In‐situ thermal reduction and effective reinforcement of graphene nanosheet/poly (ethylene glycol)/poly (lactic acid) nanocomposites

This study aims to achieve a molecule‐level dispersion of graphene nanosheets (GNSs) and a maximum interfacial interaction between GNSs and a polymer matrix. GNS‐reinforced poly (ethylene glycol) (PEG)/poly (lactic acid) (PLA) nanocomposites are obtained by a facile and environment‐friendly preparation method. Graphite oxide and GNSs are characterized by atomic force microscopy, Raman spectroscopy, and X‐ray diffraction. Scanning electron microscopy shows that the state of dispersion of the GNS in the PEG/PLA matrix is distribution. The tensile strength and Young's modulus increases by 45% and 188%, respectively, with the addition of 4.0 wt% GNSs. The thermal stability of the GNS‐based nanocomposites also improves. Differential scanning calorimetry indicates that GNSs have no remarkable effect on the crystallinity of the nanocomposites. The effective reinforcement of the nanocomposites is mainly attributed to the highly strong molecular‐level dispersion of the GNSs in the polymer matrix. Copyright © 2014 John Wiley & Sons, Ltd.     

Non-isothermal crystallization of ethylene-vinyl acetate copolymer containing a high weight fraction of graphene nanosheets and carbon nanotubes

The effect of the different geometrical dimensionality of two dimensional graphene nanosheets(2D GNSs) and one dimensional carbon nanotubes(1D CNTs) on the non-isothermal crystallization of an ethylene-vinyl acetate(EVA) copolymer at high loading(5 wt%) was studied.Transmission electron microscopy indicated a homogeneous dispersion of GNSs and CNTs in EVA obtained by a solution dispersion process.Fourier-transform infrared spectroscopy and differential scanning calorimetry measurements showed that 1D CNTs and 2D GNSs acted as effective nucleating agents,with a noticeably increased onset crystallization temperature of EVA.A high weight fraction of nano-fillers slowed the overall crystallization rate of composites.At the same crystallization temperature,the crystallization behavior of GNS/EVA composites was slowed compared to that of the CNT/EVA ones owing to larger nucleus barrier and activation energy of diffusion.Dynamic mechanical relaxation and rheology behavior of CNT/EVA and GNS/EVA composites demonstrated that the planar structure of the GNSs had an intensively negative effect on EVA chain mobility due to interactions between nanofillers and polymer chains,as well as spatial restriction.     

A DFT study of H<Subscript>2</Subscript>CO and HCN adsorptions on 3<Emphasis Type="Italic">d</Emphasis>, 4<Emphasis Type="Italic">d</Emphasis>, and 5<Emphasis Type="Italic">d</Emphasis> transition metal-doped graphene nanosheets

The binding of 3d (Sc, Ti, V), 4d (Y, Zr, Nb), and 5d (La, Hf, Ta) transition metals on graphene nanosheet (TM–GNS) with hydrogen-terminated edges and the adsorption of H₂CO and HCN molecules on the pristine and TM-doped GNSs were theoretically studied using a density functional theory method. The calculation showed that all TM atoms had strong binding with GNS, in which the Ta atom displayed the strongest interaction with GNS. The H₂CO and HCN molecules showed much stronger adsorption on the TM–GNSs than that on the pristine GNS. The H₂CO showed stronger interactions with TM–GNSs than that of HCN, in which the Ta-doping displayed the strongest interactions between the GNS and H₂CO or HCN. The adsorption interactions induced dramatic changes of TM–GNS electronic properties. The results revealed that the adsorption strength and sensor ability of GNS can be greatly improved by introducing appropriate TM dopants. Therefore, TM-doped GNSs are suitable for application in H₂CO and HCN storage and sensor.     

β-羟基丁酸与β-羟基戊酸共聚物 (PHBV)/蒙脱土纳米复合材料的结构与性能

用溶液复合法成功地制备了插层型PHBV／蒙脱土纳米复合材料。采用X射线衍射（XRD）和透射电子显微镜（TEM）研究了复合材料的结构，硅酸盐片层间距从1.8nm升至2.4nm左右。同时研究了复合材料的结晶，熔融，动态力学行为和力学性能，发现有机蒙脱土的加入，可以加快PHBV的结晶,降低熔融温度，使基体的玻璃化转变温度升高，提高了材料的力学性能，有机蒙脱土含量在3％时，其综合性能最佳。     

Influence of graphene nanosheets on stereocomplex crystallization behaviors of star‐shaped poly (D(L)‐lactide) stereoblock copolymer

