Effect of γ-Ray Irradiation on Chain Structure and Crystallization Rehavior of Isotactic Polypronylene

利用凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)和示差扫描量热(DSC)等手段对不同剂量γ射线辐照后等规聚丙烯(iPP)的分子链结构及结晶行为的变化进行了研究.结果表明,γ射线辐照使iPP的分子量下降,并在其分子链中产生羟基和羰基等极性基团,从而影响其结晶行为.在非等温结晶过程中,当辐照剂量≤50 kGy时,iPP的热结晶温度略有升高;增大辐照剂量,iPP的热结晶温度明显降低.iPP的熔融温度则随辐照剂量的增大而降低,且分裂成双峰.利用Avrami方程研究了辐照前后iPP的等温结晶动力学,发现辐照前后样品的Avrami指数n都在3左右,表明iPP的结晶遵循异相成核机理,且不受辐照剂量和等温结晶温度的影响,但总结晶速率随等温结晶温度和辐照剂量的升高而逐渐减小.探讨了iPP经过γ射线辐照后,分子链断裂、链结构变化和结晶速率之间的关系.     

镧配合物对等规聚丙烯等温结晶性能的影响

利用Avrami方程和Lauritzen-Hoffman结晶动力学理论研究了一种镧配合物LaC对等规聚丙烯(iPP) 等温结晶行为的影响. 差示扫描量热法(DSC)和X射线衍射技术(XRD)研究表明, LaC的加入并未改变iPP的结晶形态, 但LaC的存在能提高体系的结晶度并显著加速iPP的结晶过程. 在130 ℃进行等温结晶时, 含0.5%LaC(质量分数)的iPP与纯iPP相比, Avrami指数n值无显著差异, 但前者总的结晶速率常数k值比后者提高约4倍,而半结晶时间t1/2值减少到后者的62%, Avrami方程分析结果表明LaC的存在主要起到增加晶核的作用. 利用Lauritzen-Hoffman结晶动力学理论, 通过对iPP在121 ℃、124 ℃、127 ℃和130 ℃下等温结晶的数据进行分析可知, 加入0.5%的LaC后, 体系的成核常数kg从纯PP的3.3×105 K2增加到PP/LaC的3.8×105 K2, 而结晶生长时大分子在垂直于分子链方向折叠的界面自由能σe从纯PP的0.223 J·m-2降低到PP/LaC的0.154 J·m-2, 表明LaC在iPP结晶过程中不仅起到增加晶核的作用, 同时使大分子链更易排入晶格, 即起到促进结晶成长的作用.     

等规聚丙烯/二元乙丙橡胶合金相分离对结晶动力学的影响

用小角激光光散射(SALLS)、相差显微镜(PCM)、示差扫描量热仪(DSC)和偏光显微镜(POM)研究了聚丙烯/二元乙丙橡胶(iPP/EPR)共混体系的相分离行为和等温结晶行为.发现iPP/EPR(50/50,W/W)发生的液-液相分离遵循spinodal机理.通过Cahn-Hilliard方程求得了不同实验温度下iPP/EPR的表观扩散系数(Dapp)以及spinodal温度(Ts).考察了不同相分离程度的iPP/EPR体系结晶动力学,发现延长相分离时间(tps)或提高相分离温度(Tps)均会导致半结晶时间(t1/2)增大,即结晶速率降低.这被归于EPR成核作用的降低.动力学分析结果表明Avrami模型适用于描述该体系的等温结晶过程,其结晶机理基本不受相分离程度的影响,结晶均以瞬时成核和三维生长为主.     

