Analysis of the absorptive behavior of photopolymer materials. Part II. Experimental validation

In the first part of this paper, a model describing photopolymer materials, which incorporates both the physical electromagnetic and photochemical effects taking place, was developed. This model is now validated by applying it to fit experimental data for two different types of photopolymer materials. The first photopolymer material, acrylamide/polyvinyl alcohol, is studied when four photosensitizers are used, i.e. Erythrosine B, Eosin Y, Phloxine B and Rose Bengal. The second type of photopolymer material involves phenanthrenequinone in a polymethylmethacrylate matrix. Using our model, the values of physical parameters, are extracted by numerical fitting experimentally obtained normalized transmittance growth curves. Experimental data sets for different exposure intensities, dye concentrations, and exposure geometries are studied. The advantages of our approach are demonstrated and it is shown that the parameters proposed by us to quantify the absorptive behavior in our model are both physical and can be estimated.     

Co-doping with polysquaraine enhances the holographic optical data storage of PMMA/PQ photopolymers

In this study, we synthesised poly(3-octylpyrrole-co-squaric acid) (PSQ3), a polysquaraine, through the reaction of 3-octylpyrrole and squaric acid, and then co-doped it with phenanthrenequinone (PQ) into poly(methyl methacrylate) (PMMA) to improve the holographic data storage characteristics of the photopolymer. The photopolymers co-doped with relatively small amounts of PSQ3 exhibited greatly improved holographic recording characteristics, including superior diffraction efficiency and dynamic range (M#). Among the samples co-doped with PQ and PSQ3, the maximum diffraction efficiency reached 54.8% (cf. 9.0% for PMMA/PQ) without further downgrade and the value of M# reached 1.05 (cf. 0.46 for PMMA/PQ). Therefore, the holographic data storage characteristics of the photopolymer PMMA/PQ were improved through co-doping with PSQ3.     

表面改性对Cf/HA-PMMA混杂生物复合材料的结构及性能的影响

采用原位合成与溶液共混相结合的方法,制备了短切碳纤维(C_f) 增强纳米羟基磷灰石(HA)-聚甲基丙烯酸甲酯(PMMA)生物复合材料。重点研究了短切碳纤维和纳米HA粒子表面改性前后对C_f/HA-PMMA复合材料微观结构和力学性能的影响。采用XRD、FTIR、XPS和SEM等对纳米HA粒子、碳纤维和复合材料的组成结构及断面的微观形貌等进行测试和表征,使用万能材料试验机测试其弯曲、压缩性能。结果表明：经表面氧化的碳纤维和用卵磷脂改性后的纳米HA与PMMA基体的界面结合性明显得到改善;采用卵磷脂表面改性后的纳米HA及表面预氧化后的碳纤维制备的C_f/HA-PMMA复合材料的弯曲性能得到显著提高,与采用未表面改性纳米HA和未表面氧化碳纤维所制备的C_f/HA-PMMA复合材料相比,弯曲、压缩强度和弹性模量分别提高1.6倍、2倍和4.3倍。     

Damage characterization in non-isothermal stretching of acrylics. Part II: Experimental validation

Influence of temperature and strain rate on damage accumulation and large deformation behavior of acrylics was investigated under conditions similar to actual polymer processing. Poly(methyl methacrylate) (PMMA) samples were stretched to large strains at different rates under transient thermal conditions. During testing, specimens were cooled down from temperatures above glass transition temperature (θ_g) to temperatures well-below θ_g inducing a transition from rubbery state to solid state. Contrary to common practice of studying thermo-mechanical coupling in terms of adiabatic heating; in proposed experimental study, temperature effect on mechanical response of material was emphasized by externally intervening temperature variation within specimen. An improved version of dual-mechanism constitutive model presented in Part I [Gunel, E.M., Basaran, C., 2010. Damage characterization in non-isothermal stretching of acrylics. Part I: Theory. Mechanics of Materials] was proposed to predict thermo-mechanical response of amorphous polymer below and above θ_g. Applicability of proposed constitutive model for the specific case of non-isothermal stretching of PMMA at different test conditions was demonstrated by incorporating it into a finite element scheme. Constitutive model was reasonably accurate to capture observed temperature-displacement-force history in experimental study. Damage evolution under different testing conditions was studied in terms of irreversible thermal and mechanical entropy production.     

