Improving physical properties of poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels via the Hofmeister effect

Hydrogel is a kind of three-dimensional crosslinked polymer material with high moisture content.However,due to the network defects of polymer gels,traditional hydrogels are usually brittle and fragile,which limits their practical applications.Herein,we present a Hofmeister effect-aided facile strategy to prepare high-performance poly(vinyl alcohol)/montmorillonite nanocomposite hydrogels.Layered montmorillonite nanosheets can not only serve as crosslinking agents to enhance the mechanical properties of the hydrogel but also promote the ion conduction.More importantly,based on the Hofmeister effect,the presence of(NH_(4))_(2)SO_(4)can endow nanocomposite hydrogels with excellent mechanical properties by affecting PVA chains'aggregation state and crystallinity.As a result,the as-prepared nanocomposite hydrogels possess unique physical properties,including robust mechanical and electrical properties.The as-prepared hydrogels can be further assembled into a high-performance flexible sensor,which can sensitively detect large-scale and small-scale human activities.The simple design concept of this work is believed to provide a new prospect for developing robust nanocomposite hydrogels and flexible devices in the future.

有机化蒙脱土对XLPE/OMMT纳米复合电介质微观形态及水树枝老化特性的影响

文中采用熔融共混法分别制备了交联聚乙烯/有机化蒙脱土(XLPE/OMMT)纳米复合电介质,研究有机化蒙脱土种类对纳米复合电介质微观形态和水树枝老化特性的影响。对试样进行力学性能测试发现,OMMT质量分数为0.5%时,综合力学性能达到最佳;利用差示扫描量热法和扫描电子显微镜研究了试样的微观形态,经双十八烷基苄基季铵盐有机化改性并细化的有机化蒙脱土(OMMT3)起到明显的异相成核作用,使晶体更加完善,结晶度高达25.3%,晶体平均尺寸仅为16.67μm;采用水针电极法对各试样进行加速水树枝老化试验,剥离分散的OMMT3片层形成了更加曲折的迷宫路径,其对水分子的阻隔效应与XLPE交联网状结构对分子链运动束缚的共同作用,有效抑制了XLPE/OMMT3试样中水树枝的生长,引发概率下降至23.4%;傅里叶变换红外光谱对水树枝老化前后的化学结构进行了表征,纳米复合电介质水树区的羰基指数增加、羟基振动峰增强,表明水树枝老化是电化学降解的作用;在水树枝生长过程中,XLPE/OMMT3试样老化断链较少,表现出较优的耐热氧老化性能。

The Thermal and Mechanical Properties of Ultra-High Molecular Weight Polyethylene/Montmorillonite (UHMWPE/MMT) Nanocomposites Hybrid Gel Using Pressure-Induced Flow (PIF) Processing

Hybrid organic-inorganic polymer nanocomposites incorporating organically modified montmorillonite (MMT) and ultra-high molecular weight polyethylene (UHMWPE) were examined. UHMWPE/MMT hybrid nanocomposites were prepared using gel and pressure-induced flow(PIF) processing methods at a gel weight concentration of 8% UHMWPE with various organoclay contents (0, 0.4, 0.8, 1.2, and 1.6 parts per hundred parts). The interlayer properties of the nanocomposites were studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The thermal and mechanical interfacial properties of the nanocomposites were investigated through thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and the use of a universal test machine (UTM). TEM indicates that the nanocomposites are formed upon dispersion of MMT in the polymer matrix. From the DSC, TGA, and DMA results, we find that the thermal stability of the UHMWPE nanocomposites increases as the MMT content increases. The nanocomposites show higher tensile strengths than pure UHMWPE gel sheet. These findings indicate that the interfacial and mechanical properties are improved by the addition of MMT and PIF processing.

Preparation and Properties of Phenolic Resin/Montmorillonite Intercalation Nanocomposites

Phenolic resin/montmorillonite intercalation composites were prepared by using the methods of pressing intercalation and melt intercalation.Properties and structure of the composites were investigated by using XRD,TG and test of softening point.It is indicated that both the pressing intercalation and melt intercalation can be used to prepare the phenolic resin/organo-montmorillonite intercalation nanocomposites.Compared with phenolic resin,the intercalation nanocomposites have better heat-resistance,higher decomposition temperatures and less thermal weight-loss.However,these two intercalation methods have different effects on the softening point of the intercalation nanocomposites.Pressing intercalation almost does not affect the softening point of the intercalation nanocomposites,while melt intercalation significantly increases the softening point of the intercalation nanocomposites, probably due to the chemical actions happening in the process of melt intercalation.

