用FTIR定量测定聚对苯二甲酸乙二酯晶区和非晶区反式构象含量

用傅里叶变换红外分光光度计测定不同条件下退火处理的聚对苯二甲酸乙二酯膜的谱图, 用谱带分离技术对归属于反式构象的1340cm^-^1谱带进行阻尼最小两乘分峰处理, 结合属左右式构象贡献的1454cm^-^1谱带, 用线性回归分析的方法获得晶区反式构象、非晶区反式构象、非晶区左右式构象的百分含量。     

半晶聚对苯二甲酸乙二酯中的受限非晶相

当半晶聚对苯二甲酸乙二酯 (PET)的结晶度 (Xwc)处于一定范围内时 ,其物理老化后在差示扫描量热(DSC)曲线上的玻璃化转变区有吸热双峰出现 .通过对此吸热双峰分别与完全非晶试样和具有相当高Xwc 的半晶试样物理老化后在DSC曲线上出现的吸热单峰的比较 ,表明半晶PET中存在两种性质极为不同的非晶区 ,即自由非晶区和受限非晶区 .动态力学热分析 (DMTA)曲线上显示的损耗正切 (tanδ)双峰进一步证实了这两种不同非晶区的存在 .这两种不同非晶区的产生是由于试样中晶粒对非晶相中高分子链段活动性的不同限制作用所致 .研究发现 ,对于由冷结晶得到的半晶试样来说 ,出现两种不同非晶区所需的Xwc 上下限都随结晶温度 (Tc)的升高而增高 .还发现 ,在物理老化过程中 ,虽然非晶相的总量基本保持不变 ,但部分自由非晶区却逐渐转变为受限非晶区 .上述实验结果很好地符合Struik的“扩展玻璃化转变”模型 .     

变温红外法研究聚对苯二甲酸乙二酯分子链的松弛运动及其构象转变

在30～170 ℃范围内逐渐升温过程中,用红外光谱仪原位检测无定形聚对苯二甲酸乙二酯（PET）薄膜红外光谱图的变化情况。通过特征谱带吸光度与温度的变化特点,研究了PET分子链在热变化过程中的松弛运动及冷结晶过程中分子链的构象变化。实验结果表明在冷结晶过程中,随PET结晶的不断完善,对应左右式(gauche)构象的吸收峰减弱,对应反式(trans)构象的吸收峰增强,并计算出CH2面外摇摆振动结晶前和结晶后反式构象和左右式构象的相对百分含量随温度的变化关系,以及玻璃化转变和冷结晶的温区范围。     

硬弹性聚丙烯晶相和非晶相分子链取向的研究

本文用力学-振动光谱研究了硬弹性聚丙烯(HEPP)晶区和非晶区分子链在拉伸时取向的变化.我们发现在红外光谱中,1130—1190cm~(-1)波数范围内存在着三个峰,其中1167cm~(-1)处的峰是与结晶相长螺旋分子链相关的构象谱带,其谱带的强弱变化是与998cm~(-1)结晶谱带在拉伸时的变化趋势一致的.1159cm~(-1)谱带能够被归属于无定形谱带.而1152cm~(-1)处的峰也许是与短螺旋分子链构象谱带相关的.我们用计算机的二次微分、解卷积以及分峰程序测定了拉伸时HEPP晶区和非晶区分子链的取向函数,结果发现HEPP无定形分子链取向随拉伸比增加而增加,而晶区分子链的取向随拉伸比的增加先下降,直至拉伸比为1.5(第二次屈服点)后才逐渐增加.     

