Experimental impact and finite element analysis of a composite, portable road safety barrier

This thesis provides an experimental and computational platform for investigating the performance and behaviour of water filled, plastic portable road safety barriers in an isolated impact scenario. A schedule of experimental impact tests were conducted assessing the impact response of an existing design of road safety barrier utilising a novel horizontal impact testing system. A coupled finite element and smooth particle hydrodynamic model of the barrier system was developed and validated against the results of the experimental tests. The validated model was subsequently used to assess the effect of certain composite materials on the impact performance of the water filled, portable road safety barrier system.

Crystallization behaviour of polyethylene and i-polybutene-1 blends

The mutual influence of the components on the crystallization behaviour of polyblends, namely, isotactic polybutene-1 (PB) with low-density and high-density polyethylene (LDPE and HDPE), has been studied using techniques such as differential scanning calorimetry, infra-red spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy, etc. Each component in the blend is observed to crystallize independently. There is phase separation and incompatibility, as shown from tensile properties and scanning electron microscopic observation of the fracture surface of the blend. For HDPE-PE blends (<30% HDPE), unusual form I′ crystals of PB are observed along with the usual form II.

Effect of Packaging Materials and Storage on Major Volatile Compounds in Three Australian Native Herbs

Lemon myrtle, anise myrtle, and Tasmanian pepper leaf are commercial Australian native herbs with a high volatile or essential oil content. Packaging of the herbs in high- or low-density polyethylene (HDPE and LDPE) has proven to be ineffective in preventing a significant loss of volatile components on storage. This study investigates and compares the effectiveness of alternate high-barrier property packaging materials, namely, polyvinylidene chloride coated polyethylene terephthalate/casted polypropylene (PVDC coated PET/CPP) and polyethylene terephthalate/polyethylene terephthalate/aluminum foil/linear low-density polyethylene (PET/PET/Foil/LLDPE), in prevention of volatile compound loss from the three native herbs stored at ambient temperature for 6 months. Concentrations of major volatiles were monitored using gas chromatography?mass spectrometry (GC-MS) techniques. After 6 months of storage, the greatest loss of volatiles from lemon myrtle was observed in traditional LDPE packaging (87% loss) followed by storage in PVDC coated PET/CPP (58% loss) and PET/PET/Foil/LLDPE (loss of 23%). The volatile loss from anise myrtle and Tasmanian pepper leaf stored in PVDC coated PET/CPP and PET/PET/Foil/LLDPE packaging was <30%. This study clearly indicates the importance of selecting the correct packaging material to retain the quality of herbs with high volatile content.

Low density polyethylene and grafted lignin polyblends using epoxy-functionalized compatibilizer: mechanical and thermal properties

Lignin was graft copolymerized with methyl methacrylate using manganic pyrophosphate as initiator. This modified lignin was then blended (up to 50 wt%) with low density polyethylene (LDPE) using a small quantity of poly[ethylene-co-(glycidyl methacrylate)] (PEGMA) compatibilizer. The mechanical properties of the blend were substantially improved by using modified lignin in contrast to untreated lignin. Differential scanning calorimetry studies showed loss of crystallinity of the LDPE phase owing to the interaction between the blend components. Thermogravimetric analysis showed higher thermal stability of modified lignin in the domain of blend processing. This suggested that there is scope for useful utilization of lignin, which could also lead to the development of eco-friendly products. (c) 2005 Society of Chemical Industry.

Effect of morphology on electrical treeing in low density polyethylene nanocomposites

Influence of polymer morphology on the inception and the growth of electrical trees in unfilled low density polyethylene (LDPE) as well as LDPE filled with 1, 3 and 5% by weight nanoalumina samples stressed with 50 Hz ac voltage has been studied. It is seen that there is a significant improvement in tree inception voltage with filler loading in LDPE filled with nanoparticles. Tree inception voltage increased with the filler loading up to 3% by weight nanoalumina loading and showed a reduction at 5% by weight loading. Change in tree growth patterns from branch to bush as well as a slower tree growth with increase in filler loading in LDPE alumina nanocomposites were observed. The degree of crystallinity and change in crystalline morphology induced by the presence of alumina nanoparticles in LDPE was studied using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). DSC results show a similar melting behaviour for both unfilled LDPE and LDPE nanocomposites. However, there is a reduction in the degree of crystallinity for LDPE filled with 5% by weight nanoalumina. An increase in lamellae packing with increase in filler loadings and a highly disordered spherulitic structure for LDPE filled with 5% by weight nanoalumina was observed from the SEM images. The slow propagation of tree growth as well as reduction in tree inception voltage with increase in filler loadings were attributed to the morphological changes observed in the LDPE nanocomposites.

