茂金属催化线性低密度聚乙烯的光氧化稳定性

茂金属催化线性低密度聚乙烯的光氧化稳定性;茂金属线性低密度聚乙烯;Ziegler-Natta线性低密度聚乙烯; 光氧化降解     

聚烯烃复合材料的老化行为及机理研究

复合材料的耐久性是一个重要的科学和技术问题,其中牵涉的问题很多还都没有得到充分的研究.首先是聚合物本身的稳定性及其影响因素;然后是无机填料和聚合物的相互作用在复合材料的老化过程中的表现,以及无机填料的表面处理对这种相互作用的影响;此外,还需要考虑光氧化降解在空间分布上的不均匀性.本文从这些方面出发,综述了国内外近年来在...     

碳纳米管-聚乙烯复合材料的介电性能

采用熔融共混及模压的方法制备了碳纳米管(CNT)-高密度聚乙烯(HDPE)复合材料,并用介电谱仪研究了逾渗值附近的导电填料对复合材料体系在不同温度、频率条件下的介电常数、介电损耗、交流电阻率的变化规律。结果表明:复合材料的介电常数、介电损耗均随CNT质量分数增加而逐渐增大;在频率为103~106 Hz,温度为40~130℃时,HDPE基体的介电常数随频率和温度的变化较小,而添加CNT填料的复合材料的介电常数随频率和温度的增加而略微降低。当w(CNT)0.5%时,复合材料的交流电阻率表现出对频率的强烈依赖性;而当w(CNT)0.5%时,在低频处表现出直流特性,在高频处显示出交流电阻率的降低。     

碳酸钙填充聚乙烯的光老化性能研究

近年来国内外对以CaCO₃为主的无机刚性粒子增强、增韧聚烯烃的基础和应用研究取得重大进展,填充的主要目的已从降低成本转向提高材料性能,展现出钙塑材料新的更广阔的应用前景。本文用人工光老化方法和红外光谱分析手段,对涉及材料使用寿命的光老化性能进行了研究,以期为这类钙材料的进一步推广应用提供更全面的理论和实际依据。     

改性纳米碳酸钙-聚丙烯复合材料的结构与性能研究

制备了硬脂酸钙包覆的纳米碳酸钙( CaSt-nano-CaCO3),并采用熔融共混的方法制备出iPP/CaStnano-CaCO3和iPP/nano-CaCO3复合材料.与纯iPP相比,复合材料的弯曲强度和弯曲模量随着CaCO3粒子含量的增加而提高,冲击性能也得到改善.相对于iPP/nano-CaCO3,iPP/CaS...     

三氯化铁对聚丙烯光氧化降解的作用

用红外及紫外光谱法研究了三氯化铁(FeCl₃)对聚丙烯(PP)光氧化降解的影响。实验结果表明,FeCl₃对聚丙烯光氧化有显著的促进作用,但促进作用与FcCl₃含量之间不成线性关系,存在一促进作用的极大值(在本实验条件下,FeCl₃含量为0.5%时,促进作用最大)。实验还表明,FeCl₃的作用可能包含了通过光解产生自由基引发PP光氧化反应、催化分解氢过氧化物以及光屏蔽等几种作用。根据FeCl₃的作用机理,解释了FeCl₃对PP光氧化降解的促进作用与其含量的依赖关系中存在的极位现象。     

PP-SBS共混物光氧化降解的研究

和橡胶类树脂进行共混是聚丙烯(PP)改性的重要途径之一,共混有橡胶组分的PP改性树脂在其力学性能获得改进的同时,其老化性能必然也有一定的变化,我们用红外光谱方法研究了聚丙烯和苯乙烯-丁二烯星型嵌段共聚物的共混物(PP-SBS)的光氧化降解行为。     

密度对聚乙烯光氧老化特性的影响研究

利用力学试验、凝胶渗透色谱(GPC)、热重分析法(TG)、差示扫描量热法(DSC)、衰减全反射红外光谱技术(ATR-FTIR)、扫描电子显微镜(SEM)比较研究了不同密度聚乙烯(HDPE、LDPE、LLDPE和MDPE)的光氧老化特性,分析了密度对聚乙烯力学性能、分子量、热稳定性、熔融特性、化学结构和表面微观形貌的影响规律。结果表明LDPE弯曲性能、热分解特征温度和氧化诱导温度下降最明显,且区别主要集中在老化初期。老化24d后,HDPE和LDPE冲击强度均已降低。老化64d后,4种PE相对分子质量均下降,其中LDPE相对重均分子质量下降更强烈。LDPE和LLDPE不饱和度增长最快,四种样品支化度变化无明显区别,LDPE的分子链断链作用和氧化作用最为强烈,羰基指数和羟基指数增长最快,表面破坏更严重,由于支链的存在破坏了聚乙烯分子链的规整性,导致LDPE更容易发生老化。     

远程“传染”对聚丙烯光氧老化的影响

研究了聚丙烯(PP)在附近有其他聚合物存在下,其光氧老化受"传染"的现象.研究发现,PP的光氧化会受到邻近聚合物降解产物的影响而被加速,即发生光氧化降解的"传染".当"传染源"不同时,被"传染"的情况也有所不同.在PP、聚甲基丙烯酸甲酯(PMMA)、尼龙6(PA6)和苯乙烯-丙烯酸酯共聚物(PSB)中,PSB的降解产物影响最大,使得PP光氧化的降解速率成倍增长.老化后的PP或PMMA作为"传染源"时,对PP的光氧化降解速率有进一步的促进.这种"传染"行为与聚合物降解产物的种类和含量有很大的关系.     