二维红外光谱法分析聚酰胺-66晶区/非晶区结构

应用变温红外光谱法和二维红外光谱法对聚酰胺-66在303～393K范围内的晶区和非晶区结构及热稳定性进行研究。变温一维红外光谱和变温二阶导数红外光谱的试验结果表明,聚酰胺-66的晶区结构对温度变化较为敏感,而非晶区结构相对稳定。非晶区结构的热稳定性在二维红外光谱试验中得到进一步的证实。从聚酰胺-66的分子结构观察,随着温度的升高,其晶区结构(主要对应O=C-NH-)最先改变,而非晶区结构(主要对应-C-C-)则较为稳定。非晶区的异步二维红外光谱试验结果表明,其晶区结构的吸收波数为1 141cm-1(νamorphous-1)和1 138cm-1(νamorphous-2);而非晶区结构的吸收波数为939cm-1(νcrystal-1)和931cm-1(νcrystal-2)。对聚酰胺-66的非晶区结构和晶区结构还同时进行同步二维红外光谱试验,结果表明:随着温度的升高,两者的红外吸收峰的变化快慢顺序为931cm-1(νcrystal-2)1 141cm-1(νamorphous-1)939cm-1(νcrystal-1)1 138cm-1(νamorphous-2)。     

掺Tb-硅基发光材料制备过程中结构及发光性能

采用溶胶 凝胶技术,制备了不同退火温度下掺Tb3＋的SiO2玻璃,掺Tb3＋的凝胶玻璃在448,544,585,620 nm显示Tb3＋的5D4 7FJ(J=3,4,5,6)的特征发光光谱.通过不同退火温度下样品的激发光谱、发射光谱、红外光谱、远红外光谱及差热 热重谱研究了掺Tb3＋的硅基材料由凝胶向玻璃转变过程中的结构变化及对Tb3＋发光性能的影响.结果显示,在50～100 ℃退火温度下,凝胶大部分吸附水分子被除去,在150～500 ℃退火温度区,是凝胶向玻璃转变的主要结构变化区,并且其发光强度也明显增加,到800 ℃时趋于稳定.这些现象得出一个结论,Tb3＋的发光跃迁被O－H基强烈猝灭而随退火温度的升高而加强.     

掺Tb-硅基发光材料制备过程中结构及发光性能

采用溶胶-凝胶技术 ,制备了不同退火温度下掺 Tb3＋的 SiO2玻璃 ,掺 Tb3＋的凝胶玻璃在 448,544,585,620 nm显示 Tb3＋的 5D4- 7FJ(J=3,4,5,6)的特征发光光谱 .通过不同退火温度下样品的激发光谱、发射光谱、红外光谱、远红外光谱及差热-热重谱研究了掺 Tb3＋的硅基材料由凝胶向玻璃转变过程中的结构变化及对 Tb3＋发光性能的影响 .结果显示 ,在 50～ 100℃退火温度下 ,凝胶大部分吸附水分子被除去 ,在 150～ 500℃退火温度区 ,是凝胶向玻璃转变的主要结构变化区 ,并且其发光强度也明显增加 ,到 800℃时趋于稳定 .这些现象得出一个结论 ,Tb3＋的发光跃迁被 O－ H基强烈猝灭而随退火温度的升高而加强 .     

过剩热焓松弛CO_2和甲苯在PET薄膜中渗透的影响

本文研究了非晶态、未取向PET薄膜样品在低于T_g温度以下热处理,结构的变化和过剩热焓松弛对CO_2和甲苯溶剂在样品中渗透速率的影响。结果表明,随退火时间增加,从T_g转变吸热峰确定的过剩热焓松弛量、 T_g温度、密度增加,而反式构象含量减少。除分子链堆砌密度提高或自由体积下降外,没有发现非晶相有结构上的变化。因此,CO_2在样品中随退火时间的增加渗透速率下降。然而,由于样品脆性增加和甲苯的溶胀作用,样品表面出现裂纹,使甲苯在样品中的表观渗透速率增加。     

聚对苯二甲酸乙二酯非晶区反式构象结构的探讨

<正> 聚对苯二甲酸乙二酯(PET)的重复单元中有乙撑基。它的碳碳键内旋转产生反式构象(T)和左右式构象(G)。用其不同的构象来表征PET的聚集态结构,对研究结构与性能的关系是十分重要的。许多工作都已指出,乙撑基反式构象的谱带热处理时随结晶度的增加而增加。X-射线衍射的结果证实     

