On the effects of using CO2 and F2 lasers to modify the wettability of a polymeric biomaterial

Enhancement of the surface properties of a material by means of laser radiation has been amply demonstrated previously. In this work a comparative study for the surface modification of nylon 6,6 has been conducted in order to vary the wettability characteristics using CO₂ and excimer lasers. This was done by producing 50 μm spaced (with depths between 1 and 10 μm) trench-like patterns using various laser parameters such as varying the laser power for the CO₂ laser and number of pulses for the excimer laser. Topographical changes were analysed using optical microscopy and white light interferometry which indicated that both laser systems can be implemented for modifying the topography of nylon 6,6. Variations in the surface chemistry were evaluated using energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy analysis which showed that the O₂ increased by up to 1.5 at% and decreased by up to 1.6 at% for the CO₂ and F₂ laser patterned samples, respectively. Modification of the wettability characteristics was quantified by measuring the advancing contact angle, which was found to increase in all instances for both laser systems. Emery paper roughened samples were also analysed in the same manner to determine that the topographical pattern played a major role in the wettability characteristics of nylon 6,6. From this, it is proposed that the increase in contact angle for the laser processed samples is due to a mixed intermediate state wetting regime owed to the periodic surface roughness brought about by the laser-induced trench-like topographical patterns.     

PVP对Nylon 6形貌及结晶行为影响的研究

采用变温红外光谱、示差扫描量热（DSC）和偏光显微镜（POM）等方法研究了聚乙烯吡咯烷酮（PVP）与尼龙6（nylon 6）分子间的相互作用及其对nylon 6热行为及结晶形貌的影响。DSC结果表明PVP的加入明显影响了nylon 6的熔融和结晶行为：随着PVP含量增加,PVP/nylon 6共混物的结晶温度、熔融温度及结晶度均逐渐降低;POM观察显示：随着PVP含量增多,nylon 6的球晶尺寸变小、球晶逐渐变得不完善。变温红外光谱结果表明,无定形PVP分子的羰基能够与nylon 6分子的N—H基团形成新的氢键,部分破坏了nylon 6分子之间的氢键结构,从而阻碍了nylon 6分子的规整排列,使其结晶度降低并导致nylon 6结晶形貌的变化。     

尼龙6在高压退火中的晶体生长

 利用六面顶压机制备了高压退火的尼龙6样品,通过宽角X射线衍射（WAXD）、差示扫描量热（DSC）和红外光谱等手段,探索了高压退火对尼龙6结晶度以及晶体结构的变化。研究发现,在高压退火过程中尼龙6分子链段运动受到压力的限制,材料中晶体的形成主要依靠转氨基反应实现。     

Properties of Compatibilized Nylon 6/ABS Polymer Blends

Nylon 6/poly(acrylonitrile‐butadiene‐styrene)(ABS) blends were prepared in the molten state by a twin‐screw extruder. Maleic anhydride‐grafted polypropylene (MAP) and solid epoxy resin (bisphenol type‐A) were used as compatibilizers for these blends. The effects of compatibilizer addition to the blends were studied via tensile, torque, impact properties and morphology tests. The results showed that the additions of epoxy and MA copolymer to nylon 6/ABS blends enhanced the compatibility between nylon 6 and ABS, and this lead to improvement of mechanical properties of their blends and in a size decrease of the ABS domains.     

Osteoblast cell response to a CO2 laser modified polymeric material

Lasers are an efficient technology, which can be applied for the surface treatment of polymeric biomaterials to enhance insufficient surface properties. That is, the surface chemistry and topography of biomaterials can be modulated to increase the biofunctionality of that material. By employing CO₂ laser patterning and whole area processing of nylon 6,6 this paper details how the surface properties were significantly modified. Samples, which had undergone whole area processing, followed the current theory in which the advancing contact angle, θ, with water decreased and the polar component, γ^p, increased upon an increase in surface roughness. For the patterned samples it was observed that θ increased and γ^P decreased. This did not follow the current theory and can be explained by a mixed-state wetting regime. By seeding osteoblast cells onto the samples for 24 h and 4 days the laser surface treatment gave rise to modulated cell response. For the laser whole area processing, θ and γ^P correlated with the observed cell count and cover density. Owed to the wetting regime, the patterned samples did not give rise to any correlative trend. As a result, CO₂ laser whole area processing is more likely to allow one to predict biofunctionality prior to cell seeding. Moreover, for all samples, cell differentiation was evidenced. On account of this and the modulation in cell response, it has been shown that laser surface treatment lends itself to changing the biofunctional properties of nylon 6,6.     

