CDF分析方法研究取向非晶PET的结构

用对称透射法收集聚酯(PET)单轴拉伸取向非晶薄膜样的二维广角X射线散射强度I_C(K,(?)),将不同方位角(?)上的I_C(K,(?))非晶重叠峰曲线进行计算机分峰,获得伊易空间中分子链间原子散射引起的2个主峰:K_A(K=0.122),K_B(K=0.171),分子链内原子散射引起的2个主峰;K_C(K=0.310),K_D(K=0.548).进一步通过抽样转换法由强度函数I_E(K,(?))计算出实空间的圆柱分布函数CDF(R,α),得到与K_A,K_B,K_C和K_D峰对应的实空间的峰依次为R_A(R=0.658),R_B(R=0.456),R_C(R=0.253)和R_D(R=0.152).从理论上分析了上述相应峰在倒易空间和实空间中的等效关系及其分布特征,以及引起这些峰的结构起源,详细地研究了取向非晶PET的细微结构信息.     

双轴拉伸PET薄膜成膜过程非晶区分子取向的WAXS研究

本文将常应用于小的角度范围(29_(CuK_α)<50°)的结晶峰和非晶峰的计算机分峰法,推广到PET薄膜的广角度散射范围(2θ_(CuK_α)=5°—140°)。通过对分离出来的表征非晶区分子链间分布的非晶主峰特征参数的分析,探讨了在特定拉伸条件下非晶区分子取向在成膜过程的变化。     

FRS—XRSA表征双轴取向PET的结晶度

全倒易空间Ｘ－射线散射理论分析（ＦＲＳ—ＸＲＳＡ）是研究与表征择优取向高聚物结晶度与取向分布的一种新方案，它可以解决粉沫法测定结晶度时取向试样难以消取向的困难，测定拉伸和回复过程中正在形变的取向试样的结晶度．在以前的工作中，对双轴取向的薄膜，仅进行了幅度β＝０°（ＭＤ）与９０°（ＴＤ）两个轴向，△α＝１０°的ＸＲＳ测定，这样推得的结晶度事实上是ＭＴ双轴ＸＲＳ的结晶度，即ＭＴ－ＸＲＳ结晶度Ｘ，这种处理包含着ＸＲＳ沿ＭＴ方向作均匀分布的近似．本文为了澄清这一问题，作了下述三点改进：第一，利用ＦＲＳ中ＸＲＳ的强度分布，内插计算αｉ；，βｉ＝０°～９０°，△βｉ＝１０°的ＸＲＳ，由此求得较符合理论要求的ＦＲＳ－ＸＲＳ结晶度Ｘ；第二，进行了ＦＲＳ－ＸＲＳ的极角因子ｃｏｓαｉ；校正；第三，合理地处理了当极角αｉ＝９０°时出现奇点的困难．结果较合理．同时亦获得了晶粒度在ＦＲＳ中的分布情况．     

尼龙-1010结晶结构

用WAXD方法测定了Nylon-1010为三斜晶系结晶结构;α=4.9(?),b=5.4(?),c=27.8(?),α=49°,β=77°,γ=63.5°,每个聚合物单胞含有一个重复单元,空间群为P(?)。模压试样用Ruland方法分析结晶度为60％。以上。电子密度相关函数法分析了SAXS现象,求得了Nylon-1010结晶片层厚度、过渡层厚度、长周期、比内表面及电子密度差。     

工业用涤纶纤维热收缩性能与结构关系的研究

选择国内外不同厂家生产的ＰＥＴ工业用纤维,用小角Ｘ 射线散射法、广角Ｘ 射线衍射法、密度法、双折射法测定的数据详细分析其结构情况,同时测定纤维的干热空气收缩性能,进一步研究其微观结构与宏观热收缩性能之间的关系．指出用ＡｃＸＬｆｖｃ／ｆａ综合结构参数基本慨括了影响工业用ＰＥＴ纤维热尺寸稳定性的结构因素,同时特别强调晶粒的完善程度和形成完善、连续网的重要作用     

