Effect of surface modified hydroxyapatite on the tensile property improvement of HA/PLA composite

In this study, we modified the surface of hydroxyapatite (HA) particle by ring-opening polymerization of lactide (LA). The modified HA particles were characterized by IR and TGA. It was shown that LA could be graft-polymerized onto the surface of HA. A series of composites based on modified HA/PLA were further prepared and characterized. It indicated that the modified HA particles were well dispersed in PLA matrix than unmodified HA particles and the adhesion between HA particle and PLA matrix was improved. The modified HA/PLA composites showed good mechanical properties than that of unmodified HA/PLA.     

Study of surface properties of blend films using stereocomplexation between enantiomeric polylactide chains

This study investigated the stereocomplex-induced surface structure of enantiomeric poly(lactide) (PLA) blend films by differential scanning calorimeter, electron spectrometer for chemical analysis, and contact angle measurements. The design of the blend systems is based on principles of surface segregation of a modified component with a low surface energy, fluorocarbons (F), as an end group. The two blend systems, uncomplexed (F-l-PLA/l-PLA) and complexed (F-l-PLA/d-PLA), showed quite different surface structures: the surface segregation of fluorocarbon groups in the (F-l-PLA/l-PLA) blend film was observed while the surface structure of the (F-l-PLA/d-PLA) blend film was similar to its bulk one. This indicates that the interchain interaction to form stereocomplexes between l- and d-PLA is strong enough to overcome the driving force of fluorocarbon groups toward the surface.     

Interface tailoring of layered silicate/styrene butadiene rubber nanocomposites

To improve the interfacial interaction in clay/SBR nanocomposites prepared by latex compounding method, a novel clay modification for the nanocomposites was introduced before latex compounding with SBR using three kinds of organic modifiers, namely, hexadecyl trimethyl ammonium bromide (C16), bis(hexadecyl) dimethyl ammonium bromide (DC16) and 3-aminopropyl triethoxy silane (KH550). On the other hand, bis(triethoxysilylpropyl)tetrasulfide (Si69) was added into the KH550 modified clay/SBR nanocomposite during later mechanical blending, and was designed to interact with both KH550 and rubber and thus improve the interface. Structure changes of the nanocomposites were followed by study of X-ray diffraction, transmission electron microscopy and rubber process analyzer. Dynamic mechanical analysis and tensile tests were carried out to obtain information about the mechanical properties of the nanocomposites. The results revealed that, with the organic modification, clay was dispersed finely in the rubber matrix with part rubber-intercalated or part modifier-intercalated structure. Compared with the unmodified nanocomposite, the tensile strength, the stress at 300% strain, and the tear strength of modified SBR–clay nanocomposites were significantly improved. Moreover, the type of modifiers and strength of interfacial interaction determined the properties of the nanocomposites. The incorporation of KH550 and Si69 brought the best modification effect among all the modification methods.     

Ru decorated Pt nanoparticles by a modified polyol process for enhanced catalytic activity for methanol oxidation

Ru decorated Pt nanoparticles on carbon nanotubes (MWCNTs) were prepared by a modified polyol synthesis method for enhanced catalytic activity for methanol oxidation. The characterizations for the electrocatalysts were carried out by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV) and chronoamperometry (CA). The modified polyol synthesis method promoted position-controlled nucleation and growth of Ru atoms near Pt, and resulted in improved durability against catalyst poisoning compared to PtRu/MWCNTs prepared by common polyol method. This concept also allowed a high loading and dispersion of the catalyst on the carbon supports with few agglomerations of catalyst nanoparticles, resulting in high catalytic activity.     

Preparation, characterization and surface morphology of novel optically active poly(ester-amide)/functionalized ZnO bionanocomposites via ultrasonication assisted process

Novel bionanocompoites (BNCs) were prepared using zinc oxide (ZnO) nanoparticles which functionalized by γ-methacryloxypropyltrimethoxysilane (KH570) as a coupling agent. Poly(ester-amide) (PEA) based on tyrosine natural amino acid was synthesized and used as a polymer matrix. PEA/ZnO BNCs were characterized by fourier transform infrared spectra (FT-IR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and transmission electron microscopy (TEM). All the results confirmed that the surface of ZnO particle has sufficient compatibility with PEA through the link of the coupling agent between ZnO and polymer and also proved that the presence of ZnO nanoparticles appeared to be dispersed in nanosize in polymer composite matrix. In addition, thermogravimetric analysis (TGA) data indicated an enhancement of thermal stability of new BNC materials compared with the pure polymer.     