The removal of sodium dodecylbenzene sulfonate surfactant from water using silica/titania nanorods/nanotubes composite membrane with photocatalytic capability

This paper reports experimental results on removal of sodium dodecylbenzene sulfonate (SDBS), using silica/titania nanorods/nanotubes composite membrane with photocatalytic capability. This multifunctional composite membrane has been successfully prepared from colloidal X-silica/titania sols (X denotes molar percent of silica) by the sol-gel technique. The prepared nanorods/nanotubes composite membranes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), scanning probe microscope (SPM) and UV-vis diffuse reflectance spectra (DRS). XRD patterns confirmed that the embedding of amorphous silica into nanophase titania matrix helped to increase the thermal stability of titania and control the size of titania particles. The small size titania particles with anatase phase played an important role in formation of silica/titania nanorods/nanotubes composite membranes with photocatalytic capability. The percentage of anatase phase titania reached 93% when 20%-silica/titania nanorods/nanotubes composite membrane calcined at 400 °C for 2 h. Most (95%) of the pore volume was located in mesopores of diameters ranging from 1.4 to 10 nm. The experimental results showed that the removal of SDBS achieved 89% after 100 min by combining the photocatalysis with membrane filtration techniques. Although the SDBS was not completely decomposed by photocatalysis, the degradation of the SDBS helped to enhance composite membrane flux and prevent membrane fouling. It was possible to treat successfully surfactant wastewater using multifunctional silica/titania nanorods/nanotubes composite membrane by means of a continuous process; this could be interesting for industrial applications.     

聚己内酰胺-锌盐相互作用的研究

本文用X 射线衍射和傅里叶变换红外光谱法研究了聚己内酰胺与氯化锌的相互作用。实验结果表明 ,当把聚己内酰胺的甲酸溶液加入饱和氯化锌水溶液 ,沉淀析出物与在纯水中析出的聚己内酰胺有明显的不同。X 射线衍射结果表明在纯水中沉淀析出的聚己内酰胺分子链发生结晶而在饱和氯化锌水溶液中析出的聚己内酰胺却未观察到尖锐衍射峰。红外光谱研究证明 ,在饱和氯化锌水溶液中析出的聚己内酰胺中所含的锌离子与酰胺基团发生相互作用 ,致使酰胺Ⅰ ,Ⅱ带发生巨大变化。酰胺Ⅰ带发生红移证明锌离子与酰胺基团上的羰基发生络合配位 ,这种作用抑制尼龙分子链之间通过CO和N—H基团形成氢键 ,阻碍聚己内酰胺分子的自由运动和整齐堆砌 ,从而使尼龙无法结晶。尼龙与锌盐之间的这种相互作用可能为发展一种尼龙加工制造新方法提供种新的机会。     

Ultrasonic-assisted dyeing of Nylon-6 nanofibers

We first time report ultrasonic dyeing of the Nylon 6 nanofibers with two disperse dyes CI Disperse blue 56 and CI Disperse Red 167:1 by utilising ultrasonic energy during dyeing process. The Nylon 6 nanofibers were fabricated via electrospinning and dyed via batchwise method with and without sonication. Results revealed that ultrasonic dyeing produce higher color yield (K/S values) and substantially reduces dyeing time from 60 min for conventional dyeing to 30 min can be attributed to breakage of dye aggregate, transient cavitation near nanofiber surface and mass transfer within/between nanofibers. Color fastness results exhibited good to very good dye fixation. SEM images exhibit insignificant effect of sonication on morphology of the nanofibers. Our research results demonstrate ultrasonic dyeing as a better dyeing technique for Nylon 6 nanofibers with higher color yield and substantially reduced dyeing time.     

