A simple and green strategy for preparing poly(vinyl alcohol)/phosphate cellulose aerogel with enhanced flame-retardant properties

Phosphorylated celluloses (PCFs) were obtained via reaction of microcrystalline cellulose with phosphorous acid in molten urea. Fourier transform infrared spectroscopy and scanning electron microscopy were used to observe the chemical structure and microstate of the PCFs. A flame retardant glutaraldehyde cross-linked poly (vinyl alcohol)/PCF aerogel was fabricated using a melt cross-link and freeze-dried method. The results of thermogravimetric analysis confirmed that the thermal stability of the poly(vinyl alcohol) (PVA) aerogels incorporating PCF is more outstanding. The peak of heat release rate (PHRR) and the total heat release (THR) values of the PCA/PCF₁₀ aerogel deceased obviously by 33.8 and 64%, respectively, compared to the corresponding values for the pure PVA aerogel; these changes confirm that the PCA/PCF aerogel had better flame-retardant properties than the pure PVA aerogel. Moreover, the fire performance index and fire growth index indicate that the introduction of PCF would diminish the occurrence of fire.     

Cellulose Nanocrystals/ZnO as a Bifunctional Reinforcing Nanocomposite for Poly(vinyl alcohol)/Chitosan Blend Films: Fabrication,Characterization and Properties

In this study, cellulose nanocrystals/zinc oxide (CNCs/ZnO) nanocomposites were dispersed as bifunctional nano-sized fillers into poly(vinyl alcohol) (PVA) and chitosan (Cs) blend by a solvent casting method to prepare PVA/Cs/CNCs/ZnO bio-nanocomposites films. The morphology, thermal, mechanical and UV-vis absorption properties, as well antimicrobial effects of the bio-nanocomposite films were investigated. It demonstrated that CNCs/ZnO were compatible with PVA/Cs and dispersed homogeneously in the polymer blend matrix. CNCs/ZnO improved tensile strength and modulus of PVA/Cs significantly. Tensile strength and modulus of bio-nanocomposite films increased from 55.0 to 153.2 MPa and from 395 to 932 MPa, respectively with increasing nano-sized filler amount from 0 to 5.0 wt %. The thermal stability of PVA/Cs was also enhanced at 1.0 wt % CNCs/ZnO loading. UV light can be efficiently absorbed by incorporating ZnO nanoparticles into a PVA/Cs matrix, signifying that these bio-nanocomposite films show good UV-shielding effects. Moreover, the biocomposites films showed antibacterial activity toward the bacterial species Salmonella choleraesuis and Staphylococcus aureus. The improved physical properties obtained by incorporating CNCs/ZnO can be useful in variety uses.     

Molecular design and properties of intrinsic flame-retardant P-N synergistic epoxy resin

In recent years, the poor weather resistance and aging resistance of additive flame retardants have caused researchers to pay attention to reactive flame retardants. A novel P-N coacting epoxy curing agent with intrinsic flame retardancy was designed and synthesized. The mechanical properties, crosslinking curing properties and flame-retardant properties of intrinsic flame-retardant epoxy resin were characterized. The results show that the cross-linking curing performance of hexa (3,5-diamino-1,2,4 triazolyl)-cyclotriphosphonitrile) (VCP) is lower than that of DDM. This is due to the decrease in cross-linking density caused by the VCP ring molecular structure. Therefore, the mechanical properties of the epoxy resin cured with VCP decreased, but the flame-retardant properties of the material significantly improved. The limiting oxygen index of the VCP/EP flame retardant epoxy thermosets was 27.3%, reaching the UL 94 V-1 level. The peak heat release rate and total heat release rate of the VCP/EP flame retardant epoxy thermosets were significantly reduced. The flame retardancy mechanism was studied by Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, and x-ray photoelectron spectroscopy. The results show that the intrinsic flame-retardant P-N coacting epoxy resin has excellent curing and flame-retardant properties.     