Crystallization Behavior of Poly(Lactic Acid) Filled with Modified Carbon Black

A novel method was employed to modify the surface of carbon black (CB) by an organic small molecule in a Haake Rheomix mixer. The modified carbon black (MCB) was dispersed uniformly in poly(lactic acid; PLA). The crystallization behaviors of PLA, PLA/CB and PLA/MCB composites were investigated by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS) and polarizing optical microscopy. It is found that the addition of CB or MCB can influence the crystallization behavior of PLA. PLA/MCB has a faster crystallization rate and higher crystallization peak temperature than PLA/CB. For non-isothermal studies, Jeziorny and Mo equations were employed. The Mo equation can well describe the non-isothermal crystallization of the three samples. For PLA/CB and PLA/MCB composites containing 3wt% fillers, the nucleating activity for CB is about 0.32, and about 0.16 for MCB. All these results show that MCB is an effective nucleating agent. PLA/MCB has a higher nucleation rate than PLA/CB because of the finer dispersed particles size and improved interaction between MCB and PLA.     

Microwave-induced high surface functionalization of multi-walled carbon nanotubes for long-term dispersion in water

Multi-walled carbon nanotubes (MWCNTs) were functionalized by monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA) by a rapid microwave-assisted method. Surface functional groups and morphology of MWCNTs were analyzed by ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, Raman spectroscopy and transmission electron microscopy. The water dispersibility of samples was also measured over time and compared with that of MWCNT functionalized by ethylenediamine (EDA). Accordingly, the dispersibility was in the sequence MEA-MWCNTs > DEA-MWCNTs > TEA-MWCNTs > EDA-MWCNTs > pristine MWCNTs. The significant long-term dispersibility of MEA-MWCNTs was related to its exceptionally high surface functionalization (89.3 %) and lack of chemical bridging between adjacent MWCNTs. This strategy, along with the low-cost functionalizing agents, could pave the way for large-scale dispersion of CNTs in the polar solvents.     

Effects of different carbon precursors on synthesis of multiwall carbon nanotubes: Purification and Functionalization

Cyclohexanol and xylene were used as carbon precursors, for synthesis of multiwall carbon nanotubes (MWCNTs) arrays in a CVD system at temperature of 750 °C, using nitrogen as carrier gas and ferrocene as catalyst. Different characterization methods were employed to compare the MWCNTs structure synthesized by these two precursors. All scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and Raman spectroscopy results illustrated that using cyclohexanol could significantly reduce formation of amorphous carbon and catalyst particles in the as-grown CNTs. The less amorphous carbon can be attributed to in situ oxidation in presence of oxygen atom of cyclohexanol. Characterizations showed that MWCNTs with high purity could be obtained using cyclohexanol as carbon precursor. The as-grown MWCNTs were purified by oxidation and acid treatment. Characterization of the purified MWCNTs using HNO₃/H₂SO₄ (1/3 or 1/1), 8 M HCl or 8 M HNO₃ was carried out. The results showed that 8 M HNO₃ could be considered as the best chemical to obtain more pure MWCNTs, less amorphous and metal particles and less damaged MWCNTs. The Raman spectroscopy results demonstrated that HNO₃/H₂SO₄ (1/3) treatment could more disorder the MWCNTs structure and this was attributed to the bigger destroying effect of this acid treatment. Furthermore, the TEM analysis of MWCNTs before and after acid treatment revealed that acid treatment could remove encapsulated catalyst particles. The FTIR analysis illustrated that purification of the MWCNTs with nitric acid could connect the functional groups onto the outer surface of MWCNTs and this resulted in more dispersion of the MWCNTs in water.     

