Tenacificação em Nanocompósitos de Poliamida 6 e Argila

Nanocompósitos de poliamida 6 (PA6) e montmorilonita modificada com sal de amônio quaternário têm sido estudados, visando melhorar as propriedades térmicas e mecânicas. De fato os efeitos da nano-escala e da interação carga-matriz resultam em maior módulo de elasticidade e resistência à tração, porém a deformação é reduzida. Assim, nesse trabalho, optou-se por adicionar elastômeros, terpolímero de etileno-propileno-dieno (EPDM) e terpolímero de etileno-propileno-dieno modificado com anidrido maleico (EPDM-MA), ao sistema PA 6/argila organofílica para recuperar os valores de deformação. Foi utilizada montmorilonita modificada com cloreto de dimetildioctadecil amônio. A intercalação por fusão foi realizada em câmara interna de mistura. Além das propriedades mecânicas, térmicas e reológicas, foram investigadas as modificações na cristalinidade da fase PA-6 em função da adição da argila modificada, EPDM e EPDM-MA, detectando-se as variações no grau de cristalinidade e nas temperaturas de fusão e cristalização. Os difratogramas de raios-x revelaram ocorrência de intercalação/esfoliação e também modificação da forma cristalina da PA 6, indicando a formação do cristal gama

Análisis y modelización por FEM de elastómeros para silentblocks.

[ES]El objetivo de este trabajo es analizar el comportamiento de materiales elastómeros mediante el método de elementos finitos. Este análisis es necesario por la complejidad de los elastómeros y su comportamiento no común entre los materiales normalmente utilizados en ingeniería. Se pretende calcular la rigidez del material y modelizar su comportamiento.

Avaliação dos elásticos ortodônticos intra-orais de látex e de borracha sintética: estudo in vitro e in vivo

Os elásticos ortodônticos intermaxilares sintéticos vem sendo cada vez mais utilizados, sendo principalmente indicados para pacientes que apresentam hiper-sensibilidade ao látex. Afim de avaliar e comparar o comportamento de elásticos de látex e sintéticos quanto a perda de força ao longo do tempo, este estudo foi realizado tanto in vitro quanto in vivo. Para o estudo in vitro foram avaliados 15 elásticos de cada material, para cada tempo: 0, 1, 3, 12 e 24 horas. No estudo in vivo, pacientes foram avaliados (N=15), utilizando elásticos de ambos os materiais (látex e sintético), nos mesmos tempos do estudo in vitro. Os elásticos foram transferidos para a máquina de ensaios mecânicos (EMIC DL-500 MF). Os valores da força gerada foram registrados após a distensão dos elásticos a uma distância de 25mm. Foi aplicado o teste t pareado para a amostra clínica e independente para a amostra laboratorial. Foi utilizada a análise de variância (ANOVA) para verificar a variação das forças geradas entre os tempos determinados e o teste post-hoc para identificar entre quais tempos houve diferença significativa. Quanto às forças iniciais geradas (zero hora), os valores para os elásticos sintéticos foram bastante semelhantes entre os estudos laboratorial e clínico e ligeiramente superiores aos dos elásticos de látex. Nos tempos subsequentes, as forças geradas pelos elásticos de látex apresentaram valores superiores. Em relação à degradação do material, ao final de 24 horas, maior percentual foi observado para os elásticos sintéticos, tanto in vitro quanto in vivo. A maior queda nos valores das forças liberadas pelos elásticos de ambos os materiais e nos estudos clínico e laboratorial, ocorreu entre os tempos de 0 e 1 hora, seguida de uma queda gradativa e progressiva até o tempo de 24 horas. Os elásticos de látex apresentaram um comportamento mais estável no período estudado em relação aos sintéticos, em ambos os estudos.