The nanocompsites of star‐shaped poly(D‐lactide)‐co‐poly(L‐lactide) stereoblock copolymers (s‐PDLA‐PLLA) with two‐dimensional graphene nanosheets (GNSs) were prepared by solution mixing method. Crystallization behaviors were investigated using differential scanning calorimetry, polarized optical microscopy, and wide angle X‐ray diffraction. The results of isothermal crystallization behaviors of the nanocompsites clearly indicated that the GNS could remarkably accelerate the overall crystallization rate of s‐PDLA‐PLLA copolymer. Unique stereocomplex crystallites with melting temperature about 207.0°C formed in isothermal crystallization for all samples. The crystallization temperatures of s‐PDLA‐PLLAs shifted to higher temperatures, and the crystallization peak shapes became sharper with increasing GNS contents. The maximum crystallization temperature of the sample with 3 wt% GNS was about 128.2°C, ie, 15°C higher than pure s‐PDLA‐PLLA. At isothermal crystallization processes, the halftime of crystallization (t_0.5) of the sample with 3 wt% GNS decreased to 6.4 minutes from 12.9 minutes of pure s‐PDLA‐PLLA at 160°C.The Avrami exponent n values for the nanocomposites samples were 2.6 to 3.0 indicating the crystallization mechanism with three‐dimensional heterogeneous nucleation and spherulites growth. The morphology and average diameter of spherulites of s‐PDLA‐PLLA with various GNS contents were observed in isothermal crystallization processes by polarized optical microscopy. Spherulite growth rates of samples were evaluated by using combined isothermal and nonisothermal procedures and analyzed by the secondary nucleation theory. The results evidenced that the GNS has acceleration effects on the crystallization of s‐PDLA‐PLLA with good nucleation ability in the s‐PDLA‐PLLA material.     

Influence of the graphite type on the synthesis of polypropylene/graphene nanocomposites

In this work, the synthesis of polypropylene (PP)/graphene nanosheet (GNS) nanocomposites by in situ polymerization using metallocene catalysts was studied. Initial reactions were performed using rac‐Et(Ind)₂ZrCl₂ and rac‐Me₂Si(Ind)₂ZrCl₂ catalysts to select the best one to obtain good molecular weight, thermal properties, and tacticity. Subsequently, PP nanocomposites with different loadings of GNS were obtained. GNS from two different sources [Graphite Nacional (GN) and Graphite Aldrich (GA)] have been used, and the differences between the obtained nanocomposites were evaluated. The GNS and nanocomposites were studied by scanning electronic microcopy, transmission electronic microcopy, and X‐ray diffraction. They showed that the GN nanosheets had lower crystal size and diameter than the GA nanosheets and dispersed better in the PP matrix. Differential scanning calorimetry analyses of both types of nanocomposites showed an increase in the crystallization temperature with increasing graphite loading. The polymeric materials were also characterized by GPC, thermogravimetric analysis, and ¹³C NMR. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Replication and surface properties of micro injection molded PLA/MWCNT nanocomposites

Multi-walled carbon nanotube (MWCNT) reinforced polylactide (PLA) nanocomposites were injected molded into a mold with micro needle patterns. In order to alleviate the hesitation effect caused by an increased melt viscositgy of PLA/CNT nanocomposites, the effects of the injection speed and holding pressure on the replication property were investigated. The effects of MWCNTs on the crystallization, thermal behavior, replication properties, replication and surface properties of micro injection molded PLA/CNT nanocomposites were investigated. An analysis of crystallinity and thermal behavior indicated that the MWCNTs promoted the unique α’ to α crystal transition of PLA, leading to an enhancement of surface modulus and hardness, as measured using a nanoindentation technique. The specific interaction between PLA and MWCNTs was characterized using an equilibrium melting point depression technique. Furthermore, the MWCNTs increased the activation energy for thermal degradation of PLA due to the physical barrier effect. The improved replication quality of the microfeatures in the PLA/MWCNT nanocomposites has been achieved by elevating injection speed and holding pressure, which enhances the polymer filling ability within the micro cavity. A replication ratio greater than 96% for the micro injection molded PLA/CNT nanocomposites were achieved at holding pressure of 100 MPa and injection speed of 120 mm/s. This study shows that processing conditions significantly influence the replication and surface properties of micro injection molded PLA/CNT nanocomposites.     

