Single-walled carbon nanotube combing during layer-by-layer assembly: from random adsorption to aligned composites

Oriented SWNTs in polymer composites have shown dramatic improvements in the physical properties of a composite because of the anisotropic shape and properties of SWNTs. Controlled alignment of SWNTs during composite fabrication implies better material function performance. This letter reports a new fabrication technique whereby aligned SWNTs and robust SWNT-polymer composites can be made using a fusion method of SWNT combing and layer-by-layer (LBL) assembly. As we previously reported, LBL assembly demonstrated exceptional processing ability in constructing the uniform distribution of a SWNT-polymer composite. Combined with this uniformity, this SWNT combing technique endows controlled alignment of single-stranded SWNTs in a SWNT-polymer composite system. SWNT combing employs air-water interfacial forces to change the molecular topography from the random adsorption state to the stretched alignment of SWNTs. More specifically, air-water interfacial forces are associated with an excess viscous drag force and an intrinsic dewetting rate along SWNTs. Moreover, the alignment efficiency of SWNTs is high enough to construct a multilayered LBL film with horizontal-linear weaving structures. This simple method also can be applied for aligning other nanowire materials because it utilizes simple geometric features of SWNTs.     

The role of organoclay on the properties of Polymethylsilsesquioxane: A systematic study

In this study, an attempt is made to improve the properties of PMSQ, an organosilicone polymer which possesses distinguished properties, through an easy and facile route by the inclusion of organically modified montmorillonite clay. PMSQ-clay composites were prepared by solution blending of the components initially and then heat curing under load. The effect of clay content, varied at 5–40 wt.%, on mechanical, thermal and dynamic mechanical properties was evaluated and the optimum was obtained for 20%. Morphology investigation as well as microstructure analysis revealed intercalated to exfoliated morphology of PMSQ-clay composite. An appreciable improvement in mechanical properties of PMSQ, compressive strength and impact strength in particular, was achieved by clay inclusion up to 20%. The properties declined at ≥ 30% clay loading. The composites showed increased thermal stability compared to unmodified PMSQ up to 400 °C. Also, increase in clay content accelerated conversion to ceramic SiOC. PMSQ-clay composites exhibited good visco-elastic characteristics with higher T_g probably due to enhanced polymer-clay interactions. Thus, a simple and viable method to enhance the mechanical and thermal characteristics of PMSQ by way of preparing its composite with the reinforcing filler organoclay is demonstrated here.     

Effect of sunlight on the preparation and properties of cellulose/silver nanoparticle composite films by in situ method using Ocimum sanctum leaf extract as a reducing agent

Cellulose/silver nanoparticle composite films with in situ-generated silver nanoparticles (AgNPs) were prepared using Ocimum sanctum leaf extract as a reducing agent in the absence and presence of sunlight and were characterized by SEM, FTIR, XRD, and antibacterial tests. Sunlight hastened up the preparation of these composite films. The average size of the in situ-generated AgNPs was reduced by the sunlight. The antibacterial activity and other properties of the composites were enhanced by the sunlight. The cellulose/AgNP composite films with improved properties by sunlight can be considered for medical purpose as antibacterial dressing materials.     

Elastomeric flexible free-standing hydrogen-bonded nanoscale assemblies

Poly(ethylene oxide) (PEO) is a key material in solid polymer electrolytes, biomaterials, drug delivery devices, and sensors. Through the use of hydrogen bonds, layer-by-layer (LBL) assemblies allow for the incorporation of PEO in a controllable tunable thin film, but little is known about the bulk properties of LBL thin films because they are often tightly bound to the substrate of assembly. The construction technique involves alternately exposing a substrate to a hydrogen-bond-donating polymer (poly(acrylic acid)) and a hydrogen-bond-accepting polymer (PEO) in solution, producing mechanically stable interdigitated layers of PEO and poly(acrylic acid) (PAA). Here, we introduce a new method of LBL film isolation using low-energy surfaces that facilitate the removal of substantial mass and area of the film, allowing, for the first time, the thermal and mechanical characterization that was previously difficult or impossible to perform. To further understand the morphology of the nanoscale blend, the glass transition is measured as a function of assembly pH via differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The resulting trends give clues as to how the morphology and composition of a hydrogen-bonded composite film evolve as a function of pH. We also demonstrate that LBL films of PEO and PAA behave as flexible elastomeric blends at ambient conditions and allow for nanoscale control of thickness and film composition. Furthermore, we show that the crystallization of PEO is fully suppressed in these composite assemblies, a fact that proves advantageous for applications such as ultrathin hydrogels, membranes, and solid-state polymer electrolytes.     

