CaCO3/PEEK复合体系的力学行为和热行为研究

以聚醚醚酮和碳酸钙复合体系为研究对象,考察了偶联剂和填料添加量对复合材料力学行为和热行为的影响.发现磺化聚醚醚酮作为偶联剂能有效地改善材料的力学性能,提高基体树脂的玻璃化转变温度,降低基体树脂的熔点,有助于改善聚醚醚酮的加工条件     

Poly(vinyl chloride) powder as a low-cost flame retardant modifier for epoxy composites

For the purpose of the study, epoxy (EP) composites modified with 5–40?wt% of poly(vinyl chloride) (PVC) powder were manufactured. The influence of PVC powder on the fire behavior of EP-based composites was determined with a UL-94 HB test and cone calorimetry, supplemented by a thermogravimetric analysis. The fire behavior study showed that PVC powder may effectively decrease the flammability of EP in case of at least 20?wt% filler content while composites containing lower amounts of PVC powder (5 and 10?wt%) were characterized with significant improvement in tensile strength without reduction in flammability in reference to the unmodified EP.     

Non-isothermal crystallization kinetics of continuous glass fiber-reinforced poly(ether ether ketone) composites

Current studies on crystallization kinetics for glass fiber-reinforced poly(ether ether ketone) mainly focused on short glass fiber-reinforced composites and their isothermal crystallization. It is worth noting that continuous glass fiber-reinforced poly(ether ether ketone) composite (CGF/PEEK) possesses relatively higher mechanical performance than short fiber-reinforced PEEK under high temperature. Here, for the first time, we investigate the non-isothermal crystallization kinetics and melting behavior of CGF/PEEK by differential scanning calorimetry at four different cooling rates. By evaluating the crystallite size of CGF/PEEK using X-ray diffraction, it is found that with the decreasing cooling rate, the crystallite size distribution evolves more uniform, and the size of crystallites enlarges. Besides, by systematical analysis, we find the modified Avrami equation can well describe crystallization behavior of the CGF/PEEK. The higher Avrami value of CGF/PEEK than pure PEEK indicates that CGF could introduce a more complex geometry effect on the crystallization. The addition of CGF greatly reduces the absolute value of crystallization activation energy of PEEK, suggesting that CGF can reduce the nucleation energy barrier. The obtained results illustrate that CGF can accelerate the nucleation rate due to heterogeneous nucleation while reduce the growth rate due to retarded polymer chain mobility. And the cooling conditions can influence crystal growth and morphology.

     

Characterization of Engineering Polymers by Dynamic Mechanical Analysis

There is a growing need for the use of polymers in high-strength and engineering applications, and many new materials and composites have been developed to satisfy this need. Traditionally, thermosetting polymers have been employed as high-strength materials, with the incorporation of various fillers or additives to improve shortcomings in strength and temperature performance. Although these materials are largely unrivaled in high-temperature performance, some of the newer engineering thermoplastics, such as poly(ether ether ketone)(PEEK), poly(ether sulfone) (PES), poly(pheny1ene sulfide) (PPS), and the new backbone liquid-crystal polymers are becoming much more widely used. With this widespread use and with the increasing complexity of polymer blends and composites, there is a strong requirement for a universal means of characterizing such materials in terms of mechanical properties and high-temperature performance. A powerful and versatile analytical technique which is capable of application to a very wide range of materials is that of dynamic mechanical spectrometry. This technique can be used to establish basic material relaxation temperatures and frequencies, the modulus and loss behavior, as well as factors such as degree of cure, fder/matrix bonding, and phase separation.     

Thermal stability,flammability and fire hazard of butadiene-acrylonitrile rubber nanocomposites

This article presents the effect of the method of NBR cross linking on the thermal properties, flammability and fire hazard of its nanocomposites containing modified montmorillonite (NanoBent or Nanofil), using test results obtained by means of a derivatograph, oxygen index and cone calorimetry. It has been found that the thermal stability and flammability of the nanocomposites investigated depend on both the rubber network structure and the type of montmorillonite. The nanoadditives used reduce the flammability of cross-linked nitrile rubber and considerably limit its fire hazard.     

