. The ability to easily functionalize nylon with biomolecules will improve the utilization of nylon in biological systems. A potential use of the biofunctionalized nylon scaffolds is in devices for cell therapeutics that can specifically select cells present in small numbers, such as hematopoietic stem cells. This study developed a versatile and simple two-step technique combining oxygen plasma treatment with wet silanization to graft biomolecules onto nylon 6,6 3D porous scaffolds. Scaffolds that were exposed to oxygen plasma exhibited up to 13-fold increase in silane attachment ((3-mercaptopropyl)trimethoxysilane/(3-aminopropyl)trimethoxysilane) compared to untreated scaffolds. To address the limitation of nondestructive characterization of the surface chemistry of 3D scaffolds, fluorescent CdSe/ZnS nanoparticles were used as a reporting tool for -NH(2) functionalized surfaces. Scaffolds that were covalently bound with neutravidin protein remained stable in phosphate buffered saline up to four months. Functionality of the neutravidin-grafted scaffolds was demonstrated by the specific binding of CD4 cells to the scaffold via CD4-specific antibody. Ultimately, these neutravidin-functionalized 3D nylon scaffolds could be easily customized on demand utilizing a plethora of biotinylated biomolecules (antibodies, enzymes and proteins) to select for specific cell of interest. This technique can be extended to other applications, including the enhancement of cell-scaffold interactions.

Properties of bio-based polymer nylon 11 reinforced with short carbon fiber composites

In this work, micro-composite materials were produced by incorporating 3-mm long reclaimed short carbon fibers into bio-based nylon 11 via melt compounding. A systematic fiber length distribution analysis was performed after the masterbatching, compounding and an injection moulding processes using optical microscopy images. It was found that the large majority of the fibers were within the 200-300 μm in length range after the injection moulding process. The mechanical (flexural and tensile), thermo-mechanical, and creep properties of the injection moulded materials are reported. We found that an enhancement in flexural and Young's modulus of 25% and 14%, respectively, could be attained with 2 wt% carbon fiber loading whilst no significant drawback on the ductility and toughness of the matrix was observed. The creep resistance and recovery of the nylon 11, tested using dynamic mechanical thermal analysis at room temperature and 65°C, was significantly improved by up to 30% and 14%, respectively, after loading with carbon fiber. This work provides an insight into the property improvement of the bio-based polymer nylon 11 using a small amount of a reclaimed engineered material. © 2014 Society of Plastics Engineers.

Structure-property relationships in nylon 6 nanocomposites based on octaphenyl-, dodecaphenyl-POSS, montmorillonite, and their combinations

Binary and ternary nanocomposites were produced by incorporating, via melt compounding, two types of octa-and dodecaphenyl substituted polyhedral oligomeric silsesquioxanes (POSS), montmorillonite (MMT), and combinations of POSS with MMT into nylon 6. The tensile, flexural, and dynamic thermo-mechanical properties of these materials were characterized and their structure-property relationships discussed. The results show that the losses in ductility and toughness experienced after inclusion of MMT into nylon 6 can be balanced out by co-mixing MMT with the dodecaphenyl- POSS to produce a ternary nanocomposite. This trend however was less pronounced in the ternary MMT/octaphenyl-POSS system. Analysis of the microstructure organization in these materials using XRD and SEM sheds some light on understanding the differences in behavior. Both types of POSS particles mixed alone in nylon 6 were found to be polydisperse (500 nm to a few microns in size) and locally aggregated, yielding materials with similar mechanical performance. The co-mixing of MMT with the octaphenyl- POSS served to break down the POSS crystal aggregates, enhancing their micro-mechanical reinforcing action. On the other hand, the POSS crystals were not affected in the MMT/dodecaphenyl-POSS system, which led to improving their toughening ability.

Estudo da corrosao do aco ABNT 1010 em alcool etilico adicionado de inibidores

Estudou-se o comportamento do aço AISI 1010 em AISI 1010 em àlcool etílico puro com 3,5% H20 e diferentes aditivos (acetato de sódio, um aditivo comercial e trietanolamina) em meio arejado e desarejado, com e sem agitação. Os resultados experimentais mostram que os aditivos usados exercem efeito inibidor da corrosão no aço. A água (3,5%) origina um período de incubação até o aparecimento de pite. A reação de redução catódica do oxigênio apresenta duas ondas, o que permite dizer que a presença de algum filme modifica a mesma. Os ensaios em etanol carburante, a longo prazo, apresentaram corrosão localizada em meio arejado (a qual é evitada com adição de 10-² M de acetato de sódio), e corrosão generalizada em meio desarejado.

