Atomic layer chemical vapour deposition of copper

Copper films with (1 1 1) texture are of crucial importance in integrated circuit interconnects. We have deposited strongly (1 1 1)-textured thin films of copper by atomic layer deposition (ALD) using [2,2,6,6-tetramethyl-3,5-heptadionato] Cu(II), Cu(thd)₂, as the precursor. The dependence of the microstructure of the films on ALD conditions, such as the number of ALD cycles and the deposition temperature was studied by X-ray diffraction, scanning electron microscopy (SEM), and transmission electron microscopy. Analysis of (1 1 1)-textured films shows the presence of twin planes in the copper grains throughout the films. SEM shows a labyrinthine structure of highly connected, large grains developing as film thickness increases. This leads to low resistivity and suggests high resistance to electromigration.     

Nanostructured polymer blends: Synthesis and structure

Nanostructured polymer blends prepared via anionic ring opening polymerizations of cyclic monomers in the presence of a pre-made polymer melt exhibit a number of special properties over traditional polymer blends and homopolymers. Here, we report on a simple and versatile method of in situ polymerization of macrocyclic carbonates in the presence of a maleic anhydride polypropylene (mPP) matrix and a surface-active compatibilizer (i.e. PC grafted onto a mPP backbone generated in situ) to yield a micro- and nanostructured polymer blends consisting of a polycarbonate (PC) minor phase, and a polypropylene (PP) major phase. By varying the processing conditions and concentration of the macrocyclic carbonate it was possible to reduce the size of the PC dispersions to an average minor diameter of 150 nm. NMR and TEM characterizations indicate that the PC dispersions do not influence crystal content in the PP phase. Overall, the results point to a simple strategy and versatile route to new polymeric materials with enhanced benefits.     

Dynamic vulcanisation of EPDM/PE-based thermoplastic vulcanisates studied along the extruder axis

Simple blending and dynamic vulcanisation of EPDM/PE blends using the resol/SnCl₂ system was studied in an extruder using a series of sampling devices. The melting of the PE pellets occurs just in front of and in the first kneading zone. Upon complete melting of the PE phase, the EPDM/PE blends reach very quickly their final morphology. Crosslinking of the EPDM phase to high levels occurs already when the PE phase is not yet fully molten. The higher the EPDM content, the higher the viscous dissipation, the higher the melt temperature and, consequently, the higher the crosslinking rate. For the EPDM/PE (50/50; w/w) TPV a transition from continuous via co-continuous to fully dispersed EPDM is observed, which is driven by crosslinking. Although the degree of crosslinking of the EPDM rubber is very high, this does not prevent phase inversion of the blend. The EPDM/PE interface is rather blurred, because PE crystalline lamellae are growing into the EPDM domains, probably because of the high compatibility between PE and EPDM (60 wt% of ethene). This study shows that dynamic vulcanisation in extruders proceeds quite differently from that in batch kneaders, where melting, mixing and crosslinking are separated in time. In extruders mass and heat transport, melting of the thermoplastic, morphology development (including dispersion and phase inversion), distribution and dissolution of (crosslinking) chemicals and crosslinking of the rubber do not occur as independent phenomena, but mutually and/or continuously interact.     

Development of co-continuous structure in liquid crystalline polyester

We investigated liquid crystallization of liquid crystalline polyester BB-5 during isothermal annealing by digital high-fidelity microscope and light scattering. A liquid crystalline spherical domain having a radius of micrometers appeared by annealing at around 180 °C. The domain grew dendritically in all directions. Neighboring liquid crystalline regions coalesced and then interconnected. The interconnected structure changed to a co-continuous two-phase structure with increasing ordering of the liquid crystalline phase, and the interface between the liquid crystalline phase and the isotropic phase became smoother over time. Liquid crystallization stopped before volume filling the whole space, and the liquid crystalline phase and isotropic phase coexisted. The liquid crystalline region became narrower with an increase in the temperature of the liquid crystallization. Such structural development is different from the liquid-liquid phase separation via spinodal decomposition, and it may be attributed to the segregation of non-liquid crystallizable low molecular weight molecules from the growth front by fractionation of the molecular weight distribution during the liquid crystallization in terms of the instability of the diffusion-controlled interface.     

