聚酰胺─1010的辐射裂解与后裂解机理的ESR研究

用电子顺磁共振技术（ＥＳＲ）研究了γ－辐照聚酰胺－１０１０中俘获自由基的结构、升温中的转化与行为，及它们与其结构和转变多重性的联系，讨论了聚酰胺－１０１０辐射裂解和后裂解的反应机理及反应区域等问题。

用WAXD和SAXS研究辐照聚酰胺1010结构

用ＷＡＸＤ和ＳＡＸＳ方法研究了聚酰胺１０１０的聚集态结构和结晶结构的辐射损伤过程和机理。辐射交联与裂解主要在非晶区和结晶表面或中间相发生；辐射损伤并从这里开始，随辐射剂量增大，非晶化逐渐向晶区伸展，有氢键的（０１０）晶面损伤几率高于（１００）晶面；辐射后效应导致新的交联与裂解生成，主要影响（０１０）晶面的形成与完善，使Ｌ１００及Ｗｃ变小。

CRYSTAL-STRUCTURE AND THERMODYNAMIC PARAMETERS OF NYLON-1010

WAXD, SAXS, FTIR, DSC and density techniques have been used to investigate the crystal structure, crystal density rho(c), amorphous density rho(a), equilibrium heat of fusion DELTAH(m)degrees and equilibrium melting temperature T(m)degrees. By extrapolating the straight lines in the FTIR absorbance against density plot to zero intensity, rho(c) and rho(a) were estimated to be 1.098 and 1.003 g/cm3 respectively. The rho(c) obtained was too low in value. From X-ray diffraction patterns of uniaxially oriented fibres, the crystal structure of Nylon-1010 was determined. The Nylon-1010 crystallized in the triclinic system, with lattice dimensions: a = 4.9 angstrom, b = 5.4 angstrom, c = 27.8 angstrom, alpha = 49-degrees, beta = 77-degrees, gamma = 63.5-degrees. The unit cell contained one monomeric unit, the space group was P1BAR, and the correct value of rho(c) was 1.135 g/cm3. The degree of crystallinity of the polymer was determined as about 60% (at RT) using Ruland's method. SAXS has been used to investigate the crystalline lamellar thickness, long period, transition zone, the specific inner surface and the electron density difference between the crystalline and amorphous regions for Nylon-1010. The analysis of data was based upon a one-dimensional electron-density correlation function. DELTAH(m)degrees was estimated to be 244.0 J/g by extrapolation of DELTAH(m)degrees in the plot of heat of fusion against specific volume of semicrystalline specimens to the completely crystalline condition (V(sp)c = 1/rho(c)). Owing to the ease of recrystallization of melt-crystallized Nylon-1010 specimens, the well-known Hoffman's T(m)-T(c) method failed in determining T(m)degrees and a Kamide double extrapolation method was adopted. The T(m)degrees value so obtained was 487 K.

尼龙1010结晶与熔融行为的研究

用DSC研究了降温速率R对尼龙10 10结晶与熔融的影响,以及室温(RT)和液氮(LN)骤冷退火样品的熔融.降温时结晶温度随R增大线性降低;T_g以上可完成结晶时结晶度相同;结晶起始温度>181℃生成的晶体有三个熔融峰,对应于环状和放射状球晶的转化与熔融;在181℃和T_g间结晶,无放射球晶转化峰;T_g下有结晶放热峰样品加热时有冷结晶发生.RT未退火样品三个熔融峰,退火温度T_α≥180℃样品两个峰,结晶度C∝T_a;LN未退火样品单一熔融峰,T_a>160℃双峰,T_a≤160℃三峰,低温峰温与C均∝T.