Polyolefin based antibacterial membranes derived from PE/PEO blends compatibilized with amine terminated graphene oxide and maleated PE

In this study, various strategies like amine terminated GO (GO-NH2), in situ formed polyethylene grafted GO (PE-g-GO) and their combinations with maleated PE (maleic anhydride grafted PE) were adopted to reactively compatibilize blends of low density polyethylene (LDPE) and polyethylene oxide (PEO). These blends were further explored to design porous, antibacterial membranes for separation technology and the flux and the resistance across the membranes were studied systematically. It was observed that GO-NH2 led to uniform dispersion of PEO in a PE matrix and further resulted in a significant improvement in the mechanical properties of the blends when combined with maleated PE. The efficiency of various compatibilizers was further studied by monitoring the evolution of morphology as a function of the annealing time. It was observed that besides rendering uniform dispersion of PEO in PE and improving the mechanical properties, GO-NH2 further suppresses the coalescence in the blends. As the melt viscosities of the phases differ significantly, there is a gradient in the morphology as also manifested from scanning acoustic microscopy. Hence, the membranes were designed by systematically reducing the thickness of the as-pressed samples to expose the core as the active area for flux calculations. Selected membranes were also tested for their antibacterial properties by inoculating E. coli culture with the membranes and imaging at different time scales. This study opens new avenues to develop PE based cost effective anti-microbial membranes for water purification.

Polyolefin based antibacterial membranes derived from PE/PEO blends compatibilized with amine terminated graphene oxide and maleated PE

In this study, various strategies like amine terminated GO (GO-NH2), in situ formed polyethylene grafted GO (PE-g-GO) and their combinations with maleated PE (maleic anhydride grafted PE) were adopted to reactively compatibilize blends of low density polyethylene (LDPE) and polyethylene oxide (PEO). These blends were further explored to design porous, antibacterial membranes for separation technology and the flux and the resistance across the membranes were studied systematically. It was observed that GO-NH2 led to uniform dispersion of PEO in a PE matrix and further resulted in a significant improvement in the mechanical properties of the blends when combined with maleated PE. The efficiency of various compatibilizers was further studied by monitoring the evolution of morphology as a function of the annealing time. It was observed that besides rendering uniform dispersion of PEO in PE and improving the mechanical properties, GO-NH2 further suppresses the coalescence in the blends. As the melt viscosities of the phases differ significantly, there is a gradient in the morphology as also manifested from scanning acoustic microscopy. Hence, the membranes were designed by systematically reducing the thickness of the as-pressed samples to expose the core as the active area for flux calculations. Selected membranes were also tested for their antibacterial properties by inoculating E. coli culture with the membranes and imaging at different time scales. This study opens new avenues to develop PE based cost effective anti-microbial membranes for water purification.

Gestão de saúde, segurança, meio ambiente e responsabilidade social em micro e pequenas empresas recicladoras de plásticos PEBD e PET no Estado do Rio de Janeiro

A presente dissertação tem como tema a gestão de saúde, segurança, meio ambiente e responsabilidade social em micro e pequenas empresas recicladoras de plásticos PEBD e PET no Estado do Rio de Janeiro. A reciclagem de plástico contribui para minimizar os resíduos sólidos gerados pelos processos industriais. O objetivo geral deste estudo é verificar como as atividades de reciclagem impactam na saúde e na segurança do trabalhador e levantar algumas questões relacionadas com a responsabilidade sócio-ambiental, com destaque para o atendimento às normas regulamentadoras, legislação de saúde, segurança e meio ambiente aplicável e sistemas de gestão. Para atingir tal objetivo, a metodologia do presente estudo foi dividida em: pesquisa bibliográfica, elaborada através de consultas a livros, a artigos, a legislação e a bancos de dados de reconhecida credibilidade; elaboração de um questionário direcionado; visitas técnicas, e entrevistas com os encarregados ou donos das empresas, a fim de obter dados para avaliar as condições de trabalho relativas à saúde e segurança, meio ambiente e responsabilidade social. Durante esta etapa foram visitadas quatro recicladoras de plástico, todas situadas no Estado do Rio de Janeiro, sendo três do segmento de PEBD e uma de PET. Os resultados obtidos mostram que, numa avaliação global, apenas 24% dos itens avaliados foram atendidos na sua íntegra, o que demonstra um baixo índice de atendimento às questões relativas à saúde, segurança e meio ambiente e responsabilidade social. Nas avaliações individuais destes mesmos itens constatou-se que o atendimento foi de 38%, 10% e 54%, respectivamente. Enfim, o presente estudo mostra que há necessidade de maior atenção aos requisitos relativos à saúde e segurança do trabalhador, ao meio ambiente e às questões sociais, em função dos riscos do processo de produção do plástico reciclado