DISPERSION AND TENSILE BEHAVIOR OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES PRODUCED VIA MELT INTERCALATION

Most of the articles on polymer nanocomposites focus on the importance of chemistry used to modify the surface of the clay, usually montmorillonite (MMT), and characterization of the nano-scale structure obtained. The role and importance of processing were also discussed recently. However, few papers concerning the correlation between morphology of MMT and mechanical properties were published. In order to understand. the tensile behavior of PP/Montmorillonite (MMT) nanocomposites better, and to further improve the reinforcement efficiency, we first prepared the PP nanocomposites via direct melt intercalation using conventional twin-screw extrusion. The dispersion and tensile property of the composites were then investigated by SEM, XRD, TEM and a video-controlled tensile set-up. The macroscopic and microscopic dispersion of MMT in PP matrix was verified by XRD and TEM, combined with SEM. The tensile properties were obtained by video-controlled tensile set-up, which gives true stress-strain curve. It was found that a partly intercalated and partly exfoliated structure (also called incomplete exfoliation) existed in the system. Though the tensile strength of PP nanocomposites is not much improved in engineering stress-strain curves, more than 20% increase of true stress was found in a true stress-strain experiment at high true strain, which indicates that only oriented silicate layers can have a big effect on tensile properties: Not only orientation of silicate platelets but also the degree of exfoliation is a key factor to determine the reinforcement efficiency. The reinforcement efficiency of MMT has been discussed based on the 'continuum' Halpin-Tsai equations. A good agreement was found between experimental data and theoretical prediction by changing N value (number of platelets per stack) which corresponding to different state of the dispersion of MMT in PP matrix.

PROPERTIES AND MORPHOLOGY OF UNSATURATED POLYESTER/ACRYLATE-TERMINATED POLYURETHANE/ORGANO-MONTMORILLONITE NANOCOMPOSITES

Unsaturated polyester resin （UPR）/acrylate-terminated polyurethane （ATPU）/organo-modified montmorillonite （OMMT） nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene （S） and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82：15：3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.

Preparation and Characterization of Polylactide/Montmorillonite Nanocomposites

The montmorillonite, a form of layered silicate, was successfully intercalated into polylactide （PLA） matrix through solvent-casting technique. In addition, PLA/MMT nanocomposite films were produced, in which homogenous distribution of the silicate lamellae plays a key role in the mechanical properties of the films. A small amount（5wt%） of OMMT intercalated into the PLA matrix resulted in their flexibility enhancement, from 3.68%（pure PLA film） to 352.65%. The results of wide-angle X-ray diffraction （WAXD） patterns confirmed that the silicate interlayer distance increased from 3.044 nm （for OMMT） to 3.56nm （for 5wt%, maximum） with increasing OMMT contents, but decreased to 3.319 nm when OMMT content was over 8wt%. FT-IR also verified the molecular-level associations between PLA chains and OMMT lamellae by vibration variances of hydrogen bonding. DSC thermograms demonstrated that thermal stabilities of the nanocomposite films enhanced, due to the silicate lamellae dispersed into PLA matrix.

STRESS-INDUCED CRYSTALLIZATION OF POLYURETHANE/MONTMORILLONITE NANOCOMPOSITE

Exfoliated polyurethane/montmorillonite nanocomposites with both high elongation at break and high tensilestrength were studied by dynamic-infrared spectroscopy (dynamic-IR). The results show that crystallization induced byadditional stress is impeded by the nano-layered organo montmorillonite.

The Dynamic Viscoelasticity of Polyethylene Based Montmorillonite Intercalated Nanocomposites

The viscoelastic behavior of melts for two systems composed of intercalated nanocomposites based on low density polyethylene and 3 wt% loading of cetyltrimethyl- ammonium bromide modified montmorillonite was studied. The results obtained through examining the dynamic storage module G' and dynamic loss module G' values of the composite revealed that the dynamic viscoelastic properties of composite strongly depended on intercalation of polymer, and exhibited dramatically change with altering intercalation conditions. Only when modified montmorillonite content was about 3 wt%, the composite showed a trend of pseudo-solidlike at lower frequencies.

Preparation of Chinese fir wood/MMT nanocomposites and the factors affecting it

The nano intercalation compounding of wood and MMT has important implications for the modification of wood and for the development of new materials. With water-soluble phenol formaldehyde resin as an intermediary, the nanocomposites of Chinese fir （Cunningharnia lanceolata） wood and montmorillonite （MMT） were prepared via three impregnation methods, i.e. normal pressure, once and twice vacuum methods. Based on the weight percent gain （WPG） of impregnated wood, the effects of compounding wood and MMT in terms of concentration, impregnating temperature and time, wood moisture content and wood extraction treatments, on sapwood and heartwood are discussed. Results show that： 1） the optimum MMT concentration in the impregnation solution is 3% for sapwood and 5% for heartwood; 2） room temperature is suitable in practice; 3） treatment pressure should be set at a high enough value in order to ensure sufficient permeation; 4） the effects of different impregnation methods on sapwood and heartwood are different, the heartwood extractives affect WPG significantly; cell wall permeability of sapwood is better than that of heartwood; 5） the cold water, hot water and benzene-ethanol solution extractions can all greatly improve the permeability of heartwood, hot water can dissolve some hemicellulose of low aggregation and hot water extraction improves wood cell wall permeability; 6） with an increase in wood moisture content, the permeable space in wood is reduced, but with a certain amount of water, instantaneous spaces are created and the permeation dynamic increases. This effect is especially apparent for difficult impregnating situations in heartwood and impregnation under normal pressure.