Thermal,mechanical and dielectric behaviour of poly(aryl ether ketone) with low melting temperature

New poly(aryl ether ketone)s (PAEKs) with a low melting temperature (relative to PEEK) are of interest in order to simplify the manufacturing of high-performance polymers or composites. In this study, we propose to investigate the physical properties of a new PAEK from Victrex, namely PAEK LM. Combinations of thermal analyses were used as follows: standard and modulated temperature differential scanning calorimetry, dynamic mechanical analysis, dynamic dielectric analysis and guarded hot plate technique. We found that the global mechanical, dielectric and thermal properties are very similar to the PEEK reference. The glass transition temperature was observed in the same range than PEEK (∼ 150 °C) while the melting temperature T_m was measured at 307 °C for PAEK LM which is about 35 °C below the melting temperature of PEEK. The degree of crystallinity of PAEK LM was found to be 27% while for PEEK it is 38%, depending on the processing conditions. This work explored crystalline structure–property relationships to explain the behaviour of PAEK LM.

     

高性能耐高温聚合物复合材料的摩擦磨损性能研究

介绍了一些常见的高性能耐高温聚合物及其复合材料的摩擦与磨损性能的研究及其新进展,包括聚四氟乙烯(PTFE)、聚醚醚酮(PEEK)、聚苯硫醚(PPS)、聚酰亚胺(PI)等.并讨论了不同种类的填料,如纤维、固体润滑剂、无机化合物以及无机纳米粒子对高性能耐高温聚合物基复合材料摩擦系数及磨损率的影响,许多研究结果表明,适量填料的加入能提高聚合物基复合材料的耐磨性能,特别是填料的协同作用对降低复合材料的摩擦系数及磨损率有更大的帮助.     

Mechanism of thermal decomposition of poly(ether ether ketone) (PEEK) from a review of decomposition studies

A review of the literature on the flammability and decomposition of poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) (PEEK) is presented. This paper provides an overview of the flammability of PEEK and its decomposition mechanisms. Based on this literature, mechanisms have been suggested which attempt to explain the products formed at each stage of PEEK decomposition and indicate the intermediates which should be formed at each of these stages.     

Preparation of high performance composites based on aluminum nitride/poly(ether-ether-ketone) and their properties

Novel high performance aluminum nitride (AlN)/poly(ether-ether-ketone) (PEEK) composites containing 0-50 wt.% fractions of AlN were prepared by solution blending method followed by hot pressing to evaluate their density, melting temperature, crystallization, thermal stability, morphological behavior and Vickers hardness by using different characterization techniques. Differential scanning calorimetry results indicated that the AlN particles are very effective nucleating agent, which results in increase in melting point, hot crystallization temperature and crystallinity of composites as the AlN content increases. Thermogravimetric analysis showed enhanced thermal stability of the composites with respect to PEEK. Density and X-ray diffraction techniques showed that crystallinity of the composites increases as the wt.% of AlN content increases in polymer matrix. Scanning electron microscopy revealed that AlN particles were well dispersed with no porosity in composites. Vickers hardness of the samples increased from 24 kg/mm² for the pure PEEK to 35 kg/mm² for AlN/PEEK composites.     

A review on flammability of epoxy polymer,cellulosic and non‐cellulosic fiber reinforced epoxy composites

Natural fiber is well‐known reinforcement filler in polymer‐matrix composites. Composite components like organic polymers and natural fibers are natural fire conductors as the natural fiber consists of cellulose, hemicellulose, and lignin, and hence are as highly flammable as wood. Natural fiber reinforced composite materials are progressively being used in a variety of applications where their fire response is a hazardous consideration, for example, in the automotive (transportation) and building‐construction industries. As a result, an awareness of their performance or response during a fire and the use of conventional fire retardants are of great importance, as they are subject to thermal decomposition when exposed to intensive high heat or fire sources. In this review paper, fire flammability is the main concern for cellulosic and non‐cellulosic fiber‐reinforced polymer composites, especially epoxy composites. This paper reviews the literature on the recent developments in flammability studies concerning polymers, epoxy polymers, cellulosic‐fibers, and non‐cellulosic fiber‐reinforced epoxy bio‐composites. The prime objective of this review is to expand the reach of “fire retardants for polymer materials and composites” to the science community, including physicists, chemists, and engineers in order to broaden the range of their applications. Copyright © 2015 John Wiley & Sons, Ltd.     