Packaging and storage studies of dried lizard fish

Packaging and storage studies of salted and dried lizard fish (Saurida sp.) have been conducted using different synthetic films like low density polyethylene (LDPE) of different gauges, high density polyethylene (HDPE) of 200 gauge, polyvinylidene chloride (PVDC) coated 400 MXXT cellophane, 100 gauge polypropylene (PP) and paper laminate of 100 gauge polythene. The films found most effective in the preliminary studies were subsequently used for packaging and storage of dried fish at atmospheric and lower temperature and humidity conditions for confirming their suitability under these conditions. Polyethylene films of higher gauges showed better results under both sets of conditions. PVDC coated cellophane film also performed satisfactorily under the latter conditions which under the former condition got easily attacked by insects. Lower temperature and humidity conditions in general enhanced the storage life of the dried product.

Study on shelf life of fish cake prepared from surimi of silver carp (Hypophthalmichthys molitrix) during frozen storage

Surimi was prepared from silver carp with an aim to put this underutilized fish for profitable use. The mince prepared was washed twice with chilled water (5°C) using mince to water ratio (w/v) of 1:2 for 5-6 minutes each. After final dewatering to moisture content to about 80%; half the quantity of washed minced meat was mixed with cryoprotectants (4% sorbitol, 4% sucrose and 0.3% sodium tripolyphosphate) to produce surimi. The prepared surimi and the dewatered minced meat were packed in LDPE bags, frozen using a plate freezer and stored at -20°C. Surimi and dewatered minced meat from frozen storage were used as base material for production of fish cakes. These were fried at 160°C for 3 to 4 minutes before serving for organoleptic test. Changes in salt soluble nitrogen, total volatile base nitrogen, non-protein nitrogen, peroxide value and free fatty acid of surimi and dewatered mince were estimated at every ten days interval during the storage period of 3 months. The study has indicated that frozen storage of surimi could be a potential method for effective utilization of silver carp. This surimi when incorporated in fish cakes yielded products which retained the shelf life even up to 90 days of storage.

新型导电高分子烷基取代聚噻吩及其共混改性

烷基取代聚噻吩（P3ATs），属新型导电高分子材料，可溶于普通有机溶剂，具有可熔融加工性，具有巨大的潜在应用价值。针对P3ATs的研究现状，本论文在P3ATs的结构与性能以及3ATs与低密度聚乙烯（LDPE）的共混改性方面做了大量的研究工作，对于P3ATs家族研究方向的拓展与深化是很有意义的。本论文选取八烷基取代聚噻吩（P3OT）、十二烷基取代聚噻吩（P3DDT）和十八烷基取代聚噻吩（P3ODT）作为研究体系。利用多种测试分析手段细致而系统地研究了烷基取代基团的不同对P3ATs的结构和性质的影响，探讨了随烷基侧链长度的不同，P3ATs的晶体结构、熔融结晶行为、热稳定性、谱学特性及掺杂后的电导特性的规律性变化。详细地解析了P3ATs的X射线衍射图谱，绘出了P3ATs的超分子结构模型和单胞结构模型。开展了P3ATs的固态掺杂实验，研究了氧化掺杂对P3ATs微结构的影响，同时发现了电导松弛行为以及升温过程中掺杂剂解离反应的存在。探讨了氧化聚合过程中不同催化剂用量对P3DDT的合成产物的结构和性质的影响，发现合适的催化剂用量将有助于提高骨架链上噻吩环的HT－HT连接方式的含量，从而可提高分子链的共轭长度。开辟了P3ATs结晶行为研究的新方向, 对P3ATs的等温结晶、非等温结晶以及外场诱导结晶行为展开了研究，发现热历史的不同将对P3ATs的重熔结晶行为以及随之形成的晶体结构的影响有所不同。为获得可控电导，改善机械性能，将P3DDT与LDPE以不同比例熔融共混，并对共混物进行了多种性质表征和性能测试。

