Features of ZnO Nanocrystal Size Distribution in a Polymer Matrix

Physics of the Solid State - X-ray diffraction patterns of a photocurable epoxy acryl-based polymer composite with addition of ZnO nanocrystals are analyzed. We recover the size distribution...     

Studies on kinetics and thermodynamics of ion adsorption reactions by applications of short-lived radioactive tracer isotopes

The short-lived radiotracer isotopes were applied to study the kinetics and thermodynamic feasibility of iodide as well as bromide ion adsorption reactions using industrial-grade resin materials. Free energy of activation (ΔG ^?) and energy of activation (E _a) were calculated by using Arrhenius equation, enthalpy of activation (ΔH ^?), and entropy of activation (ΔS ^?) calculated by using the Eyring-Polanyi equation. These parameters were used to predict the thermodynamic feasibility of the two ion adsorption reactions performed by using Dowex SBR LC and Indion-810 resins. It was observed that during iodide ion adsorption reactions, the values of energy of activation (?18.79 kJ mol^?1), enthalpy of activation (?21.37 kJ mol^?1), free energy of activation (58.13 kJ mol^?1), and entropy of activation (?0.26 kJ K^?1 mol^?1) calculated for Indion-810 resins were lower than the respective values of ?4.28 kJ mol^?1, ?6.87 kJ mol^?1, 64.97 kJ mol^?1, and ?0.23 kJ K^?1 mol^?1 calculated for Dowex SBR LC under similar experimental conditions. Identical trends were observed for the two resins during bromide ion adsorption reactions. The low values of different thermodynamic parameters obtained for Indion-810 resins during both the ion adsorption reactions indicate that the reactions are thermodynamically more feasible using Indion-810 resins as compared to Dowex SBR LC resins. It is expected here that the present nondestructive technique can be extended further for different ions in the solution in order to predict the thermodynamic feasibility of different ion adsorption reactions for the range of resins which are widely used for treatment of industrial waste water effluent.     

Multiphase Polymeric Materials for Rapid Prototyping and Tooling Technologies and Their Applications

Rapid prototyping (RP) and tooling (RT) are the technologies for quickly fabricating functional components and tooling inserts directly from CAD data by selectively adding material layer by layer. In this paper, multiphase polymeric materials for RP and RT technologies and their applications, which are developed by the Rapid Manufacturing (RM) Center of Huazhong University of Science and Technology (HUST) in China, were introduced. Selective laser sintering (SLS) is a powder-based RP process. Multi-types of multiphase polymer materials for SLS process were successfully developed in the RM center, and the SLS components were formed from these materials by using the commercial SLS machines HRPS series for various applications. High impact polystyrene (HIPS)/wax blend SLS parts were used as lost patterns for the investment casting process to make complex metal parts rapidly; nylon-12/organically modified rectorite and nylon-12/nanosilica composite powders were used to fabricate functional parts, which showed higher thermal and mechanical properties than neat nylon-12 SLS parts. As a RT application, Fe/epoxy composite tooling inserts were rapidly fabricated by SLS and post-processing. Stereolithography (SLA) uses photocurable resins to rapidly manufacture components with high accuracy and mechanical properties. A freeradical and cationic mixed-type radiation curable composite resin was also successfully developed, and SLA parts without obvious distortion were built on the SLA machines HRPL series from this hybrid resin, successfully and efficiently.     

Polymer photodegradation initiated by ZnO nanoparticles

The photodegradation initiated by semiconductor nanoparticles in an acrylic photocurable polymer doped with p-ZnO nanoparticles has been investigated. A mechanism and formula of the photoinduced chemical reaction stimulated by primary photochemical processes of water photolysis on the surface of semiconductor ZnO nanoparticles are proposed. The mass loss in this reaction reaches 12%, which confirms the validity of photodegradation for polymer waste disposal.     

Self-grown fiber fabrication by two-photon photopolymerization

We demonstrate a new fiber growth mechanism in a photocurable resin by ultrafast laser illumination. A high-repetition rate (∼1 MHz) ultrafast laser beam at the wavelength of ∼523 nm was focused into an ultraviolet photocurable resin to trigger two-photon photopolymerization process. Time-resolved shadowgraphs and scattered light imaging revealed that the curing commenced in the neighborhood of the geometric focal point of the laser beam and that the fiber growth progressed mostly towards the laser source. The cured fiber was thinner and longer than the profile of the focused laser beam, facilitated by nonlinear propagation and absorption of the ultra-fast laser beam. The achieved aspect ratio of the fiber was higher than 180 with ∼10 μm mean diameter, and the average growth rate was up to ∼2 mm/s.     