A model for the erosive wear of rubber at oblique impact angles

A model has been developed to predict the erosive wear behaviour of elastomers under conditions of glancing impact by small hard particles. Previous work has shown the erosive wear mechanism of elastomers under these conditions to be similar in nature to that of abrasive wear by a sharp blade. The model presented here was developed from the model of Southern and Thomas for sliding abrasion, by combining their treatment of the growth of surface cracks with a model for particle impact in which the force - displacement relationship for an idealized flat-ended punch on a semi-infinite elastic solid was assumed. In this way an expression for the erosive wear rate was developed, and compared with experimental measurements of wear rate for natural rubber, styrene - butadiene rubber and a highly crosslinked polybutadiene rubber. Good qualitative agreement was found between the predictions of the model and the experimental measurements. The variation of erosion rate with impact velocity, impact angle, particle size, elastic modulus of the material, coefficient of friction and fatigue properties were all well accounted for. Quantitative agreement was less good, and the effects of erosive particle shape could not be accounted for. The reasons for these discrepancies are discussed. © 1992 IOP Publishing Ltd.

Photonics and lasing in liquid crystal materials

Owing to fundamental reasons of symmetry, liquid crystals are soft materials. This softness allows long length-scales, large susceptibilities and the existence of modulated phases, which respond readily to external fields. Liquid crystals with such phases are tunable, self-assembled, photonic band gap materials; they offer exciting opportunities both in basic science and in technology. Since the density of photon states is suppressed in the stop band and is enhanced at the band edges, these materials may be used as switchable filters or as mirrorless lasers. Disordered periodic liquid crystal structures can show random lasing. We highlight recent advances in this rapidly growing area, and discuss future prospects in emerging liquid crystal materials. Liquid crystal elastomers and orientationally ordered nanoparticle assemblies are of particular interest. © 2006 The Royal Society.

Computational analysis of liquid crystalline elastomer membranes: Changing Gaussian curvature without stretch energy

Liquid crystalline elastomers (LCEs) can undergo extremely large reversible shape changes when exposed to external stimuli, such as mechanical deformations, heating or illumination. The deformation of LCEs result from a combination of directional reorientation of the nematic director and entropic elasticity. In this paper, we study the energetics of initially flat, thin LCE membranes by stress driven reorientation of the nematic director. The energy functional used in the variational formulation includes contributions depending on the deformation gradient and the second gradient of the deformation. The deformation gradient models the in-plane stretching of the membrane. The second gradient regularises the non-convex membrane energy functional so that infinitely fine in-plane microstructures and infinitely fine out-of-plane membrane wrinkling are penalised. For a specific example, our computational results show that a non-developable surface can be generated from an initially flat sheet at cost of only energy terms resulting from the second gradients. That is, Gaussian curvature can be generated in LCE membranes without the cost of stretch energy in contrast to conventional materials. © 2013 Elsevier Ltd. All rights reserved.