The addition of clay on the mechanical properties of surface‐treated CF‐filled PA66 composites

Polyamide 66 (PA66) composites filled with clay and carbon fiber (CF) were prepared by twin‐screw extruder in order to study the influence of nanoparticle reinforcing effect on the mechanical behavior of the PA66 composites (CF/PA66). The mechanical property tests of the composites with and without clay were performed, and the fracture surface morphology was analyzed. The results show that the fracture surface area of the clay‐filled CF/PA66 composite was far smoother than that of the CF/PA66 composite, and there formed a tense interface on the CF surface after the addition of clay. The tensile and flexural strength of CF/PA66 composites with clay was improved. The impact strength decreased because of the high interfacial adhesion. In conclusion, the addition of clay favored the improvement of the higher interface strength and so had good effect on improving the tensile and flexural properties of the composites. Copyright © 2017 John Wiley & Sons, Ltd.     

Synthesis of montmorillonite-based tris(2-ethylamine)-Schiff-base composites with remarkable antibacterial activity

A range of heterogeneous, inexpensive and benign Schiff bases-montmorillonite composites were synthesized and screened for their antibacterial activity against common microbial pathogens. Sodium montmorillonite (Na-MMT) clay was modified with tris(2-ethylamine) in the presence of dilute HCl to yield a quaternary salt of tris(2-ethylamine) modified clay. The Schiff bases were then fabricated from the reaction of the modified montmorillonite using different aldehydes. The structures of the obtained compounds were confirmed by Fourier transformer Infrared (FT-IR), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). All the obtained composite materials were screened for their antibacterial activities against the multi-drug resistant (MDR) strains. It was reasoned that the modified MMT-based composites has the ability to absorb the different micro-organisms onto the surface, and accordingly act as an effective antibacterial agent. All the composites showed significant antibacterial activity between 2.5 and 20 mg/mL against the MDR bacterial strains. The benzyl-based/modified MMT and the tertiary amino-based/modified MMT was found to be the most effective antibacterial agent.     

Characterization and antibacterial activity of chitosan‐based composites with polyester

The effects of replacing poly(butylene succinate adipate) (PBSA) with acrylic acid‐grafted PBSA (PBSA‐g‐AA) on the structure and the properties of a PBSA/chitosan composite were investigated. The properties of both PBSA‐g‐AA/chitosan and PBSA/chitosan were compared using Fourier transform infrared (FTIR), ¹³C nuclear magnetic resonance (NMR), X‐ray diffraction (XRD), and an antibacterial activity test. With PBSA‐g‐AA in the composite, the compatibility with chitosan and, consequently, the properties of the composite became greatly improved due to the formation of ester and imide groups that conferred better dispersion and homogeneity of chitosan in the matrix. Composites containing PBSA‐g‐AA/chitosan exhibited superior mechanical properties due to greater compatibility between the two components. Moreover, chitosan enhanced the antibacterial activity of the composites. Composites of PBSA‐g‐AA or PBSA that contain chitosan have better antibacterial activity. The functionalized PBSA‐g‐AA/chitosan composites showed markedly enhanced antibacterial properties due to the carboxyl groups of acrylic acid, which acted as coordination sites for the chitosan phase, allowing the formation of stronger chemical bonds. Copyright © 2011 John Wiley & Sons, Ltd.     

Effects of clay and surface plasma‐treated carbon fiber on wear behavior of thermoplastic POM composites

In engineering applications, experimental data and insight from scientific investigations on wear properties of polyoxymethylene (POM) composites are important for engineers to understand how to design and formulate POM materials with high resistance to wear. In this work, clay and carbon fiber were utilized and incorporated into POM and the mechanical and wear properties, in specific wear rate, were then assessed. The experimental results suggested that the addition of clay increased the tensile modulus and strength. The mechanical and wear properties of POM composites were found to improve with the addition of the carbon fiber. Carbon fiber/clay/POM composite exhibited the lowest specific wear rate and friction coefficient.     