The effect of thermal stability of carbon nanotubes on the flame retardancy of epoxy and bismaleimide/carbon fiber/buckypaper composites

Single-walled carbon nanotube (SWCNT) and multi-walled carbon nanotube (MWCNT) membranes (buckypaper) were incorporated onto the surface of epoxy and bismaleimide (BMI) carbon fiber composites. Their flammability behaviors were investigated by a cone calorimeter. The composites with buckypaper reduced the heat release rate (HRR) by more than 60% peak and smoke generation by 50% during combustion. The effects of different buckypaper on the flame retardancy of epoxy and BMI were compared and discussed. Our research team found that buckypapers acted as an effective flame-retardant shield to dramatically reduce the fire hazards of composites if they survived during fire combustion. Thermogravimetric analyses was used to compare the thermo-oxidation stability of the resins and buckypapers to explain the different effects of SWCNT and MWCNT buckypaper on flammability of epoxy and BMI carbon fiber composites.     

Influence of modified mesoporous silica SBA‐15 on the flammability of intumescent high‐density polyethylene

This work aims to investigate the fire retardant properties of a novel type of high‐density polyethylene composites. Our intumescent system consists in using classical flame retardants such as ammonium polyphosphate, pentaerythritol in combination with porous mesostructured silica (SBA‐15) fillers. Prior to use, SBA‐15 was chemically modified using different organic and inorganic grafts in order to obtain some specific properties, such as an improved compatibility with the polymer, or different types of surface acidity in order to increase charring reactions. Limiting oxygen index, UL‐94, pyrolysis flow combustion calorimetry and thermogravimetric analysis were used to assess the burning behavior and thermal stability, respectively, of the processed composites. By keeping the total amount of additives always equal to 25 wt%, the better flammability characteristics were in general obtained at low SBA‐15 loadings (<2 wt%). X‐ray diffraction and Fourier transform infrared spectroscopy analyses of the residues showed that the formation of a barrier mainly constituted by crystalline silicon phosphates is probably a key to enhance the fire properties. Further slight improvements brought by the surface modification of SBA‐15 nanofillers are discussed according to type of incorporated particles. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation of piperazine cyanurate by hydrogen‐bonding self‐assembly reaction and its application in intumescent flame‐retardant polypropylene composites

Piperazine cyanurate (PCA) is designed and synthesized via hydrogen‐bonding self‐assembly reactions between piperazine and cyanuric acid. Chemical structure and morphology of PCA are investigated by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The prepared PCA is combined with ammonium polyphosphate (APP) to prepare flame‐retardant polypropylene (PP) composites. Thermostability, flammability, and combustion characteristics of PP composites are analyzed. The maximum thermal decomposition rate of flame‐retarded PP composites has an apparent reduction compared with that of pure PP, and obvious char is left for this intumescent flame retardant (IFR) system of APP and PCA. A high limiting oxygen index value and UL‐94 V‐0 rating are achieved with addition of APP and PCA. In cone calorimetry test, heat and smoke releases of PP are significantly decreased by this IFR system. Gaseous decomposition products during the thermal decomposition of flame‐retardant composites are studied. Chemical structure and morphology of char residues are analyzed. The results illustrate that APP and PCA have a superb synergistic action in the aspect of improvement in fire safety of PP. A possible flame‐retardant mechanism is concluded to reveal the synergism between APP and PCA.     

Applications of micro-scale combustion calorimetry to the studies of cotton and nylon fabrics treated with organophosphorus flame retardants

Effective testing methods are critical for developing new flame retardant textiles by the industry. However, the current testing methods all have limitations. In this research, we applied micro-scale combustion calorimetry (MCC) for evaluating the flammability of the cotton woven fabric treated with a traditional reactive organophosphorus flame retardant in combination with a synergistic nitrogen-containing additive and the nylon-6,6 woven fabric treated with a hydroxyl-functional organophosphorus oligomer and crosslinkers. We found that MCC is capable of differentiating small differences among the treated fabric samples with similar flammability. MCC is able to make quantitative measurement of the peak heat release rate, the most important parameter related to fire hazard of materials, of textile whereas such analysis is more difficult using cone calorimetry due to textile fabrics’ low thickness. By using the thermal combustion parameters measured by MCC, we were able to calculate the limiting oxygen index (LOI) of various treated cotton fabric samples with near-perfect agreement between the experimentally measured and the predicted LOI values of treated cotton fabrics. We also compared the capability of MCC and differential scanning calorimetry for analyzing flame retardant cotton textiles.     