改性PU/PMMA半IPNs与BaTiO3纳米复合体系相容性研究

从分子结构设计出发,以丙烯酸改性聚氨酯与聚甲基丙烯酸甲酯为原料,通过同步互穿工艺,制备了室温固化互穿聚合物网络,进而与BaTiO3纳米粉复合,获得纳米复合体系,分别采用IR、TMA,TEM等技术检测了互穿聚合过程和网络的相容性。结果表明：通过确定的同步互穿工艺可有效地控制两相间的分离程度;IPN中大量的互穿缠结结构使体系的玻璃化转变温区有效衔接,且体系中化学交联结构的引入,可大大改善组分间的相容性,使聚合物两相间及复合体系的相畴尺寸控制在纳米级范围内。     

Characterization of fatigue resistance in photochromic composite materials for 3D rewritable optical memory applications

Fatigue resistance of the photochromic diarylethene molecules 1,2-bis[2-methylbenzo[b]thyophen-3-yl]-3,3,4,4,5,5-hexafluoro-1-cyclopentene embedded in three different acrylic polymers is studied upon multiple coloration–decoloration cycles. The resistance to photofatigue is found to be different in the three polymeric materials when one-photon excitation was used for the reversible photoconversion experiment. In particular, the photochromic molecules lose their photoisomerization ability faster if they are embedded in poly(methyl methacrylate) (PMMA) with respect to poly(ethyl methacrylate-co-methyl acrylate) (PEMMA) and poly(ethyl methacrylate) (PEMA). We propose several explanations based on the physico-chemical properties of the matrix and of the photochromic molecules. In the case of two-photon excitation, which is necessary for 3D optical writing, the fatigue resistance is found to be poorer than in the one-photon case. The accelerated photodegradation can be assigned to the non-linear nature of interaction between the polymeric composite material and light.     

Biodegradable polymers and their layered silicate nanocomposites: In greening the 21st century materials world

This review aims at highlighting on recent developments in preparation, characterization, properties, crystallization behaviors, melt rheology, processing, and future applications possibilities of biodegradable polymers and their layered silicate nanocomposites. These materials are attracting considerable interest in materials science research. Montmorillonite and hectorite are among the most commonly used smectite-type layered silicates for the preparation of nanocomposites. In their pristine form they are hydrophilic in nature, and this property makes them very difficult to disperse into biodegradable polymer matrices. The most common strategy to overcome this difficulty is to replace the interlayer clay cations with quarternized ammonium or phosphonium cations, preferably with long alkyl chains.

A wide range of biodegradable polymer matrices is described in this review with a special emphasis on polylactide because of more eco-friendliness from its origin as contrast to the fully petroleum-based biodegradable polymers and control of carbon dioxide balance after their composting.

Preparative techniques include (i) intercalation of polymers or prepolymers from solution, (ii) in situ intercalative polymerization method, and (iii) melt intercalation method.

This new family of composite materials frequently exhibits remarkable improvements of mechanical and material properties when compared with virgin polymers or conventional micro- and macro-composites. Improvements can include a high storage modulus both in solid and molten states, increased tensile and flexural properties, a decrease in gas permeability and flammability, increased heat distortion temperature and thermal stability, increase in the biodegradation rate, and so forth.     