Preparation and Antibacterial Effect of Bamboo Charcoal/Ag on Staphylococcus Aureus and Pseudomonas Aeruginosa

Bamboo charcoal supporting silver (BC/Ag) was prepared by activation and chemical reduction. The BC/Ag composites were characterized by silver particle size and distribution, silver ion (Ag⁺) release and antibacterial properties. Scanning and transmission electron microscopy (SEM and TEM) showed that the Ag particles were distributed uniformly on the BC matrix. The Ag particle size was found to be less than 150 nm based on TEM. The Ag⁺ release increased initially which was followed by a marginal increase between the 8th and 24th hour. Composites contained higher amounts of silver exhibited a further rise in Ag⁺ release from the 24‐hours of storage in water. The antibacterial effects of the BC/Ag composite powders against Pseudomonas aeruginosa and Staphylococcus aureus were assessed from the minimum inhibitory concentrations (MICs) and minimum bactericidal concentrations (MBCs) method, and an excellent antibacterial performance was discovered.     

基于水滴模板法的微纳复合超疏水结构制备的研究

利用粒子辅助水滴模板法的实施获得规则蜂窝状图案化多孔结构模板,并进一步利用聚二甲基硅氧烷(PDMS)复制转移技术获得表面具有微米尺寸蜂窝状突起阵列的反向图案化结构.以这种图案化突起结构作为微米尺寸所提供的微米级粗糙度为基础,设计了2种的简单的二次纳米结构的引入过程,最终实现了微米级阵列和纳米级粗糙度的复合.第一种方法借助银镜反应来实现纳米银结构的化学沉积,最终在PDMS阵列表面获得了致密的纳米银颗粒沉积层,并成功获得了表面接触角达166度的超疏水性质.第二种方法利用了聚电解质/二氧化硅粒子层层静电自组装的方法引入纳米结构,结果在仅仅进行了2个组装循环的条件下即可获得超疏水性质的表面复合结构.通过简单的实验设计试图提供一种基于水滴模板法的微纳复合超疏水结构的普适性制备方法.     

尼龙6/抗菌蛭石复合材料的制备及性能研究

通过离子交换法对蛭石进行载银和有机化改性,制备出3种抗菌蛭石,进一步采用熔融共混法制备了尼龙6/抗菌蛭石复合材料,测试了复合材料的抗菌性能和物理力学性能,利用TEM和SEM观察了蛭石在尼龙6中的分散情况和拉伸断面.研究结果表明,载银并有机化的蛭石与尼龙6的复合材料对大肠杆菌和金黄色葡萄球菌均具有明显的抑菌圈,对大肠杆菌...     

Hematite spindles with optical functionalities: growth of gold nanoshells and assembly of gold nanorods

The layer-by-layer (LBL) assembly method, combined with the seeded growth technique, have been used to deposit gold shells on the surface of hematite (alpha-Fe(2)O(3)) spindles. While the LBL method yields dense coatings of preformed Au nanoparticles, when AuCl(-)(4) ions are further reduced by a mild reducing agent, thicker, rough nanostructured shells can be grown. The deposition process was monitored by TEM and UV-visible spectroscopy, demonstrating a gradual change in the optical features of the colloids as the surface is more densely covered. The particles so-prepared can find useful applications in cancer therapy and as SERS substrates. Additionally, we show that Au nanorods can be assembled on hematite spindles, providing a flexible way to tune the optical properties of the resulting composite colloids.     

Rapid,Selective Extraction of Silver from Complex Water Matrices with a Metal–Organic Framework/Oligomer Composite Constructed via Supercritical CO2

Every year vast quantities of silver are lost in various waste streams; this, combined with its limited, diminishing supply and rising demand, makes silver recovery of increasing importance. Thus, herein, we report a controllable, green process to produce a host of highly porous metal–organic framework (MOF)/oligomer composites using supercritical carbon dioxide (ScCO₂) as a medium. One resulting composite, referred to as MIL-127/Poly-o-phenylenediamine (PoPD), has an excellent Ag⁺ adsorption capacity, removal efficiency (>99 %) and provides rapid Ag⁺ extraction in as little as 5 min from complex liquid matrices. Notably, the composite can also reduce sliver concentrations below the levels (<0.1 ppm) established by the United States Environmental Protection Agency. Using theoretical simulations, we find that there are spatially ordered polymeric units inside the MOF that promote the complexation of Ag⁺ over other common competing ions. Moreover, the oligomer is able to reduce silver to its metallic state, also providing antibacterial properties.     

