RGO/Al复合材料界面性质第一性原理研究

本研究采用基于密度泛函理论的第一性原理方法, 在广义梯度近似下, 分别建立了具有不同碳氧比的“铝/氧化石墨烯/铝(Al/GO/Al)”界面模型以及含缺陷“Al/GO/Al”三层界面模型。探讨了含氧官能团和单空位缺陷、双空位缺陷以及拓扑缺陷对还原氧化石墨烯增强铝基复合材料界面性质的影响。研究结果表明: 在“Al/GO/Al”界面模型中, 环氧基优于碳原子而与铝原子产生明显的电荷交互作用, 氧原子净电荷为-0.98 e, 铝原子净电荷为0.46 e, 环氧基有利于复合材料中还原氧化石墨烯与铝基体之间的界面结合。当缺陷存在时, 含缺陷的“Al/GO/Al”界面模型中缺陷处碳原子净电荷在-0.05 e至-0.38 e区间, 环氧基与碳原子之间存在较弱的相互作用, 与铝原子间相互作用明显较强。环氧基抑制了空位缺陷处碳原子与铝原子之间的反应, 可保护含空位还原氧化石墨烯中碳原子结构的完整性。本研究可为开发高性能Al/GO/Al基复合材料提供理论指导。     

Al-TiO2-B2O3-C系XD合成铝基复合材料的反应机理及力学性能

研究了Al-TiO2-B2O3-C反应系XD合成铝基复合材料的反应机理.结果表明在Al-TiO2-B2O3-C系中,当B2O3/TiO2摩尔比=0.5,C/TiO2摩尔比=0时,TiO2和B2O3分别与Al结合生成热力学稳定的Al2O3和活性Ti原子、B原子,B原子和Ti原子分别穿过各自反应层结合生成热力学稳定的TiB2,过剩的Ti原子则与Al结合生成棒状物Al3Ti;加入碳粉后,Ti原子将优先与C和C与Al的化合物Al4C3反应生成TiC,Al3Ti逐渐减少,在C/TiO2摩尔比为0.5时,Al3Ti相基本消失,力学性能得到改善,其拉伸强度和延伸率分别从266MPa和3%增加到315MPa和7%.     

氧化石墨烯在生物医学领域的应用

氧化石墨烯(GO)是石墨烯的衍生物,具有较高的比表面积和丰富的官能团:底面含羟基和环氧基,边缘含羧基。这些官能团赋予了氧化石墨烯良好的亲水性、分散性和生物相容性,易于修饰和功能化,加之其优良的光学性质,使得氧化石墨烯在生物医学领域具有广阔的应用前景。着重介绍了氧化石墨烯在生物传感器、生物成像、药物/基因传送、光热/光动力治疗、抗菌材料、生物安全性方面的研究现状和进展。     

基体合金元素对SiC/Al界面结合影响的第一性原理及实验研究

采用基于密度泛函理论的第一性原理及实验相结合的方法, 探讨了Al基体中分别掺杂Mg、Si、Cu合金元素对SiC/Al界面结合的影响, 重点考察了合金元素在界面偏聚时的电子结构和成键情况。研究表明: 在未掺杂Al/SiC体系界面结构优化时, 以Si原子为终止面的Brigde结构是最稳定的结合方式; 当合金元素分别替换界面处的Al原子后, 界面处原子的分波态密度、Muliken电荷及成键原子集居数等电子结构参数均有不同程度的变化, 这不仅增加了界面处 Si与Al原子结合, 同时也增强了界面处和亚界面处的Al基体和SiC增强相原子之间的相互作用, 使体系更加稳定, 界面黏着功均有不同提升; 其中掺Mg提升效果最明显, 其次为掺Cu和掺Si; 利用第一性原理计算的掺杂Al/SiC体系黏着功和实验值较为接近且变化规律相同。     

氧化石墨烯对聚丙烯/尼龙6两组分聚合物的增容作用

采用改进的Hummers法制备氧化石墨烯,然后将其与聚丙烯/尼龙6(PP/PA6)两组分聚合物进行熔融共混制备聚丙烯/尼龙6/氧化石墨烯纳米复合材料。通过拉伸强度测试、差示扫描量热测试并结合扫描电子显微镜对尼龙6分散相尺寸大小观察表明,由于氧化石墨烯表面环氧官能团与尼龙6中端氨基能发生化学反应,有效提高了各组分之间的界面相互作用;少量的氧化石墨烯使尼龙6分散相尺寸大幅度减小,并使复合材料拉伸强度大幅度提高,由此表明石墨烯对热力学不相容聚丙烯/尼龙6两组分聚合物具有良好的增容作用。     