ABS／PC／MMA类共聚物Q三元共混体系的性能和形态

本文研究了ABS/PC甲基丙烯酸甲酯(MMA)共聚物Q三元共混物的性能与Q含量的关系,对不同Q含量下共混物的拉伸、冲击、弯曲、耐热、熔体指数等性能进行了测试,并用扫描电镜观察了该三元共混物的形态。结果表明,加入共聚物Q可增加共混体系的相容性,在适当组成下可使共混物的弯曲强度提高到原来的1.7倍,同时其他力学性能有所提高或不受损失;共混物的熔体指数能符合工业生产要求。从经济角度看,Q价格也较低。因而ABS/PC/Q三元共混物可望开发为具有重要实际意义的塑料合金。     

Effect of pH on the Crystallization of Homogeneously Precipitated Nanosized PZT Powder

Nanosized lead zirconate titanate (PZT) powder with Zr:Ti ratio in the morphotropic phase boundary region was synthesized by homogeneous precipitation of metal ions. The powder precipitated at 90°C and at pH 6.7 resulted single-phase perovskite lead zirconate titanate powder when calcined at 550°C and above for 4 hours in air. The solution pH and the precipitation temperature strongly affect the composition of the calcined powder. The results obtained by structural characterization of homogeneously precipitated powder were compared with that obtained from the conventional precipitation method using ammonia in terms of crystallization, homogeneity, and microstructure. The homogeneously precipitated powder showed smaller particle size, minimum agglomeration and uniform shape on calcination and annealing. Powdered samples that precipitated by homogeneous precipitation crystallized directly to perovskite PZT, without any intermediate pyrochlore phase formation. In contrast, the NH₃ precipitated powder converted to perovskite PZT via metastable pyrochlore and it showed phase segregation upon annealing at higher temperatures. The reaction kinetics has been studied by X-ray diffraction, differential thermal analysis, and differential scanning calorimetry.     

EPDM/PP热塑性弹性体相态研究

采用透射电镜(TEM)研究动态硫化EPDM/PP热塑性弹性体制备工艺及增容改性对形态结构的影响,研究发现通过添加增容剂可使EPDM相呈颗粒分布于连续相中。     

Evaluation of Morphology—Stable Critical Size of KNbO3 Crystals

Skeletal form of KnbO3 crystals growing in Li2B4O7 solvent was in-situ observed at 900℃ and it was found that shallow depression started to develop on the surface of KnbO3 crystals when the crystal size exceeded several micron,typically 7 micron.Based on the quantitative criterion derived by Chernov,the estimated critical size of KNbO3 crystals was 1 micron,which was consistent with the experimental measurement.The kinetic coefficients,Kcorner and Kcr,in the criterion were experimentally obtained in the diffusive-convective and diffusive-advective flow states respectively.     

High performance LDPE/thermoplastic starch blends: a sustainable alternative to pure polyethylene

Thermoplastic starch (TPS), as opposed to dry starch, is capable of flow and hence when mixed with other synthetic polymers can behave in a manner similar to conventional polymer-polymer blends. This paper presents an approach to preparing polyethylene/thermoplastic starch blends with unique properties. A one-step combined twin-screw/single screw extrusion setup is used to carry out the melt-melt mixing of the components. Glycerol is used as the starch plasticizer and its content in the TPS is varied from 29 to 40%.Under the particular one-step processing conditions used it is possible to develop continuous TPS (highly interconnected) and co-continuous polymer/TPS blend extruded ribbon which possess a high elongation at break, modulus and strength in the machine direction. The PE/TPS (55:45) blend prepared with TPS containing 36% glycerol maintains 94% of the elongation at break and 76% of the modulus of polyethylene. At a composition level of 71:29 PE/TPS for the same glycerol content, the blend retains 96% of the elongation at break and 100% of the modulus of polyethylene. These excellent properties are achieved in the absence of any interfacial modifier and despite the high levels of immiscibility in the polar-nonpolar TPS-PE system. The 55:45 blend possesses a 100% continuous or fully interconnected TPS morphology, as measured by hydrolytic extraction. This highly continuous TPS configuration within the blend should enhance its potential for environmental biodegradation. The elongation at break in the cross direction of these materials, although lower than the machine direction properties, also demonstrates ductility at high TPS concentrations. At a glycerol content of 36% in the TPS, the blends demonstrate only very low levels of sensitivity to moisture. A high degree of transparency is maintained over the entire concentration range due to the similar refractive indices of PE and TPS and the virtual absence of interfacial microvoiding.Effective control of the glycerol content, TPS concentration and processing conditions can result in a wide variety of morphological structures including spherical, fiber-like, highly continuous and co-continuous morphologies. These various blend morphologies are shown to be the determining parameters with respect to the observed mechanical properties.This material has the added benefit of containing large quantities of a renewable resource and hence represents a more sustainable alternative to pure synthetic polymers.     

Morphology control of titanium oxides by tetramethylammonium cations in hydrothermal conditions

The effect of tetramethylammonium cations (TMA⁺) on TiO₂ crystal morphology in hydrothermal conditions has been studied. The as-synthesized samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) methods. The morphologies including besom-like particle, nanosheet and nanotube have been observed. The different ways TMA⁺ cations in the hydrothermal bases affect the crystal growth manner are suggested to be responsible for the different morphologies of the as-synthesized samples.