聚丙烯“催化合金”组成对结晶行为的影响

用示差扫描量热仪(DSC)和偏光显微镜(POM)研究了聚丙烯“催化合金”(PP-cats)组成对等温结晶行为与动力学的影响,并与等规聚丙烯(iPP)进行比较.结果表明,与纯PP相比较,PP-cats的平衡熔融温度明显下降,表明PP-cats中作为主要组分的丙烯均聚物和乙丙无规共聚物之间存在较强的相互作用.PP-cats的结晶初期动力学可用Avrami模型很好地描述,结晶过程均为预先成核和三维生长方式.PP-cats的结晶速率随体系中乙丙共聚物含量的增加而增大,而PP-cats的晶体生长速率随体系中乙丙共聚物含量的增加而减小.由于PP-cats熔体的粘度远高于纯PP,使得PP-cats中PP分子链运动能力降低,导致了PP-cats较低的晶体生长速率.此外,与纯PP相比,PP-cats的成核密度大幅度提高,被认为是PP-cats具有快的结晶速率的主要原因.     

取向、结晶、γ辐照聚对苯二甲酸乙二醇酯(PET)驻极体的陷阱性质

用拉伸、热处理和γ射线辐照的方法制备了一系列具有不同平面取向度、不同结晶度和不同分子链长度的PET试样.随平面取向度、结晶度和辐照剂量的增大,平均陷阱深度加深.由拉伸取向形成的结构陷阱俘获载流子能力随取向度增大而提高;由γ辐照形成的结构陷阱对俘获载流子的限制能力随辐照剂量增大而降低;由热结晶形成的结构陷阱俘获载流子能力在结晶度为20％时达到极值.提出了相应的三种陷阱模型.     

取向、结晶、γ辐照聚对苯二甲酸乙二醇酯(PET)驻极体的陷阱性质

 用拉伸、热处理和γ射线辐照的方法制备了一系列具有不同平面取向度、不同结晶度和不同分子链长度的PET试样.随平面取向度、结晶度和辐照剂量的增大,平均陷阱深度加深.由拉伸取向形成的结构陷阱俘获载流子能力随取向度增大而提高;由γ辐照形成的结构陷阱对俘获载流子的限制能力随辐照剂量增大而降低;由热结晶形成的结构陷阱俘获载流子能力在结晶度为20％时达到极值.提出了相应的三种陷阱模型.     

聚乙交酯非等温结晶行为研究

利用差示量热扫描热分析仪(DSC)测得了不同降温速率下聚乙交酯(PGA)的非等温结晶的温度-热焓曲线。分别通过Ozawa法、Jeziorny法和莫志深法对PGA的非等温结晶机理进行了分析。Ozawa法结果表明:在给定的温度范围内,Ozawa法并不适用于描述PGA的非等温结晶行为;Jeziorny法结果表明:不同降温速率下,PGA结晶过程的Avrami指数(n)接近4,PGA非等温结晶为均相成核、晶粒三维增长的过程;莫志深法结果表明:Avrami指数与Ozawa指数的比值(a)基本无变化,动力学参数f(T)随降温速率增加逐渐增大,即在更快的降温速率下,PGA结晶更充分,可获得更高的结晶度。通过Kissinger方程计算得到的PGA结晶扩散活化能为-66.9kJ/mol。     

在高压CO_2中聚乙二醇-聚己内酯嵌段共聚物的结晶行为

通过广角X射线衍射(WAXD)和小角X射线散射(SAXS)方法研究了PEO-b-PCL在CO2中的结晶形貌和片晶厚度的变化,利用高压示差扫描量热仪(HP DSC)考察了压力对熔融和等温结晶过程的影响.结果表明,PEO-b-PCL的结晶度、片晶厚度、熔融温度均随压力的升高而减小,结晶结构变得不完善.在等温结晶过程中,结晶速率随压力的升高而下降,结晶过程处于成核控制区,Avrami指数n在3.7~4.7,表明晶体的生长方式为三维生长.     

温度对iPP和TMB-5/iPP结晶行为的影响

通过DSC和同步辐射WAXS技术测定了结晶温度对iPP和TMB-5/iPP结晶行为的影响.结果表明,随等温结晶温度升高,iPP总结晶度变化不大,但是β晶型含量降低的同时α晶型含量增加.TMB-5是一种具有温度依赖的选择性成核剂,当等温结晶温度高于140℃时,含TMB-5成核剂的iPP的β晶型的含量急剧降低.本文进一步探讨了TMB-5对iPP结晶行为影响的机理.     