辐照聚乙烯单晶的退火研究

用红外光谱、ＤＳＣ、ＳＡＸＳ和ＷＡＸＤ等方法考察了辐照５ＭＧｙ后的聚乙烯单晶在退火前后的结构变化，对比未辐照样品在同样条件下的变化，提出在９０℃以下和１０５℃聚乙烯有不同的退火机理，辐照引起的交联和晶区结构损伤，限制了退火对晶体结构的改善程度．     

FOURIER TRANSFORM INFRARED STUDIES OF POLY (ETHYLENE TEREPHTHALATE) FILM IN THE GLASS TRANSITION REGION

Three specimens from a solution-cast poly (ethylene terephthalate) (PET) film, one being liquid-N_2 quenched from 92℃(Q), one being slowly cooled from 92℃(SC) and one being quenched and sub-T_g annealed at 67℃(AN), have been studied by specimen difference spectra Q-SC and AN-Q and temperature difference spectra T-70 and T_2-T_1 for every 2℃steps on heating to 90℃at 2℃/min. SC and AN showed more gauche conformers than Q. That means that the PET chain has more trans conformers at higher temperatures and some of these are frozen during quenching through T_g. A band at 1340 cm~(-1) has been found to be complex containing overlapping bands reflecting trans in crystalline regions and trans in amorphous regions. The temperature difference spectra on heating through T_g showed that the spectral changes in Q are gradual while a rather abrupt change occurs in AN at 80—82℃for the bands at 1340, 1042 and 1020 cm~(-1). No new conformational structure or new vibrational mode is involved. A kind of locking mechanism is suggested which hinders the molecular vibrational changes in AN below T_g until a sudden release occurs at T_g. These locking sites can be nothing else than sites of tighter local packing of chain segments. Consequently it is believed that inter-chain van der Waals attraction energy plays a dominating role in the volume relaxation and sub-T_g annealing of quenched amorphous polymers.     

Structural and conformational changes during thermally‐induced crystallization of poly(trimethylene terephthalate) by infrared spectroscopy

Conformational changes occurring during thermally‐induced crystallization of poly(trimethylene terephthalate) (PTT) by annealing have been studied using density measurement, differential scanning calorimetry (DSC), and mid‐infrared spectroscopy (MIR). Infrared spectra of amorphous and semicrystalline PTT were obtained, and digital subtraction of the amorphous contribution from the semicrystalline PTT spectra provided characteristic MIR spectra of amorphous and crystalline PTT. The normalized absorbance of 1577, 1173, and 976 cm^?1 were plotted against the crystallinity showing that these bands can be used unambiguously to represent the trans conformation while the band at 1358 cm^?1 can be used to represent gauche conformation of methylene segment. The presence of a weak band at 1358 cm^?1 in the amorphous spectrum suggested that a small amount of gauche conformation is present in the amorphous phase. Infrared spectroscopy has been used for the first time as a means to estimate the trans and gauche conformations of methylene segments in PTT as a function of T_a. The amount of gauche conformation was plotted against the crystalline fraction and the extrapolation of this plot to zero crystalline fraction provided a value of 0.07, suggested that the pure amorphous phase consist of ～ 7% gauche conformation. It was found that the amorphous and crystalline gauche conformation increases at the expense of amorphous trans conformation during thermally induced crystallization of PTT. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1497–1504, 2008     

聚对苯二甲酸乙二酯中正电子湮没寿命参数温度效应的研究

对聚对苯二甲酸乙二酯的非晶、低温热处理(54℃)、高温热处理(180℃)以及双轴拉伸等四种不同试样,测量了室温到180℃范围内不同温度在的正电子湮没寿命谱.根据最小二乘曲线拟合解谱结果,可知最长寿命成份的湮没参数τ和I的温度曲线分别灵敏地反映了聚对苯二甲酸乙二酯的玻璃转变过程和结晶过程.据此讨论了正电子湮没寿命参数与PET转变的关联以及PET玻璃转变的有关性质.     

