类富勒烯碳薄膜的结构演变及摩擦学性能研究

通过等离子体增强化学气相沉积技术,以不同沉积时间在硅表面上制备类富勒烯碳薄膜,探究类富勒烯碳薄膜结构演变和摩擦学性能随沉积时间变化规律。利用拉曼光谱和透射电子显微镜,考察类富勒烯碳薄膜微结构和表面形貌随沉积时间的变化。结果表明:碳薄膜内类富勒烯结构含量随沉积时间先增加后保持不变;采用沉积时间为3 h的类富勒烯碳薄膜组成摩擦配伍对,当载荷从8 N增加到14 N时,摩擦因数从0.013降至0.006,即随载荷的增加实现了由低摩擦向超滑的转变。这是因为摩擦诱使类富勒烯碳薄膜发生结构转变,并形成有利于减少摩擦的类球状或外部石墨壳层闭合的纳米颗粒。     

Reactions of microcrystalline fullerene C60 with amino and aza macrocyclic ligands under solvent-free conditions

We evaluated the reactivity under solvent-free conditions of 2-aminomethyl-15-crown-5 (AM15C5), 2-aminomethyl-18-crown-6 (AM18C6), 1,4,8,12-tetraazacyclopentadecane (TACPD) and rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (tet b) with microcrystalline fullerene C₆₀. The reactions of nucleophilic addition were carried out at temperatures of about 160°C for 5 h in the case of crown ethers and TACPD, and at 180–190°C for 24 h in the case of tet b. Characterization of the products obtained was performed by using Fourier-transform infrared (FTIR) and Raman spectroscopy, laser desorption/ionization time-of-flight (LDI-TOF) mass spectroscopy, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). To provide an additional insight into the reactivity of macrocyclic compounds with C₆₀ molecules, we employed theoretical calculations in the frame of density functional theory (DFT). According to the results of SEM imaging, macrocyclic reagents are generally unable to deeply penetrate into the bulk of fullerene microcrystals (with a possible exception of TACPD). According to TGA measurements, the reaction efficiency is very low for tet b, whereas the average content of organic fraction in C₆₀-AM15C5 and C₆₀-AM18C6 reaches about 29%, and in C₆₀-TACPD, almost 40%. According to LDI-TOF mass spectral analysis, the products of TACPD, tet b and AM15C5 reactions with fullerene have oligomeric or polymeric structure. By using DFT theoretical calculations, the latter observation was explained by enhanced reactivity of secondary amino groups toward nucleophilic addition onto fullerene cage.     

Fabrication of fullerene decorated by iron compound and its effect on the thermal stability and flammability for high-density polyethylene

Fullerene decorated by iron compound (C₆₀-Fe) is fabricated via solution reaction and characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), wide-angle X-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Upon incorporating C₆₀-Fe into high-density polyethylene (HDPE) matrix by melt blending, the thermal and thermo-oxidative stability of HDPE are considerably increased, the oxidative induction time (OIT) is dramatically extend. When the concentration of C₆₀-Fe reached 5 wt%, the onset degradation temperature in air increased from 352°C to 422°C, and the OIT dramatically delayed from 4.5 to 47.8 minutes. Moreover, from microscale combustion calorimetry (MCC), C₆₀-Fe can reduce the peak heat release rate (PHRR), heat release capacity (HRC), and total heat release (THR) values of the composites, all of which are very important parameters for evaluating the fire retardancy of a polymeric material.     

Adsorption of amino acids by fullerenes and fullerene nanowhiskers

We have investigated the adsorption of some amino acids and an oligopeptide by fullerene (C₆₀) and fullerene nanowhiskers (FNWs). C₆₀ and FNWs hardly adsorbed amino acids. Most of the amino acids used have a hydrophobic side chain. Ala and Val, with an alkyl chain, were not adsorbed by the C₆₀ or FNWs. Trp, Phe and Pro, with a cyclic structure, were not adsorbed by them either. The aromatic group of C₆₀ did not interact with the side chain. The carboxyl or amino group, with the frame structure of an amino acid, has a positive or negative charge in solution. It is likely that the C₆₀ and FNWs would not prefer the charged carboxyl or amino group. Tri-Ala was adsorbed slightly by the C₆₀ and FNWs. The carboxyl or amino group is not close to the center of the methyl group of Tri-Ala. One of the methyl groups in Tri-Ala would interact with the aromatic structure of the C₆₀ and FNWs. We compared our results with the theoretical interaction of 20 bio-amino acids with C₆₀. The theoretical simulations showed the bonding distance between C₆₀ and an amino acid and the dissociation energy. The dissociation energy was shown to increase in the order, Val < Phe < Pro < Asp < Ala < Trp < Tyr < Arg < Leu. However, the simulation was not consistent with our experimental results. The adsorption of albumin (a protein) by C₆₀ showed the effect on the side chains of Try and Trp. The structure of albumin was changed a little by C₆₀. In our study Try and Tyr were hardly adsorbed by C₆₀ and FNWs. These amino acids did not show a different adsorption behavior compared with other amino acids. The adsorptive behavior of mono-amino acids might be different from that of polypeptides.     

