氟碳化合物涂料的进展

聚合物的稳定性取决于它们的组成。某些分子结构在氧或射线作用下是不稳定的。例如:带有吸电子基团(如芳基环)的亚甲基很容易氧化,碳—氯键容易被光化学裂解。而含氟的聚合物能提供优良性能,这是因为C-F键特别稳定的缘故。图1是两种溶剂涂料的光泽保持率比较图。     

糠醇树脂炭化产物作为锂离子电池炭电极材料的研究（Ⅰ）：炭化产物？…

测试分析了炭化处理条件对糠醇树脂炭化产物组成和结构的影响。结果表明：糠醇树脂炭化裂解过程首先是五员杂环内的碳氧键发生断裂，引起碳氢键断裂，然后经过重排又转变成了一个具有碳碳双键的六员环体系，并在此基础上进一步发生脱氢反应，还原性气氛中，经６２０℃炭化处理的样品出现了明显尖锐的（１００）晶面特征衍射峰，同时还发现了（１１０）和（００６）晶面特征衍射峰，表明糠醇树脂是一种较易石黑化的树脂材料，碳化样品     

单组分硅酮密封胶的分类及其应用研究

<正>单组分硅酮密封胶结构含有硅氧键(Si-O键),其键能高达425kJ/mol,远远大于碳碳键(C-C键)键能(345kJ/mol)和碳氧键(C-O键)键能(351kJ/mol),因此其稳定性好,具有很强的耐候性;再加上聚硅氧烷分子体积大     

低温炭化温度梯度对聚丙烯腈预氧纤维结构演变及碳纤维性能的影响

聚丙烯腈(PAN)预氧纤维在低温炭化阶段经热裂解重组而转化为具有乱层石墨结构雏形的低温炭化纤维,此阶段的温度调控对最终碳纤维的结构与性能有着重要影响。采用¹³C固体核磁共振谱图(¹³C-NMR)、拉曼光谱(Raman)、X射线衍射(XRD)和力学性能分析等手段,研究预氧纤维在低温炭化阶段的反应进程、温度梯度调控对预氧纤维的结构演变和碳纤维结构及性能的影响。结果表明:PAN预氧纤维在低温炭化过程中,经450℃热处理后碳结构的支链化程度达到最大值0.99,当处理温度达到550℃后,以芳环链段的重组交联为主要反应。低温炭化温度梯度影响预氧纤维的结构演变进程,当采用350—450—650℃的梯度升温模式时,先经450℃处理的低碳纤维中—C—C基团的¹³C-NMR位移最大,表明纤维内的支化交联反应最多,再经650℃处理的纤维d₀₀₂以及相应高碳纤维的I_A/I_G达到最大,说明其无定形碳相对含量最多,因而最终碳纤维的力学性能最差;当采用350—550—650℃的梯度升温模式时,纤维内裂解与重组交联反应有序开展,低碳和高碳纤维的碳结构更优,最终碳纤维的致密性及力学性能得到提升。     

糠醇树脂炭化产物作为锂离子电池炭电极材料的研究(I)--炭化产物的组成和结构参数测试分析

测试分析了炭化处理条件对糠醇树脂炭化产物组成和结构的影响.结果表明:糠醇树脂炭化裂解过程首先是五员杂环内的碳氧键发生断裂,引起碳氢键断裂.然后经过重排又转变成了一个具有碳碳双键的六员环体系,并在此基础上进一步发生脱氢反应.还原性气氛中,经620 ℃炭化处理的样品出现了明显尖锐的(100)晶面特征衍射峰,同时还发现了(110)和(006)晶面特征衍射峰,表明糠醇树脂是一种较易石墨化的树脂材料.炭化样品比表面积均随着处理温度升高而下降.还原性气氛中700 ℃和1 000 ℃炭化处理的样品与620 ℃炭化处理的样品相比,比表面积分别下降了约11.2 %和35.2 %.处理气氛对炭化产物比表面积的影响表现得更为显著.700 ℃惰性气氛中炭化处理的样品与还原性气氛中处理的样品相比,比表面积降低了约61.5 %.     