Application of fourier transform infrared spectroscopy to the study of semicrystalline polymers: Poly(ethylene terephthalate)

An infrared absorbance subtraction technique has been used to “isolate” bands in the composite spectrum of semicrystalline polymers according to their crystalline or amorphous character. Amorphous and crystalline spectra for annealed, melt-quenched, and solution-cast poly(ethylene terephthalate) have been separated. The spectra of the amorphous component show an increased intensity of bands associated with the trans configuration of oxygen about the C? C bond when the polymer is annealed. This increased “trans” band intensity reflects the increased proportion of trans structures as a result of annealing. The amorphous trans bands are shifted approximately 1–3 cm^?1 from their positions in the crystalline “trans” spectrum. The frequency shift of these bands can be attributed to the differences in chain interactions that exist in the amorphous phase and the crystalline lattice. We have also found that under identical anealing conditions the amorphous phase of the melt-quenched polymer contains an increased intensity of conformational trans bands compared to the sample cast from solution.     

THE ORIENTATION AND CRYSTALLIZATION OF POLYETHYLENE TEREPHTHALATE

The drawing behavior of three types of PET spherulites and PET amorphous samples have beenstudied. Two different sample preparation techniques were used in this study: (1) The films withnormal positive, normal negative or abnormal spherulites were prepared by solution casting tech-niques, then the films were deformed by uniaxial drawing. The uniaxial drawing behavior of PETspherulites appears to be dependent on the angles between the c-axis and the radius direction of thespherulites and that the deformation of spherulites becomes more difficult the larger the angles. (2)Amorphous films of PET were prepared first, then the films were deformed under uniaxial drawingto achieve c-axis orientation at a temperature near the glass transition temperature. The orientedfilms were subsequently annealed with fixed length at 215℃The films prepared in this way ex-hibit excellent c-axis orientation along the stretching direction. The degree of perfection of thecrystalline structure is much greater than that of the spherulites.     

涤纶工业丝等温收缩中的结构变化

采用广角X 射线衍射、密度梯度、声速和差示扫描量热等实验方法对 145 5dtex/ 110f成品涤纶工业丝等温收缩的结构变化进行了表征 ,外加张力为 0 3N ,测定温度范围 375～ 494K .结果表明 ,涤纶工业丝的热收缩在宏观上表现为速率不同的两个过程 ,对应两种不同机理 .其中快过程对应非晶区的解取向 ,对收缩的贡献是主要的 ;慢过程对应晶区的变化 ,包含了晶粒的增长 ,新的不完善晶粒的形成和晶区的完善 .晶粒的增长在较短的时间内基本完成 ,再结晶则存在于整个收缩过程 .随温度的升高 ,晶区变化速度明显加快 ,对非晶区解取向的抑制效应因此变大 .     

二维傅里叶变换红外(2D FTIR)相关光谱技术研究聚羟基丁酸酯(PHB)的熔融与结晶

应用新型二维傅里叶变换红外(2DFTIR)相关光谱研究细菌合成聚羟基丁酸酯(PHB)在升温时的预熔行为以及降温后的重结晶过程.在25～220℃的变温过程中测得动态红外光谱.着重讨论了在热力学干扰导致红外谱图中羰基峰(1700～1770cm^-1)和醚键(1230～1310cm^-1)吸收强度的波动.结果表明,这种影响来自样品中PHB的结晶态和非晶态之间的相态变化.二维谱图分析表明,在热熔过程中,结晶态的消失并不同时引起完全非晶态的出现,暗示在分子排列高度有序的晶态和非晶态之间存在某种中间态,PHB晶体向非晶态转变时必须经过一个预熔过程.在红外谱图上这个中间态很可能对应着由二维分析显示出来的位于1730cm^-1的吸收峰.同时,在PHB熔体从非晶态逐渐生成晶体的过程中也探测到了中间态的存在.