SiC陶瓷与Zn界面结合特性的第一性原理研究

低温焊接SiC陶瓷是金属/陶瓷连接领域非常重要的研究方向,而与之相关的理论研究相对匮乏,同时,通过实验手段难以描述金属/陶瓷界面原子之间的相互作用。为研究低温Zn基钎料与SiC陶瓷的界面结合方式,采用第一性原理方法,计算了Zn(0001)和SiC(0001)的表面能,6种不同堆垛方式的Zn(0001)/SiC(0001)界面模型的分离功,并分析了其中最稳定两种模型的电荷密度图、电荷密度差分图和Mulliken布局。结果表明:Zn/SiC界面只形成了Zn-Si离子键,Si终端孔穴型界面的Zn-Si键结合强度高于C终端孔穴型。     

Ti(CN)/TiC/Al2O3/TiN多层涂层的结构和界面结合力研究

采用中温、高温复合化学气相沉积技术(MHCVD)在WC- (6％wt)Co硬质合金基体表面制备了Ti(CN)/TiC/Al2O3/TiN 多层陶瓷涂层.通过光学显微镜(OM)、扫描电镜(SEM)、X射线衍射仪(XRD)和数显显微硬度计等手段分析多层陶瓷涂层的表面及断面形貌、物相组成、显微硬度;采用表面划痕实验,结合形貌观察及X射线能谱分析(EDS)研究多层陶瓷涂层/硬质合金基体的界面结合力及其影响因素.结果表明:Ti(CN)/TiC/Al2O3/TiN 多层陶瓷涂层结构均匀致密,涂层后硬质合金的显微硬度明显提高,约2600 HV,多层陶瓷涂层与基体界面结合良好,划痕实验显示临界载荷高达105 N,多层陶瓷涂层界面间的原子扩散作用对涂层/基体界面附着力有较大贡献,而涂层内部少量Ti2O3、W6Co6C 等物相的存在对提高界面结合力也有帮助.     

Ti基复合材料界面反应扩散的微观分析

通过SiC连续纤维增强Ti基复合材料的制备及在不同条件下的热处理试验,利用TEM,SEM,EDS及XRD分析技术研究复合材料的界面反应以及产物相的形成.研究结果表明:SiC /Ti复合材料界面发生了反应扩散,反应元素C,Ti,Si在界面反应层中出现浓度波动;界面反应产物被确认为是Ti3SiC2 ,TiC和 Ti5Si3,在靠近SiC侧出现Ti3SiC2和Ti5Si3单相区,靠近Ti基体侧为Ti5Si3单相区,中间为TiC Ti5Si3双相区;SiC/Ti复合材料界面相序列为SiC┃Ti3SiC2┃Ti5Si3┃TiC Ti5Si3┃Ti5Si3┃Ti.     

氧原子在Be(0001)表面吸附的第一性原理研究

采用第一性原理的计算方法研究了不同覆盖度下O原子在Be(0001)的表面吸附性质。首先确定O吸附在Be(0001)表面的最稳定吸附构型。通过O原子的吸附能,发现O原子更易吸附在hcp位,并且与Be表面发生氧化反应形成BeO。此外,研究了不同覆盖度下的力学性质,结果表明:不同覆盖度下O原子吸附在Be(0001)表面时,基态下均具有稳定结构;铍的抗断裂和拉伸能力随着O原子覆盖度的增大而增大。     

Ti-N薄膜与钢基体界面显微结构的透射电镜研究

用透射电镜分别研究了空心阴极离子镀加Ti底层和不加Ti底层的Ti-N薄膜与不锈钢和高速钢基体之间界面的显微结构。在较厚Ti底层与不锈钢基体间的界面上有厚约20nm的FeTi界面层,Ti底层由具有[0001]取向的α-Ti相组成,TeTi相有[311]、[310]、[321]、[320]等几种择优取向。此外,较薄Ti底层与不锈钢基体间的界面比较光滑,界面层很薄。在基体温度为500℃时镀得的加Ti底层的Ti-N膜与高速钢基体的界面上,也观察到了Ti底层。它由细小的α-Ti晶粒组成,其中弥散分布着一些TiC的微小晶粒。在邻近膜/基界面的基体内断续分布着一些FeTi相的晶粒。在不加Ti底层的Ti-N膜与高速钢基体的界面上,观察到了TiN晶粒在基体中的碳化物MC(VC)上的外延生长,它们之间存在[310]_(vc)∥[100]_(TiN)的晶体学取向关系。与此类似,在高速钢中马氏体的晶粒上也外延生长出了TiN晶粒。在M_6C上生长的TiN初始晶粒很小,晶界不清晰。TiN与高速钢中碳化物和马氏体间的界面均较光滑,未观察到界面相。     