C60 and C60-arginine aqueous solutions: In vitro toxicity and structural study

Abstract

Small-angle X-ray and neutron scattering was applied for the structural characterization of aggregates in water dispersions of fullerene C₆₀ prepared by dialysis method and its conjugate with amino acid arginine. Two compounds are also compared with respect to their toxic properties. Experiments on the cytotoxicity of these systems on the A549, HepG2 and HeLa cells showed no toxic effects of the dispersions.     

Eu@C86 isomers: Calculated relative populations

Abstract

Relative populations of four energy-lowest IPR (isolated-pentagon-rule) isomers of Eu@C₈₆ are computed using the Gibbs energy based on characteristics from density functional theory calculations (M06-2X/3-21G?～?SDD entropy term, M06-2X/6-31G*～SDD or B2PLYP(D)/6-31G*～SDD energetics). The calculations confirm that the recently isolated Eu@C₁(7)-C₈₆ species is a major isomer in a relevant temperature region. Relationship to the empty C₈₆ cages is discussed, too.     

Direct comparison of charge transport and electronic traps in polymer–fullerene blends under dark and illuminated conditions

A direct comparison of charge transport and electronic traps in representative polymer–fullerene blend, poly (3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PCBM), is carried out in dark and illuminated conditions based on the measurements of temperature-dependent current–voltage characteristics. In dark condition, the charge transport presents a transition from Ohmic to trap-limited current. While the trap-filled space charge limited current is observed under illumination at the same applied bias. From evaluations of trap density and energy distribution by a differential method, it is reveal that the diverse charge transport in dark and illuminated conditions is mainly caused by the different trap states distribution, which strongly affects the space charges and the electrical field in P3HT: PCBM blends.     

Enhanced intrinsic stability of the bulk heterojunction active layer blend of polymer solar cells by varying the polymer side chain pattern

Organic photovoltaics (OPVs) have acquired huge attention over the past years as potential renewable energy sources, adding attractive features such as aesthetics, semi-transparency, flexibility, large area printability, improved low-light performance, and cost-effectiveness to the well-known Si-based photovoltaics. Steady improvements in OPV power conversion efficiencies are continuously reported, notably for bulk heterojunction solar cells based on conjugated polymer:fullerene blends. However, apart from efficiency and cost, the stability of organic solar cell devices is of particular concern. Among the different factors contributing to OPV instability, gradual loss of the optimum phase-separated nanomorphology of the photoactive layer blend is a critical parameter. In this paper, we present the results of ‘shelf-life’ accelerated lifetime tests performed for devices containing a range of functionalized poly(3-alkylthiophene) (P3AT) donor polymers upon prolonged thermal stress. By the incorporation of functional moieties on the side chains of P3HT-based copolymers, a remarkable improvement of the intrinsic stability of the active layer blend morphology is accomplished, even for fairly low built-in ratios (5–15%) and without crosslinking to covalently anchor the polymer and/or fullerene molecules. Moreover, these alterations do not influence the initial power conversion efficiencies to a large extent. As such, the presented approach can be regarded as an attractive paradigm for OPV active layer stability.     

Influence of fullerenes on the thermal and flame-retardant properties of polymeric materials

At present, the application of fullerene in polymer materials has become an attractive issue. Fullerene can enhance the thermal and flame-retardant properties of polymers due to its high capacity to trap free radicals. Fullerene also has good synergistic effect with inorganic metal flame retardant, intumescent flame retardant, brominated flame retardant (BFR), clay, carbon nanotubes, graphene oxide, and so on. In this review, the impact and mechanism of fullerene and its derivatives on the thermal and flame-retardant properties of polymeric materials are discussed. And the prospect of fullerene in flame-retardant polymer composites is also briefly introduced by analyzing the research progress in the recent years. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47538.