用X射线研究煤中大分子的结构

煤的大分子结构可用化学方法和物理方法进行研究。在化学方法中,煤结构统计分析法占有重要地位,但其结果存在一定统计误差。本文研究了一系列不同级别煤的高角X射线散射强度,结果表明,随煤级别增高,煤大分子结构的X射线参数的变化是连续的。显然,这一工作对于研究煤中大分子的结构是很有意义的。     

聚丙烯腈基碳纤维中微孔洞的一维多取向小角X射线散射研究

应用一维多取向小角X射线散射(SAXS)方法研究了聚丙烯腈(PAN)基碳纤维中微孔洞的形态.结果表明,这些微孔洞沿纤维轴方向呈针状,并与纤维轴呈Φ=14°角的取向排列;微孔洞投影在碳纤维横截面上的平均半径R=1.14nm,投影在碳纤维轴向上的平均长度L=17.97nm.建立的一维多取向SAXS方法可以得到若干二维SAXS方法才能得到的微孔洞形态及分布信息等参数(如Φ和L),且在各种纤维的微孔洞或微纤维的表征方面具有一定的普适性.     

非晶态镍硼酸盐结构的EXAFS研究

由摩尔比分别为1:2和1:8的NiCl₂·6H₂O和Na₂B₄O₇·10H₂O作为反应物, 合成两种非晶态镍硼酸盐, 同时通过水热法合成β-Ni(OH)₂. 化学分析和热重-微商热重法(TG-DTG)分析结果确定两种非晶态镍硼酸盐的分子组成分别为NiO·0.8B₂O₃·4.5H₂O和NiO·B₂O₃·3H₂O. 激光拉曼(Raman)实验结果表明镍硼酸盐样品中主要存在的硼氧阴离子为B₃O₃(OH)₅^2-和B₂O(OH)₆^2-. 同步辐射扩展X射线吸收精细结构(EXAFS)方法对样品进行结构解析, 通过数据拟合给出样品中Ni 原子周围近邻配位原子种类、配位数以及原子间距离. 用不同晶体结构作为标准对两种非晶态镍硼酸盐进行拟合的结果表明, 样品中Ni 原子周围局域结构与Ni₃B₂O₆晶体(ICSD No.31387)中的吻合较好. Ni 原子周围配位原子为O、B和Ni, 对于NiO·0.8B₂O₃·4.5H₂O, 配位数分别为5.7、3.8和3.8, 配位距离分别为0.208、0.263 和0.311 nm; 对于NiO·B₂O₃·3H₂O, 配位数分别为6.0、4.0 和4.0, 配位距离分别为0.207、0.262和0.310 nm.     

低温等离子体处理聚酯(PET)表面润湿性与表面结构的研究

研究了O₂、N₂、He、Ar、H₂和CH₄气体低温等离子体改性聚酯(PET)的表面润湿性与表面结构的关系.用已知表面张力的液体测定接触角,作Zisman曲线,求得试样的临界表面张力γ_c;并按扩展的Fowkes式计算试样的表面张力γ_s及其三组分值γ_s^a(色散力)、γ_s^c(偶极矩力)和γ(氢键力),发现经O₂、N₂、He和Ar等离子体短时间处理的聚酯表面自由能显著增大,表面润湿性增强,主要是聚酯表面张力的氢键力成分的贡献,X射线光电子能谱分析表明,这是由于聚酯表面含氧或含氮极性基团增加所致.     