Fabrication of three-dimensional structures by three-photon polymerization

We report the fabrication of three-dimensional structures of submicrometer resolution by three-photon polymerization. This resolution has been achieved by polymerizing ORMOCER, a UV photocurable organic-inorganic hybrid material, with an ultrafast laser irradiation at 1028 nm. To our knowledge, this is the first demonstration of three-photon polymerization, a process that may allow the fabrication of components of very high resolution.     

NMR detection of thermal damage in carbon fiber reinforced epoxy resins

Composite materials of epoxy resins reinforced by carbon fibers are increasingly being used in the construction of aircraft. In these applications, the material may be thermally damaged and weakened by jet blast and accidental fires. The feasibility of using proton NMR relaxation times T1, T1rho, and T2 to detect and quantify the thermal damage is investigated. In conventional spectrometers with homogeneous static magnetic fields, T1rho is readily measured and is found to be well correlated with thermal damage. This suggests that NMR measurements of proton T1rho may be used for non-destructive evaluation of carbon fiber-epoxy composites. Results from T1rho measurements in the inhomogeneous static and RF magnetic fields of an NMR-MOUSE are also discussed.     

婆罗洲和马达加斯加柯巴树脂红外光谱特征及其与外观相似琥珀的快速鉴别

琥珀是古植物的液态树脂经过多种地质作用后形成的石化树脂。柯巴树脂是形成年代较短且成熟度较低的半石化树脂,其外观与琥珀较为相似。柯巴树脂与琥珀都是天然树脂在石化过程中的产物,两者的化学成分存在过渡、重叠,具有较多的相似性,导致二者的鉴别有一定难度。近期市场上出现两个产地的柯巴树脂,其中棕红色-棕色的婆罗洲柯巴树脂常被误认为缅甸琥珀,淡金色-金色的马达加斯加柯巴树脂常与波罗的海琥珀混淆,已引起较为广泛的注意。为此,以外观相似的婆罗洲柯巴树脂与缅甸琥珀,马达加斯加柯巴树脂与波罗的海琥珀,为研究对象每类选取四块代表性样品,共16块。红外光谱测试在中国地质大学(北京)珠宝学院宝石研究实验室完成。测试仪器为BRUKER TENSOR 27型傅里叶变换红外光谱仪,扫描16次,分辨率为4 cm-1, 扫描范围为4 000~400 cm-1,室温。研究结果显示,外观相似的柯巴树脂和琥珀红外光谱吸收峰位置和吸收强度存在可识别的差异,因此可以利用红外光谱特征对其进行科学有效的鉴别。婆罗洲柯巴树脂的红外光谱主要特征为3 000~2 800 cm-1范围内的4处吸收峰和1 710 cm-1处较强吸收峰,1 730 cm-1处肩峰、887与824 cm-1处弱吸收峰。马达加斯加柯巴树脂的红外光谱主要特征为与CC双键相关的3处组合吸收峰、1 697 cm-1处强吸收峰,1 724 cm-1处肩峰和由1 271与1 176 cm-1吸收峰组成的“W 图形”。与婆罗洲柯巴树脂外观相似的缅甸琥珀可以通过3 000~2 800 cm-1范围内的2处吸收峰、1 724 cm-1处强吸收峰、1 300~1 100 cm-1范围内的一个“W图形”进行快速鉴别。与马达加斯加柯巴树脂易混淆的波罗的海琥珀可以通过“波罗的肩”进行快速区分。另外,婆罗洲柯巴树脂R (A_{1 383 cm-1}/A_{1 464 cm-1})值为0.823~0.860,大于缅甸琥珀0.605~0.643;马达加斯加柯巴树脂R值为0.900~0.985,大于波罗的海琥珀0.704~0.783,该值也可作为区分特征。国内有关琥珀和柯巴树脂的研究主要为气相色谱质谱(GC-MS)划分的Ⅰ类琥珀和柯巴树脂(主要化学成分为半日花烷型双萜化合物的聚合物),柯巴树脂针对新西兰和哥伦比亚这两个产地,缺乏婆罗洲和马达加斯加柯巴树脂的红外光谱分析。该研究对外观相似的婆罗洲柯巴树脂和缅甸琥珀,马达加斯加柯巴树脂和波罗的海琥珀进行红外光谱的对比分析,揭示了婆罗洲和马达加斯加柯巴树脂的红外光谱特征,并为快速区分外观相似的柯巴树脂与琥珀提供科学依据。结合前人研究,认为红外光谱在不同产地柯巴树脂的分类及外观相似的柯巴树脂和琥珀的快速鉴别提供了重要的科学依据。     

