Effects of surfactant/silica and silica/cerium ratios on the characteristics of mesoporous Ce-MCM-41

Using the surfactant CTMABr (cetyltrimethyl ammonium bromide) and cerium(IV) sulfate, mesoporous Ce-MCM-41 molecular sieves were produced under a hydrothermal condition with various surfactant/silica (surfactant/Si) and silica/cerium (Si/Ce) ratios. Changes to the structural traits caused by changing the molar ratios of both surfactant/Si and Si/Ce were investigated. XRD (X-ray diffraction), FT-IR (fourier transform infrared spectroscopy), and SEM (scanning electro microscopy) were used for the characterization of prepared mesoporous samples. Among the tested molar ratios, surfactant/Si ratio of 0.5 and 0.2 showed highest values of d_1 0 0 and intensity, respectively, for the Si-MCM-41. XRD analysis also identified a quintessential hexagonal structure of Ce-MCM-41 for the Si/Ce molar ratio higher than 40 (maintaining the surfactant/Si ratio at 0.2). When cerium content was increased to have the Si/Ce molar ratio of 20, the hexagonal structure of Ce-MCM-41 was collapsed due to the structural stress of substituted cerium. FT-IR results confirmed calcination of Ce-MCM-41 and the incorporation of Ce⁴⁺ ions of cerium sulfate into the silica surface with proper removal of the surfactant. Rod-like shape with rounded edges of the prepared Ce-MCM-41 samples was identified by SEM. These results suggest surfactant/Si ratio of 0.2 and Si/Ce ratio of 40 for the production of Ce-MCM-41 with the highest level of crystallinity.     

Viscoelasticity of oxidized starch/low methoxy pectin mixtures in the presence of glucose syrup

The structural properties of mixtures of pectin, oxidized starch and glucose syrup were investigated using small deformation dynamic oscillation. In the absence of added calcium, preparations of low methoxy pectin with glucose syrup formed viscous solutions, which remained crystal-free at subzero temperatures. Samples of oxidized starch and glucose syrup, on the other hand, exhibited solid-like behaviour because of the crystalline nature of the amylose-like helices. Mixtures of the two polysaccharides with the co-solute clearly showed phase inversion from liquid to solid-like behaviour with increasing amounts of starch in the formulation. The transformation was reflected in the textural properties of samples, which varied from thick solutions to firm gels. The viscoelasticity of the system was modified further by the introduction of high methoxy pectin. Preparations of high methoxy pectin and glucose syrup formed rubbery gels whose amorphous nature underwent a glass transition during cooling.     

Confocal Raman study of poly(ethylene terephthalate) fibres dyed in supercritical carbon dioxide: dye diffusion and polymer morphology

Confocal Raman microscopy (CRM) has been used to extract dye diffusion data from poly(ethylene terephthalate) (PET) fibres dyed with Disperse Yellow 23 under supercritical CO₂ conditions. Spectral information as a function of depth was measured in a non-destructive manner using dry and oil objectives in confocal Raman mode. Mapping along the radius of the fibre cross-section was performed and compared to the data from the confocal measurements. A significant dye concentration gradient has been observed along the line normal to the fibre surface which the data from the oil confocal measurements accurately describes to a depth of 45 μm. The effect of the supercritical CO₂ dyeing process on the fibre morphology has also been evaluated using CRM.     

Influence of copolymerisation on fracture behaviour of aliphatic polyketones

High strain rate tensile impact properties of aliphatic polyketone terpolymers were investigated and related to the polymer chain structure. Aliphatic polyketones were used as a model system, by changing the termonomer content and type. Aliphatic polyketone is a perfectly alternating copolymer and the structure was changed with the addition of a few mol% of termonomer: propylene, hexylene and dodecene. Studied were the thermal properties with DSC and DMTA, tensile behaviour, notched tensile impact behaviour, notched Izod properties and the temperature development during deformation. The perfectly alternating copolymer had a melting point of 257 °C, a T_g at 15 °C, a high crystallinity (48%), a high yield stress (77 MPa) and yield strain (31%) but a relatively low fracture strain (85%) and an impact strength (notched Izod) of 13 kJ/m². Increasing the propylene content to 6%, lowered the melting temperature to 224 °C, without changing the T_g. The modulus and yield stress were lowered but the impact strength improved. Increasing the length of the termonomer while keeping the T_m at 224 °C lowered the T_g, the modulus, the yield stress but strongly improved the impact resistance. The longer termonomers, with a lower yield stress, reduced the necking behaviour. The temperature increase in front of the notch was about 85 °C. By adding termonomers to aliphatic ketones, the notched impact behaviour improved significantly at the cost of modulus and yield stress.     

The structure of parts produced by stereolithography injection mould tools and the effect on part shrinkage

Stereolithography (SL) tooling for plastic injection moulding provides a low cost and quick alternative to hard tooling methods when producing a small quantity of parts. However, work by the authors has shown that a different rate of polymer shrinkage was experienced in semi-crystalline parts when produced from SL moulds as compared to those from conventional metal tooling methods. Different shrinkage means the parts are not truly the same as those that would be produced by metal tooling and highlights a disadvantage to SL tooling.This work associates the increased shrinkage experienced to a greater percentage crystallinity developed in the parts due to their thermal history during processing. In these experiments the cooling rate, which is imparted due to the heat transfer characteristics of the mould has been identified as the controlling factor of a parts % crystalline content and the cause of shrinkage anomalies.The morphology analysis results show that there is 30% more crystallinity developed in the nylon (PA66) parts produced in SL moulds than those produced from aluminium moulds. The results also reveal different characteristics during thermal analysis that may also be due to the thermal history imparted by the mould.The work utilises the thermal analysis technique differential scanning calorimetry (DSC) to quantify the different levels of crystallinity in the parts. The thermal characteristics of the mould are demonstrated by real-time data acquisition.     