Preparation of nickel hydroxide nanorods/nanotubes and microscopic nanorings under hydrothermal conditions

A new kind of structure nickel hydroxide nanorods/nanotubes and nanorings were prepared using hydrothermal conditions at 180°C. The structures of the products were characterized using X-ray diffractometer. The morphologies were observed using transmission electron microscopy (TEM) and selected area electron diffraction (SAED). The results show the nanorods/nanotubes were about 40–60 nm in diameter, several micrometer in length. The inner diameters of the nanotubes and nanorings were all around 20 nm. The formation mechanism of the nanorings was discussed.     

Development of high efficiency nanofilters made of nanofibers

Electrospinning is a fabrication process that uses an electric field to control the deposition of polymer fibers onto a target substrate. This electrostatic processing strategy can be used to fabricate fibrous polymer mats composed of fiber diameters ranging from several microns down to 100 nm or less. In this study, optimized conditions to produce nanofibers using Nylon 6 are investigated and the Nylon 6 nanofilters using nanofibers of 80–200 nm in diameter are designed and evaluated the filtration efficiency and pressure drop across the filter. When the Nylon 6 concentration is 15 wt.%, electrospun fibers have an average diameter of 80 nm, but there are many beads, and the concentration increases to 24 wt.%, the fiber diameter gradually thickens to 200 nm, but there are not any beads. When the spinning distance is small, the thinner nanofibers are produced and the more fibers are collected on the grounded electrode. The filtration efficiency of Nylon 6 nanofilters is 99.993% superior to the commercialized HEPA filter at the face velocity of 5 cm/s using 0.3 μm test particles. Even though the high pressure drops across the nanofilter, they show the potential to have the application of HEPA and ULPA grade high efficiency filter.     

Surface modification of recycled carbon fiber and its reinforcement effect on nylon 6 composites: Mechanical properties,morphology and crystallization behaviors

Recycled carbon fiber (RCF) was employed as a reinforcement material for preparation of nylon 6-based thermoplastic composites. An effective approach was developed to clean and modify the surface condition of RCF with nitric acid and then with an epoxy macromolecular coupling agent. The interfacial adhesion between RCF and nylon 6 matrix was improved significantly as a result of such a surface modification. Consequently, the reinforcing potential of the RCF was enhanced substantially, and thus, the mechanical properties and thermal stabilities of nylon 6 composites were improved remarkably. The morphologies of fracture surfaces indicated that RCF achieved a homogeneous dispersion in nylon 6 matrix due to good interfacial boding between fibers and matrix. The studies of non-isothermal and isothermal crystallization behaviors showed that RCF acted as a nucleation agent for the crystallization of nylon 6; therefore, the crystallization rate and nucleation density increased notably due to the heterogeneous nucleating effect of RCF in the matrix. These crystallization features may be advantageous for the enhancement of mechanical performance and processability of nylon 6-based composites. This study may provide a design guide for RCF-reinforced nylon 6 composites with a great potential as well as a low cost for industrial and civil applications.     

碳纳米管对MC尼龙6结晶行为的影响

通过甲苯二异氰酸酯(TDI)改性多壁羟基碳纳米管并用已内酰胺封端,采用单体浇铸的方法制备MC尼龙6、改性碳纳米管纳米复合材料.红外光谱(FTIR)结果证明TDI改性后碳纳米管上成功接有异氰酸酯基团.X射线衍射(XRD)结果表明,改性碳纳米管的加入没有改变MC尼龙6结晶的品型结构;而未改性碳纳米管的加入则抑制了其α2晶的...     

磷酸-氨水蒸沉γ晶型聚酰胺6的热行为研究

尼龙6是一种多晶型的半结晶高聚物。实验采用蒸沉法制备出尼龙6,首先通过XRD和FTIR的手段进行表征,与采用沸水处理的尼龙6样品表征结果对比,确定其为γ晶型,然后在130～211℃的温度范围内进行热处理,通过DSC研究其在低于熔点热处理时的整个热行为变化过程,并运用FTIR观察其在不同条件下热处理发生的晶型变化。发现蒸沉法制备的γ晶型尼龙6随着热处理温度的升高,整体结晶完善度以及晶片厚度随着处理温度的升高而增加。而且在这个过程中,样品厚度不同的晶片在不同温度下发生了γ晶型向α晶型的转化,最终在接近熔点(211℃)热处理时,样品变为以α晶型为主。     