Observation of tunable optical filtering in photosensitive composite structures containing liquid crystals

We report on the investigation and characterization of an optically tunable filtering effect, observed in a waveguide grating made of alternated strips of photocurable polymer and a mixture of azo-dye-doped liquid crystal. The grating is sandwiched between two borosilicate glasses, one of which includes an ion-exchanged channel waveguide, which confines the optical signal to be filtered. Exposure to a low power visible light beam modifies the azo-dye molecular configuration, thus allowing the filtered wavelength to be tuned over a 6.6 nm range. Simulations of the filtering response are well described with our experimental findings.     

胜利油田稠油组分的光谱法研究

用红外光谱, 紫外光谱及同步荧光光谱对胜利油田稠油中的沥青质和胶质进行了分析。红外光谱分析结果表明,胶质、沥青质分子含有可形成氢键的羟基、胺基、羧基、羰基等极性基团,说明原油中 胶质分子之间、沥青分子之间及二者相互之间有强烈的氢键作用,具有很强的极性。通过紫外吸收光谱及同步荧光光谱的测定,并与模型化合物的紫外吸收特征峰及荧光光谱的特征峰相比较,结果表明, 芳香单片是研究稠油中胶质、沥青质组分结构的最基本单位。单元芳香片中芳香环的个数以3～4个环为主,共轭芳香环的排列形式主要为“线性排列”,即渺位缩合。但胶质和沥青质的结构也存在着差异, 即胶质中主要含有3～4个环的共轭芳香片,而沥青质中含有少量多于5个环的共轭芳香片,并且这些共轭芳香片有部分“面性排列”,即迫位缩合。     

Use of combinatorial chemistry to develop photocurable thermoplastic polyurethane elastomers (TPUs)

Combinatorial chemistry was used to develop photocurable thermoplastic polyurethane elastomers through the incorporation of photoreactive diacetylene diols as chain extenders. The methodology applied allowed, in 36 experiments, the choice of the best compromise between mechanical properties and lack of colour. The combinations chosen were scaled up and their properties were evaluated in terms of mechanical properties. The combinatorial approach reduced the estimated time tenfold in developing such type of materials.     

Tunable microlens arrays using polymer network liquid crystal

A tunable-focus microlens array based on polymer network liquid crystal (PNLC) is demonstrated. The PNLC was prepared using an ultraviolet (UV) light exposure through a patterned photomask. The photocurable monomer in each of the UV exposed spot forms an inhomogeneous centro-symmetrical polymer network which acts as a lens when a homogeneous electric field is applied to the cell. The focal length of the microlens arrays is tunable with the applied voltage.     

近红外吸收带在高折射率光学塑料结构表征中的应用

我们合成了 MESDMA、TBBDA、TDGDMA等光学塑料单体 ,并用它们聚合成光塑料。用红外光谱法对它们进行表征 ,对一些吸收谱带的吸收和结构的关系进行了讨论 ,得出了一些规律     

含稀土化合物透明树脂的合成与光学性质

我们采用三种不同方法制备了含稀土化合物的光学树脂。第一种是含稀土甲基丙烯酸盐的透明树脂,第二种是采用直接掺杂法制备的含稀土配合物透明树脂,第三种是采用原位复合法制备的含稀土配合物透明树脂。通过对三种透明树脂的热稳定性、抗冲击性、紫外-可见吸收光谱、红外光谱、荧光光谱及核磁等方面的表征,结果表明获得的第二、第三种透明树脂具有非常好的透明性、发光性和相关物理机械性能,进一步比较三种透明树脂的发光性质发现第三种采用原位复合法制备的含稀土配合物透明树脂最好,这说明原位复合法是一种简便快捷合成透明荧光高分子材料的好方法。     

Maskless fabrication of small-scale structures through controlling phase interactions

We present a technique to create three-dimensional (3-D) microstructures using optical phase interactions with photocuring chemistry. We formulated a photocurable poly(dimethylsiloxane) (photoPDMS) consisting of a (methacryloxypropyl)methylsiloxane-dimethylsiloxane copolymer and a photoinitiator 2,2-dimethoxy-2-phenyl-acetophenone. By activating the photoPDMS, in combination with controlling the phase interactions between photoPDMS and an immiscible liquid, in situ fabrication of 3-D polymeric microstructures was achieved. This method has potential applications in a variety of fields including building 3-D complex structures for small-scale tissue engineered scaffolds and using these fabricated optical polymer lenses in lab-on-chip technology.     