工业配煤焦炭中复杂微结构、组分及其化学状态分析

用XRD、HRTEM、XPS以及SEM/EDS等手段对配合煤大生产焦炭进行表征和分析,研究了焦炭基质中碳质微晶结构、碳与氧等元素的结合形态,以及矿物质在焦炭基体中的存在形态,揭示了焦炭的本征结构。结果表明,焦炭中碳质结构是由结构规整的类石墨微晶和形状结构不规则的无定形炭构成,其中类石墨层片大小约为4 nm,堆叠厚度约为1.9 nm,且空间排列较为有序。碳与氧的结合形式主要是碳氧单键,其次是羧基和羰基,碳氧键合对焦炭中的类石墨微晶结构有一定的破坏,从而对焦炭的反应性(CRI)、反应后强度特性(CSR)产生影响。焦炭中的灰分主要有SiO_2和"Al-Si-金属元素"两种矿物形式存在,且复合氧化物熔点较低,在焦炭基质中呈现球状形态。     

预氧化聚碳硅烷先驱体转化法制备SiC陶瓷介电和吸波性能研究

通过聚碳硅烷(PCS)预氧化后在800~1 200℃热解制备了SiC陶瓷,采用傅里叶转化红外光谱(FTIR)与拉曼光谱分别对不同温度交联后PCS及裂解产物进行了表征。并用矩形波导法测试了SiC陶瓷在8.2~12.4GHz(X波段)频段的复介电常数,利用传输线理论计算了试样的反射率。结果表明,氧化交联过程中PCS通过Si—H键和Si—CH_3键与氧反应形成Si—OH键。SiC陶瓷中自由碳有序度随着热解温度的升高而增加,导致复介电常数实部及虚部增加。170℃交联,1 200℃热解,试样厚度为3.5 mm的SiC陶瓷,吸收峰值为-18dB,X全波段反射率低于-10dB,呈现出较好的吸波性能。     

一种碳前驱物热解反应的热力学和动力学研究

根据量子化学理论研究了碳前驱物CH3－Ar-CH2-NH2的热裂解机理,利用Gaussian98程序包听AM1法,用UHF计算对化合物五种可能的热裂解路径进行了热力学和动力计算,结果表明,碳前驱物CH3－Ar-CH2-NH2将首先发生生成自由基CH3－Ar-CH2和NH2．的热裂解主反应,活化能Ea=230.78kg/mol,而碳前驱物CH3－Ar-CH2-NH2的实验表观活化能Ea=206.78kg/mol.键能的计算值与实验值符合得比较好,通过分析优化的反应物及产物自由基的部分结构参数,了解了理论支持主反应原因,计算的产物自由基的空间构型表明主反应路径生成的产物自由基相互间若进行筒环缩合反应,获得得分子平面取向性很好的稠环芳烃产物。     

超支化聚碳硅烷的掺硼改性与陶瓷化研究

通过二甲基胺硼烷(DMAB)与烯丙基超支化聚碳硅烷(AHPCS)反应合成含硼聚碳硅烷先驱体,后经170℃热交联及高温裂解制备出碳化硅陶瓷。采用傅立叶红外光谱、热重分析、X射线衍射分析及扫描电子显微镜对上述过程进行研究。结果表明,DMAB中的B—H键可分别与AHPCS中的CC键及Si—H键发生硼氢化反应和脱氢偶合反应,从而促进AHPCS的热交联,并显著提高陶瓷产率。此外,硼的引入还可有效抑制β-SiC在高温下的结晶。     

聚二甲基硅烷质量的评估方法

聚碳硅烷(PCS)是生产碳化硅陶瓷和碳化硅纤维的先驱体,由聚二甲基硅烷(PDMS)经高温热解重组获得。文中采用在线热裂解-气相色谱-质谱对PDMS热裂解碎片进行分离和结构分析。通过将不同的PDMS谱图与标准样品谱图进行对比,定量确定不同PDMS的相似度,然后根据PCS的纺丝性能评价PDMS的质量,从而建立PDMS热裂解-气相色谱-质谱图与PDMS质量等级之间的相关性,以及建立以Pearson相关系数为定量指标、评估PDMS质量等级的方法。     

氧化石墨烯/呋喃树脂复合材料的制备及其性能

用改良的Hummers法制备出氧化石墨烯(GO),再通过溶液共混,逐步升温固化制备得到GO/呋喃树脂复合材料。利用FTIR、XRD和SEM对GO/呋喃树脂复合材料的微观结构和形貌进行表征,同时对其黏度、玻璃化转变温度、热分解温度、残炭率及硬度进行了检测。结果表明,GO较均匀地分散于呋喃树脂基体中,且两者界面相容性较好。GO/呋喃树脂复合材料的热性能和力学性能相对于纯树脂都有一定的提高。与纯呋喃树脂相比,当GO的添加量为0.3wt%时,GO/呋喃树脂复合材料的玻璃化转变温度提高了36℃,热失重5%时的温度提高了16℃;当GO的添加量为0.1wt%时,GO/呋喃树脂复合材料的残炭率从50.7%提高到53.9%,邵氏硬度从90提高到97。     

