The boundary lubrication of chemically grafted and cross-linked hyaluronic acid in phosphate buffered saline and lipid solutions measured by the surface forces apparatus

High molecular weight hyaluronic acid (HA) is present in articular joints and synovial fluid at high concentrations; yet despite numerous studies, the role of HA in joint lubrication is still not clear. Free HA in solution does not appear to be a good lubricant, being negatively charged and therefore repelled from most biological, including cartilage, surfaces. Recent enzymatic experiments suggested that mechanically or physically (rather than chemically) trapped HA could function as an "adaptive" or "emergency" boundary lubricant to eliminate wear damage in shearing cartilage surfaces. In this work, HA was chemically grafted to a layer of self-assembled amino-propyl-triethoxy-silane (APTES) on mica and then cross-linked. The boundary lubrication behavior of APTES and of chemically grafted and cross-linked HA in both electrolyte and lipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) solutions was tested with a surface forces apparatus (SFA). Despite the high coefficient of friction (COF) of μ ≈ 0.50, the chemically grafted HA gel significantly improved the lubrication behavior of HA, particularly the wear resistance, in comparison to free HA. Adding more DOPC lipid to the solution did not improve the lubrication of the chemically grafted and cross-linked HA layer. Damage of the underlying mica surface became visible at higher loads (pressure >2 MPa) after prolonged sliding times. It has generally been assumed that damage caused by or during sliding, also known as "abrasive friction", which is the main biomedical/clinical/morphological manifestation of arthritis, is due to a high friction force and, therefore, a large COF, and that to prevent surface damage or wear (abrasion) one should therefore aim to reduce the COF, which has been the traditional focus of basic research in biolubrication, particularly in cartilage and joint lubrication. Here we combine our results with previous ones on grafted and cross-linked HA on lipid bilayers, and lubricin-mediated lubrication, and conclude that for cartilage surfaces, a high COF can be associated with good wear protection, while a low COF can have poor wear resistance. Both of these properties depend on how the lubricating molecules are attached to and organized at the surfaces, as well as the structure and mechanical, viscoelastic, elastic, and physical properties of the surfaces, but the two phenomena are not directly or simply related. We also conclude that to provide both the low COF and good wear protection of joints under physiological conditions, some or all of the four major components of joints-HA, lubricin, lipids, and the cartilage fibrils-must act synergistically in ways (physisorbed, chemisorbed, grafted and/or cross-linked) that are still to be determined.     

以TDI和IPDI为单体合成聚氨酯微胶囊及其摩擦学性能

分别以甲苯-2,4-二异氰酸酯(TDI)和异佛尔酮二异氰酸酯(IPDI)为单体,通过原位聚合法制备了离子液体@聚脲(PU)微胶囊,并与环氧树脂共混制得环氧树脂复合材料.利用扫描电子显微镜分析了微胶囊及复合材料的表面形貌,通过电子万能试验机和摩擦磨损试验机探究了微胶囊改性复合材料在不同情况下的力学性能和摩擦学性能,用傅里叶变换红外光谱对微胶囊进行表征.分析结果表明,以IPDI为单体合成的微胶囊摩擦学性能更加优异,并且随着微胶囊用量的增加,复合材料的摩擦学性能有明显提高,当微胶囊添加质量分数为20%时,含有微胶囊的复合材料具有较低的滑动摩擦系数并且摩擦面较光滑,这是由于在实验过程中,随着微胶囊壁材的破损,芯材离子液体被释放,形成了一层致密的润滑膜.     