Micro via and line patterning for PCB using imprint technique

Today’s electronic devices such as mobile phones, PDA, computers, etc. have more functions in a smaller size. Thus conducting lines and via holes of PCB (printed circuit board) which has a role of land for all kinds of electronic components are getting finer. In this study, the conducting lines and via holes are produced using thermal imprint technique rather than the conventional photo-lithography process. Imprint technique is a press process that transfers patterns of stamp to resins. Imprint technique is used to produce micro size trench lines and via holes in epoxy resins.Resins used in this work are silica (SiO₂) reinforced epoxy. Resins were imprinted using 10 * 10 mm size Ni or polymer stamp. Line/space of pattern is 10/10 μm while diameter of via hole is 30 μm. The depths of lines and via holes are 15 and 30 μm, respectively. The anti-sticking treated stamp and epoxy resins were pressed at 100 °C for 30 min in vacuum. The stamp was released after resins were cured for 1 h at 130 °C. All patterns of stamp were successfully transferred with high fidelity and any noticeable defect was not observed within imprinted area. Imprinted resins were de-smeared to remove the residue at the bottom of via holes and to enhance the adhesion of resins with Cu. Electro/less copper plating was followed to fill in the imprinted patterns. Since the excess Cu layer was formed on the resins during Cu plating, the planarization process was introduced to obtain isolated lines and via holes.     

Application of Huygens-Fresnel diffraction principle for high aspect ratio SU-8 micro-/nanotip array

A high-aspect-ratio (approximately 30) SU-8 micro-/nanotip array whose shape is defined by diffraction was fabricated by a single UV photolithography procedure and its exposed dose control. The fabrication result of the tip agrees well with the Rayleigh-Sommerfeld solution of the Huygens-Fresnel principle at wide observation distances. In a near field below distance 2 microm (only several times of wavelength), necking points also agree with the solution, although it is assumed that the distance is much larger than wavelength. It can be also applied to control the shape of the tip and to determine the critical dose D(c) of SU-8 and other photocurable polymers.     

新型醇胺螯合树脂的合成及其红外光谱研究

合成了两种具有醇胺结构的新型螯合树脂，测定了该树脂及其合成中间体的红外光谱，并借助水解，成盐及羟值测定等化学方法对其主要吸收谱带作了归属，确认了其结构。     

Wetting behavior of modified vinylester resins on the surface of UHMWPE materials

A new testing method was used to observe on-line the dynamic wetting course of liquid resins on PE fabric. The measure procedures and data processing were introduced in detail. To aim at some applications of vinylester resins/polyethylene fiber composites, vinylester resins (VRs) were at first modified by three kinds of additives, including elastomer, liquid rubber and isocyanate-terminated prepolymer. Then the wetting behaviors of these modified resins on the surface polyethylene (PE) materials were observed. After they were modified by six kinds of elastomers, the infiltrate-steady-times of these resins on the surface of PE fabric all increased; only the contact angle of natural rubber-modified VR on the surface of PE film decreased. After VRs were toughened by three kinds of liquid rubbers, their wetting velocities all became slower and the contact angles on the surface of PE film all decreased. In addition, VRs were also modified by three kinds of isocyanate-terminated prepolymers, which were the products of different hydroxyl-terminated polymers reacted with methylene bisphenyl isocyanate and whose structures were characterized by means of GPC, DSC and FT-IR, respectively. The wetting state of these modified resins on the surface of PE materials suggested that the interfacial compatibility of modified VRs and PE fabric did not decrease at the same time when the other properties of vinylester resins changed.     

Effects of ZnS:Mn concentrated vinyl ester matrices under flexural loading on the triboluminescent yield

This paper investigates the feasibility of using zinc sulfide manganese (ZnS:Mn) concentrated vinyl ester resin as a photon emitter for damage monitoring of polymer composites under flexural loading. Unreinforced vinyl ester resins doped with optical emitting materials (ZnS:Mn phosphors) in ratios of 5–50% by weight were cast, and subjected to flexural loading using standard 3-point bend tests. The intent of this work was to observe the transient response of triboluminescence (TL) throughout the failure cycle. Results indicate TL crystals emit light at various intensities corresponding to crystal concentration and imminent matrix fracture. Consequently, concentrated samples showed nearly 50% reductions of mechanical moduli. Scanning electron microscopy (SEM) revealed particulate inclusions with shearing bands and semblance of particle to resin adhesion. Despite significant parasitic effect to mechanical properties, the triboluminescent properties occur at yielding and point of matrix fracture.