Preparation and XPS study of X-ray photochromic transparent BiOI/nylon11 composite film

Nylon11 film immersed in BiI₃–ethanol solution was used for in situ generation of transparent BiOI/nylon11 X-ray photochromic composite materials via integration of the hydrolyzate (BiOI) of BiI₃ into nylon11. The obtained BiOI/nylon11 composite film shows a reversible photochromic effect, changing the color from orange-red to brownish black under soft X-ray irradiation and back to orange-red after air exposure. X-ray photoelectron spectroscopy (XPS) results show that the oxidation state of Bi atoms in BiOI/nylon11 composite film does not change before and after changing the color. Angle-resolved XPS analysis reveals that BiOI in nylon11 film is well distributed within an infiltration depth of about 10 nm. The source of the X-ray photochromic effect for transparent BiOI/nylon11 composite film may be related to oxygen as well as the interaction between BiOI and the amide groups. The oxygen AT% in the composite film decreases with increasing X-ray irradiation time. The present method for preparing transparent BiOI/nylon11 X-ray photochromic composite materials is facile and low cost. The X-ray photochromic effect has potential applications in some technology fields. For example, it can be used to create temporary patterning in a colored composite material surface.     

FM-AFM crossover in vanadium oxide nanomaterials

The magnetic properties of nanomaterials based on vanadium oxide (multiwall nanotubes, nanorods, and nanolayers) have been investigated in the temperature range of 1.8–220 K by high-frequency (60-GHz) EPR. A transition from a ferromagnetic temperature dependence to an antiferromagnetic temperature dependence has been observed in nanorods and nanotubes with a decrease in the temperature. The FM-AFM crossover observed near T _C ∼ 110 K is accompanied by a low-temperature increase in the Curie constant by a factor of 2.7–7. The comparison of the experimental data for various VO _x nanoparticles indicates that the most probable cause of the change in the type of magnetic interaction is a change in the concentration of V⁴⁺ magnetic ions.     

Detection of Pyrophosphate and Alkaline Phosphatase Activity Based on PolyT Single Stranded DNA - Copper Nanoclusters

The determination of pyrophosphate and alkaline phosphatase activity plays a significant role in medical diagnosis. In this work, a label-free “ON-OFF-ON” fluorescence strategy is developed for the analysis of pyrophosphate and alkaline phosphatase activity. Using PolyT single strand DNA as templates to synthesize fluorescent copper nanoparticles, the coordination effect of pyrophosphoric acid on Cu²⁺ inhibited the generation of fluorescence. Afterwards, the addition of alkaline phosphatase into hydrolyze pyrophosphoric acid resulted in the release of Cu^2+, whereby the fluorescence intensity could be recovered. Thereupon enhanced-sensitivity for alkaline phosphatase was obtained (0.1 mU/L), much better than previously reported methods. Meanwhile, it could be performed directly in homogeneous solution, which was very close to the actual activity level of alkaline phosphatase under physiological conditions. Likewise, satisfactory results were also obtained in specificity assessment, which demonstrated its potential application in clinical diagnosis. Notably, a new, sensitive, low-cost, short-time, and high-sensitivity platform for alkaline phosphatase detection was constructed, and the design of biosensor using DNA-templated Copper nanoclusters (CuNCs) was instructed in this study.

     

氯化钙对尼龙6无定形转变过程的在位红外研究

采用在位红外分析、X射线衍射方法研究了氯化钙对尼龙 6结晶的影响。结果表明 ,随尼龙 6中氯化钙含量的增加 ,尼龙 6的结晶度逐渐减小直至变为无定形态。由于氢键作用使尼龙 6分子链规整排列产生结晶 ,因此文章通过在位红外光谱方法研究了尼龙 6 /氯化钙复合材料中与氢键相关的胺基、酰胺Ⅰ带和酰胺Ⅱ带随温度及氯化钙含量的变化情况 ,证实了钙离子能通过与尼龙 6分子链上的羰基发生配位作用 ,插入尼龙 6分子链 ,破坏尼龙 6的氢键 ,降低了尼龙 6分子链的规整排列 ,使尼龙 6的结晶度减小 ,最终使尼龙 6由结晶态转变为无定形态     