纳米耐油型全硫化热塑性弹性体的制备与形态、结构及性能研究

本文以过氧化物为引发剂，采用反应挤出的方法，制备了甲基丙烯酸缩水甘油酷官能化聚丙烯，采用化学滴定法和红外光谱法均证实了接枝共聚物的存在，并研究了反应条件对PP-g-GMA接枝率、接枝效率和熔体流动速率的影响，结果表明：1．当DCP含量一定时，随着单体含量的增加，接枝产物的接枝率出现了一个峰值。这表明一味地增加单体浓度未必有利于接枝率的提高；2．当GMA单体浓度一定时，PP-g-GMA的接枝率和熔融指数均随着引发剂含量的增加而逐渐增大，这表明引发剂浓度的增加在促进接枝反应的同时也引入了更多的副反应；3．助剂苯乙烯的加入大大地提高了PP-g-GMA的接枝率和接枝效率，且产物的熔融指数与纯聚丙烯相比变化很小，这表明助剂苯乙烯的加入有效地抑制了副反应的发生，且促进了接枝反应的发生。研究了官能化聚丙烯PP-g-GMA的形态、结构与性能，结果表明：1．官能化对聚丙烯的结晶行为有显著的影响，不仅结晶温度和熔融温度有显著的增加，而且结晶度也有一定程度的增加；2．纯聚丙烯的结晶结构为典型的a型结晶，而接枝聚丙烯的结晶则以a型结晶为主，并出现了少量的Y型结晶；3．采用Avrami方程可以很好的描述官能化聚丙烯的初级结晶行为，纯聚丙烯和官能化聚丙烯的 tl几和tmax均随着结晶温度的增加而增加，这表明它们的结晶过程由成核控制；4．采用Jeziornn法研究了官能化聚丙烯的非等温结晶动力学，非等温结晶过程可以分为初级结晶和次级结晶两部分，在次级结晶阶段，曲线偏离了初级结晶部分的直线，表明在次级结晶阶段，官能化聚丙烯的成核与生长方式发生了变化；5．采用DMA研究了官能化聚丙烯的动态热机械行为，官能化后聚丙烯的耐热性提高了，而且随着接枝率的升高，耐热性又有进一步的提高。以官能化聚丙烯作为反应型增容剂，采用反应共棍的方法，制备了耐油型全 硫化CNBR/PP热塑性弹性体，并研究了热塑性弹性体的形态、结构与性能。主要 结果如下：1．采用红外光谱法表征了梭基丁睛粉末橡胶和PP-g-GMA间的反应。 2．透射电子显微镜和原子力显微镜结果表明，当一部分聚丙烯被官能化聚丙烯替代后，体系中橡胶粒子的尺寸明显变小了，分布也更加均一了。在CNBR/PP-g-GMIA 体系中，原位增容反应形成的共聚物位于cNBR和PP-g-GMA两相的界面处。3．加入少量接枝聚丙烯后共混物的力学性能，如拉伸强度、100％定伸强度和断裂伸长 率均有明显的提高，而且，对于CNBR/PPPP-g-GMA共混物，只需少量的界面增 容剂便可以使两相界面达到饱和并达到较好的增容效果。4．动力学和热力学因素 均影响共混物中聚丙烯的结晶行为，在CNBR/PP体系中，动力学因素占主导地位，而CNBR/PP-g-GMA体系中热力学因素占主导作用。另外，采用Avromi方程描述了CNBR/PP和CNBR/PP-g-GMA体系的等温结晶动力学。5．接枝聚丙烯的加入阻碍了接枝聚丙烯与梭基丁睛橡胶两相间的界面层滑移，因此提高了体系的粘度。以官能化聚丙烯作为反应型增容剂，采用反应共混的方法，制备了耐油型全硫化NBR/PP热塑性弹性体，并研究了热塑性弹性体的形态、结构与性能。主要结果如下：1．采用红外光谱法表征了官能化聚丙烯与端氨基液体丁睛橡胶间的反应，但仅从红外光谱的结果很难断定产物的分子结构；2．采用透射电子显微镜观察了NBR/PP共混物的微观形态，结果表明，NBR／PP共混物体系中除了含有直径为几十纳米的小橡胶粒子外，还有直径为几微米甚至几十微米的大橡胶粒子存在，且随着橡胶含量的增加，体系中大橡胶粒子的数量增多了，小橡胶粒子的分布也变得密集了；3．采用差示扫描量热法表征了NB侧PP共混物的受限结晶行为，结果表明，（1）在220℃的高温下，部分丁睛橡胶分子产生了一定的运动，从而限制了聚丙烯分子的运动，使聚丙烯分子产生了受限结晶行为；（2）随着橡胶含量的增加，橡胶粒子间的距离逐渐变小，这使得位于橡胶粒子间隙的聚丙烯分子的运动受到限制，因此聚丙烯表现出受限结晶的行为；（3）受限的聚丙烯分子更倾向于Y型结晶。

Integrated processing-structure-property analysis on rubber in-mold vulcanization

On the basis of the quantitative relationship among rubber processing, structure and property, the methodology of the integrated processing-structure-property analysis on rubber in-mold vulcanization is presented, and then the temporal evolution and spatial distribution characteristics of silicone rubber hot processing parameters, crosslinking structure parameters and mechanical property parameters are obtained by means of the finite element method. The present work is helpful for optimizing curing conditions, and then the design of rubber vulcanization processes according to certain requirements can be done.