Photo-oxidation and ozonization of poly(3-hexylthiophene) thin films as studied by UV/VIS and photoelectron spectroscopy

The kinetics and the mechanisms of degradation of thin P3HT layers have been investigated quantitatively for ozonization and photo-oxidation. Both, decay kinetics and product evolution of the polymer degradation are monitored by in situ UV/VIS and X-ray photoelectron spectroscopy (XPS). The degradation pathways of ozonization and photo-oxidation of P3HT turn out to be significantly different. Ozone attacks the thiophene units mainly by direct addition to the double bonds, leading to the loss of UV/VIS absorption, while the aliphatic side chains [1] are hardly affected. During photo-oxidation, the polymer is primarily attacked at the alkyl side chain which leads to the formation of reactive peroxide species. These subsequently cause the oxidation of sulfur and concomitantly the destruction of the thiophene ring, resulting in the loss of absorption. From the kinetics of the blue shift of the optical absorption it is concluded that the polymer is mainly attacked at the terminal thiophene rings the case of photo-oxidation whereas ozone attacks positions more or less randomly distributed along the chain. The rate of photo-oxidation under AM 1.5 conditions is at least one order of magnitude faster than the decomposition of P3HT by ozone.     

Infectious Behavior in Photo-oxidation of Polymers

When a polymer is used together with others,its aging process will be affected by the adjacent polymers.This infectious behavior between polymers makes the aging process more complex than that of an individual material.In this study,infectious behavior in photooxidation of polymers was investigated.Polypropylenes(PPs),an unstabilized PP and a commercial PP,were chosen as the infection sources.Six typical polymers,high density polyethylene(HDPE),low density polyethylene(LDPE),polystyrene(PS),polycarbonate(PC),poly(ethylene terephthalate)(PET),and polyamide 6(PA6),were used as the targets.The degree of oxidation of the targets was evaluated by attenuated total reflection-Fourier transform infrared spectroscopy(ATR-FTIR).An accelerating effect of two infection sources on the photo-oxidation of the target polymers was observed.Potential infectious agents from the infection sources were detected by pyrolysis-gas chromatography-mass spectrometry(Py-GC-MS)and gas chromatography(GC).The acceleration effect of two main infectious agents,i.e.acetone and acetic acid,on the photo-oxidation of the commercial PP was verified.The infectious effect of the infection source on the target polymer was considered to be a comprehensive result of the effects of a variety of infectious agents.     

Kinetics and Mechanism of the Photo-oxidation of Thiophene by O2 Adsorbed on Molecular Sieves

Photochemical oxidation of thiophene in n-octane/water extraction system using O2 as oxidant was studied. The reaction mechanism ofthiophene oxidation was proposed. Results obtained here can be used as the reference for the oxidative desulfurization of gasoline because thiophene is one of the main components containing sulfur in fluid catalytic cracking gasoline. Thiophene dissolved in n-octane was photodecomposed and removed into the water phase at ambient temperature and atmospheric pressure. A 500 W high-pressure mercury lamp （main wave length 365 nm, 0.22 kW/m） was used as light source for irradiation, and air was introduced by a gas pump to supply O2. Thiophene can be photo-oxidized to sulfone, oxalic acid, SO4^2-, and CO2. The desulfurization yield of thiophene in n-octane is 58.9% under photo-irradiation for 5 h under the conditions of air flow at 150 mL/min and V（water）：V（n-octane）=1：1. It can be improved to 92.3% by adding 0.15 g zeoliteartificial into 100 mL reaction system, which is the adsorbent for O2 and thiophene. And under such conditions, the photo-oxidation kinetics of thiophene with O2/zeoliteartificial is first-order with an apparent rate constant of 0.5047 h^-1 and a half-time of 1.37 h. The sulfur content can be depressed from 800 μL/L to less than 62 μL/L.     

