微观结构对中间相沥青基炭/炭复合材料力学性能的影响

借助偏光显微镜、扫描电镜、透射电镜以及力学性能测试研究了微观结构对中间相沥青基炭/炭复合材料力学性能的影响. 结果表明: 基体炭在偏光显微镜下呈现出光学各向异性, 在SEM和TEM下呈片层条带状结构. 基体炭与纤维之间的界面不连续, 为“裂纹型”界面. 材料受载破坏时裂纹通过改变扩展路径而延缓其扩展速度, 在纤维-基体界面处以及基体炭层片之间引起滑移, 在断口形貌上体现出断裂台阶适中且与纤维拔出交替进行, 表现出韧性破坏的断裂特征. 材料具有较高的力学性能, 抗弯强度达到257MPa, 断裂韧性达到11.4MPa·m ^1/2.     

碳质中间相形成机理研究

碳质中间相是制备高性能炭材料制品的优质前驱体，其产品已在高性能复合材料、超高功率石墨电极和二次锂离子电池用负极材料等方面得到了成功应用。碳质中间相产品的结构复杂、形态各异，造成了生产这些产品涉及的原料和处理过程的多样化。为了分析和预测一定条件下获得的碳质中间相产品的性能，进而确定其具体的用途，需要弄清碳质中间相的形成机理。通过系统地探讨碳质中间相的形成过程，对以往文献中的解释给予了归纳和分析。分析认为传统解释中存在许多不合理的地方，不能对一些现象给予合理的解释；“微域构筑”理论在传统解释的基础上有了很大进步，但由于该理论中引入了实际上并不存在的片层微晶单元而使其存在缺陷；“颗粒基本单元构筑”理论摒弃了以上两种理论中的不合理成分，能够对碳质中间相的形成过程进行很好的解释。此外，对“颗粒基本单元构筑”理论的一些应用也进行了讨论。     

同步氢化/热缩聚法制备中间相沥青的工艺研究

系统地研究了在氢化剂量固定情况下,反应温度与时间对同步氢化/热缩聚法所制得的中间相沥青(MP)性质的影响,并制得了可纺MP。研究表明反应时间同为4h时,MP的软化点和不溶分含量随反应温度的提高而升高;偏光结果显示,低温产物为中间相小球和各向同性基质的混合物,高温产物为连续中间相。反应温度同为410℃时,MP软化点和不溶分含量均随反应时间的延长而显著提高,经历了从中间相小球到小球发生融并,最后形成了马赛克织构的中间相。纺丝性能测试表明,反应温度为410或420℃,反应4h制得的中间相沥青,可以熔融纺丝,经氧化和碳化后制得两组碳纤维。     

沥青基碳/碳复合材料的组织特性

以 １Ｋ ＰＡＮ基碳纤维为增强体、以调制中温煤沥青为基体前躯体,分别在常压下和高压（４０ＭＰａ、８０ＭＰａ）下制备出了沥青基碳／碳复合材料。借助偏光显微镜对碳／碳复合材料试样进行的微观组织的观察发现,碳基体中既有域组织,也有镶嵌组织,而焦炭主要为细镶嵌组织．偏光试样经过酸液氧化腐蚀处理后,利用电子显微镜对其扫描观察,发现各向异性区域呈现出流线组织特征,流线纹路的疏密与沥青碳化时的压力有关．压力越高,纹路越密实,表明碳层面的取向性也就越好．     

溶胶-凝胶法制备二元炭质-TiO_2气凝胶前驱体

以炭质水性中间相和四氯化钛为原料 ,分别制取了炭质溶胶 -凝胶和钛溶胶 -凝胶 ,然后将二者充分搅拌混合后 ,再进行超临界干燥制得了二元炭质 /二氧化钛气凝胶粉末前驱体。利用 FT- IR,XRD和 TEM技术对二元炭质 /氧化钛粉末进行了表征。研究结果表明 ,二元炭质 /氧化钛粉末具有小于 10 nm的颗粒尺寸 ,炭和氧化钛混合均匀且具有较高的比表面和疏松的表观结构。     

Morphological structure study of pitch fibre surfaces by scanning tunnelling microscopy: influence of the mesophase content

The surface morphology of pitch fibres with different mesophase contents was studied by scanning tunnelling microscopy (STM) and the results were related to their mechanical properties. The tensile strength and modulus increase with the mesophase content and correspondingly the surface structure becomes more anisotropic. Inversely, the STM method can also be used to evaluate the precursor mesophase content of a pitch-based carbon fibre.     