Enhanced tribology properties of ZnO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite nanoparticles as liquid lubricating additives

Monodispersed and hydrophobic ZnO/Al₂O₃ composite nanoparticles are prepared by a nonhydrolytic sol–gel method. ZnCl₂ and AlCl₃ are dissolved in acetone and used as precursors. Oleic acid is adopted as an oxygen donor. The tribology properties of the prepared ZnO/Al₂O₃ composite nanoparticles are studied by the four-ball friction and thrust ring friction test. It is demonstrated that the average friction coefficient and the wear scar diameter are reduced by 37.5 and 26.2%, respectively, in comparison with pure lubricating oil. Moreover, the ZnO/Al₂O₃ composite nanoparticles bear the merits of ZnO and Al₂O₃ when used as lubricant additives, exhibiting both excellent antifriction and antiwear behaviors simultaneously. The ZnO/Al₂O₃ composite nanoparticles improve the lubrication effect not only by turning the sliding friction into rolling friction, but also forming a hard Al₂O₃ protective film onto the thrust-ring surface containing ZnO/Al₂O₃ nanoparticles, which have much potentiality in industrial applications.     

Superlubricity behaviors of Si3N4/DLC Films under PAO oil with nano boron nitride additive lubrication

The tribological properties of Si₃N₄ ball sliding against diamond‐like carbon (DLC) films were investigated using a ball‐on‐disc tribometer under dry friction and oil lubrications, respectively. The influence of nano boron nitride particle as lubricant additive in poly‐α‐olefin (PAO) oil on the tribological properties of Si₃N₄/DLC films was evaluated. The microstructure of DLC films was measured by Raman spectroscopy and X‐ray photoelectron spectroscopy. The experimental results show coefficient of friction (COF) of Si₃N₄/DLC films was as low as 0.035 due to the formation of graphite‐like transfer films under dry friction condition. It also indicates that the tribological properties of Si₃N₄/DLC films were influenced significantly by the viscosity of oil and the content of nano boron nitride particle in PAO oil. COF increases with the viscosity of PAO oil increasing. Si₃N₄/DLC films exhibit the superlubricity behaviors (μ=0.001 and nonmeasurable wear) under PAO 6 oil with 1.0 wt% nano boron nitride particle lubrication, indicating that the improved boundary lubrication behaviors have indeed been responsible for the significantly reduced friction. Nano boron nitride additive is used as solid lubricant‐like nano scale ball bearing to the pointlike contact and a soft phase bond with the weak van der Waals interaction force on the contact surface to improve the lubrication behaviors of Si₃N₄/DLC films. The potential usefulness of nano boron nitride as lubricant additive in PAO oil for Si₃N₄/DLC films has been demonstrated under oil lubrication conditions. The present work will extend the wide application of nano particle additive and introduce a new approach to superlubricity under boundary lubrication in future technological areas. Copyright © 2013 John Wiley & Sons, Ltd.     

改性生物柴油碳烟的制备、表征及水基润滑特性

为了探索生物柴油碳烟(BDS)作为水基润滑添加剂的应用, 采用热氧化法制备了热氧化处理的BDS(TO-BDS); 通过场发射透射电子显微镜、 X射线光电子能谱仪和Zeta电位仪等表征了TO-BDS的形貌、 组成和分散性, 并与BDS进行了对比; 利用球-盘往复摩擦磨损试验机、 3D激光扫描显微镜、 场发射扫描电子显微镜、 光学法接触角/界面张力仪和拉曼光谱仪考察了含TO-BDS的纯水(H₂O)的摩擦磨损性能和润滑机理. 结果表明, TO-BDS表面的含氧官能团和负电荷比BDS更多, 从而导致TO-BDS在H₂O中具有更好的分散性; 在H₂O中添加质量分数为0.2%的TO-BDS, 可显著改善H₂O的减摩抗磨性能. 这主要是因为在摩擦过程中, TO-BDS起到滚动轴承的功效, H₂O+TO-BDS比H₂O在摩擦副表面的润湿性能更好, 更易于形成润滑膜且TO-BDS会因摩擦力诱导剥离产生石墨片, 从而降低摩擦磨损.     