Preparation and characterization of covalently bonded PVA/Laponite/HAPI nanocomposite multilayer freestanding films by layer‐by‐layer assembly

The layer‐by‐layer (LBL) assembly technique is an attractive method to make functional multilayer thin films and has been applied to fabricate a wide range of materials. LBL materials could improve optical transmittance and mechanical properties if the film components were covalently bonded. Covalently bonded nanocomposite multilayer films were prepared by employing hydrophilic aliphatic polyisocyanate (HAPI) as the reactive component, to react with Laponite and polyvinyl alcohol (PVA). FT‐IR spectra suggested that HAPI reacted with Laponite and PVA at ambient temperature rapidly. Ellipsometry measurement showed that the film thickness was in linear growth. The influences of HAPI on the optical, mechanical and thermal properties of the films were investigated by UV‐Vis spectroscopy, tensile stress measurement, DSC and TGA. The obtained results showed that the optical transmittance and mechanical strength were enhanced when the film components were covalently bonded by HAPI. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 545–551     

Mechanical, thermal, and fire properties of polylactide/starch blend/clay composites

Polylactide (PLA)/starch blend/clay and PLA/clay composites are prepared by melt blending. Structural and thermal characterizations are performed by differential scanning calorimetry, X-ray diffraction analysis, and thermogravimetric analysis. The fire properties are assessed on a dual cone calorimeter. Combustion residue and char formation is characterized by optical microscopy and attenuated total reflection infrared spectroscopy. Although the clay is not fully intercalated/exfoliated, the composites exhibit a higher thermal stability and much reduced peak heat release rate, and the PLA/starch blend composite retains its mechanical properties. For the PLA/starch blend composite, smoke release is also considerably reduced. Catalyzed, oxidative decomposition is shown to occur early in the thermal decomposition of the composites, prior to increased thermal stability. The inclusion of clay promotes char formation and increases the quantity of carbonaceous char in the combustion residue. There is minimal migration of the clay to the surface prior to ignition and char is formed mainly after ignition and during burning. During the later stages of burning some of the char formed is converted to CO₂.     

Multilayered gold-nanoparticle/polyimide composite thin film through layer-by-layer assembly

A novel type of composite thin film consisting of gold nanoparticles (AuNPs) and polymide (PI) was fabricated through layer-by-layer (LBL) assembly. To fabricate such films, bare AuNPs and a poly (amic acid) bearing pendant amine groups, namely, amino poly (amic acid) or APAA, were synthesized and assembled in an LBL fashion. Without any organic encapsulation layer on their surface, AuNPs were bound directly to APAA chains at the amine sites; X-ray photoelectron spectroscopy study suggested that the binding was based on a combined effect of metal-ligand coordination and electrostatic interaction, with the former dominating over the latter. An approximately linear growth of the film started from the second layer of AuNP as revealed by the UV-vis spectroscopy, and the degree of particle aggregation was higher in the first AuNP layer than in the subsequent layers due to the differences in the density of binding sites. The resultant assembly was heated to imidize the APAA, thereby creating a robust composite structure.     

脉冲电化学驱动壳聚糖原位调控制备羟基磷灰石/银复合涂层

采用脉冲电化学驱动壳聚糖原位调控制备了具有抗菌性的羟基磷灰石/银纳米复合涂层.考察了电解液中银离子浓度、钙磷盐浓度等对复合涂层的形貌及成分的影响.探讨了壳聚糖调控羟基磷灰石和银纳米粒子的形成机理,发现在本研究的较佳实验条件为电位-1.3 V,Ag~+浓度为0.06 g·L~(-1),Ca~(2+)浓度为5 mmol·L~(-1).在此基础上对复合涂层的生物活性、生理稳定性能、抗菌性能进行分析.结果表明:复合涂层呈纳米球状,由羟基磷灰石、银、壳聚糖三相组成,并且表面有一层壳聚糖覆盖.银纳米粒子和羟基磷灰石纳米粒子在复合涂层中均匀分布.将复合涂层浸泡在SCPS溶液中37°C浸泡矿化10天后,在复合涂层表面生产细针状排列整齐的羟基磷灰石,且在(002)晶面25.8°处发生显著择优生长,表明复合涂层在快速矿化液中能诱导磷灰石生成,生物活性好.将复合涂层浸泡在37°C PBS溶液中考察其生理稳定性,壳聚糖对复合涂层中Ca~(2+)和Ag~+实现双重离子释放,且降低了离子释放速度,涂层具有良好的生理稳定性.抗菌实验表明复合涂层对大肠杆菌和金黄色葡萄球菌抗菌率达到99%以上,抗菌能力强.     