GMA/苯乙烯多组分单体接枝聚丙烯结晶行为研究

使用差示扫描量热计 (DSC)研究了甲基丙烯酸缩水甘油酯 苯乙烯 (GMA St)多单体熔融接枝聚丙烯[PP g (GMA co St) ]的等温和非等温结晶行为 ,用偏光显微镜观察了结晶的形态 ,并利用Avrami方程对其结晶动力学进行了分析 .研究发现接枝聚丙烯的结晶模式与PP相似 ,属于异相成核控制的球晶三维生长 ;但接枝聚丙烯的结晶温度 (Tc)显著提高 ,幅度高达 16～ 19℃ ,总结晶速率与纯PP相比明显加快 .接枝聚丙烯上GMA co St支链的存在 ,降低了成核界面自由能 ,促进了聚丙烯结晶的异相成核 .在接枝率不太高的情况下 ,随着接枝率的提高 ,接枝聚丙烯的结晶温度升高 ,总结晶速率加快 .在高接枝率范围内 ,随着接枝率的提高 ,接枝PP的Tc 不再升高 ,且由于接枝链的增长严重阻碍了球晶生长 ,导致接枝PP的总结晶速率反而随接枝率的升高而下降     

等规聚丙烯自成核的等温结晶动力学

近年来 ,有关等规聚丙烯 (i PP)的自成核研究已引起了人们的关注 [1 ] ,但有关其结晶动力学的报道并不多见 .Carfagna等 [2 ]用膨胀计法研究了 i PP在未完全熔融重结晶情况下的等温结晶动力学 ,得到的 Avrami指数远远小于 3 .张新远等[3 ] 研究了 i PP未完全熔融情况下的非等温结晶动力学 .到目前为止 ,i PP自成核的熔体降温等温结晶动力学尚未见报道 .本文在 i PP自成核研究的基础上 [4] ,用 DSC方法研究了 i PP自成核在较高温度下的等温结晶动力学 ,讨论了结晶机理 .结果表明 ,在本实验的自成核条件下 ,i PP依然是三维球晶生长 ,…     

Systematic fabrication of chitosan nanoparticle by gamma irradiation

The present investigation is mainly focused on the systematic preparation of chitosan nanoparticle in the potential range 1–100 nm using γ-ray irradiation. The effect of irradiation conditions in terms of physical form of chitosan, i.e. flake, colloidal and acidic solution, and γ-ray dose was studied. The molecular weights of chitosan were 10, 25, and >1000 times reduced when irradiated with the γ-ray dose as high as 100 kGy in Chi-flake, Chi-colloid, and Chi-acid, respectively. The particle size reduced to 70 nm after being irradiated to only 10 kGy γ-rays and it showed a tendency to decrease when the γ-ray doses were increased. The γ-rays effectively induced the reduction of chitosan particle size to <100 nm with narrow size distribution. The effective size reduction was particularly observed in Chi-colloid. Heterogeneous chemical conjugation of deoxycholic acid onto 10 kGy irradiated Chi-colloid resulted in narrow particle size as small as 50 nm.     

Isothermal and nonisothermal crystallization kinetics of irradiated nylon 1212

The crystallization behavior of nylon 1212, irradiated at ⁶⁰Co γ‐rays (50 kGy), was studied by a rheometer, polarized optical microscopy (POM), and differential scanning calorimeter (DSC). The results showed that irradiated nylon 1212 samples exhibited abnormal crystallization behavior during the crystallization process: The Avrami exponent n was calculated and was found to be in the range from 2.06–2.41 for isothermal crystallization, and from 2.67–4.91 for nonisothermal crystallization; the spherulite morphology also changed largely by polarized optical microscopy (POM); the crystallization activation energy ΔE for isothermal and nonisothermal crystallization process of irradiated nylon 1212 are determined to be 57.4 kJ/mol and 78.65 kJ/mol, respectively, which are lower than that of nonirradiated nylon 1212. At the same time, a new method by a combination of the Avrami and Ozawa equations was successfully applied to analyze the noncrystallization process of irradiated nylon 1212. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2326–2333, 2005     