Nonisothermal crystallization and morphology of poly(butylene succinate)/layered double hydroxide nanocomposites

Biodegradable poly(butylene succinate) (PBS) and layered double hydroxide (LDH) nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within PBS matrix were characterized by transmission electron microscopy (TEM), which showed that LDH nanoparticles were found to be well distributed at the nanometer level. The nonisothermal crystallization behavior of nanocomposites was extensively studied using differential scanning calorimetry (DSC) technique at various cooling rates. The crystallization rate of PBS was accelerated by the addition of LDH due to its heterogeneous nucleation effect; however, the crystallization mechanism and crystal structure of PBS remained almost unchanged. In kinetics analysis of nonisothermal crystallization, the Ozawa approach failed to describe the crystallization behavior of PBS/LDH nanocomposites, whereas both the modified Avrami model and the Mo method well represented the crystallization behavior of nanocomposites. The effective activation energy was estimated as a function of the relative degree of crystallinity using the isoconversional analysis. The subsequent melting behavior of PBS and PBS/LDH nanocomposites was observed to be dependent on the cooling rate. The POM showed that the small and less perfect crystals were formed in nanocomposites.     

Functionalized graphene/thermoplastic polyester elastomer nanocomposites by reactive extrusion‐based masterbatch: preparation and properties reinforcement

A reactive extrusion process was developed to fabricate polymer/graphene nanocomposites with good dispersion of graphene sheets in the polymer matrix. The functionalized graphene nanosheet (f‐GNS) activated by diphenylmethane diisocyanate was incorporated in thermoplastic polyester elastomer (TPEE) by reactive extrusion process to produce the TPEE/f‐GNS masterbatch. And then, the TPEE/f‐GNS nanocomposites in different ratios were prepared by masterbatch‐based melt blending. The structure and morphology of functionalized graphene were characterized by Fourier transform infrared, X‐ray photoelectron spectroscopy, X‐ray diffraction and transmission electron microscopy (TEM). The incorporation of f‐GNS significantly improved the mechanical, thermal and crystallization properties of TPEE. With the incorporation of only 0.1 wt% f‐GNS, the tensile strength and elongation at break of nanocomposites were increased by 47.6% and 30.8%, respectively, compared with those of pristine TPEE. Moreover, the degradation temperature for 10 wt% mass loss, storage modulus at ?70°C and crystallization peak temperature (T_cp) of TPEE nanocomposites were consistently improved by 17°C, 7.5% and 36°C. The remarkable reinforcements in mechanical and thermal properties were attributed to the homogeneous dispersion and strong interfacial adhesion of f‐GNS in the TPEE matrix. The functionalization of graphene was beneficial to the improvement of mechanical properties because of the relatively well dispersion of graphene sheets in TPEE matrix, as suggested in the TEM images. This simple and effective approach consisting of chemical functionalization of graphene, reactive extrusion and masterbatch‐based melt blending process is believed to offer possibilities for broadening the graphene applications in the field of polymer processing. Copyright © 2014 John Wiley & Sons, Ltd.     

β-羟基丁酸与β-羟基戊酸共聚物 (PHBV)/蒙脱土纳米复合材料的等温结晶动力学

用差热量热分析（DSC）方法研究了β－羟基丁酸与β－羟基戊酸共聚物（PHBV）／蒙脱土纳米复合材料的等温结晶行为。结果表明，PHBV的Avrami方程指数n、成核机理、结晶生长方式基本不受蒙脱土的影响，加入少量的蒙脱土可明显降低PHBV结晶成核自由能，使其结晶速率增大。     

Novel nanocomposite based on EVA/PHBV/[60]Fullerene with improved thermal properties

A novel nanocomposite was prepared from ethylene-co-vinyl acetate copolymer (EVA) and poly-3-hydroxy butyrate-co-valerate (PHBV) in combination with small amounts of [60]Fullerene (C₆₀). The thermal degradation as well as the incorporation effect of C₆₀ on the thermo-oxidative decomposition of EVA/PHBV/C₆₀ nanocomposites was investigated using thermogravimetric analysis (TGA). In order to assess the level of stabilization of nanocomposites, the oxidation induction time test was also determined. The obtained results indicated that the dispersion of C₆₀ even at low loading (0.3, 0.5 and 0.7 wt.%) exerts a significant increase on the thermal stability properties of nanocomposite. The oxidation induction time values of nanocomposites were remarkably increased with the increase of C₆₀ amounts. Surprisingly, the oxidation induction time of EVA/PHBV/C₆₀ (0.3 wt.%) is 1643 s higher than that of unfilled EVA/PHBV blend.The flammability properties investigated in pyrolysis combustion flow calorimetry (PCFC) showed that the addition of C₆₀ could prolong the time to peak of Heat Release Rate (pHRR) of around 30 °C compared to EVA/PHBV blend. It was demonstrated that C₆₀ is inhibitor of the thermal and thermo-oxidative degradation of EVA/PHBV blend.     