Synthesis of the polyethylene glycol solid-solid phase change materials with a functionalized graphene oxide for thermal energy storage

Polyethylene glycol (PEG) as a phase change material possesses three obstacles, such as leakage, low thermal conductivity and low thermal stability. A novel solid-solid phase change material (PCM) based on functionalized graphene oxide (GO), Polyethylene glycol (PEG) was prepared, and the three obstacles of PEG as a PCM was solved in one and the same material. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Raman and Transmission electron microscope (TEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and thermogravimetric analysis/infrared spectrometry (TG-IR) were used to study the properties of supporting material and composite PCM (CPCM). The results indicated that the PEG was grafted on the surface of the supporting material; Compared with pure PEG, the latent heat of CPCM with 9.6 wt% supporting material decreased only 5.3%, however, the thermal conductivity of CPCM increased 111% and the heat peak release rate of CPCM decreased 33.4%.     

Spectroscopic analysis of the tribological behavior of a model boundary layer lubricant

Highly ordered alkanethiol self-assembled monolayers (SAMs) on gold substrates are suitable models of boundary layer lubricants and may be used in actual nanoscale device applications. Here, such monolayers were studied by spectroscopic methods as a function of tribological wear (rubbing) using a pin-on-disk microtribometer. The coefficient of friction (COF) (ratio of the frictional force to the load) was measured with the tribometer, and reflectance infrared spectra and X-ray photoelectron spectra were obtained as the monolayer film failed and the COF changed. The results show that it is possible to correlate disorder in the monolayer film with tribological failure of the film, and that continued rubbing produces a chemical change in the monolayer film. Disorder in the monolayer is distinct from the influence of wear in the underlying gold substrate. Aged SAMs, having sulfonate rather than thiol headgroups and initially less well ordered, behave differently to the well-ordered freshly prepared SAMs. Interestingly, they show a lower COF over many more cycles of exposure to the rubbing pin. The impact of the mechanism of film failure in boundary layer lubrication is discussed.     

有机混合稀土化合物与有机锡化合物作为润滑添加剂的协同效应

用四球摩擦磨损试验机考察了环烷酸混合稀土、环烷酸亚锡及它们的复配物添加在26#白油中的摩擦学性能, 并用俄歇尔电子能谱研究了磨斑表面边界膜的化学组成. 结果表明: 环烷酸亚锡和环烷酸稀土在抗磨性能和减摩性能方面均存在明显的协同效应, 其复配物具有比ZDDP更好的抗磨减摩性能, 有望作为新型的高效多功能润滑添加剂在工业实际中得到应用, 复配物在摩擦表面形成的含稀土元素和锡元素的边界润滑膜是其具有良好摩擦学性能的主要原因.     

Adhesion and stable low friction provided by a subnanometer-thick monolayer of a natural polysaccharide

Using a surface forces apparatus, we have investigated the adhesive and lubrication forces of mica surfaces separated by a molecularly thin, subnanometer film of a high-molecular-weight (2.3 MDa) anionic polysaccharide from the algae Porphyridium sp. adsorbed from aqueous solution. The adhesion and friction forces of the confined biopolymer were monitored as a function of time, shearing distance, and driving velocity under a large range of compressive loads (pressures). Although the thickness of the dilute polysaccharide was <1 nm, the friction was low (coefficient of friction = 0.015), and no wear was ever observed even at a pressure of 110 atm over 3 decades of velocity, so long as the shearing distances were less than twice the contact diameter. Atomic force microscopy in solution shows that the biopolymer is able to adsorb to the mica surface but remains mobile and easily dragged upon shearing. The adhesion (adsorption) of this polysaccharide even to negatively charged surfaces, its stable low friction, its robustness (high-load carrying capacity and good wear protection), and the weak (logarithmic) dependence of the friction force on the sliding velocity make this class of polyelectrolytes excellent candidates for use in water-based lubricant fluids and as potential additives to synovial fluid in joints and other biolubricating fluids. The physical reasons for the remarkable tribological properties of the ultrathin polysaccharide monolayer are discussed and appear to be quite different from those of other polyelectrolytes and proteins that act as thick "polymer brush" layers.     