NaCl、KCl、Na_2CO_3、K_2CO_3等电解质溶液对含水卵磷脂液晶结构影响的SAXS研究

关于电解质溶液对卵磷脂液晶结构的影响前人有过报导。例如Chapman和G. Shiply等在研究碱金属氯化物对卵磷脂液晶结构的影响时指出:随着Li~ 到Cs~ 离子半径增加,脂双层的厚度也发生相应变化。Plainer等也指出KCI,NaCl溶液使磷脂层厚度发生变化。关于磷脂蛋白复合膜与Na~ ,K~ 、Ca~(2 )离子的作用也有一些报导。本文报导用小角X射线散射(SAXS)方法研究几种电解质溶液对卵磷脂形成液晶结构的影响。     

温度对液态水结构的影响：中子及X射线散射研究

采用中子散射和X射线散射研究了液态水在298～373 K温度范围内的结构,通过偏径向分布函数(PDF)、配位数分布(CN)、角分布(ADF)及空间密度分布(SDF)等讨论了温度对液态水结构的影响。整体来看,液态水具有"不规则四面体"氢键网络的短程有序结构,该有序度可延续到第三水合层。液态水分子的第一水合层中,围绕中心水分子约有4.8个水分子,然而其中仅有约3.3个水分子与中心水分子通过氢键相键合,约1/3进入到第一水合层的水分子并未与中心水分子直接键合,也正是这些间隙水分子的存在加剧了液态水结构的复杂性。温度对液态水的有序度存在一定的影响,在298～373 K的有限温度变化范围内,温度对液态水中氢键的键长、键角分布及第一水合层SDF的影响不大。从298K升温到373K,O(W)-O(W)距离仅增加0.03?,氢键数目也仅有微小减少,温度对第二和第三水合层的影响则要显著很多。     

Structure and anisotropy in polycarbonate. I. Short range order of amorphous polycarbonate revealed by WAXS

Wide angle X-ray scattering (WAXS) was performed on isotropic and uniaxial drawn samples of polycarbonate (PC). The density correlation functions are calculated from X-ray scattering intensity data and the short range order is discussed. A distinction between intra- and intermolecular correlations can be made. Orientation of PC does not change the short range order up to 1.5 nm.Dedicated to Prof. Dr. H.-G. Kilian of his 60th birthday. With gratitude for the vivid introduction into the science of polymers.     

Investigation of Voids in Polyacrylonitrile Fibers by USAXS and SAXS

The void structure of polyacrylonitrile(PAN) fibers was investigated using ultra-small angle X-ray scattering(USAXS) and small angle X-ray scattering(SAXS). A quantitative method was developed to analyze connected USAXS/SAXS data and thus determine the void parameters of PAN fibers. The results showed that voids affected the mechanical performance of PAN fibers and were present throughout the entire wet-spinning process. When the absolute quantity and size of voids decreased, the tensile strength and modulus of PAN fibers increased. The void parameters were optimized by controlling the production process, and thus the tensile strength and modulus of PAN fibers were increased. The method for analyzing the void structure developed in this study is useful for analyzing voids over with larger size range, as well as the effect of the void structure on the mechanical performance of fibers.     

Structural study of oriented non-crystalline PET by CDF method

The two-dimensional wide angle X-ray scattering (WAXS) intensities of oriented non-crystalline polyethylene terephthalate (PET) films extended umaxially are collected by the symmetrical transmission method; he-sides,the overlapped non-crystalline peaks at WAXS intensity curves,I(K) obtained at different azimuthal angles are also separated by computer,resulting in two peaks caused by interchain atomic scattering in the reciprocal space,KA(K=0.122),KB(K=0.171),and the other two peaks from intracham atomic scattering,Kc(K=0.310) and KD(K=0.548); their cylindrical distribution functions (CDF),CDF(R,α) in the real space are further calcu lated from the intensity functions,IE(K) using sampled transforms,thereof arising in turn the peaks in the real space as,RA(R=0.658),RB(R=0.456),RC(R=0.253) and RD(R=0.152),corresponding to KA,KP,K,and KD The equivalent relationships and distribution characteristics of the above-mentioned corresponding peaks in the reciprocal and real space,as well as their sources of struc     

WAXS analysis of structural changes of poly(ethylene terephthalate) fibers induced by supercritical-fluid dyeing