一种尼龙老化评价的新方法

作为一种广泛使用的工程塑料,尼龙的老化备受关注。当作为电力系统芯片的封装材料时,尼龙在自然环境下的老化有可能会导致封装失效,从而影响芯片使用的可靠性,严重时甚至导致芯片的失效,给电力行业带来巨大损失。常规的自然老化和人工加速老化评价周期非常漫长,不同因素对尼龙老化的影响机理十分复杂,且这种影响难以研究,使得评价尼龙的老化稳定性成为一大难题。采用自主开发的原位老化评价系统,对尼龙6（PA6）和尼龙66（PA66）的老化稳定性及湿度对老化的影响进行了研究。该系统可以实现光照/温度/湿度/氧气等环境因素的加载,通过高灵敏度地测定材料在综合环境因素作用下产生的气相降解产物来评价材料的老化稳定性,评价时间缩短到几小时。实验表明,PA6和PA66的气相降解产物以H₂O和CO₂为主,由于H₂O在气相中的浓度不稳定,因此以CO₂的产生量作为老化评价指标。通过对不同自然老化时间PA6和PA66的原位老化评价,并与其ATR-FTIR红外光谱图进行对照,证明了原位老化评价方法能够较好地反映尼龙的老化程度,自然老化时间越长,PA6和PA66的稳定性越低,CO₂的产生量越大。进一步,采用该方法研究了湿度对PA6和PA66老化反应的影响,证明增大湿度对尼龙老化存在促进作用,而且升高温度会进一步促进湿度对老化的促进作用。研究表明,原位老化评价方法是一种快速评价尼龙老化稳定性及环境因素影响的有力手段。     

Comparing the Effect of Micro- and Nano-Scale Silica on the Rheological,Dynamic Mechanical Properties and Flame Resistance of Nylon 6,6

Nylon 6,6 micro- and nano-silica composites were prepared by melt processing using a twin-screw extruder. Three nanocomposites containing 4, 8, and 12 wt.% of nanosilica were prepared. In order to compare the effect of size, a microcomposite containing 4 wt.% of micron-size silica was also prepared. The effects of particle type (micro- and nano-size) on the dynamic thermomechanical and rheological properties, morphology, and flame resistance of the composites were examined. The dynamic thermomechanical properties (DMTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic rheometry, thermogravimetry analysis (TGA), and limiting oxygen index (LOI) data are reported. The particles were observed to be dispersed uniformly, but with a different level of coalescence, by means of SEM and TEM. The DMTA results showed that the damping factor peak positions of the nanocomposites at low content of nanofiller shifted more to higher temperature compared to those of nanocomposites containing high concentrations of nanofiller. Dynamic rheometry, using a parallel plate rheometer, showed that the rheological moduli of the nanocomposites increased with increase in nanofiller concentration; however, this increase was greater in the high-frequency region. These results showed that increasing the concentration of nanofiller, and the consequent coalescence effect within the nanocomposites, led to rheological moduli values similar to those of the microcomposite. The TGA and LOI results of the microcomposite and nanocomposite containing 4wt.% of nanosilica showed that nanosilica had a more significant effect to enhance the heat and flame resistance of nylon 6,6 compared to that of micron-sized silica.     

Fast and selective Cu2O nanorod growth into anodic alumina templates via electrodeposition

The fast and selective growth of cuprous oxide (Cu₂O) nanorods into anodic aluminum oxide (AAO) templates is achieved under optimized alkaline conditions via electrochemical deposition. The growth rate of Cu₂O nanorods at room temperature reached 360 nm/min, the fastest rate reported to date. The synthesis of Cu₂O nanorods by applying a constant current by using Cu₂O nanotubes as a transition state is extensively discussed; a Pt pottery-shaped layer played a key role as a seed layer for the fast Cu₂O growth. We report here the existence of regions of nanostructured Cu₂O based on our studies and previous relevant works, which include potential-pH curves for Cu²⁺-lactate solutions.