Preparation and characterization of wood/montmorillonite nanocomposites

With montmorillonite （MMT） organically modified as organophilic MMT （OMMT） and water-soluble phenol formaldehyde resin （PF） as intermediate, Chinese fir （Cunningharnia lanceolata） wood/MMT nanocomposites （WMNC） were prepared via nano intercalation compounding and characterized by XRD, SEM and FTIR. Results show that： 1） the preparation of OMMT is very successful; 2） the self-made PF can effectively intercalate into MMT to increase markably its gallery distance and even exfoliate its nano silicate laminae; 3） the XRD analysis indicates that some exfoliated MMT enters the non-crystallized region of microfibrils in wood cell walls and the crystallinity degree of wood in WMNC decreases; 4） the SEM graphs show that multiform MMT exists in WMNC. Some grains block in wood cell lumen, some layers adhere to the wood surface of the inner cell wall and some exfoliated nanolaminae even insert into wood cell walls; and 5） the FTIR analysis suggests that MMT and wood in WMNC perhaps interact via certain chemical bonding.

Flame Retardant and Pyrolytic Behaviors of Polyamide 6/Montmorillonite Nanocomposite

Na +-montmorillonite(Na +-MMT) was converted to organic montmorillonite(OMMT) using modifier which was synthesized at authors’ laboratory. PA6/OMMT nanocomposite was prepared via in situ intercalative polymerization. The limiting oxygen index (LOI), UL 94V flame retardancy and thermal stability of PA6/OMMT using thermal gravity analysis (TGA) were measured. The Fourier transform infrared (FTIR) technique was used to analyze the pyrolytic residuum and the cone calorimeter (CONE) was applied to determine a number of combustion parameters which were closely related to fire safety, including heat release rate, mass loss rate, effective combustion heat, total heat release, specific extinction area and the time of ignition. In addition, the elemental composition of the surface pyrolytic residuum and the corresponding X-ray photoelectron spectroscopy (XPS) data were obtained, and the morphology of the residuum from CONE measurement was examined by scanning electron microscope (SEM).

Rheological Behavior of the Melts for Polyethylene-based Montmorillonite Nanocomposites

The viscoelastic properties of melts of nanocomposites with partially exfoliated structures, which were composed of low-density polyethylene （LDPE）, ethylene vinyl acetate copolymer （EVA）, and montmofillonite and modified by cetyltrimethyl ammonium bromide and octadecyltrimethyl ammonium bromide, were studied. The results obtained through measurements of the dynamic storage modulus G′, the dynamic loss modulus G″, and the transiem stress relaxation modulus G（t） of the composites, reveal that the viscoelastic properties of the composites strongly depend on the amount of montmorillonite that is exfoliated into the composites. With the increase in montmoriUonite content, the composites show an obvious property of pseudo solid-like materials within the region of lower frequencies （ω）. The montmorillonite layers are aligned along the stress direction, and the dependence of dynamic modulus on ω, appears quite different for the composites before and after being exposed to a large amplitude oscillatory shears.

5-Fluorouracil Loaded Chitosan–PVA/Na^+MMT Nanocomposite Films for Drug Release and Antimicrobial Activity

In the present study, chitosan and polyvinyl alcohol(PVA) were blended with different concentrations of sodium montmorillonite(Na^+MMT) clay solution by a solvent casting method. X-ray diffraction and transition electron microscope results show that the film properties are related to the co-existence of Na^+MMT intercalation/exfoliation in the blend and the interaction between chitosan–PVA and Na^+MMT. 5-Fluorouracil(5-FU) was loaded with chitosan–PVA/Na^+MMT nanocomposite films for in vitro drug delivery study. The antimicrobial activity of the chitosan–PVA/Na^+MMT films showed significant effect against Salmonella(Gram-negative) and Staphylococcus aureus(Gram-positive), whereas5-FU encapsulated chitosan–PVA/Na^+MMT bio-nanocomposite films did not show any inhibition against bacteria. Our results indicate that combination of a flexible and soft polymeric material with high drug loading ability of a hard inorganic porous material can produce improved control over degradation and drug release. It will be an economically viable method for preparation of advanced drug delivery vehicles and biodegradable implants or scaffolds.