Functionalization of multiwalled carbon nanotubes for reinforcing of poly(l-lactide-co--caprolactone) biodegradable copolymers

Up to now, synthetic polymers and biomacromolecules have been grafted or assembled onto the convex surface of carbon nanotubes (CNTs) via covalent bonds or chemisorptions. In this research, poly(l-lactide-co--caprolactone)-functionalized multiwalled carbon nanotubes (MWCNT-OH-g-PCLA)s are synthesized by in situ ring-opening copolymerization of l-lactide (LA) and -caprolactone (CL) using stannous octanoate and hydroxylated MWCNTs (MWCNT-OHs) as the initiating system. The pristine MWCNTs are modified to possess carboxyl groups and then hydroxyl groups. MWCNT-OHs are used as coinitiators to polymerize LA and CL by the surface-initiated ring-opening polymerization. The FT-IR spectra, SEM and TEM micrographs revealed that the PCLA grafted form the sidewall of MWCNTs strongly. The TGA analysis indicates that about 75 wt% of functionalized MWCNTs with PCLA belongs to grafted PCLA and the remaining 25 wt% to the initial MWCNT-OH.     

Preparation and Properties of Nano‐SiO2/Epoxy Composites Cured by Mannich Amine

Nano‐SiO₂/epoxy composites cured by Mannich Amine (type T‐31) were prepared and studied and the results are reported in this paper. The nano‐SiO₂ was pretreated by a silane coupling agent (type KH‐550) and mixed with epoxy resin (type E‐51) using an ultrasonic processor. Amounts of filler loading ranged from 1% to 5% of the weight of the epoxy resin. Some properties of the resulting composites were characterized by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results of tensile tests and impact tests showed that the composite with 3% nano‐SiO₂ loading presented the best mechanical performances. The tribological performance and thermal stability of the materials were also improved with the addition of nano‐SiO₂.     

Effects of corona discharge on the surface structure, morphology and properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were modified by corona discharge and then heat treated in the air. The influences of corona discharge parameters such as treatment time and processing power were investigated. The results of energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA) indicated the introduction of oxygen-containing functional groups onto the surface of the MWCNTs after heat treatment. The water contact angle tests showed that the hydrophobicity of the MWCNTs was decreased to some extent. The static water contact angle was reduced from 146° to 122° when the time of the corona discharge treatment reached 3 min at the processing power of 200 W. The enhanced thermomechanical and mechanical properties of epoxy nanocomposites filled with the corona discharge treated MWCNTs were observed. The modified MWCNTs conferred better properties on the composites than the pristine MWCNTs because of the improved dispersion of MWCNTs in matrix and the enhanced interfacial interaction between the treated MWCNTs and epoxy.     

Deposition of silver nanoparticles on carbon nanotube by chemical reduction method: Evaluation of surface,thermal and optical properties

Silver was stabilized on multi-walled carbon nanotubes (MWCNTs) by chemical-reduction technique using N,N-dimethylformamide (DMF) as a reducing agent. The influence of silver on the performance of carbon nanotubes (CNTs) was investigated by employing Fourier-transform infrared spectra (FTIR), Raman spectroscopy (RAS), thermal gravimetric analysis (TGA), zeta potential measurement, scanning electron microscope (SEM), electron dispersive X-ray spectrometer (EDX), transmission electron microscopy (TEM), and reflectance spectroscopy (RS). FTIR as well as RS methods evidenced the synthesis procedure using chemical reduction method was successful. Performing TGA of the samples under oxygen atmosphere demonstrated that the silver nanoparticles (Ag NPs) generated on MWCNTs surface can decrease the thermal stability of the particles by the catalytic oxidation of CNTs. In contrary, the thermal stability of the MWCNTs has improved under nitrogen atmosphere. EDX results showed the presence of Ag, Au and Co on the surface of deposited sample. The synthesised silver multi-walled carbon nanotubes (Ag–MWCNTs) were found to have higher UV reflection activity compared with untreated particles. The Ag–CNTs can be used in producing anti-UV composites.     

Sulfur grown around carbon nanotubes as a cathode material for Li/S battery

Sulfur/multi-walled carbon nanotubes (MWCNTs) composites have been successfully prepared by an in situ growth strategy as a cathode material for lithium/sulfur battery. The microstructure and morphology of the sulfur/MWCNTs composites are characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). From the results, it is found that the nano-sulfur (shell) grows around the MWCNTs (core) and is well-dispersed over the whole surface of the MWCNTs. Tested by coin type cells, the composite materials exhibited the sulfur utilization approaching to 78% for the first cycle, the capacity retention closing to 84% after 100 cycles at various rates. The excellent electrochemical performance could be attributed to the nano-size sulfur and the homogeneous distribution of sulfur on MWCNTs matrix, resulting from this novel in situ growth method, which not only enhances the reactive activity of sulfur during charge–discharge processes but also provides stable electrical and ionic transfer channels.     