Synthesis,stereocomplex crystallization and properties of poly(l‐lactide)/four‐armed star poly(d‐lactide) functionalized carbon nanotubes nanocomposites

Functionalized carbon nanotubes (F‐CNTs) were synthesized through the nucleophilic substitution reaction between four‐armed star poly(d ‐lactide) (4PDLA) and acryl chloride of carbon nanotubes and were characterized using Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy and thermogravimetric analysis. The results indicated that the 4PDLA was successfully grafted onto carbon nanotubes, and it contained 45.5 wt% of 4PDLA. Poly(l ‐lactide) (PLLA) nanocomposites with different F‐CNTs content were prepared by solution casting. Optical microscopy and scanning electron microscopy results showed that F‐CNTs were uniformly dispersed in the nanocomposites. Crystallization behavior and crystal structure of PLLA nanocomposites were investigated using differential scanning calorimetry, polarizing microscope and X‐ray diffraction. The results found that poly(lactide) stereocomplex crystal could be formed between PLLA and F‐CNTs. F‐CNTs played different roles in the process of solution casting and melting crystallization. Polarizing microscope also revealed that crystallization temperature had a significant effect on the nucleation and spherulites growth of PLLA. Thermal stability and mechanical properties of the nanocomposites were also investigated by thermogravimetric analysis, dynamic mechanical analysis and tensile testing. These results demonstrated that the addition of F‐CNTs obviously improved thermal stability and tensile strength of PLLA. The results showed that PLLA/F‐CNTs would have potential values in engineering fields. Copyright © 2015 John Wiley & Sons, Ltd.     

Tribological properties of graphene nanosheets as an additive in calcium grease

The addition of graphene nanosheets (GNSs) in lubricating grease could significantly reduce the interfacial friction and improve the load-bearing capacity of the parts. Therefore, it has been considered as having great potential as lubricant additives. In this study, we synthesized GNSs that are prepared by a modified Hummer method, and investigated the effect of GNS with different concentration (0.5%, 1%, 2%, 3%, and 4?wt%) on the tribological properties of the calcium grease. The friction and wear experiments were performed using a four-ball tribometer. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were employed to examine the GNS and the friction mechanisms. Results indicate that the friction reduction ability and anti-wear property of the base grease can be improved with the addition of GNS. It was also found that the friction reduction decreases by 61%, and the wear scar diameter (WSD) decreases by 45%, and the extreme-pressure (EP) properties increased 60% at 3?wt% GNS. It is clear that the GNS in grease easily forms protective deposited films to prevent the rubbing surfaces from coming into direct contact, thereby improving the entire tribological behavior of the grease.     

Morphology, crystallization and mechanical properties of poly(ɛ-caprolactone)/graphene oxide nanocomposites

A series of nanocomposites based on poly(ε-caprolactone) (PCL) and graphene oxide (GO) were prepared by in situ polymerization. Scanning electron microscopy observation revealed not only a well dispersion of GO but also a strong interfacial interaction between GO and the PCL matrix, as evidenced by the presence of some GO nanosheets embedded in the matrix. Effects of GO nanofillers on the crystal structure, crystallization behavior and spherulitic morphology of the PCL matrix were investigated in detail. The results showed that the crystallization temperature of PCL enhanced significantly due to the presence of GO in the nanocomposites, however, the addition of GO did not affect the crystal structure greatly. Thermal stability of PCL remarkably increased with the addition of GO nanosheets, compared with that of pure PCL. Incorporation of GO greatly improved the tensile strength and Young’s modulus of PCL without a significant loss of the elongation at break.     

Influence of graphene nanoscrolls on the crystallization behavior and nano‐mechanical properties of polylactic acid

Graphene nanoscrolls (GNS), one‐dimensional carbon‐based nanomaterials, have been predicted to possess extraordinary characteristics due to their unique open topology with scrolled graphene monolayers. In this study, the conversion of planar 2‐D graphene nanoplatelets (GNPs) to tubular and scrolled 1‐D GNSs is described. The effects of GNS as a nucleating agent to modulate the morphology, crystallization, and nano‐mechanical properties of polylactic acid (PLA) were studied. The nucleating effect of GNS and its unique topological characteristics proves to influence the crystallization of PLA. Fourier transform infrared (FTIR) spectroscopy indicated nonpreferential interactions of PLA chains around GNS due to the bulky and helical PLA macromolecular chains. Superior interfacial interactions and strain in GNS provide better load transfer between GNS and PLA matrices, resulting in higher modulus and hardness. This study is the first detailed analysis to elucidate the role of unique GNS to favorably modulate the properties of a polymer.     