Nanocomposites of Poly(Vinyl Alcohol)/Functionalized-Multiwall Carbon Nanotubes Conjugated With Glucose Oxidase for Potential Application as Scaffolds in Skin Wound Healing

A novel nanocomposite scaffold based on poly(vinyl alcohol) (PVA) and multiwalled carbon nanotubes (MWNT) were synthesized and characterized regarding to morphological, physical, and mechanical properties and also the preliminary biocompatibility was assessed by MTT assay. Additionally, the concept of developing hybrid systems was tested by bioconjugating functionalized MWNT to glucose oxidase and dispersed in the PVA matrix. The nanocomposites have presented mechanical properties, degree of swelling, and cytocompatibility comparable to the skin tissues. Moreover, the bionanocomposite with enzyme showed bioactivity toward injecting glucose with simultaneous antimicrobial behavior against bacterial pathogens due to the generation hydrogen peroxide.     

Thermal Degradation Behaviors of Poly(vinyl chloride)/Halloysite Nanotubes Nanocomposites

Poly(vinyl chloride) (PVC)/halloysite nanotubes (HNTs) nanocomposites were prepared by melt blending. Transmission electron microscopy (TEM) results showed that HNTs were uniformly dispersed in the PVC matrix. The thermal properties of PVC/HNTs nanocomposites were investigated in detail. The apparent activation energies (Ea) were analyzed by means of Kissinger and Flynn-Wall-Ozawa methods. Thermogravimetric analysis results showed that the thermal properties of PVC/HNTs nanocomposites were improved. Cone calorimetry was used to measure the smoke evolution and fire properties. The addition of HNTs led to a remarkable reduction in the smoke production rate, the total smoke production, and the peak heat release rate.     

UF/MPOP与PEA/MPOP对木材燃烧性能的影响

分别以脲醛树脂(UF)和纯丙乳液(PEA)树脂为基料,三聚氰胺聚磷酸盐(MPOP)、三聚氰胺(MEL)、季戊四醇(PER)为膨胀阻燃体系,制备了膨胀型阻燃涂料。通过热重分析仪对制备的MPOP热稳定性及阻燃机理进行了表征,利用锥形量热仪、极限氧指数测试仪对涂料阻燃性能进行分析。结果表明,与PEA/MPOP相比,UF/MPOP对木材具有更好的阻燃性能,热稳定性和抑烟性能,极限氧指数提高了9.4 %,热释放速率、总热释放量、烟气释放速率降低,在木材表面形成的炭层更加完整。     

Microstructure and shape memory effect of acidic carbon nanotubes reinforced polyvinyl alcohol nanocomposites

Specimens of acidic multi‐walled carbon nanotubes (AMWNTs) reinforced polyvinyl alcohol (PVA) nanocomposites (AMWNTs‐PVA) were prepared using different amounts of AMWNTs by the traditional solution casting, involving ultrasonic wave agitation. The microstructures and tensile properties of AMWNTs‐PVA were investigated by scanning electron microscopy, dynamic mechanical analysis, and quasi‐static tensile testing. AMWNTs had good compatibility with PVA and dispersed evenly in the PVA matrix. The incorporation of AMWNTs improved the tensile modulus and strength of the PVA. The shape recovery testing revealed the shape recovery capacity of AMWNTs‐PVA. It was observed that the recovery ratio increased, and the shape recovery rate slightly decrease with the increase of AMWNTs content. The results showed that the AMWNTs had strong interaction with the segments of the PVA and hence affected the shape recovery behavior of PVA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

PVA/锑搀杂二氧化锡纳米复合材料的结构与性能研究

采用溶液共混的方式制备聚乙烯醇/锑搀杂二氧化锡(PVA/ATO)纳米复合材料,采用红外光谱(FTIR)、差示扫描量热仪(DSC)、光学显微镜、扫描电镜对复合材料的结构及微观形态进行了表征,对复合材料的导电性能及机械性能进行了测试。结果表明:PVA与ATO之间在共混膜中存在强烈的相互作用,这种相互作用可使纳米ATO在PVA基体中分散良好,在ATO含量较低的情况下就可获得导电性能及机械性能良好的复合材料;纳米ATO明显的异相成核效应,能够提高PVA的结晶温度及熔融温度。     

Halloysite nanotube reinforced biodegradable nanocomposites using noncrosslinked and malonic acid crosslinked polyvinyl alcohol