Electrospun PVA Nanofibrous Membranes Reinforced with Silver Nanoparticles Impregnated Cellulosic Fibers: Morphology and Antibacterial Property

To enhance the mechanical and antibacterial properties of silver nanoparticle impregnated cellulosic fibers, carboxy-cellulose nanocrystals(CCNs) were grafted with chitooligosaccharide(COS), which was used as a stabilizer for silver nanoparticles (AgNPs). Nanofibrous membranes reinforced with silver nanoparticle impregnated cellulosic fibers(CCN-COS-AgNP) were prepared via electrospinning using polyvinyl alcohol(PVA) as a matrix. The effects of CCN-COS-AgNP contents on the morphology, surface composition, mechanical properties, and antibacterial performances of the prepared CCN-COS-AgNP/PVA membranes were examined. The addition of CCN-COS-AgNP certainly improved the mechanical properties and antibacterial performances of the PVA nanofibers. The tensile strength was significantly increased from 4.40 MPa to 8.60 MPa when 8% CCN-COS-AgNP(mass ratio) was introduced. When 10%(mass ratio) CCN-COS-AgNP was added, the nanofibers showed an excellent antibacterial activity for S. aureus(Staphylococcus aureus) and E. coli(Escherichia coli), with the maximum inhibition zones of 2.30 and 1.60 cm, respectively. Moreover, the 2%(mass ratio) CCN-COS-AgNP/PVA fibrous membrane showed 126% cell viability for mg63 human osteoblasts. The electrospun PVA membrane has great potential application in biomedical field.     

Improving polylactide/starch biocomposites by grafting polylactide with acrylic acid--characterization and biodegradability assessment

In this article, the properties of a polylactide and starch composite (PLA/starch) and an acrylic acid grafted polylactide and starch composite (PLA-g-AA/starch) were compared. The composite containing PLA-g-AA was found to have much better dispersion and homogeneity of starch in the polymer matrix than the composite containing PLA, indicating better compatibility between the two phases. Better mechanical and thermal properties of the PLA-g-AA/starch composite, notably an increase in tensile strength and elongation at breakpoint, evidenced its superiority to the PLA/starch composite. Furthermore, the lower viscosity of PLA-g-AA/starch makes it easier to process than PLA/starch. Weight loss on exposure to a soil environment over a period of three months showed that the starch in the composites was almost completely biodegradable, even at a high degree of substitution (60 wt.-% starch). After three months in soil, a reduction in the mechanical properties of the blends was observed, especially in those with higher starch contents.     

Influence of graphene oxide incorporation and chemical cross‐linking on structure and mechanical properties of layer‐by‐layer assembled poly(Vinyl alcohol)‐Laponite free‐standing films

Functional fillers in multilayered films provide opportunity in tailoring the mechanical properties through chemical cross‐linking. In this study, Laponite‐graphene oxide co‐dispersion was used to incorporate graphene oxide (GO) easily into polyvinyl alcohol (PVA)/Laponite layer‐by‐layer (LBL) films. The LBL films were found to be uniform and the layer thickness increased linearly with number of depositions. The process was extended to a large number of depositions to investigate the macroscopic mechanical properties of the free‐standing films. The LBL films showed remarkable improvements in mechanical properties as compared to neat PVA film. The GO‐incorporated LBL films displayed higher enhancements in the tensile strength, ductility, and toughness as compared to that of PVA/Laponite LBL films, upon chemical cross‐linking. This suggests the advantageous effects of GO incorporation. Interestingly, cross‐linking of LBL films for longer time period (>1 h) and higher temperature (～80 °C) was not found to be much beneficial. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2377–2387