Interfacial friction and adhesion of polymer brushes

A bead-probe lateral force microscopy (LFM) technique is used to characterize the interfacial friction and adhesion properties of polymer brushes. Our measurements attempt to relate the physical structure and chemical characteristics of the brush to their properties as thin-film, tethered lubricants. Brushes are synthesized at several chain lengths and surface coverages from polymer chains of polydimethylsiloxane (PDMS), polystyrene (PS), and a poly(propylene glycol)-poly(ethylene glycol) block copolymer (PPG/PEG). At high surface coverage, PDMS brushes manifest friction coefficients (COFs) that are among the lowest recorded for a dry lubricant film (μ ≈ 0.0024) and close to 1 order of magnitude lower than the COF of a bare silicon surface. Brushes synthesized from higher molar mass chains exhibit higher friction forces than those created using lower molar mass polymers. Increased grafting density of chains in the brush significantly reduces the COF by creating a uniform surface of stretched chains with a decreased surface viscosity. Brushes with lower surface tension and interfacial shear stresses manifest the lowest COF. In particular, PDMS chains exhibit COFs lower than PS by a factor of 3.7 and lower than PPG/PEG by a factor of 4.7. A scaling analysis conducted on the surface coverage (σ) in relation to the fraction (ε) of the friction force developing from adhesion predicts a universal relation ε ~ σ(4/3), which is supported by our experimental data.     

胍盐离子液体对Si3N4/钢摩擦副的摩擦性能

两种具有较高热稳定性的胍盐离子液体用于Si₃N₄/钢摩擦副摩擦学性能的研究,在扫描电子显微镜下观察了磨斑表面形貌,并与烷基咪唑离子液体进行对比。 用X射线光电子能谱仪(XPS)分析了润滑机理。 结果表明,胍盐离子液体对Si₃N₄/钢摩擦副具有非常好的润滑作用,其承载能力强,摩擦系数小,磨痕浅。 摩擦过程中,Si₃N₄/钢摩擦副界面发生了复杂的摩擦化学反应并形成了边界润滑膜,起到减摩抗磨的作用。     

Examination of wear mechanisms of hard coatings

PVD-CrN and -TiN coatings are abraded in a wear test equipment which simulates the sliding-rolling friction of a screw rotor used in screw compressors. The coatings show significant differences concerning their durabilities. The worn-out coatings as well as the debris particles produced by abrasion are analyzed by means of X-ray induced photoelectron spectroscopy and Auger electron spectroscopy. The failure mechanism of TiN coatings can be explained by spalling off small debris particles, whereas the failure mechanism of CrN coatings has to be attributed to tribooxidation, because in this case the analyzed particles exclusively consist of chromium oxide. Nevertheless, CrN coatings show the lowest wear rate. When changing the environment (inert atmosphere or water lubrication) in the test equipment, the tribooxidation of CrN can be reduced or totally stopped, but a decrease in wear rate cannot be achieved. In this case tribooxidation leads to a better wear resistance.     

可见光高催化活性GO/Ag3PO4/Ni复合薄膜的制备和性能

以磷酸铵和氧化石墨烯悬浊液的混合液为电解液,采用电化学共沉积法制备了Ag3PO4基GO/Ag3PO4/Ni复合薄膜。运用扫描电子显微镜(SEM)、能量色散谱(EDS)、X射线衍射(XRD)、拉曼光谱(Raman)和紫外可见漫反射光谱(UV-Vis DRS)等对其形貌、物相和光谱特性进行分析。最佳工艺制备的GO/Ag3PO4/Ni复合薄膜呈现出GO包覆在直径为100 nm左右的Ag3PO4纳米球外的表面形貌。GO片与Ag3PO4纳米球之间存在强电荷相互作用。与单独的Ag3PO4纳米球相比,GO片的附着导致带隙缩小,可见光区的吸收率增强。可见光下考察了复合薄膜降解罗丹明B的光催化活性和稳定性,并利用荧光光谱和捕获剂法对薄膜的光催化机理进行了探索。结果表明,GO片的加入不仅显著提高了Ag3PO4的光催化活性,而且提高了Ag3PO4的结构稳定性。光催化降解罗丹明B 60 min时,GO/Ag3PO4/Ni复合薄膜的降解率是Ag3PO4/Ni薄膜的1.32倍。在保持薄膜光催化活性基本不变的前提下可循环使用7次。GO优异的电荷传导性能,以及Ag3PO4纳米球与GO片之间的正协同效应是提高复合薄膜光催化性能的主要原因。     