Mild hydrothermal treatment to prepare highly dispersed multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) with improved dispersion property have been prepared by a mild and fast hydrothermal treatment. The hydrothermal process avoids using harsh oxidants and organic solvents, which is environmental friendly and greatly decreases the damage to intrinsic structure of MWCNTs. The modified MWCNTs were highly soluble in polar solvents such as water, ethanol and dimethylformamide. Morphological observation by TEM indicated that the diameter and inherent structure were well reserved in modified MWCNTs. X-ray photoelectron spectroscopy and Raman spectroscopy were used to quantify functional groups created on the MWCNT surface, and to determine rational parameters of hydrothermal process.     

红外光谱法测定聚(乳酸-苯丙氨酸)共聚物的含量

分别以苯丙氨酸和乳酸为原料合成了3-苯甲基-2,5-吗啉二酮(PMD)与丙交酯(LA),以PMD和LA作为聚合单体经开环聚合分别得到PMD均聚物(PPMD)、丙交酯均聚物(PLA)及聚(乳酸-苯丙氨酸)共聚物。对合成的均聚物进行红外分析,确定1 671.53和870.82 cm-1处的吸收峰分别为PPMD和PLA的特征峰。根据以上两种特征吸收峰并以朗伯-比耳定律为理论依据,建立了利用红外光谱法测定聚(乳酸-苯丙氨酸)共聚物含量的方法。实验测定的标准工作曲线为y=0.055 67x+0.1091,r=0.999 3。利用该标准工作曲线定量测定了共聚物组分含量,其结果与1H NMR测定值一致,相对误差在2％以内,证明红外光谱法可方便、快捷地测定聚(乳酸-苯丙氨酸)共聚物组分含量,且适用于其他聚(乳酸-氨基酸)共聚物的含量测定,具有一定的实用性及推广性。     

RTV Silicone Rubber Filled with Surface Modified Montmorillonite

The surface modification of pristine montmorillonite (MMT) with four kinds of coupling agents for reinforcement of the room temperature vulcanized vinyl-terminated polydimethylsiloxane (RTV PDMS) networks was investigated. The four coupling agents containing γ-glycidoxypropyltrimethoxysilane (KH-560), γ-methacryloxypropyltri methoxysilane (KH-570), isopropyl trioleic titanate (NDZ-105), and stearic acid (SA) without N, P, or S compounds were used because the coupling agents harmless to the platinum catalyst used normally in the curing of RTV vinyl-terminated PDMS. The interaction between MMT particles and coupling agents was confirmed by diffused reflectance infrared spectroscopy (DR-FTIR) tests. By scanning electron microscopy (SEM) characterization, surface modified MMT was dispersed heterogeneously in the PDMS matrix for all four coupling agents. By X-ray diffraction (XRD) characterization, the interlayer distances of the four surface modified MMT were not changed. Dielectric tests showed that the dielectric constant and dielectric loss of PDMS filled with KH-560, KH-570, and SA treated MMT were decreased comparing with those of PDMS filled with pristine MMT. With the increasing content of MMT treated with KH-570, the dielectric constant and dielectric loss value of PDMS composites increased.     

Two‐Photon Imaging of a Cellular Line Using Organic Fluorescent Nanoparticles Synthesized by Laser Ablation

A comparative study of the optical properties of organic fluorescent nanoparticles fabricated by laser ablation (NPs‐LA), reprecipitation (NPs‐RP), and microemulsion (NPs‐ME) methods is presented. These nanoparticles contain a fluorene‐based p‐conjugated molecule (BT2). Distinctive electronic transitions are observed in samples due to the specific way in which the molecule BT2 is assembled in each type of nanoparticles; for instance, transitions involved in absorption and emission spectra of NPs‐LA result in blueshifting with respect to the molecular solution of BT2, whereas redshifting is observed in NPs‐RP and NPs‐ME. Further, the results show that under infrared excitation, the aqueous suspensions of NPs‐LA exhibit the highest fluorescence induced by two‐photon absorption (≈790 GM at 740 nm), as well as the best photostability, compared with aqueous suspensions of NPs‐RP and NPs‐ME. The nanoparticles synthetized by the three aforementioned methods are employed as exogenous agents for the visualization of human cervical cancer cell line (HeLa) using confocal and two‐photon microscopy. Under similar experimental conditions, it is found that microscopy images of the best quality are obtained with NPs‐LA. These results show that laser ablation is a suitable technique for the fabrication of organic fluorescent nanoparticles used as contrast agents for in vitro fluorescence microscopy.     