Polipropileno graftizado com metacrilato glicidila como agente compatibilizante em blendas de PP e nylon 6

Neste trabalho foi feito uma avaliação do polipropileno funcionalizado com metacrilato de glicidila (PP-GMA) como agente compatibilizante em blendas reativas de polipropileno e nylon 6. As reações de funcionalização do polipropileno (PP) com metacrilato de glicidila (GMA) foram feitas em estado fundido e os polímeros modificados (PP-GMA) foram utilizados em misturas de PP com nylon 6, para a avaliação das propriedades mecânicas, térmicas e morfológicas da blenda. As blendas foram preparadas variando a concentração de nylon 6 e também do agente compatibilizante. Após o estudo da ação da concentração de nylon 6 e do agente compatibilizante nas blendas, foi verificado o comportamento do PP-GMA com diferentes teores de incorporação molar do GMA no polipropileno. Utilizou-se dois tipos de nylon 6, um deles com maior número de terminais carboxílicos, a fim de avaliar o efeito desses grupos na compatibilidade do sistema. As blendas obtidas foram caracterizadas por calorimetria diferencial de varredura, microscopia eletrônica de varredura e análise das propriedades mecânicas e dinâmico-mecânicas. Os resultados mostraram que a adição do PP-GMA provoca alterações na morfologia das blendas, apresentando uma melhor dispersão e redução no tamanho das partículas dispersas. Além disso, há um aumento nas propriedades mecânicas comparado com as propriedades das blendas não compatibilizadas, que pode ser atribuído a melhor adesão entre as fases para ambos os nylons utilizados neste trabalho. Foi feito estudo comparativo entre as blendas de PP/PP-GMA/Ny6 e PP/PP-MA/Ny6 na proporção de 63/7/30. O efeito do tipo de agente compatibilizante foi caracterizado por calorimetria diferencial de varredura, microscopia eletrônica de varredura e análise das propriedades mecânicas e dinâmico-mecânicas. Os resultados indicaram que o polipropileno modificado com anidrido maleico (PP-MA) mostrou um melhor efeito compatibilizante nesses sistemas. Ou seja, a interação dos terminais amino do nylon foram mais suscetíveis a ação do grupamento anidrido no PP-MA, do que o grupamento epóxido no PP-GMA.

Adição de plastificante à polianilina sintetizada quimicamente e avaliação dos filmes plastificados como proteção contra a corrosão do aço AISI 1010

Filmes de polianilina (PAni) puros não apresentam propriedades mecânicas satisfatórias quando depositados sobre metais e mergulhados em soluções aquosas. Propriedades mecânicas melhoradas podem ser obtidas adicionando um plastificante ao polímero. Neste caso foi utilizado o dodecilfenol (DDPh) e as condições mais adequadas de adição do DDPh a PAni previamente solubilizada em N-metilpirrolidinona (NMP) foram determinadas a partir da avaliação das propriedades dos filmes depositados sobre eletrodos metálicos de aço carbono. As melhores condições foram: adição de 5% de DDPh á PAni seguido de aquecimento sob vácuo a 200o C durante uma hora. A PAni sintetizada quimicamente foi utilizada nas condições dedopada e dopada com 5% de ácido para-toluenosulfônico (TSA). Também foi preparada uma mistura de PAni com poli(orto-metóxianilina) (POMA) em diversas proporções e igualmente dedopadas e dopadas com 5% de TSA. Os filmes obtidos nestas condições foram analisados por técnicas variadas (espectroscopia infravermelho, Raman e de massa), testados por técnicas eletroquímicas (voltametria cíclica e medida do potencial de corrosão ao longo do tempo) e ensaios acelerados de corrosão (névoa salina e câmara úmida) O melhor desempenho como filme protetor contra a corrosão foi apresentado pela PAni plastificada com 5% de DDPh e dopada com 5% de TSA. No ensaio de potencial de corrosão contra o tempo, este filme foi capaz de manter o potencial do sistema PAni-DDPh-TSA / aço carbono durante sete dias num valor positivo. Filmes da mistura PAni-POMA plastificados e dopados com TSA também atuaram conforme um mecanismo do mesmo tipo, porém por um período de tempo inferior, demonstrando a influência da POMA nas propriedades da PAni. Os ensaios acelerados de corrosão mostraram que os filmes de PAni plastificados com 5% de DDPh e dopados com 5% de TSA são muito superiores na proteção contra a corrosão do aço quando comparados ao filme de PAni pura. No ensaio de névoa salina o aço revestido pelo filme de PAni plastificado com 5% de DDPh e dopado com 5% de TSA, não apresentou corrosão por um período de sete dias.

Effect of cooling rate on properties of plasma nitrided AISI 1010 steel

In this work, AISI 1010 steel samples were plasma nitrided into 20% N 2 100 Pa and 400 Pa for N 2 and H 2 , respectively), temperatures of 500 and 580 °C, during 2 h. Three different procedures for cooling were accomplished after nitriding. In the first procedure the cooling occurred naturally, that is, the sample was kept on substrate holder. In the second one the sample was pulled off and cooling in a cold surface. Finally, in the third cooling process the sample was pulled off the substrate holder down into special reservoir filled with oil held at ambient temperature. The properties of the AISI 1010 steel samples were characterized by optical and electron microscopy, X-ray diffraction, Mössbauer spectroscopy and microhardness tests. Thermal gradient inside the sample kept on substrate holder during cooling process was measured by three inserted thermocouples at different depths. When samples were cooled rapidly the transformation of ϵ-Fe 2 − 3 N to γ′-Fe 4 N was inhibited. Such effect is indicated by the high concentration of ϵ-Fe compound zone. To get solid state solution of nitrogen in the diffusion zone, instead of precipitates of nitride phases, the cooling rate should be higher than a critical value of about 0.95 °C/s. When this value is reached at any depth of the diffusion zone, two distinct diffusion zones will appear. Temperature gradients were measured inside the samples as a consequence of the plasma treatment. It's suggested the need for standardization of the term “treatment temperature” for plasma treatment because different nitrided layer properties could be reported for the same “treatment temperature”.