Synthesis and characterization of carboxymethyl cellulose/organic montmorillonite nanocomposites and its adsorption behavior for Congo Red dye

A series of carboxymethyl cellulose/organic montmorillonite （CMC/OMMT） nanocomposites with different weight ratios of carboxymethyl cellulose （CMC） to organic montmorillonite （OMMT） were synthesized under different conditions. The nanocomposites were characterized by the Fourier transform infrared （FT-IR） spectrophotometer, X-ray diffraction （XRD） method, transmission electron microscope （TEM）, scanning electron microscope （SEM）, and thermal gravimetric （TG） analysis. The results showed that the introduction of CMC may have different influences on the physico-chemical properties of OMMT and intercalated-exfoliated nanostructures were formed in the nanocomposites. The effects of different reaction conditions on the adsorption capacity of samples for Congo Red （CR） dye were investigated by controlling the amount ofhexadecyl trimethyl ammonium bromide （CTAB）, the weight ratio of CMC to OMMT, the reaction time, and the reaction temperature. Results from the adsorption experiment showed that the adsorption capacity of the nanocomposites can reach 171.37 rag/g, with the amount of CTAB being 1.0 cation exchange capacity （CEC） of MMT, the weight ratio of CMC to OMMT being l：l, the reaction time being 6 h, and the reaction temperature being 60~C. The CMC/OMMT nanocomposite can be used as a potential adsorbent to remove CR dye from an aqueous solution.

Structure Characterization and Thermal Properties of PMMA/Montmorillonite Nanocomposites via Emulsion Polymerization

Montmorillonite(MMT) modified with sodium silicate can change the arrangement of its layers from edge-face and edge-edge to face-face. With the fine dispersion of the modified MMT in water,the cation-exchange reaction was carried out with cetyltrimethyl ammonium bromide(CTAB) to obtain organo-montmorillonite(OMMT). As OMMT was uniformly dispersed in methyl methacrylate(MMA) monomer,PMMA/OMMT nanocomposites were formed via a common emulsion polymerization. The products were extracted with hot acetone and characterized by FTIR,molecular weight,X-ray diffraction(XRD),transmission electron microscopy(TEM),DSC and TGA. These results show that most of the OMMT layers have been exfoliated,while the thermal stability is increased obviously. By means of FTIR spectral analysis,the ratios of the macromolecular radicals′ termination of disproportionation patterns to combination are increased with the addition of OMMT. This result further confirms the increase of the thermal degradation temperatures and glass transition temperatures of the PMMA/OMMT nanocomposites.

Synthesis and Characterization of Soy Protein Isolate/MMT Nanocomposite Film for the Control Release of the Drug Ofloxacin

Nanocomposites were prepared by blending soy protein isolate with different percentage of MMT by melt extrusion technique. The nanocomposites were characterized by using, XRD, TEM, SEM and TGA methods. The XRD studies indicated the absence of diffraction peaks for the bio-nanocomposites. From the TEM studies it was ascertained that the degree of exfoliation increased with increase in MMT content. The morphology of the nanocomposites was ascertained from the SEM studies. The degradation pattern of the nano-composites was evaluated from the TG analysis. The drug delivery system of the nanocmposites was investigated by blending the nanocomposites with ofloxacin at different pH media. The various kinetic parameters were evaluated and the mechanism of drug delivery has been postulated based on the kinetic data.

Structure and Properties of Self-reinforced Material Made from Ultra-high Molecular Weight Polyethylene-montmorillonite Nanocomposite

High-strength and high-modulus ultra-high molecular weight polyethylene(UHMWPE), named self-reinforced material, was obtained by the elongation of UHMWPE-montmorillonite nanocomposite at melting temperature. According to the scanning electron microscope(SEM) analysis, a great deal of fibrillar texture formed in the direction of elongation, and the tensile fractured surface was similar to that of highly oriented fiber. The transmission electron microscope(TEM) and selective area electron diffraction(SAED) analyses reveal that the reinforced phase of the self-reinforced material is an extended chain crystal and its size is about 50_200 nm wide and several microns long, and the montmorillonite layers are broken up to pieces in the size from 100 to 10 nm. The broken layers which have a huge surface area interacting strongly with macromolecules reduces the entanglement density of UHMWPE and induces the chain orientation in flow field. It is supposed that the astriction of montmorillonite layers to polyethylene chains is not only end-tethered but also side-tethered. The differential scan calorimetry(DSC) analysis shows that there are two endothermal peaks for the self-reinforced material, of which the peak at a higher temperature(136.4 ℃) is ascribed to the melting of the reinforced phase.