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) and poly(aryl ether ether ketone)

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) (M‐PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring‐banded spherulites in the M‐PAEK/PEEK blends is strongly dependent on the blend composition. In the M‐PAEK‐rich blends, upon cooling, an unusual ring‐banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M‐PAEK/PEEK blend, ring‐banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M‐PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring‐banded spherulite formation in the blends. In addition, the effects of M‐PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3011–3024, 2007     

Mechanical and thermal properties of poly-ether ether ketone reinforced with CaCO3

CaCO₃/PEEK (poly-ether ether ketone) composites were prepared on a twin-screw extruder with different mass ratio of CaCO₃/PEEK from 0% to 30%. Four types of particles were used as filler in PEEK matrix. The influence of surface treatment with sulfonated PEEK (SPEEK) of the particles on the mechanical and thermal properties of the composites was studied. The experiments included tensile tests, flexural tests, notched Izod impact tests, TGA, DSC and SEM. The modulus and yield stress of the composites increased with CaCO₃ particles loadings. This increase was attributed to the bonding between the particles and the PEEK matrix, as can be proved by the SEM pictures of tensile fracture surface of the composites. The impact strength of the composites was modified by the SPEEK coated on the CaCO₃ particle surface. DSC experiments showed that the particle content and surface properties influenced the glass transition temperature (T_g) and melting temperature (T_m) of the composites. The T_g increased with the content of fillers while T_m decreased. In this study the fillers treated were found to give better combination properties, which indicated that SPEEK played a constructive role in the CaCO₃/PEEK composites.     

用Raman光谱研究碳纤维/聚醚醚酮复合材料的界面结构

用Ｒａｍａｎ光谱研究碳纤维／聚醚醚酮复合材料的界面结构李铁骑章明秋曾汉民（中山大学材料科学研究所聚合物复合材料及功能材料国家教委开放研究实验室广州５１０２７５）关键词界面结构，Ｒａｍａｎ光谱，碳纤维／聚醚醚酮复合材料随着近年来热塑性聚合物的加工...     

The curing kinetics and mechanical properties of epoxy resin composites reinforced by PEEK microparticles

In this paper, a polyether-ether-ketone (PEEK)/epoxy composite was prepared by using PEEK microparticles as the reinforcement. The nonisothermal differential scanning calorimetry (DSC) test was used to evaluate the curing reaction of PEEK/epoxy resin system. The curing kinetics of this system were examined utilizing nonisothermal kinetic analyses (Kissinger and Ozawa), isoconversional methods (Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose) and an autocatalytic reaction model. During these analyses, the kinetic parameters and models were obtained, the curing behavior of PEEK/epoxy resin system under dynamic conditions was predicted. The results show that isoconversional methods can adequately interpret the curing behavior of PEEK/epoxy resin system and that the theoretical DSC curves calculated by the autocatalytic reaction model are in good agreement with experimental data. Furthermore, the tensile elongation at break, tensile strength, flexural strength, compression strength and compression modulus increased by 81.6%, 33.66%, 36.53%, 10.98% and 15.14%, respectively, when PEEK microparticles were added in epoxy resin composites.     

刚性聚芳醚腈合成与性能研究

用２，６ 二氟苯甲腈和间苯二酚为原料，在碱性条件下，于非质子极性溶剂中，通过溶液高温缩聚法制备聚芳醚腈［Ｐｏｌｙ（ｃｙａｎｏａｒｙｌｅｔｈｅｒ）ＰＣＥ］．并用ＩＲ、ＤＳＣ、ＴＧ、ＷＡＸＤ等手段对其结构及热性能、结晶行为进行了研究．结果表明，ＰＣＥ高聚物不仅具备较好的耐高温和耐热老化性能，而且具有较好的结晶性能．同时，用对比的方法，对ＰＣＥ的晶体结构进行了初步的探讨．     

热塑性聚酰亚胺与聚醚醚酮共混物的等温结晶动力学

采用熔融共混方法制备了热塑性聚酰亚胺(TPI)与聚醚醚酮(PEEK)的共混物; 用示差扫描量热分析(DSC)研究了共混物的等温结晶动力学. 分别采用Avrami方程和Hoffman-Lauritzen方程分析共混物的等温结晶动力学、端表面自由能(σe)和分子链折叠功(q). 结果表明, 加入TPI后PEEK的结晶速率降低, 结晶活化能、σe和q均增加. 但这些数值的变化与TPI含量不呈线性关系, 并从共混物的相容性和表面形貌给出了可能的解释.