 Supercritical CO₂ fluid, a new environmentally friendly dyeing medium, changes the fiber structure to a certain extent in dependence on the treatment temperature and pressure used. Therefore the changes of crystalline structure in poly(ethylene tereph-thalate) (PET) fibers as brought about under the influence of supercritical CO₂ fluid were investigated. For the data collection of wide-angle X-ray diffraction full patterns a two-circle goniometer, equipped with a position sensitive detector, was used. From the observed two-dimensional fiber diffraction patterns the crystallinities of various treated fibers were evaluated. The equatorial scanning yielded the dimensions of crystallites. To elucidate the fiber-surface morphology changes SEM analyses were performed. The supercritical fluid dyeing of PET fibers with highly developed microfibrillar structure under taut-ends conditions promotes changes which are characterized by an increase in crystallinity and by diminution of the apparent crystallite dimensions. Some changes of surface morphology of dyed fibers were observed as well. Received: 14 May 1997 Accepted: 23 September 1997     

Structures of 18-Crown-6 Complexes with Alkali Cations in Methanolic Solution as Studied by X-ray Absorption Fine Structure

The structures of 18-crown-6 (18C6) complexes with K⁺ and Rb⁺ in methanolic solutions have been studied by X-ray absorption fine structure (XAFS) at the Br K-edge as well as at the K and Rb K-edges. The XAFS spectrum at the K or Rb K-edge has indicated that either Br⁻ or solvent (methanol) molecules are present in the first coordination shell of K⁺ or Rb⁺ complexed by 18C6. However, the spectra obtained at the Br-K edge have strongly suggested that the alkali cations do not exist in the vicinity of Br⁻, indicating that no direct ion-pairing occurs between the 18C6 complex and Br⁻. The 18C6-K⁺ complex maintains D _3d symmetry even in methanol, and two methanol molecules coordinate the cation possibly from above and below the crown plane. In contrast, the corresponding Rb⁺ complex possibly forms an umbrella-shaped complex, in which Rb⁺ is situated slightly off the crown plane and three solvent molecules bind With the cation.     

Structure of AcMet-Gly and Its Interaction with Palladium(II) Tetraaqua Complex Studied by Electrospray Mass Spectrometry and Density Functional Theory

Introduction Palladium(II) complexes, as a promising artificial metallopeptidase, have been extensively studied for se-lective cleavage of methionine and histidine-containing dipeptides,1-11 oligopeptides12-16 and proteins.16-20 Dipeptides AcMet-aa and AcHis-aa, in which the amino-terminus is protected by acetylation and aa is an amino acid residue, are usually cleaved at the Met-aa and His-aa bond with a modest but significant turn-over.6,7,9 In oligopeptides which contain Met or His or b…     

Ammonia Catalyzed Hydrolysis-Condensation Kinetics of Tetraethoxysilane/Dimethyldiethoxysilane Mixtures Studied by <Superscript><Emphasis Type="Bold">29</Emphasis></Superscript>Si NMR and SAXS

In-situ ²⁹Si liquid-state nuclear magnetic resonance (NMR) was used to investigate the ammonia catalyzed hydrolysis and condensation of the mixed systems of tetraethoxysilane (TEOS) and dimethyldiethoxysilane (DDS) dissolved in methanol. With ammonia catalysis, the hydrolysis reaction orders for TEOS and DDS in the mixed systems remained first order, which is similar to that observed for their corresponding single silane component precursor systems. The hydrolysis rate constant for TEOS in the mixed systems was larger than that of TEOS in the single silane component precursor systems. Meanwhile, the hydrolysis rate constants of DDS in the mixed precursor systems were smaller than those of DDS in the single silane component precursor systems. The hydrolysis and condensation kinetics showed more compatible hydrolysis-condensation relative rates between TEOS and DDS, which remarkably affected the final microstructure of the resulting silica particles. Small angle X-ray scattering (SAXS) experiments showed a typical double fractal structure in the particulate networks.