Porous Titania Thin Films Grown by Anodic Oxidation for Hydrogen Sensors

Porous titanium dioxide (Titania) thin films were grown by anodic oxidation using high purity (99.7%) titanium foil in a dilute sulphuric acid (1 M) medium. The anodization process was carried out for 30 minutes with 20 mA/cm² and 50 mA/cm² current densities. The samples were characterized by XRD, SEM, and AFM techniques. It was found that the grown porous titania films were less sensitive to 500 ppm hydrogen in air ambient below 300°C; however, the sensitivity and response behavior of the film at 300°C are very much dependent on the growth conditions. Particularly, the films grown at current density 50 mA/cm² and 1 M acid concentration exhibited the lowest response time of 151 sec at 300°C.     

Polyaniline as a Gas-Sensor Material

Polyaniline (PANI) was synthesized by oxidative polymerization of aniline using ammonium persulfate in an acid medium. The polyaniline salt was converted to base form by treatment with ammonium hydroxide. The polyaniline base was dissolved in N-methyl pyrrolidone (NMP) for film casting. The cast film was doped with HCl for obtaining higher conductivity. Both doped and undoped PANI films were characterized by UV-visible, FTIR, and XRD analyses. The electrical conductivity of the PANI film was studied by a four-point probe method at room temperature. Finally, ammonia gas-sensing characteristics of the prepared polyaniline film were studied by measuring the change in electrical conductivity on exposure to ammonia gas at different concentrations. The influence of concentration of acid during polymerization of aniline and dopant concentration on the gas sensing characteristics of PANI film are reported in this paper.     

γ射线辐照对超高分子量聚乙烯片材机械性能和结晶度的影响

采用钴源以剂量率为2.5 k Gy·h~(-1)的γ射线对超高分子量聚乙烯(Ultra-high Molecular Weight Polyethylene,UHMWPE)片材在空气、水、甲醇和乙醇氛围中进行了辐照,吸收剂量范围为0 200 k Gy。通过机械性能、凝胶含量、差示扫描量热仪(Differential Scanning Calorimetry,DSC)、傅里叶变换红外光谱仪(Fourier Transform Infrared Spectrometer,FTIR)等对不同辐照氛围中辐照前后UHMWPE样品进行了测试和表征。机械性能测试结果表明,在空气中UHMWPE的断裂伸长率随吸收剂量呈幂指数下降,同时屈服强度略有下降,而在水、甲醇、乙醇为辐照体系中UHMWPE的断裂伸长率随吸收剂量也是呈下降趋势,但下降的程度依次减轻,同时屈服强度基本保持不变;DSC测试结果显示,在空气氛围中,随着吸收剂量的增加,UHMWPE样品的初始熔融温度、熔点、结晶温度和结晶度逐渐降低;而在空气、水、甲醇和乙醇氛围中,UHMWPE样品的初始熔融温度、熔点和结晶度依次上升;红外光谱测试结果显示在空气中辐照,UHMWPE样品表面随着吸收剂量的增加其氧化程度加重,而在水、甲醇和乙醇中辐照UHMWPE分子链生成了不饱和的分子双键。     

Characterization of cellulose structure of Populus plants modified in candidate cellulose biosynthesis genes

The recalcitrant nature of lignocellulosic biomass is a combined effect of several factors such as high crystallinity and high degree of polymerization of cellulose, lignin content and structure, and the available surface area for enzymatic degradation (i.e., accessibility). Genetic improvement of feedstock cell wall properties is a path to reducing recalcitrance of lignocellulosic biomass and improving conversion to various biofuels. An advanced understanding of the cellulose biosynthesis pathway is essential to precisely modify cellulose properties of plant cell walls. Here we report on the impact of modified expression of candidate cellulose biosynthesis pathway genes on the ultra-structure of cellulose, a key carbohydrate polymer of Populus cell wall using advanced nuclear magnetic resonance approaches. Noteworthy changes were observed in the cell wall characteristics of downregulated KORRIGAN 1 (KOR) and KOR 2 transgenic plants in comparison to the wild-type control. It was observed that all of the transgenic lines showed variation in cellulose ultrastructure, increase in cellulose crystallinity and decrease in the cellulose degree of polymerization. Additionally, the properties of cellulose allomorph abundance and accessibility were found to be variable. Application of such cellulose characterization techniques beyond the traditional measurement of cellulose abundance to comprehensive studies of cellulose properties in larger transgenic and naturally variable populations is expected to provide deeper insights into the complex nature of lignocellulosic material, which can significantly contribute to the development of precisely tailored plants for enhanced biofuels production.     

Comparison of steam-alkali-chemical and microwave-alkali pretreatment for enhancing the enzymatic saccharification of oil palm trunk

This paper demonstrates two different pretreatment protocols for oil palm trunks (OPT); steam-alkali-chemical (SAC) and microwave-alkali (Mw-A) method. The composition, morphology, structure and crystallinity of OPT before and after pretreatment were analyzed. The effectiveness of the pretreated methods was investigated by performing enzymatic saccharification on the OPT. The physiochemical factors namely: enzyme ratio (cellulase to β-glucosidase), pH, temperature and substrate loading (w/v) on enzymatic saccharification were also investigated. The pre-determined optimal conditions were then used for further enzymatic hydrolysis of raw and pretreated OPT substrates. The results revealed a huge degree of reduction in lignin, up to 89% for SAC treated OPT and at least 15% for Mw-A treated OPT sample as compared to untreated ones. High glucose accumulation (79.4%) was obtained after 72 h saccharification for both pretreated OPT samples.