具有中间相沥青过渡层的炭/炭复合材料的微观结构与力学性能

采用液相浸渍-炭化和CVI复合工艺, 制备出在炭纤维和热解炭之间具有中间相沥青过渡层的炭/炭复合材料, 借助偏光显微镜、扫描电镜、透射电镜以及力学性能测试研究了所制备的炭/炭复合材料的微观结构与力学性能. 结果表明: 在偏光显微镜下中间相沥青炭的光学活性高于热解炭的光学活性, 中间相沥青炭在SEM和TEM下均呈片层条带状结构, 热解炭在SEM下呈“皱褶状”片层结构, 在TEM下为粒状结构; 在HRTEM下, 中间相沥青炭、热解炭和炭纤维的晶化程度依次降低. 在加载过程中, 材料内部多层次的界面通过改变裂纹扩展路径而延缓其扩展速度, 在断口形貌上体现出锯齿状的断裂形式, 纤维拔出长度适中, 材料表现出韧性破坏的断裂特征. 材料具有较高的力学性能, 抗弯强度达到244MPa, 断裂韧性达到9.7MPa·m^1/2.     

Blending mesophase pitch to improve its properties as a precursor for carbon fibre Part 1 Blending of PVC pitch into coal tar and petroleum-derived mesophase pitches

The blending of mesophase pitch with isotropic PVC pitch was studied to improve their properties as a precursor for carbon fibre. PVC pitch prepared at 420° C which remained almost isotropic was found to be miscible with coal tar-derived mesophase pitch without reducing the anisotropic content and spinnability. The tensile strength of pitch fibres remained unchanged by the blending; however, the reactivity for stabilization was enhanced. The resultant carbon fibres from the blend exhibited slightly higher tensile strength. In contrast, petroleum-derived mesophase pitch failed to dissolve the PVC pitch, leaving a number of isotropic droplets. The structural factors of mesophase pitches with regard to their compatibility with PVC pitches are briefly discussed.     

Alignment change of hexahexylthiotriphenylene in the helical columnar phase by infrared laser irradiation

Alignment change of discotic liquid crystal domains induced by infrared irradiation was investigated for the helical columnar phase of hexahexylthiotriphenylene. A uniform and anisotropic alignment change was observed when a linearly polarized infrared light was irradiated. It was found that the IR laser irradiation leads to a homogeneous planar alignment even in the helical columnar phase which is highly ordered mesophase. The in-plane order parameter of triphenylene ring was estimated to be 0.82 from the dichroic ratio obtained by polarized infrared absorption measurements. The results strongly imply that the infrared irradiation is a possible technique for device fabrication by use of the helical columnar phase which exhibits a high carrire mobility (~ 10^− 1 cm² V^− 1 s^− 1).     

Quantum phase measurements and non-classical polarization states of light

Abstract

In our paper we consider the non-classical behaviour of both the Hermitian (observable) Stokes parameters of light and the phase difference of two modes that describe the quantum polarization states of optical field. To characterize the degree of polarization of light we introduce a new quantity taking into account the quantum properties of different quantum states of two orthogonally polarized modes. The problem of determination of the phase difference in two modes of optical field for the quantum polarization states of light is discussed. To describe in general such a quantum field we introduce two pairs of the phase operators: the phase angles for the Stokes parameters of light in a three-dimensional picture of the Poincaré sphere. We also consider a special type of the eight-port polarization interferometer (polarimeter) for simultaneous homodyne detection of both the Stokes parameters of light and the polarization phase operators and their fluctuations as well. Using an anisotropic (spatioperiodic) Kerr-like nonlinear medium associated with the polarization interferometer we could generate and also observe the polarization-squeezed phase states of light. The fluctuations in the phase difference between two orthogonally polarized modes for these non-classical states are less than the fluctuations for light in coherent state.     