聚碳酸亚丙酯对聚(β-羟基丁酸酯-β-羟基戊酸酯)结晶行为的影响

用FTIR和DSC研究了PHBV及其与聚碳酸亚丙酯(PPC)熔融共混样的熔融结晶行为和等温结晶动力学.结果表明,PHBV与PPC熔融共混过程中发生了酯交换反应,两组分间存在一定的相互作用.PPC虽然能降低PHBV结晶折迭链的表面自由能,但同时也能够降低PHBV的结晶度、球晶径向生长速率、平衡熔点和结晶能力.     

Mechanical, thermal and degradation properties of poly(d,l-lactide)/poly(hydroxybutyrate-co-hydroxyvalerate)/poly(ethylene glycol) blend

The mechanical, thermal and biodegradable properties of poly(d,l-lactide) (PDLLA), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(ethylene glycol) (PEG) blends were studied. The influence of PEG on the tensile and impact strengths of the blends was investigated. The results showed that the toughness and elongation at break of the PDLLA/PHBV (70/30) blends were greatly improved by the addition of PEG, and the notched Izod impact strength increased about 400% and the elongation at break increased from 2.1% to 237.0%. The thermal and degradation properties of the blends were investigated by differential scanning calorimeter (DSC) and thermogravimetric analyzer (TGA), it was found that the thermal stability of PHBV in the presence of PDLLA was improved. The degradation test showed that the addition of PEG could notably accelerate the biodegradation of the blends in the soil at room temperature, and the mass loss is about 20% after 30 days of the storage.     

Graphene-based multifunctional iron oxide nanosheets with tunable properties

We report the synthesis of graphenes with tunable properties due to the growth of needlelike iron oxide (IO) nanoparticles on their surfaces. The electrical conductivity, flexibility, and magnetic properties of graphene nanosheets (GNSs) could be tuned on demand by fine controlling both the surface coverage and the length of the IO nanoneedles. The degree of coverage of the IO nanoparticles on the surface of the GNSs made it possible to control the resulting properties of the IO/GNSs on demand. As examples of their utility, paperlike materials were generated by simple filtration, and the resulting IO/GNS nanocomposites showed extraordinary removal capacity and fast adsorption rates for As(V) and Cr(VI) ions in water. Another possible application is the preparation of multifunctional films equipped with conductivity, flexibility, and magnetic properties. The fabrication process is easy to scale up at a low cost. In addition, both the colloidal solution and film forms of the resulting IO/GNSs were effective for removal of heavy metal ions, meaning this material could be utilized for actual industrial applications.     

不相容PHBV/PS、PHBV/PMMA结晶/非晶共混体系的结晶行为研究

在不同的共混比例、不同的结晶温度下对不相容PHBV/PS、PHBV/PMMA结晶/非晶共混体系的结晶行为做了系统的研究.研究发现当PHBV含量为75wt%时,共混体系仍然和纯PHBV一样生成环带球晶;而当PHBV含量为50wt%时,共混体系在略低于非晶组分玻璃化转变温度时呈现花瓣状的球晶形貌;当PHBV含量为25wt%时,PHBV/PS体系出现不规则的晶体形貌,而PHBV/PMMA体系在偏光显微镜下没有观察到晶体.在这种不相容共混体系中,非晶组分的分散状态以及共混比例对共混体系中PHBV环带球晶的形成起到决定性的作用,而非晶组分对PHBV球晶的片晶前端生长的影响是形成花瓣状球晶的主要原因.     

Study on formation of poly(β-hydroxybutyrate-co-hydroxyvalerate) (PHBV) fiber

In this paper, the crystallization behavior, thermal degradation properties, rheological behavior and the spinnability of poly(β-hydroxybutyrate-co-hydroxyvalerate) (PHBV) fiber were studied. Experimental results indicated that the spherulite growth rate of PHBV was very slow and its size was very large. PHBV began to degrade above 170°C. The flowing curve indicated that the processing temperature and the residential time had important effects on PHBV melts. When the equipment of melting spinning was improved and processing conditions were strictly controlled, the mechanical properties of the PHBV filament can comply with the requirements of the American Pharmacopoeia. __________ Translated from Journal of Donghua University (Natural Science Edition), 2007, 33(4): 425–430