Halloysite nanotubes (HNTs) based thin membrane‐like fully biodegradable nanocomposites were produced by blending individualized HNT dispersion with polyvinyl alcohol (PVA). Stable individualized HNT dispersion was obtained using several separation techniques, sequentially, prior to blending with PVA. PVA was crosslinked using malonic acid (MA) as crosslinker and phosphoric acid as catalyst, to increase the mechanical and thermal properties of HNT–PVA nanocomposites. Crosslinking was also intended to make PVA water‐insoluble and hence more useful in commercial applications. Examination of the composites indicated that HNTs were uniformly dispersed in both PVA as well as crosslinked PVA. Excellent mechanical properties of the HNT–PVA nanocomposites were achieved. These nanocomposites are intended to be composted at the end of their life rather than ending up in landfills as most of today's traditional petroleum based non‐biodegradable plastics. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

l-Phenylalanine amino acid functionalized multi walled carbon nanotube (MWCNT) as a reinforced filler for improving mechanical and morphological properties of poly(vinyl alcohol)/MWCNT composite

Carbon nanotube dispersion in polymer matrix is one of the most crucially important aspects in carbon nanotube/polymer composites. This paper is aimed to discuss the considerable improvement in dispersion of multi walled carbon nanotubes (MWNTs) in poly(vinyl alcohol) (PVA) matrix that was attained through bio-functionalization of MWCNTs. Initially, for getting better dispersion in water, pure MWCNTs have been functionalized by l-phenylalanine amino acid. The functionalized MWCNTs (f-MWCNTs) show much enhanced solubility in water. So, effects of modified MWCNT on dispersion in PVA matrix and certain properties of the resulting composites, like; mechanical, thermal and morphological properties were studied. The prepared composites were examined by Fourier transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. Also, the mechanical and thermal properties of composite films have been investigated and revealed that incorporation of just a few percent of f-MWCNTs can improve the PVA mechanical and thermal properties significantly.     

Preparation of Poly(Vinyl Alcohol) Nanocomposite Films Reinforced with Poly(Amide–Imide)/CuO Having N-trimellitylimido-L-valine Linkages for the Improvement of Mechanical and Thermal Properties

In this investigation, nanocomposite films were fabricated by dispersion of poly(amide–imide)/CuO nanocomposites as nanofiller in the poly(vinyl alcohol) matrix via an ultrasonic process. The nanofiller was prepared and mixed with PVA matrix. After dispersion of nanofiller into the poly(vinyl alcohol), the mechanical properties of the nanocomposites were improved. For example, the addition of 6 wt% nanofiller into the poly(vinyl alcohol) matrix enhanced the tensile modulus by 39%. The residual weight at 800°C was 7% for pure poly(vinyl alcohol) while the nanocomposites illustrated 12–19% residue at this temperature.     

A chitosan/poly(vinyl alcohol) nanocomposite film reinforced with natural halloysite nanotubes

Biodegradable polymer/clay nanocomposites have attracted tremendous attentions because of their excellent properties and ecofriendly advantages. In this article, a series of nanocomposite films were prepared by introducing of halloysite nanotubes (HTs) into chitosan (CS)/poly(vinyl alcohol) (PVA) matrix using the solution casting method, and the effect of HT as nanofillers on the properties of polymer/HT nanocomposites was explored. The results indicated that the tensile strength of CS/PVA/HT3 and elongation at break of CS/PVA/HT2 sharply increased by 39.72% and 26.14% in comparison with the pure CS/PVA film, respectively. The water resistance and thermal stability of polymer/HT nanocomposites were also improved compared with the pure CS/PVA film, but the optical property of the nanocomposite films was not affected by introducing HT into the CS/PVA matrix. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Preparation and characterization of graphene/poly(vinyl alcohol) nanocomposites

Graphene (GE)‐based nanocomposites are emerging as a new class of materials that hold promise for many applications. In this article, we present a general approach for the preparation of GE/poly(vinyl alcohol) (PVA) nanocomposites. The basic strategy involved the preparation of graphite oxide from graphite, complete exfoliation of graphite oxide into graphene oxide sheets, followed by reduction to GE nanosheets, and finally, the preparation of the GE/PVA nanocomposites by a simple solution‐mixing method. The synthesized products were characterized by X‐ray diffraction, field emission scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetry, and differential scanning calorimetry analysis. The GE nanosheets were well dispersed in the PVA matrix, and the restacking of the GE sheets was effectively prevented. Because of the strong interfacial interaction between PVA and GE, which mainly resulted from the hydrogen‐bond interaction, together with the improvement in the PVA crystallinity, the mechanical properties and thermal stability of the nanocomposites were obviously improved. The tensile strength was increased from 23 MPa for PVA to 49.5 MPa for the nanocomposite with a 3.25 wt % GE loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Indentation size effect and wear characteristics of spark plasma sintered,hard MWCNT/Al2O3 nanocomposites