聚丙烯腈基炭纤维的扫描隧道显微镜研究

用扫描隧道显微镜研究聚丙烯腈基炭纤维的表面结构以及经过电化学腐蚀、拉伸试验和高温处理后的表面变化。未处理的纤维表面由沿纤维轴向排列的宽度不等的带状细纤维组成。随着放大倍数增加，表面显得粗糙，细纤维上分布着许多小晶粒，另外，还发现了构面炭纤维的细纤维呈螺旋结构环绕、沿轴向伸长，经电化学腐蚀后，纤维内部仍存在螺旋结构，经过拉伸的炭纤维。在其临近裂的区域里，观察到扩展的孔洞及周围不均匀区。     

Structure of mesophase pitch-based carbon fibres

The structure of five samples of commercially available carbon fibres with ultra-high modulus produced from mesophase pitch was studied by the complementary techniques of high resolution electronmicroscopy, X-ray diffraction and transverse magnetoresistance effect. The fibres with high strength and elongation to failure were found to be composed of turbostratic carbon structure, which was different from the three-dimensional graphite structure in ultra-high modulus carbon fibres. Transmission electron microscope examination revealed that the mesophase pitch-based fibres with high strength have a basic structure unit with folded sheets arranged nearly parallel to the fibre axis similar to those of high modulus carbon fibres produced from PAN. The present fold structure was suggested to contribute consequently to the lower graphitizability of the fibres and to the strong effects on the fibre strength. By controlling the microstructure, it is expected that the crystallographic as well as the mechanical properties could be improved significantly even from the same kind of precursor materials such as mesophase pitch.     

沥青基炭纤维的制备及其表征

石油沥青在氮气氛中420℃热缩聚7h,制得软化点为295℃的炭纤维前驱体沥青.此前驱体沥青在单孔纺丝器中熔纺获得沥青纤维.将沥青纤维于空气中320℃稳定化处理,最后在氮气流中1000℃炭化制成炭纤维.应用SEM、TGA、FTIR和XRD对石油沥青、前驱体沥青、沥青纤维、预氧化纤维和炭纤维分别进行表征.发现:前驱体沥青中含有质量分数70.5%中间相组分,炭纤维具有径核结构,其最大抗拉强度为650MPa.     

New azobenzene polymers for light-controlled optical elements

Three new azobenzene polymers have been synthesized by polymerization of cyanazobenzene monomers with different numbers of methylene groups attached to the cyanazobenzene dye. The rearrangement of the anisotropic azobenzene moieties in them was initiated by illumination with linearly polarized light (488 nm), and the optical anisotropy due to this arrangement has been investigated. The photobirefringence can be erased by illumination with circularly polarized light and re-induced to the same value with linearly polarized light. We show that films from these polymers can be used as optically controlled reversible polarization elements.     

从煤焦油软沥青和苯基硅烷制备硅取代聚芳烃中间相的研究

过滤后的煤焦油沥青分别与一,二,三,四苯基硅烷在1MPa氩气气氛和420℃～460℃温度下共炭化,合成了硅取代聚芳烃中间相。在四种合成中间相中,元素硅的起始加入量均为2%。测定了裂解残留物和硅的收率、可溶性、玻璃转化温度以及裂解残留物的炭收率;并分别以偏光显微镜和电子探针微分析法考察了残留物的微结构和相应的硅分布,硅的收率取决于不同的苯取代硅烷的挥发性和反应性。裂解残留物显示出三种不同的共存相:(a)含有粗镶嵌织构和痕量硅的光学各向异性相;(b)硅含量较高的光学各向同性相;(c)含细镶嵌织构和中等硅含量的光学各向异性相。最后这种中间相主要来自二,三苯取代硅烷与煤沥青的共炭化,是由于硅取代聚芳烃中碳原子并破坏了其分子的平面结构而引起的。     