Fundamentals, processes and applications of high-permittivity polymer-matrix composites

There is an increasing need for high-permittivity (high-k) materials due to rapid development of electrical/electronic industry. It is well-known that single composition materials cannot meet the high-k need. The combination of dissimilar materials is expected to be an effective way to fabricate composites with high-k, especial for high-k polymer-matrix composites (PMC). This review paper focuses on the important role and challenges of high-k PMC in new technologies. The use of different materials in the PMC creates interfaces which have a crucial effect on final dielectric properties. Therefore it is necessary to understand dielectric properties and processing need before the high-k PMC can be made and applied commercially. Theoretical models for increasing dielectric permittivity are summarized and are used to explain the behavior of dielectric properties. The effects of fillers, fabrication processes and the nature of the interfaces between fillers and polymers are discussed. Potential applications of high-k PMC are also discussed.     

Novel carboxymethyl derivatives of chitin and chitosan materials and their biomedical applications

Chitin and chitosan are natural biopolymers that are non-toxic, biodegradable and biocompatible. In the last decade, chitin and chitosan derivatives have garnered significant interest in the biomedical and biopharmaceutical research fields with applications as biomaterials for tissue engineering and wound healing and as excipients for drug delivery. Introducing small chemical groups to the chitin or chitosan structure, such as alkyl or carboxymethyl groups, can drastically increase the solubility of chitin and chitosan at neutral and alkaline pH values without affecting their characteristics; substitution with carboxyl groups can yield polymers with polyampholytic properties. Carboxymethyl derivatives of chitin and chitosan have shown promise for adsorbing metal ions, as drug delivery systems, in wound healing, as anti-microbial agents, in tissue engineering, as components in cosmetics and food and for anti-tumor activities. This review will focus on the preparative methods and applications of carboxymethyl and succinyl derivatives of chitin and chitosan with particular emphasis on their uses as materials for biomedical applications.     

Polymer/carbon based composites as electromagnetic interference (EMI) shielding materials

The extensive development of electronic systems and telecommunications has lead to major concerns regarding electromagnetic pollution. Motivated by environmental questions and by a wide variety of applications, the quest for materials with high efficiency to mitigate electromagnetic interferences (EMI) pollution has become a mainstream field of research. This paper reviews the state-of-the-art research in the design and characterization of polymer/carbon based composites as EMI shielding materials. After a brief introduction, in Section 1, the electromagnetic theory will be briefly discussed in Section 2 setting the foundations of the strategies to be employed to design efficient EMI shielding materials. These materials will be classified in the next section by the type of carbon fillers, involving carbon black, carbon fiber, carbon nanotubes and graphene. The importance of the dispersion method into the polymer matrix (melt-blending, solution processing, etc.) on the final material properties will be discussed. The combination of carbon fillers with other constituents such as metallic nanoparticles or conductive polymers will be the topic of Section 4. The final section will address advanced complex architectures that are currently studied to improve the performances of EMI materials and, in some cases, to impart additional properties such as thermal management and mechanical resistance. In all these studies, we will discuss the efficiency of the composites/devices to absorb and/or reflect the EMI radiation.     

Mechanical properties of graphene and graphene-based nanocomposites

In this present review, the current status of the intrinsic mechanical properties of the graphene-family of materials along with the preparation and properties of bulk graphene-based nanocomposites is thoroughly examined. The usefulness of Raman spectroscopy for the characterization and study of the mechanical properties of graphene flakes and their composites is clearly exhibited. Furthermore, the preparation strategies of bulk graphene-based nanocomposites are discussed and the mechanical properties of nanocomposites reported in the literature are analysed. In particular, through the analyse of several hundred literature papers on graphene composites, we have found a unique correlation between the filler modulus, derived from the rule of mixtures, and the composite matrix. This correlation is found to hold true across a wide range of polymer matrices and thus suggests that the common assumption that the filler modulus is independent of the matric is incorrect, explaining the apparent under performance of graphene in some systems. The presence of graphene even at very low loadings can provide significant reinforcement to the final material, while the parameters that affect the nanocomposite strongly are thoroughly reviewed. Finally, the potential applications and future perspectives are discussed with regard to scale up capabilities and possible developments of graphene-based nanocomposite materials.