High Detectivity Graphene‐Silicon Heterojunction Photodetector

A graphene/n‐type silicon (n‐Si) heterojunction has been demonstrated to exhibit strong rectifying behavior and high photoresponsivity, which can be utilized for the development of high‐performance photodetectors. However, graphene/n‐Si heterojunction photodetectors reported previously suffer from relatively low specific detectivity due to large dark current. Here, by introducing a thin interfacial oxide layer, the dark current of graphene/n‐Si heterojunction has been reduced by two orders of magnitude at zero bias. At room temperature, the graphene/n‐Si photodetector with interfacial oxide exhibits a specific detectivity up to 5.77 × 10¹³ cm Hz^1/2 W^‐1 at the peak wavelength of 890 nm in vacuum, which is highest reported detectivity at room temperature for planar graphene/Si heterojunction photodetectors. In addition, the improved graphene/n‐Si heterojunction photodetectors possess high responsivity of 0.73 A W^?1 and high photo‐to‐dark current ratio of ≈10⁷. The current noise spectral density of the graphene/n‐Si photodetector has been characterized under ambient and vacuum conditions, which shows that the dark current can be further suppressed in vacuum. These results demonstrate that graphene/Si heterojunction with interfacial oxide is promising for the development of high detectivity photodetectors.     

氧化石墨烯改性玄武岩纤维及其增强环氧树脂复合材料性能

为了改善玄武岩纤维/环氧树脂复合材料的界面性能,通过偶联剂对氧化石墨烯进行改性,并将改性后的氧化石墨烯引入到上浆剂中对玄武岩纤维进行表面涂覆改性,同时制备了氧化石墨烯-玄武岩纤维/环氧树脂复合材料.采用FTIR表征了氧化石墨烯的改性效果;运用SEM分析了改性上浆剂处理对玄武岩纤维表面及复合材料断口形貌的影响和作用机制.结果表明:偶联剂成功接枝到氧化石墨烯表面;玄武岩纤维经氧化石墨烯改性的上浆剂处理后,表面粗糙度及活性官能团含量增加,氧化石墨烯-玄武岩纤维/环氧树脂界面处的机械齿合作用及化学键合作用增强,界面黏结强度得到改善,玄武岩纤维的断裂强力提高了30.8%,氧化石墨烯-玄武岩纤维/环氧树脂复合材料的层间剪切强度提高了10.6%.     

Improvement of mechanical properties by incorporating graphene oxide into cement mortar

ABSTRACT

As a two-dimensional nanomaterial, graphene oxide has attracted much attention for its use in reinforcing cementitious materials. However, the dispersion of graphene oxide in cementitious materials has been found unsatisfactory due to crosslinking of divalent calcium ions. In this study, we propose a modified mixing procedure to improve graphene oxide dispersion in cement mortar by utilizing silica sand to mechanically separate graphene oxide nanosheets. Apart from the improved graphene oxide dispersion, adhesion between sand and cement matrix is also believed to be enhanced due to the improved roughness of the sand surface. According to our mechanical properties study, with the introduction of 0.02% by weight graphene oxide in cement mortar, compressive strength was significantly improved by more than 25% and tensile splitting and flexural strength were improved by around 15%. In a microstructural investigation, the interfacial transition zone in cement mortar was found to be denser due to the addition of graphene oxide. Moreover, graphene oxide incorporated cement mortar also showed pore structure refinement and porosity reduction. Therefore, improvement in mechanical properties may result from an improved interfacial transition zone and a more refined pore structure with the introduction of a small quantity of well-dispersed graphene oxide nanosheets.     

On the bonding of porcelain on titanium

The interface structure and bond strength between Ti and porcelain were studied using various firing times and vacuum levels. During firing an interfacial oxide layer was formed between Ti and porcelain. Fracture occurred between this oxide layer and Ti. A correlation was observed between the thickness of the interfacial layer and the bond strength: the thicker the layer, the weaker was bonding. An improved vacuum was found to increase the bond strength. Oxygen was observed by ESCA to dissolve into Ti, causing brittleness in the uppermost Ti layer with prolonged firing time.     

基于π-π/H-键协同作用制备含芘小分子增强高韧性石墨烯纸

轻质高强且具备高韧性的石墨烯组装材料在抗冲击防护领域有着潜在的应用价值.在这项工作中,我们通过在还原氧化石墨烯层间界面交联1-氨基芘AP和1-芘丁酸PB共轭小分子,可以获得具有高导电、高韧性的超强复合石墨烯纸(AP/PB-GPs).结果表明,超过10μm厚度的复合石墨烯纸具有超高的平均韧性(~69.67±15.3 MJ m^-3),同时抗拉伸强度接近1 GPa;尤其在抗冲击性能方面,在高速弹道冲击速度下,仍然可以获得优异的比穿透能量吸收值(~0.17 MJ kg^-1).详细的界面和结构分析表明,界面增强是由相邻石墨烯层间与共轭分子之间的π-π相互作用和氢键连接共同决定的.尤其是石墨烯纳米片内的孔洞及边缘缺陷更有利于共轭小分子充分的吸附,这必然会使界面结合最大化,在连续高的加载应力下能够有效促进裂纹的偏转和塑性变形.密度泛函理论(DFT)模拟表明,石墨烯纳米片边缘的–COOH极性官能团与AP/PB分子表面的–NH₂、–COOH之间的耦合对氢键网络的形成起着关键作用.     