Electroanalytical Determination of Paracetamol Using Pd Nanoparticles Deposited on Carboxylated Graphene Oxide Modified Glassy Carbon Electrode

The study presents a novel paracetamol (PA) sensor based on Pd nanoparticles (PdNPs) deposited on carboxylated graphene oxide (GO?COOH) and nafion (Nf) modified glassy carbon electrode (GCE). The morphologies of the as prepared composites were characterized using high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and fourier transform infrared spectroscopy (FTIR). The experimental results demonstrated that Nf/GO?COOPd displayed excellent electrocatalytic response to the oxidation PA. The linear range was 0.04–800 μM for PA with limit of detection of 0.012 μM and excellent sensitivity of 232.89 μA mM^?1 cm^?2. By considering the excellent performance of Nf/GO?COOPd composite such as wider linear range, lower detection, better selectivity, repeatability, reproducibility, and storage stability, the prepared composite, especially GO?COOH support, with satisfactory electrocatalytic properties was a promising material for the modification of electrode material in electrochemical sensor and biosensor field.     

Conducting polymer engineered covalent organic framework as a novel electrochemical amplifier for ultrasensitive detection of acetaminophen

Two-dimensional covalent organic framework(COF) has distinctive properties that offer potential opportunities for developing advanced electrode materials.In this work,a core-shell material composed of TAPB-DMTP-COF(TAPB,1,3,5-tris(4-aminophenyl)benzene;DMTP,2,5-dimethoxyterephaldehyde)core and conducting polymer shell,TAPB-DMTP-COF@PANI,was synthesized solvothermally using a polymerization method.The structural cha racteristics of the prepared composite were revealed by X-ray diffraction patterns(XRD),fourier transform infrared spectra(FTIR),X-ray photoelectron spectroscopy(XPS),transmission electron microscopy(TEM).The electrochemical analyses were verified by subsequent monitoring of trace levels of acetaminophen.This resultant composite not only facilitated acetaminophen to interact with absorption sites by π-π stacking effect and hydrogen bonding but also overcame the poor conductivity of COF.Under the optimal conditions,a low limit of detection of0.032 μmol/L and wide linear range of 0.10-500 μmol/L were obtained.The electrochemical platform was almost unaffected by other interfering substances,and successfully applied for the practical detection of acetaminophen in commercial tablet,human blood serum and urine.The enhanced performance makes this COF based core-shell composite a promising material in electrochemical senso r.     

Tribological characteristics of composites based on poly(tetrafluoroethylene) and fullerene carbon

The effect of fullerene carbon fillers on the antifriction characteristics and wear resistance of PTFE during its sliding friction on steel and water lubrication has been studied. The structures of the modified PTFE and the fullerence carbon filler are analyzed by small-angle and wide-angle X-ray diffraction. The hypothetical mechanism of reinforcing effect provided by the fullerene carbon filler during friction is proposed.     

Nanotribology of surface-grafted PEG layers in an aqueous environment

The lubrication properties of adsorbed poly(L-lysine)-graft-poly(ethylene glycol) in aqueous buffer solution were studied with the surface forces apparatus. In general, the polymer brushes revealed extremely low friction forces. Two distinct regimes could be identified. In response to lateral shear, the friction forces of intact polymer films at moderate loads were below the detection limit. At high loads, when the films were compressed to about 10% of the original equilibrium film thickness, the friction showed a reversible increase with load. Under certain conditions, film destruction was observed, immediately followed by a dramatic increase in the frictional force and an expansion of the adsorbed brush layer. By the addition of free polymer to the buffer solution, the resistance of the polymer brushes to abrasion was dramatically increased by readsorption of the polymer following friction-induced desorption. This self-healing capacity and the extremely low friction of the adsorbed copolymer films contribute to their excellent properties as lubricant additives for water-based lubrication under boundary conditions.     