稀土氧化物对聚丙烯等温结晶动力学的影响

本文用差示扫描量热法测定了3种稀土氧化物对聚丙烯等温结晶行为的影响。结果表明,Avrami方程指数n、成核机理、晶体生长方式以及结晶晶型基本上不受稀土氧化物的影响。少量稀土氧化物可使结晶晶格垂直于分子链方向单位面积的界面自由能降低,结晶速率加大,其中Y_2O_3的效果最为显著,La_2O_3效果最低,混合稀土的作用效果与Y_2O_3相似。填加1wt%的Y_2O_3可使聚丙烯的结晶速度常数增大一个数量级。     

Radiation degradation of polypropylene

Post-irradiation degradation of isotactic polypropylene irradiated by Co⁶⁰-γ-ray has been followed for 12 months. Effects of irradiation doses (10–100 kGy) up on the change of the structure and mechanical properties as well as flowability of this polymer has been studied. Carbonyl index increases with increasing post-irradiation time. The rate of which was much higher for doses above 50 kGy. Tensile strength declines with time and those samples irradiated above 50 kGy become quite brittle, just after irradiation. Results reveal that post-irradiation degradation of polypropylene irradiated by γ-ray occurs via chain scission mechanism.     

Effect of γ-ray radiation on the polyacrylonitrile based carbon fibers

To investigate the effect of γ-ray radiation on the microstructural and mechanical properties of carbon fibers, carbon fibers were irradiated by ⁶⁰Co source. The interlayer spacing d₀₀₂ of carbon fibers decreased after irradiation. The Young’s modulus and density of the fibers increased with increasing dose. The tensile strength of fibers was found to increase at low dose and decrease at high dose. Additionally, Compton scattering effect caused by γ-ray is proposed to be responsible for the structural and mechanical changes of fibers. The results indicated that γ-ray irradiation was an effective method for improving the mechanical properties and graphitization degree of polyacrylonitrile based carbon fibers.     

Enhancement in sensitivity of nitro blue tetrazolium polyvinyl alcohol film dosimeters by sodium formate and Triton X-100

Nitro blue tetrazolium polyvinyl alcohol film dosimeters, NBT-PVA were prepared and evaluated based on radiation-induced reduction of NBT²⁺. NBT-PVA film dosimeters containing different concentrations of NBT dye from 1 to 5 mM were prepared in a solution of ethanol. The dosimeters were irradiated with ?-ray from ⁶⁰Co source at doses up to 50 kGy. UV/vis spectrophotometer was used to investigate the optical density of un-irradiated and irradiated films in terms of absorbance at 529 nm. The absorbance increases with absorbed dose up to 50 kGy for NBT-PVA film dosimeters. The dose sensitivity of NBT-PVA film increases strongly with increase of concentrations of NBT dye. The effects of irradiation temperature, humidity, dose rate and the stability of the response of the films after irradiation were investigated. A considerable increase was observed in the dose response of NBT-PVA film by adding appropriate concentration of sodium formate and Triton X-100.     

聚酰胺6／聚醚砜共混体系的结晶与熔融行为

聚醚砜（ＰＥＳ）是一种非晶特种工程塑料，具有强度好，使用温度高等特点，但熔体粘度高，加工上有一定困难．聚酰胺６（ＰＡ６）是部分结晶的工程塑料，有很好的强度和耐磨性能．加入适量的ＰＡ６，可显著地降低ＰＥＳ的熔体粘度，且可基本保持ＰＥＳ的原有性能［１］．...