Interfacial debonding strength between the edge surfaces of pyrolytic graphite and epoxy resins

The edge surfaces of pyrolytic graphite have been treated by anodic oxidation and the interfacial debonding strength (IFDS) between the oxidized edge surfaces and epoxy resin measured. The unoxidized and oxidized edge surfaces were examined by X-ray photoelectron spectroscopy. The edge and epoxy resin surfaces after debonding test were examined by a field-emission scanning electron microscope. Carboxyl groups were expected to be added in great quantities by breaking the carbon-carbon bonds at the edge surface. On the other hand, hydroxyl groups could be added to edge carbon atoms at the edge surface without breaking the carbon-carbon bonds. The rise in IFDS with anodic oxidation does not correspond directly to the O/C ratios or the amount of carboxyl groups present on the edge surface. Hydroxyl groups added to the edge surface are considered to play an important role in improving the adhesion between the edge surface and epoxy resin through covalent bonds between hydroxyl and epoxy groups. In the case of epoxy resin used in this study, IFDS initially increased to 9 MPa with increasing -OH/C ratio up to about 0.02; thereafter it remains constant at this value. This strength is lower than those of PG and epoxy resin.     

酚醛树脂/木粉复合材料制备木材陶瓷结构变化过程研究

酚醛树脂/椴木木粉复合材料经高温真空碳化制成了木材陶瓷。利用XRD、SEM和FTIR技术对碳化温度和酚醛树脂/木粉质量比对木材陶瓷物相、微观结构和物理化学结构变化的影响进行了表征和研究。结果表明,木材陶瓷具有拓扑均匀的连通孔的三维网络结构,是含有C C、C—O—C和C—H等基团的类石墨结构的碳/碳复合材料;随碳化温度的升高,(002)峰强度增大,晶面间距d₍₀₀₂₎降低,碳化木粉收缩,其间隙增大;酚醛树脂/木粉质量比增大,浸渍树脂的木粉成形能力改善,所得木材陶瓷结构更均匀,但其对木材陶瓷的XRD衍射花样影响不大。      

孔道可控的酚醛树脂多孔碳支架的制备研究

利用光固化快速成型技术, 设计制作了有网格孔道结构的制件阴模, 制成了孔道结构可控的多孔碳支架. 用TGA研究了光固化树脂、酚醛树脂和淀粉的热分解行为; 用XRD、FTIR和SEM技术研究了碳支架的物相组成和微观结构; 用Archimedes法测定了热解碳的显气孔率和密度. 结果表明: 碳支架为非结晶性物质, 呈无定形乱层石墨结构, 随碳化温度的升高石墨化程度提高; 碳支架中仍含有微量的C-H键; 碳支架中的气孔相包括孔道、大孔(d=10～50μm)和微孔(d=1～3μm); 构造的孔道有利于避免碳支架的破裂.     

碳纤维增强酚醛树脂/石墨复合材料双极板的低温热模压试验研究

介绍了国外制备树脂/石墨复合材料双极板的研究结果.研究了低温热模压成型工艺制备酚醛树脂/石墨复合材料双极板,结果表明:酚醛树脂含量为15wt%时,复合材料的导电性能满足双极板的要求,但力学性能偏低.提出了碳纤维增强的解决方案,研究了碳纤维表面处理方法以及碳纤维含量对复合材料导电性能与力学性能的影响.得到对碳纤维进行液相氧化处理,碳纤维含量3wt%是综合性能较好的一种试验方案.采用低温热模压工艺制备低成本酚醛树脂/石墨复合材料双极板,双极板材料的性能突破必将促进燃料电池的商业化发展.     

Friction and Wear Behavior of Resin/Graphite Composite under Dry Sliding

The friction and wear behavior of resin/graphite composite has been investigated using a pin-on-disc configuration under dry sliding condition. The results showed that the resin/graphite composite exhibited much better mechanical and tribological properties compared with the unimpregnated graphite. The friction coefficient was reduced by addition of furan resin, which could also prevent the"dusting" wear at loads more than 15 MPa. The steady and lubricated transfer film was easily formed on the counterpart surface due to the interaction of furan resin and wear debris of graphite, which was useful to reduce the wear rate of the resin/graphite composite. The composite is highly promising for mechanical sealing application and can be used at high load for long time sliding.     