Preparation of a blocked isocyanate compound and its grafting onto styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer

The epsilon-caprolactam was used to block the isocyanate group to enhance the storage stability of allyl (3-isocyanate-4-tolyl) carbamate. The spectra of FTIR and NMR showed that blocked allyl (3-isocyanate-4-tolyl) carbamate (BTAI) possesses two chemical functions, an 1-olefin double bond and a blocked isocyanate group. The FTIR spectrum showed BTAI could regenerate isocyanate group at elevated temperature. DSC and TG/DTA indicated the minimal dissociation temperature was about 135 degrees C and the maximal dissociation rate appeared at 226 degrees C. Then the styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS) was functionalized by BTAI via melt free radical grafting. The effect of temperature, monomer and initiator concentrations on the grafting degree and grafting efficiency was evaluated. The highest grafting degree was obtained at 200 degrees C. The grafting degree and grafting efficiency increased with the enhanced concentration of BTAI or initiator.

Thermal analysis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) irradiated under vacuum

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was irradiated by Co-60 gamma-rays (doses of 50, 100 and 200kGy) under vacuum. The thermal analysis of control and irradiated PHBV, under vacuum was carried out by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The tensile properties of control and irradiated PHBV were examined by using an Instron tensile testing machine. In the thermal degradation of control and irradiated PHBV, a one-step weight loss was observed. The derivative thermogravimetric curves of control and irradiated PHBV confirmed only one weight-loss step change. The onset degradation temperature (T-o) and the temperature of maximum weight-loss rate (T-p) of control and irradiated PHBV were in line with the heating rate (degreesC min(-1)). T-o and T-p of PHBV decreased with increasing radiation dose at the same heating rate. The DSC results showed that Co-60 gamma-radiation significantly affected the thermal properties of PHBV. With increasing radiation dose, the melting temperature (T-m) of PHBV shifted to a lower value, due to the decrease in crystal size. The tensile strength and fracture strain of the irradiated PHBV decreased, hence indicating an increased brittleness.

Morphologies in solvent-annealed thin films of symmetric diblock copolymer

We have systematically studied the thin film morphologies of symmetric poly(styrene)-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer after annealing to solvents with varying selectivity. Upon neutral solvent vapor annealing, terraced morphology is observed without any lateral structures on the surfaces. When using PS-selective solvent annealing, the film exhibits macroscopically flat with a disordered micellar structure. While PMMA-selective solvent annealing leads to the dewetting of the film with fractal-like holes, with highly ordered nanoscale depressions in the region of undewetted films. In addition, when decreasing the swelling degree of the film in the case of PMMA-selective solvent annealing, hills and valleys are observed with the coexistence of highly ordered nanoscale spheres and stripes on the surface, in contrast to the case of higher swelling degree. The differences are explained qualitatively on the basis of polymer-solvent interaction parameters of the different components.

Synthesis and characterization of a novel biodegradable, thermoplastic polyurethane elastomer

A series of biodegradable, thermoplastic polyurethane elastomers poly (epsilon-caprolactone-co-lactide)polyurethane [PCLA-PU] were synthesized from a random copolymer Of L-lactide (LA) and epsilon-caprolactone (CL), hexamethylene diisocyanate, and 1,4-butanediol. The effects of the LA/CL monomer ratio and hard-segment content on the thermal and mechanical properties of PCLA-PUs were investigated. Gel permeation chromatography, IR, C-13 NMR, and X-ray diffraction were used to confirm the formation and structure of PCLA-PUs. Through differential scanning calorimetry, tensile testing, and tensile-recovery testing, their thermal and mechanical properties were characterized. Their glass-transition temperatures were below -8 degrees C, and their soft domains became amorphous as the LA content increased. They displayed excellent mechanical properties, such as a tensile strength as high as 38 MPa, a tensile modulus as low as 10 MPa, and an elongation at break of 1300%. Therefore, they could find applications in biomedical fields, such as soft-tissue engineering and artificial skin.