辐射交联对聚乙烯/碳黑复合物PTC/NTC效应的影响

绝缘的聚乙烯中添加导电碳黑，就可以得到导电复合物。当碳黑浓度超过临界浓度（渗闭浓度），导电复合物的电阻率会随着温度的增加而增加（正温度系数效应，PTC effect）。由于聚乙烯／碳黑复合物的PTC效应引起了越来越多的研究兴趣，并且PTC特性得到了广泛的应用。本论文研究了辐射交联对聚乙烯／碳黑复合物PTC效应、NTC效应以及复合物稳定性的影响，以及交联结构对PTC效应和NTC效应的影响，并对PTC效应和NTC效应形成的机理进行了深入的研究。聚乙烯／碳黑复合物的渗闭浓度与聚乙烯的结晶度和碳黑的结构有关。同一种碳黑填充到聚乙烯中，渗闭浓度随着聚乙烯结晶度的减小而增加；而在同一种聚乙烯基质中，聚乙烯／乙炔黑复合物的渗闭浓度要小于Cabot X一72碳黑复合物的渗闭浓度。经过多次升一降温循环后，未交联LDPE/CB复合物的PTC效应的稳定性变差。经过辐射交联后，复合物的稳定性显著增强，并且NTC效应得到有效的抑制，在辐照剂量达到400KGy时，NTC效应基本被消除。在有氧条件辐照，400KGy后，随着辐照剂量的增加，NTC效应又重新出现，而在真空条件下辐照400KGy后，NTC效应消除后不再重新出现。将交联的LDPE/CB复合物的溶胶（聚乙烯中未交联的部分）抽提出去后，得到的纯凝胶复合物的PTC强度显著降低，而NTC强度很小，随辐照剂量变化不大。LDPE/CB复合物的PTC突变是在聚乙烯熔点附近晶区膨胀和与碳黑发生相互作用的无定形区膨胀存在差异的结果。因此PTC效应的形成是聚合物基质的体积膨胀和电子隧道效应共同作用的结果。

茂金属线性低密度聚乙烯的光氧化和热力学降解研究

聚乙烯是广泛应用的合成高分子材料之一，工业化己有几十年历史，为适应不断扩展的加工及应用的要求，氧化降解反应一直是较活跃的研究领域。目前为止，一些氧化降解的规律和机理已经确定，某些还在积极地研究探索之中。茂金属线性低密度聚乙烯（m-LLDPE）是进入九十年代以后才出现的采用新型茂金属催化剂催化合成的树脂，与传统 Ziegler-Natta线性低密度聚乙烯（LLDPE）相比，其具有分子量分布窄，共聚单体在主链中分布均匀的特点，决定了它具有比传统LLDPE更加优异的使用性能，因而在生产生活中得到广泛应用。目前对其氧化降解的研究较少，因此对m-LLDPE的氧化及稳定性的研究对指导其应用有着积极的意义。本论文选择催化剂和共聚单体类型不同的三种m-LLDPE和两种传统LLDPE对比研究了m-LLDPE的光氧化和热力学降解稳定性，而且研究了过渡金属化合物光敏化剂对它的热力学降解的影响，热力学降解和光敏化剂对m-LLDPE的光、热氧化稳定性的影响。化测试方法表征m-LLDPE的光氧俐反应，长时间光氧化后支化度和结晶度都有不同程度的上升，光氧化速率主要受亚乙烯基双链浓度的影响，受支化度的影响不明显。因此在合成m-LLDPE的过程中应该合理设计茂金属催化剂，降低聚合产品中亚乙烯基双键的浓度，提高它的光氧化稳定性。采用熔体流动速率、流变法和红外光谱法研究了m-LLDPE和传统LLDPE在密炼过程中的热力学降解反应，和光敏化剂对热力学降解反应的影响，利用氧化诱导温度法快速表征热力学降解对m-LLDPE和LLDPE的氧化稳定性的影响，并利用自然光曝晒测试碳基指数和力学性能的变化和热氧化观察脆化时间的方法研究了热力学降解对它们的光、热氧化稳定性的影响，为m-LLDPE在气候条件下应用提供理论依据。共聚单体类型相同的m-LLDPEI和m-LLDPEZ相比较，m-LLDPEI在热力学降解过程中生成更多的氧化产物，光敏化剂硬脂酸钻和乙酰基丙酮钻对m-LLDPEI热力学降解生成氧化产物的敏化作用更强，也更显著地降低了密炼后样品的氧化诱导温度。流变法不仅表征了m-LLDPEI热力学降解过程中的分子结构的变化，也反映了样品的热稳定性。共聚单体类型不同的m-LLDPE3和LLDPEZ相比较，热力学降解后熔体流动速率下降得多，但拨基指数上升较少，这是m-LLDPE3密炼过程中熔融粘度较高的原因。光敏化剂更强烈得增强了LLDPE2的热力学降解过程中氧化产物的形成。热力学降解明显的降低了 LLDPE2的光氧化稳定性而没有对m-LLDPE3的光氧化稳定性产生明显作用，同时敏化剂对LLDPE2的光氧化敏化作用也更强烈一些。本文还研究了光敏化剂硬脂酸钻和硬脂酸铁对三种共聚单体类型不同的传统LLDPE和LDPE的光敏化效果，发现光敏化剂对不同链结构的聚乙烯的光敏化效果存在很大的差异，光敏化作用的顺序为：乙烯一辛烯共聚LLDPE＜乙烯一丁烯共聚LLDPE＜LDPE，光敏化效果并不随敏化剂浓度的增大而增强。从红外光谱可以分析聚乙烯中亚乙烯基浓度越高，光照过程中形成的氢过氧化物浓度越高，光敏化剂的敏化效果越强。