Change in the chemical structures of carbon black and active carbon caused by CF4 plasma irradiation

Carbon black and active carbon were fluorinated by exposure to CF₄ plasma. Their surface chemical structures were studied by means of elemental analysis, X-ray photoelectron spectroscopy, and inverse gas chromatography as a function of treatment time. Fluorine is mainly introduced onto the carbon black and active carbon surfaces during the CF₄ plasma treatment. The amount and type of carbon-fluorine (C-F) functionality formed on the surfaces of the carbon materials depends on the C-C framework structure as well as the plasma treatment time. C1s chemical shifts caused by C-F bonds on the fluorinated active carbon and carbon black surfaces are slightly different from those reported on the various types of fluorinated organic polymers, and have a somewhat ionic character. For the fluorinated active carbon the C-F bond is relatively stable, whereas for the fluorinated carbon black the C-F bond is unstable and has a significant ionic character. In addition, CO₂ gas adsorption characteristics on the fluorinated active carbon can be controlled by the surface C-F functionality.     

苯酚电聚合膜修饰炭纤维表面对 环氧基复合材料性能的影响

将连续炭纤维束用自制的空气梳分散成单丝状长带后, 通过采用循环伏安法的电化学方法将单体苯酚在炭纤维表面聚合成膜, 对炭纤维进行表面修饰, 以提高复合材料中炭纤维与树脂基体的界面粘结性能。红外光谱分析表明, 苯酚电聚合膜能够增加炭纤维表面的羟基、 醚键等活性官能团, 从而提高炭纤维与环氧树脂基体的界面粘结强度。与未进行表面修饰的炭纤维增强环氧树脂复合材料相比, 以聚苯酚膜修饰的炭纤维单丝带增强的环氧树脂基复合材料横向拉伸强度最大提高了90%, 纵向拉伸强度最大提高了45%, 层间剪切强度最大提高了110%。实验也表明, 将炭纤维束分散成炭纤维单丝带后能够更有效地增强复合材料的各项力学性能。      

Anthraquinonedisulfonate electrochemistry: a comparison of glassy carbon, hydrogenated glassy carbon, highly oriented pyrolytic graphite, and diamond electrodes

The electrochemistry of anthraquinone-2,6-disulfonate (2,6-AQDS) at glassy carbon (GC), hydrogenated glassy carbon (HGC), the basal plane of highly oriented pyrolytic graphite (HOPG), and boron-doped diamond was investigated by cyclic voltammetry and chronocoulometry. Quantitative determination of the surface coverage and qualitative assessment of the physisorption strength of 2,6-AQDS adsorption on each of these electrodes were done. The diamond and HGC surfaces are nonpolar and relatively oxygen-free, with the surface carbon atoms terminated by hydrogen. The polar 2,6-AQDS does not adsorb on these surfaces, and the electrolysis proceeds by a diffusion-controlled reaction. Conversely, the GC and HOPG surfaces are polar, with the exposed defect sites terminated by carbon-oxygen functionalities. 2,6-AQDS strongly physisorbs on both of these surfaces at near monolayer or greater coverages, such that the electrolysis proceeds through a surface-confined state. Less than 40% of the initial surface coverage can be removed by rinsing and solution replacement, reflective of strong physisorption. The results show the important role of the surface carbon-oxygen functionalities in promoting strong dipole-dipole and ion-dipole interactions with polar and ionic molecules such as 2,6-AQDS. The results also support the theory that diamond electrodes may be less subject to fouling by polar adsorbates, as compared to GC, leading to improved response stability in electroanalytical measurements. The relationship between the 2,6-AQDS surface coverage, the double-layer capacitance, and the heterogeneous electron-transfer rate constant for Fe(CN)(6)(3)(-)(/4)(-) for these four carbon electrodes is presented.     

Development of a carbonization-in-nitrogen method for measuring the fiber content of carbon fiber reinforced thermoset composites

Carbon fiber reinforced thermoset composites such as carbon fiber epoxy composites are widely used in aircraft and aerospace, and are being increasingly used in automotive applications because of their lightweight characteristics, high specific strength, and stiffness. The carbon fiber content in the composite plays a critical role in enhancing structural performance. The carbon fibers contribute to the strength and stiffness; therefore, the mechanical properties of the composite are greatly influenced by the carbon fiber content. Measurement of carbon fiber content is essential for product quality control and process optimization. In this work, a novel carbonization-in-nitrogen (CIN) method is developed to characterize the fiber content in carbon fiber thermoset composites. A carbon fiber composite sample is carbonized in a nitrogen environment at elevated temperatures, alongside a neat resin sample. The carbon fibers are protected from oxidization while the resin (the neat resin and the resin matrix in the composite sample) is carbonized under nitrogen environment. The neat resin sample is used to calibrate the resin carbonization rate and calculate the amount of the resin matrix in the composite sample. The new method has been validated on several thermoset resin systems, and found to yield accurate estimation of fiber content in carbon fiber thermoset composites.