等温熔体结晶尼龙1010的晶体结构

WAXD研究表明,在结晶温度T_c≤196℃时,尼龙1010等温熔体结晶样品的结晶度X_c和微晶尺寸L_(100)随T_c升高近乎线性增大,而氢键面上的相对衍射强度R却降低;T_c>196℃后三者与T_c关系发生相反变化。结晶速率快时有利于分子链在垂直于氢键平面方向上堆砌,反之有利于在平行于氢键平面方向上生长。

尼龙-1010非等温结晶动力学

尼龙-1010是我国独创的工程塑料品种,已被较广泛地应用于精密机械零件、仪表制造、家用电器、航空等方面。有关尼龙-1010的基础研究大多在我国学者中间进行,由于在实际加工生产过程中,如通常的融熔纺丝、注射、模压等工艺均是在非等温条件下进行,有关它的非等温结晶动力学尚未见报道,本文用几种理论方法对尼龙-1010的非等温结晶动力学过程进行研究。

X-射线衍射法测定尼龙1010结晶度

根据X-射线散射强度理论,使用图解多重峰方法对尼龙1010三个结晶峰及非晶峰的衍射强度进行校正,首次导出了尼龙1010结晶度计算公式,所得结果与密度及量热测定结果具有很好可比性。

结晶聚合物的辐射效应 Ⅰ.γ-辐照尼龙1010的聚集态结构

本文通过WAXD和DSC等方法研究了γ-辐照尼龙1010聚集态结构的变化,结晶损伤和无定形化的过程。这些过程和结晶与非晶界面原子参与化学反应密切相关,结晶损伤从结晶表面开始,随着辐照剂量增加逐渐向结晶内伸展,直到完全无定形化。

尼龙1010骤冷退火样品的晶体结构

尼龙1010的晶体结构属三斜晶系.作者最近导出了X射线衍射法(WAXD)测定尼龙1010结晶度的公式,进而考查了等温结晶时结晶温度T_C对结晶度X_C、晶粒尺寸L_(100)和氢键面相对衍射强度R的影响.发现X_C和L_(100)均随T_C升高而增大,达196℃后又减小;而R与T_C的关系则相反,呈线性降低.结晶速率快有利于分子链在垂直于氢键面的(100)晶面生长,但R值却降低了.本文利用WAXD考查了尼龙1010不同骤冷退火条件样品的晶体结构.

尼龙1010骤冷样品的冷结晶与熔融

本文用DSC研究了尼龙1010熔体以—320K/min速率骤冷样品在不同升温速率(R)时的冷结晶与熔融过程。发现冷结晶温度不随R变化,冷结晶时间t_c=153R~(-1.07),冷结晶热ΔH_c=-19.1R~(-0.75);R对熔融温度无影响,当R≤40K/min时,熔融热ΔH_m变化不大;由ΔH_m和ΔH_c求得的结晶度有一定差值,是由于熔融过程伴有结晶作用所致,可定性地用熔融峰的ΔT_1=T_(onset)—T_i表征。

等温熔体结晶尼龙1010的熔融

本文用DSC研究了等温熔体结晶尼龙1010薄膜试样的熔融。发现结晶温度T_c<190℃时有三个峰T_m、T_2和T_3,其低温转化峰T_3=13.5±0.94T_c;T_c<170℃时T_2=175℃,到180℃升至190℃;熔融热随T_c线性升高,至192℃后又线性降低;结晶度随低规整度晶体增加而增加;结晶时间长时高规整度晶体增多。

CHARACTERIZATION OF GAMMA-IRRADIATED CRYSTALLINE POLYMER .3. THERMAL-BEHAVIOR OF GAMMA-IRRADIATED POLYAMIDE-1010

Thermal behaviour of gamma-irradiated plain PA1010 and PA1010 containing different amounts of difunctional cross-linking agent BMI was investigated. In DSC endo- and exotherm, it was found that during irradiation, the presence of BMI markedly changes the melting and crystallisation characteristics of PA1010. A supposition that the network of BMI-containing specimens is rather loose in structure was proposed to explain the discrepancy in thermal behaviour between these two kinds of specimens. The supposition was further ascertained by the less brittleness in mechanical property of specimens containing BMI. Besides, the complexity of the thermal behaviour of gamma-irradiated PA1010 was discussed and attributed mainly to the increase in sigma-e, the fold surface free energy of chain fold crystals.

尼龙-1010 SAXS研究

用一维电子密度相关函数方法,分析了国产尼龙-1010不同拉伸比时的SAXS现象,由实验相关函数曲线可算得长周期(L),中间层厚(d_(tr)),片晶层厚(d_?),非晶层厚(A_?),平均片层厚(d),积分不变量(Q),比内表面O_s以及(η_c-η_a)等数值及其变化规律。实验结果表明尼龙-1010的结晶结构是由结晶层、非晶层以及结晶-非品中间层三部分组成。

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。