Modification of multi-walled carbon nanotubes for electric double-layer capacitors: Tube opening and surface functionalization

Multi-walled carbon nanotubes (MWCNTs) obtained opening the closed ends and using surface functionalization by means of a combination of partial oxidation in air and chemical modifications are characterized systematically in 0.3 M H₂SO₄ between 0 and 1.0 V, and these nanotubes were planned to be used as electrode materials in electric double-layer capacitors (EDLCs). Opening of MWCNTs, clearly observed by means of transmission electron microscopy (TEM), can be easily achieved by the partial oxidation in air through a seven-step temperature program identified by thermogravimetric/differential thermal analyses (TG/DTA). An increase in 175% specific capacitance is obtained for the MWCNTs, partially oxidized in air and chemically modified in H₂SO₄+HNO₃. The temperature-programmed desorption (TPD) data showed that evolutions of CO and CO₂ are, respectively, promoted by the application of partial oxidation in air and chemical modification in H₂SO₄+HNO₃. The above increase in specific capacitance for modified MWCNTs is attributed to an obvious increase in the BET surface area (double-layer capacitance) and the density of oxygen-containing surface functional groups (pseudocapacitance).     

Sol-Gel Synthesis of Multi-Walled Carbon Nanotubes Reinforced Alumina-Silica Fibers

Multi-walled carbon nanotubes (MWCNTs) reinforced alumina-silica fibers were prepared by the sol-gel dry-spinning method. Aluminum isopropoxide (AIP), aluminum nitrite (AN), and tetraethyl orthosilicate (TEOS) were used as starting materials to prepare spinnable aluminosilicate sols in aqueous media. Polyvinylpyrrolidone (PVP) was used as dispersant agent to homogeneous disperses MWCNTs in the spinnable aluminosilicate sol through an in-situ process. The structure and mechanical properties of the MWCNTs reinforced alumina-silica fibers were studied. The results revealed that homogeneous dispersion of MWCNTs in alumina-silica fibers improved their mechanical properties considerably. The addition of only 0.5 wt% acid-treated MWCNTs into alumina-silica fibers result in a 60% increase in tensile strength to 398 ± 45 MPa.     

Influence of Carbon Nanotubes on the Crystallization and Directional Tensile Behavior of High-Density Polyethylene Prepared by Dynamic-Packing Injection Molding

The influence of multi-walled carbon nanotubes (MWCNTs) on the crystallization and directional tensile properties of high-density polyethylene (HDPE) was studied for samples prepared by dynamic-packing injection molding (DPIM). Oscillatory shear was imposed on the gradually cooled melt during the packing solidification stage of DPIM. For the oriented composites containing 1.8 wt% MWCNTs, the tensile fracture behavior showed typical brittle features along the flow direction (FD) and perpendicular direction (PD), which were almost the same as those that occurred in oriented pure HDPE. The elongation at break along both directions decreased due to the incorporation of MWNCTs in the oriented composites compared with the oriented pure HDPE. However, the tensile strength of the oriented HDPE/MWCNT composites was greatly improved along the FD due to the presence of carbon nanotubes; meanwhile, it was not weakened along the PD. In scanning electron microscopy observations, it was found that there were some oriented hybrid shish-kebab structures in a nanometre scale in the oriented HDPE/MWCNT composites, but not in its isotropic composites. This suggests that MWCNTs were involved in the shear-induced crystallization of HDPE. Differential scanning calorimetry measurements confirmed that the crystallinity of oriented HDPE composites with 1.8 wt% MWCNTs was higher than those of isotropic HDPE and isotropic composites, but was not obviously higher than that of oriented pure HDPE. These findings demonstrate that MWCNTs indeed affected the formation of crystalline structures, but did not greatly influence the crystallinity of HDPE under shear flow. The transition of crystalline morphology might be the reason for change in tensile behavior for the oriented HDPE/MWCNT composites compared with the oriented pure HDPE.