First-Row Transition-Metal Cations (Co2+, Ni2+, Mn2+, Fe2+) and Graphene (Oxide) Composites: From Structural Properties to Electrochemical Applications

Composites of graphene (oxide) (GO) and first-row transition-metal cations (Co²⁺, Ni²⁺, Mn²⁺, Fe²⁺) are prepared by mixing GO and aqueous metal salt solutions. The amount of metal cation bound to GO nanosheets is calculated by using inductively coupled plasma mass spectrometry (ICP-MS) and the possible binding sites of the metals are investigated by means of attenuated total reflectance infrared (ATR-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) measurements. Electrodes loaded with the metal/GO composites are prepared by a simple drop-casting technique without any binders or conductive additives. The effect of electrochemical reduction on the structure of the composite electrodes is investigated by Raman spectroscopy, XPS, X-ray diffraction (XRD) analysis, and field emission scanning electron microscopy (FESEM). A detailed electrochemical characterization is performed for the utilization of the composite electrodes for electrochemical capacitors and possible oxygen reduction reaction electrocatalysts by cyclic voltammetry (CV) and rotating disk electrode measurements. The highest areal capacitance is achieved with the as-deposited Fe/GO composite (38.7 mF cm⁻² at 20 mV s⁻¹). In the cyclic stability measurements, rCo/GO, rNi/GO, rMn/GO, and rFe/GO exhibit a capacitance retention of 44, 1.1, 73, and 87 % after 3000 cycles of CV at 100 mV s⁻¹, respectively.     

PEG接枝氧化石墨烯的制备与细胞成像

通过酯化反应将不同分子量的聚乙二醇（PEG）接枝到氧化石墨烯（GO）表面,得到系列GO-PEG。利用傅里叶变换红外光谱（FTIR）、拉曼光谱（Raman）、扫描电子显微镜（SEM）对GO-PEG的结构和形貌进行了表征,用热重分析（TGA）测定了GO-PEG中PEG的接枝量。SEM结果表明GO-PEG的剥离程度高于GO。GO-PEG在磷酸盐缓冲溶液中具有良好的分散稳定性,稳定性与接枝量呈正相关。GO-PEG通过非共价键合作用对荧光素（Flu）的负载量可达1.75mg·mg^-1,且负载量受接枝量影响;另外,GO-PEG对Flu的释放行为具有pH值触发药物释放性能。将接枝PEG的端羟基与Flu共价键合,所得GO-PEG₆₀₀₀-Flu荧光探针实现了对HepG₂细胞的成像。     

改进液相氧化还原法制备高性能氢气吸附用石墨烯

以液相氧化还原法为基础,并在分散剂十二烷基苯磺酸钠(SDBS)作用下制备得到高质量石墨烯,有效避免了在此过程中石墨烯大量团聚的现象.采用X射线衍射(XRD)、拉曼光谱(RS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和原子力显微镜(AFM)等分析手段对石墨烯样品进行了表征.XRD结果体现了石墨、氧化石墨和石墨烯晶型结构的区别;SEM和TEM结果显示石墨烯呈网格状,表面平整,缺陷少;AFM分析表明样品中单层石墨烯厚度约为1.3 nm,同时也存在少许双层结构.BET测试法得到石墨烯的比表面积高达1206 m2·g-1,考察了石墨烯在高压条件下对H2的吸附性能.通过对方法改进前后所制备的石墨烯样品进行比较,结果表明,十二烷基苯磺酸钠的加入有效地减小了石墨烯的大量团聚,且得到了高质量的石墨烯.在25和55℃条件下,高质量石墨烯对氢气的吸附量分别达到1.7％(w)和1.1％(w),比之前研究结果有了很大提高.