Magnesia doped multiwalled carbon nanotube (CNT)/α-alumina nanocomposites have been fabricated by spark plasma sintering at 1500°C under 50 MPa in argon. Owing to combined grain refining effect of nanotube and magnesia, nanocomposites possessed smaller matrix grains and extensively lower matrix crystallites than pure alumina. Thermal expansion mismatch between matrix and filler rendered up to four times higher compressive lattice microstrain to the nanocomposites over pure alumina. Despite very low CNT loading (e.g. 0·13?wt-%), nanocomposites offered considerably higher hardness (as high as 24·42?GPa), negligible indentation size effect (Meyer exponent?=?1·906???1·941) and enhanced elastic response over pure alumina. Up to 0·27?wt-% nanotube loading, much higher wear resistance was observed for the nanocomposites over pure alumina. The presence of uniformly dispersed and structurally intact nanotubes coupled with lower matrix grains and crystallites having compressive lattice strain were the key factors behind achieving such improved mechanical properties of the present nanocomposites.     

Thermal cross-linking and anti-meltdrop properties of copolyester containing phosphorus/magnesium salt composites by in situ polymerization

Polyester is widely used in household products because of its good mechanical properties and wears resistance, but polyester is easy to ignite and inclined to produce droplet, so its application range is limited. The cross-linkable magnesium hydroxide nanoparticles were incorporated into flame-retardant polyester, which enables the phosphorus-containing copolyester with thermal cross-linking and anti-meltdrop properties. The nanoparticles were achieved by in situ polymerization and acted as a nucleating agent for improving the crystalline properties of the copolyester. Furthermore, the nanoparticles also enhanced anti-meltdrop properties and reduced the heat and gas release during the combustion process of the copolyester. The maximum heat release rate and total smoke release reduced by 39.8% and 74.4% compared with pure polyester. Specifically, the combustion products of the nanoparticles and phosphorus flame retardant could act a barrier role by covering the carbon layer to isolate air and heat, thereby resulting in excellent anti-meltdrop properties. The simple modification method reported here realizes the collaborative modification of flame retardant and anti-meltdrop properties of phosphorous flame-retardant copolyesters by thermal cross-linking.     

The utilization of poly(amide-imide)/SiO2 nanocomposite as nanofiller for strengthening of mechanical and thermal properties of poly(vinyl alcohol) nanocomposite films

The present investigation reports the preparation and characterization of the thermally stable poly(vinyl alcohol)/(poly(amide-imide)-SiO₂) nanocomposite (PVA/PAI-SiO₂ NC) films. For this reason, the surface of SiO₂ nanoparticles (NPs) was modified with N-trimellitylimido-l-methionine and subsequently, 5 wt.% of modified SiO₂ NPs were dispersed in the PAI matrix via sonochemical reaction. The resulting NC was studied by different techniques. Finally, the PAI-SiO₂ NC was employed as nanofiller and was incorporated into the PVA matrix for the enhancement of its mechanical and thermal properties. The synthesized NCs were studied by Fourier transform infrared and X-ray diffraction spectroscopy analysis. The surface topography and morphology of the NCs were studied by atomic force microscopy techniques, field emission scanning electron microscopy and transmission electron microscopy. The micrographs demonstrated that the nanofillers were homogeneously dispersed in the PVA matrix. The thermo gravimetric analysis curves indicated that the thermal decomposition of the PVA/PAI-SiO₂ NC films shifted toward higher temperature in comparison with the pure PVA. The effect of nanofiller on the mechanical properties of NC films was also explored.     