不同形状中间相沥青炭纤维的横断面结构

在场发射扫描电子显微镜（ＦＥ－ＳＥＭ）下观察了圆形、中空、条形和Ｙ－形中间相沥青炭纤维的横断面结构,用流变学理论分析了纺丝过程中几种炭纤维结构的形成,提出中空纤维纺制时沥青流体的最大流速线在喷丝孔中心线的内侧,并根据中空炭纤维横断面的显微照片对此加以证实,用催化缩聚中间相沥青制备的条形炭纤维显示出的特殊弧形对称结构,起因于中间相沥青的流变性质和条形喷丝孔的形状设计,非圆形中间相沥青炭纤维趋向于以线     

双基体炭/炭复合材料的微观结构与力学性能

借助偏光显微镜、扫描电镜,透射电镜以及力学性能测试研究了微观结构对双基体炭/炭复合材料力学性能的影响.结果表明:基体炭在偏光显微镜下呈现光学各向异性,材料内部形成多层次的界面结构,热解炭呈现"皱褶状"片层结构,中间相沥青炭呈现片层条带状结构,基体炭片层的走向基本上平行于纤维轴向.材料受载破坏时裂纹通过改变扩展路径而延缓其扩展速度,在纤维-基体界面处以及基体炭片层之间引起滑移,在断口形貌上体现出锯齿状的断裂形式,材料具有韧性断裂的特征,抗弯强度最高可达223MPa.     

Morphology change in carbons prepared from pitch-polyvinylchloride mixtures under pressure

Mixtures of fractionated pitches with different molecular weights and polyvinylchloride (PVC) were carbonized at 650°C under a pressure of 30 MPa. The morphology of the carbons obtained was studied under a scanning electron microscope and the optical texture under a polarized light microscope. Gradual changes in morphology are observed, from lump-type to coralloidal through botryoidal with gradual diminution in the size of the primary particles. The content of PVC and also the number-averaged molecular weight were found to govern the morpohology of the resultant carbon.     

Cellulose‐Based Microparticles for Magnetically Controlled Optical Modulation and Sensing

Responsive materials with birefringent optical properties have been exploited for the manipulation of light in several modern electronic devices. While electrical fields are often utilized to achieve optical modulation, magnetic stimuli may offer an enticing complementary approach for controlling and manipulating light remotely. Here, the synthesis and characterization of magnetically responsive birefringent microparticles with unusual magneto‐optical properties are reported. These functional microparticles are prepared via a microfluidic emulsification process, in which water‐based droplets are generated in a flow‐focusing device and stretched into anisotropic shapes before conversion into particles via photopolymerization. Birefringence properties are achieved by aligning cellulose nanocrystals within the microparticles during droplet stretching, whereas magnetic responsiveness results from the addition of superparamagnetic nanoparticles to the initial droplet template. When suspended in a fluid, the microparticles can be controllably manipulated via an external magnetic field to result in unique magneto‐optical coupling effects. Using a remotely actuated magnetic field coupled to a polarized optical microscope, these microparticles can be employed to convert magnetic into optical signals or to estimate the viscosity of the suspending fluid through magnetically driven microrheology.     

前驱体对炭泡沫孔结构的影响

分别以煤沥青、石油中间相沥青和AR沥青为前驱体制备炭泡沫材料。采用GPC测定前驱体分子量,SEM观察所制炭泡沫的孔结构,光学显微镜测量所制炭泡沫的孔径及其分布。结果发现,由于煤焦油沥青不含中间相,且QI含量较高,导致在实验条件下不能直接制备出合格的炭泡沫。以石油中间相沥青和AR沥青为原料均能制备出具有分布均匀开孔结构,且微观各向异性的炭泡沫。由AR沥青制备的炭泡沫呈现平均孔径较小(212μm)、孔壁较薄、孔径分布较窄(180μm~300μm)、开孔率较高、以及韧带排列较规整等特点,表明低QI含量、低分子量且分布较窄的前驱体有利于发泡。