Photo-oxidation of thick isotactic polypropylene films I. Characterisation of the heterogeneous degradation kinetics

Photo-oxidation kinetics of thick isotactic polypropylene films have been compared to thermal-oxidation kinetics of thin films, and noticeable differences have been found. The non-classical kinetic trend of the former can be described as a three step evolution: a typical induction/autoacceleration POOH build-up at the beginning, an intermediate slower POOH content increase and, finally, a gentler POOH increase, which can be better described by quadratic functions of the oxidation time than by a linear dependence. In addition, a series of oscillations appearing from the beginning of the photo-oxidation are found. This kinetic heterogeneity is suggested to be related to the progression of the oxidation to the inside of the strips. However, the FTIR analysis of the evolution of the POOH band position in both photo and thermal oxidation, enables the observed shape changes to be associated to kinetic stages.     

Photo-oxidation behaviour of polyethylene/multi-wall carbon nanotube composite films

The resistance to accelerated photo-oxidation of polyethylene/multi-walled carbon nanotubes (MW-CNTs) composite films was compared with the photo-oxidation behaviour of pristine polyethylene film. The polyethylene/MW-CNTs films containing different CNTs loading were subjected to accelerated UV-B exposure. At short exposure time, i.e. under 200 h, the rates of carbonyl formation are very similar to that observed for pristine polyethylene film but at longer irradiation times the carbonyl formation increases for lower MW-CNTs contents (0.1, 0.2 and 0.5% wt./wt.), and decreases for higher MW-CNTs contents (1 and 2% wt./wt.). By adding a UV-stabilizer to the films their photo-oxidation rates are drastically decreased also at low MW-CNTs concentration. Addition of a metal deactivator (MD) produced no observable effect.     

Photo-oxidation of acrylic-urethane thermoset networks. Relating materials properties to changes of chemical structure

Acrylic-urethane thermoset photo-ageing was investigated by various techniques including IR spectroscopy, dynamic-mechanical thermal analysis (DMTA), and micro-hardness testing. These results were used to identify the sites at which the chain oxidation reaction is initiated and the main pathways through which the degradation reaction proceeds. The chemical modifications induced by photo-ageing were qualitatively and quantitatively correlated with the modifications observed in the architecture and mechanical properties of the thermoset network. The results of this work also allow for the development of a quantitative kinetic model based on the identified mechanisms and a multi-scale approach from the molecular to the macroscopic level, which highlights the effect of the changes of the chemical structure on the modification of the macromolecule arrangement and thus on the mechanical properties. Finally, the impact of stabilisers on material ageing was studied.     

空气下光诱导有机金属卤化钙钛矿薄膜的降解机理

近几年来钙钛矿材料作为新兴光伏材料取得了巨大的发展进步,但有机无机杂化钙钛矿较差的环境稳定性限制了它的大规模应用。因此深入研究钙钛矿材料的降解机制有助于开发更稳定的钙钛矿光伏器件。本文基于透射电子显微学的微观形貌观察、晶体结构及元素成分表征,详细研究了杂化钙钛矿CH_3NH_3PbI_3薄膜在光照以及空气共同作用下的降解机理。研究发现,光诱导下CH_3NH_3PbI_3薄膜会与空气中的氧气发生交互作用,同时生成六方晶态PbI_2甚至氧化为非晶态化合物PbI_(2-2x)O_x (0.4 x 0.6),而其衰减位点主要存在于薄膜与空气接触的表面。降解过程中,由于存在着挥发性分解产物(I_2,CH_3NH_2)的大量丢失,薄膜的表面会产生许多小孔洞,继而形成一种蜂窝状的介孔衰竭通道。而这种衰竭方式主要与光照下钙钛矿中光生电子与氧气结合形成超氧根自由基(O_2~(·-))有关,该基团诱导了CH_3NH_3PbI_3向PbI_2和非晶氧化态的转变。本文揭示了空气中光照诱导钙钛矿薄膜的降解机理,这将为未来设计和优化更稳定的钙钛矿太阳能电池提供全面的实验数据与理论支持。     

Photo-oxidation behaviour of polyethylene/polyamide 6 blends filled with organomodified clay: Improvement of the photo-resistance through morphology modification

The impact of small amounts of organomodified clay (OMMT) on the photo-degradation behaviour of two blends obtained by mixing either low-density polyethylene (LDPE) or high density polyethylene (HDPE) with polyamide 6 (PA6) (LDPE/PA6 and HDPE/PA6 75/25 wt-%) was studied. The complex photo-degradation behaviour was followed by monitoring the main physical-mechanical properties of the blends. In particular, mechanical and spectroscopic tests were performed in conditions of accelerated artificial aging. An accurate mechanical and morphological characterization was previously carried out. The presence of the OMMT promotes the unexpected formation of a co-continuous morphology for the HDPE/PA6 blend without significantly improving the interfacial adhesion. Differently, the OMMT-filled LDPE/PA6 blend exhibits a finely distributed morphology, and some apparent improvement of the interfacial adhesion was noticed. Probably due to these differences in microstructure, a different impact of the nanoparticles on the photo-resistance behaviours was observed for the two families of samples. In particular, the HDPE-based nanocomposite blend exhibits an improved photo-resistance, while the opposite occurs for the LDPE-based system.