聚合物共混体系的辐射交联反应

本文研究了低密度聚乙烯/乙烯、乙酸乙烯（LDPE/EVA），低密度聚乙烯/1，2—聚丁二烯（LDPE/1，2-PDB），乙丙橡胶/丁苯橡胶（EPR/SBR），以及聚偏氟乙烯/聚丙烯酸乙酯（PVF_2/PEA），聚氧化乙烯/聚乙酸乙烯酯（PEO/PVAc）五个共混体系的辐射关联反应情况。其中采用了机械共混、溶液共混两种方法制备了第一个共混体系，而后四个共混体系均只采用了溶液共混一种制备方法。首先，采用了电子显微镜以及DSC等方法，研究了以上五个共混体系组分间的相溶性。结果表明前三个共混体系属于多相聚合物共混体系。电子显微镜观察表明LDPE/1.2-PBD以及EPR/SBR两共混体系存在着明显的相分离现象，当LDPE含量为50%左右，EPR含量为30～50%时两共混体系均有相倒转发生。对于LDPE/1.2-PBD共混体系，共混样品的熔点虽然随加入1.2-PBD的量的增加而下降，但下降很小，不符合由热力学导出的表示相溶半晶聚合物共混体系熔点随组成变化的关系式：1/(φ1) (1/(Tm) - 1/(Tm)) = - (R V_(2u))/V_(1u) H_(2u))[(1/(u_2) - 1/(u_1)) + X_(12 φ_1]。而PVF_2/PEA、PEO/PVAc二共混体系相溶性明显提高。二共混体系结晶聚合物的溶点均随加入另一组分而急剧下降，由上式求得PVF_2/PEA、PEO/PVAc二共混体系的lory-Huggins相互作用参数X_(12)分别为：-0.28和-0.35。正是由于组分间有强烈的相互作用，至使以上二共混体系相溶性提高。LDPE/1.2-PDB和PVF_2/PEA二共混体系，在被r—射线照射击后，性能的变化情况很不一样。对于PVF_2/PEA共混体系在被r—射线照射后，我们首次发现共混样品用DSC测得的熔融峰由未照射时的一个分裂成照射后的两个。由此近似求得PVF_2/PEA共混体系中含有含PEA为19%及6%的两种结晶相。而LDPE/ 1。2-PBD共混体系组分间相溶性差，共混样熔融峰没有分裂现象，只是熔点随辐照剂量稍有下降。以上五个共混体系发生辐射交联后，其溶胶分数S与辐照剂量R的关系仍可用下式R(S + S~(1/2)) = 1/(q_oU_1) + (α_o)/(q_o)R~β表示。但发现，有些含有双链及分子链较柔顺的橡胶态单一聚合物（丁苯橡胶、PEA、1.2-PBD）的β值有极低的值（<0.5）。我们把此现象归因于以上这些聚合物发生辐射交联反应时有强化交联效应。对于共混样的β值—β_b值，与共混组分、组分间相溶性、及共混比例有并，实验结果表明以上关系可由下式近似表示。β_b = [(β_1 + (K'β_2 - β_1)φ_2]/[1 + (K' - 1)φ_2]式中，β_b为共混样的β值；β_1，β_2分别为组分1及2的β值；φ_2分别为组分1及2的体积分数；而K’值为一特征参数，它与共混体系性质有关。实验结果表明，共混体系组分间相溶性愈好，X_(12)值愈负，则K’值偏离1愈远。K’值表示了组分间参加反应时的协同效应。