Effect of Nanoparticles on Mechanical and Flame-retardant Properties of Polyether-Block-Polyamide Polymer Nanocomposites

In this study, polyester elastomer-based thermoplastic (TPEE) nanocomposites were fabricated for flame-retardant applications. Small amounts of graphene and nanoclay were added to the nanocomposites to investigate their effects on the mechanical and thermal properties of the nanocomposites. The addition of a phosphorous flame-retardant additive resulted in a significant improvement of the Young’s modulus and thus yield stress in the synthesized nanocomposites as compared to those made with the virgin TPEE. There was no synergistic improvement in mechanical properties with the addition of graphene and nanoclay to the nanocomposites. However, thermal properties, mainly the heat deflection temperature and fire performance (UL-94 V0), were improved significantly by the addition of graphene and nanoclay and a synergistic effect was observed. Heat distortion temperature and thermogravimetric analysis were used to analyze the thermal properties of the nanocomposites. The UL-94 testing method was used to investigate the fire performance of the nanocomposites. Scanning electron microscopy was used to observe the polymer fracture surface morphology. The dispersion of the graphene and nanoclay particles was confirmed by transmission electron microscopy analysis.     

尼龙12/OMMT纳米复合粉末的制备及性能

利用十八烷基三甲基溴化铵(OTAB)对蒙脱土(MMT)进行有机改性,并通过溶液插层法制备尼龙12/有机蒙脱土(PA12/OMMT)纳米复合粉末。利用X射线衍射、傅立叶变换红外光谱、扫描电子显微镜等手段对改性后的MMT及PA12/OMMT纳米复合粉末的结构和微观形貌进行表征,并将复合粉末热压成型制成标准件,测试其力学性能和热性能。结果表明,经过有机改性,MMT的层间距由1.24 nm增加到了2.13 nm,且改性后的MMT能均匀地分散在PA12基体中,PA12/OMMT纳米复合粉末的成型件在拉伸强度、弯曲强度、冲击强度和热性能方面都优于纯PA12粉末。PA12/OMMT纳米复合粉末为选择性激光烧结技术(SLS)提供了一种性能良好的粉末材料。     

Magnesium hydroxide nanoparticles grafted by DOPO and its flame retardancy in ethylene-vinyl acetate copolymers

Magnesium hydroxide (MH) nanoparticles have been considered as an excellent nonhalogen flame-retardant. However, the drawbacks of easy aggregation and relatively low flame retardancy limit their applications in polymer materials. In this research, MH nanoparticles were successfully grafted by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) through the bridge of vinyl silane coupling agents (WD70). The grafted MH nanoparticles (MH-WD70-DOPO) were characterized by Fourier transform infrared spectra, ³¹P nuclear magnetic resonance spectra, thermogravimetric analysis, transmission electron microscopy, and X-ray photoelectron spectroscopy spectra. MH-WD70-DOPO nanoparticles were incorporated into ethylene-vinyl acetate copolymer (EVA) matrix by melt blending method. The results indicated that MH-WD70-DOPO nanoparticles were much homogenously dispersed in EVA matrix than unmodified MH particles. EVA/MH-WD70-DOPO nanocomposites with 51.32 wt% loading showed higher flame retardancy, better mechanical and processing properties compared with EVA/MH-WD70 sample. These findings could provide a novel method to enhance the flame-retardant efficiency of inorganic hydroxide flame retardants, while keeping good mechanical and processing properties of polymer materials.     

Evaluation and modeling of the mechanical behavior of carbon nanoparticle/rubber‐modified polyethylene nanocomposites

Recently, the production of polymers loaded with inorganic nanomaterials has been one of the most economical techniques playing a special role in improving the physical and mechanical properties of nanocomposites. Rubbers loaded with different concentrations of carbon nanoparticles (CNPs) were synthesized. The mechanical properties were tested according to standard methods. It was found that the properties of the investigated nanocomposites were improved, depending on the concentration of CNPs in the investigated composite. The optimum concentration was found to be 1.3 vol %. Affine deformation based on the Mooney–Rivilin model was used to visualize the effect of CNPs on the rubber. When polyethylene (PE) was added to rubber/CNPs at the optimum concentration (12.4 vol %), the modulus, tear resistance, and fatigue life were increased, whereas the tensile strength decreased, and the strain at rupture remained almost same. A crosslink model was used to explain the influence of PE on the rubber/CNP nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011