石墨烯/纳米TiO2复合材料的制备及其光催化性能

以氧化石墨烯（GO）和钛酸四丁酯（Ti（OBu）₄）作为初始反应物,采用乙醇溶剂热法合成了石墨烯/纳米TiO₂复合材料,并利用XRD、FE-SEM、TEM、RAMAN和XPS等手段对石墨烯/纳米TiO₂复合材料的晶体结构、形貌及元素形态等性质进行了表征,同时将复合材料应用于光催化降解甲基橙溶液,进行光催化性能评价。结果表明：Ti（OBu）₄在乙醇溶剂中通过化学静电引力吸附到GO表面,经过溶剂热反应,GO被还原成石墨烯的同时,石墨烯的表面负载生长锐钛矿TiO₂颗粒。随着溶剂热反应时间的延长,GO表面的活性基团减少,还原更加彻底,同时TiO₂晶粒有一定的增大趋势;与纯TiO₂相比,石墨烯/纳米TiO₂复合材料光催化活性明显提高,石墨烯含量对复合材料的光催化活性有直接的影响。     

Enhanced interfacial strength of graphene reinforced aluminum composites via X (Cu,Ni, Ti)-coating: Molecular-dynamics insights

The poor interface bonding between graphene and aluminum is one of the main challenges which could impede wider application of graphene/Al composites. Coating metals on graphene layer could be an effective method to solve this problem. In this research, the pullout processes and uniaxial tensile tests were performed by using molecular dynamics (MD) simulation method to explore how the coating metals, such as Ni, Cu and Ti, affect the interfacial strength between C-Al bonds and the mechanical properties of nanocomposites, respectively. The results reveal that Ni is the most powerful coating metal among these three candidates in enhancing interfacial strength since it has the highest value of pullout force. Also, it leads to an enhancement of 26.39% in the Young’s modulus when compared with the one without coating treatment. As for the impact of various amounts of Ni coating, it is demonstrated that the interfacial bonding can be enhanced up to 87.65%, 92.67%, 111.27% and 145.34% with the percentage of Ni coating was 25%, 50%, 75%, 100%, respectively. In terms of the mechanical property, the various percentage of Ni has little impact on Young’s modulus while the value of tensile strength falls slightly, from 58.94 GPa to 51.88 GPa.     

氧化石墨烯表面稀土改性机理

石墨烯独特的物理、化学和力学性能为复合材料的开发奠定了重要基础,是各种复合材料的理想增强体,但石墨烯分散性和湿润性差的问题严重限制了其在复合材料中的进一步应用。采用浸润法和加热改性剂法制备了稀土改性氧化石墨烯(RE-M-GO),利用X射线衍射(XRD)和扫描电子显微镜(SEM),能谱仪(EDS)对RE-M-GO的形貌和相结构进行表征;并结合傅里叶变换红外(FTIR)和紫外光谱仪器(UV),分析改性氧化石墨烯的官能团结构的变化,探讨其改性机理。结果表明:稀土改性的氧化石墨烯的分散性有明显的改善,主要是由于稀土元素与氧化石墨烯的含氧官能团进行反应形成配位键,生成了新的官能团,降低了氧化石墨烯的界面能及表面能,从而改善了氧化石墨烯的分散性。     

Diazonium functionalization of graphene nanosheets and impact response of aniline modified graphene/bismaleimide nanocomposites

For developing high performance of graphene-based nanocomposites, dispersibility of graphene sheets in matrices and interfacial interaction are challenging due to the strong tendency of agglomeration and surface inertia of graphene. Here we report an efficient way to functionalize graphene nanosheets with aniline groups on their surfaces, to attain the functionalized graphene nanosheets (FGS) by diazonium treatment following reduction of graphene oxide with hydrazine hydrate. Two kinds of nanocomposites based on diallyl bisphenol A modified bismaleimide (BMI-BA) resin which was filled with functionalized graphene and reduced graphene oxide nanosheets were prepared, and the FGS were linked with BMI resin by chemical bonds. The FGS/BMI-BA composite at a loading of 0.3 wt% revealed a 39% increase in impact strength and a slightly improvement in flexural strength, and the resulting composite remains stable at high temperature. This work provides more possibilities for incorporation of graphene into polymer matrices and an efficient method to toughening the BMI resin.