Surface-esterified cellulose fiber in a polypropylene matrix: impact of esterification on crystallization kinetics and dispersion

Cellulose powders hydrophobized by surface esterification with carboxylic acids with different chain lengths (3, 10 and 18 carbons) were dispersed in a polypropylene matrix. Quality of the dispersion and nucleation activity of the filler were investigated by means of differential scanning calorimetry and optical microscopy. The results showed that the esterification decreases the crystallization rate in case of cellulose esterified with propionic or decanoic acid. On the other hand, the oleic acid ester demonstrated slightly higher crystallization rates than the unmodified cellulose, which was ascribed primarily to the newly arisen non-esterified surface after disintegration of the filler. Optical microscopy with hot stage showed the high nucleation ability of the natural cellulose fiber and its suppression in case of esterified surfaces. A complete inability to nucleate polypropylene crystallization was observed in case of decanoyl ester, while the other two retained some activity, but lower than that of the natural fiber. Finally, analysis of the filler dispersion and distribution revealed that the decanoyl and octadecanoyl esters disintegrate during melt mixing, while both dispersion and distribution of the fibers modified with propionic acid are poor.     

碳纤维对聚丙烯结晶行为的影响

本文用偏光显微镜和示差扫描量热计(DSC)方法研究了碛纤维对聚丙烯结晶行为的影响。碳纤维表面对聚丙烯结晶过程具有明显的促进作用,纤维表面成核密度轻高,结晶生长成为横穿结晶,结晶特征温度随碳纤维加入而有不同程度的升高。结晶动力学表明:结晶生长本质仍是球晶机理,促进聚丙烯结晶的原因是碳纤维使结晶过程的表面自由能降低。     

热致液晶共聚酯对聚丙烯结晶的诱导作用

用差示扫描量热法和光学解偏振法研究了热致液晶性芳香共聚酯与聚丙烯共混物的等温和非多温结晶行为.结果表明,这一热致液晶聚合物对聚丙烯结晶有诱导成核和加速作用.当共聚酯含量在2-5％之间时,聚丙烯的结晶速率最快.偏光显微镜的观察揭示出在聚丙烯熔体中原位形成的液晶聚合物微纤诱导了聚丙烯横穿晶的形成.     

Imaging SIMS for the investigation of substrate surfaces for CVD diamond deposition

The influence of substrate surface preparation on diamond nucleation is a major topic in the investigation of CVD-diamond deposition. The substrate, polishing material, its grain size, and the resulting surface roughness all influence diamond nucleation. Diamond can nucleate at scratches or residues of the polishing process which are providing nucleation sites. In this paper the surface of molybdenum and substrates polished with SiC and diamond powder was studied by imaging (2- and 3-dimensional) secondary ion mass spectrometry. The distribution and grain size of polishing residues (SiC, diamond) were determined and the reaction of diamond with the substrate during heating to deposition temperature was investigated. In this case a laterally inhomogeneous system of carbon containing species had to be characterized. Therefore compound-specific secondary ion mass spectrometry had to be performed. The results suggested that diamond residues on molybdenum substrates are partly dissolved during the heat treatment. The measurements indicate that a fraction of the diamond residues is still present after heat treatment and can provide nucleation sites for diamond deposition.     

Surface attachment of nanoparticles using oligonucleotides

Colloidal polymer particles are widely used in a variety of applications ranging from chromatography to surface modified bioreactors in protein arrays. In the present study, surface attachment of polystyrene particles to a polystyrene substrate has been performed using oligonucleotide hybridization. Thiolated complementary oligomers of cytosine and guanine have been covalently coupled to a pyridyl disulphide (PDS) modified polyethyleneglycol tether, forming part of a triblock copolymer which is adsorbed to the polystyrene surfaces via hydrophobic polypropylene oxide center blocks. The ability to withstand shear forces was studied using a laminar flow cell and the uptake of oligomers on the particles was quantified using two complementary techniques: UV-spectroscopy and sedimentation field flow fractionation. The possibility to tether particles in a flow cell suitable for practical use in e.g. a FIA-system is demonstrated.     

Influence of wood mercerization on the crystallization of polypropylene in wood/PP composites

Mercerization process is very significant because the alkali treatment facilitates reactivity of lignocellulosic fillers, thus allowing better response to chemical modification. In the present study, the effect of mercerization of pine wood on the nucleation ability of polypropylene was investigated by means of differential scanning calorimetry. We discovered that for the composites with wood containing cellulose II, the decrease in the crystal conversion of the polymer matrix and increase in the half-time of crystallization values are significant. It can be concluded that the amount of cellulose II formed upon alkalization of lignocellulosic fillers determines their nucleation ability. To evaluate the transcrystalline effects caused by various woods, which were untreated or treated with sodium hydroxide, the polarized optical microscopy was also performed. The nucleation of polypropylene on the surface of wood was investigated by induction time measurement. It was found that surfaces of the unmodified wood generate epitaxial nucleation, whereas the mercerized wood generates nonepitaxial nucleation. The differences in the type of nucleation suggest that the effectiveness of formation of transcrystalline structures depends on the contribution of cellulose I and cellulose II. Moreover, the presence of epitaxy is not necessary for the appearance of transcrystalline structures. The results showed that the transcrystalline structures appeared in each system, even with wood containing significant contribution of cellulose II. The only difference noted was the change in the nucleation abilities of the wood surface. Results of this study imply the necessity of quantitative determination of the contributions of cellulose I and cellulose II, whose presence determine the type of nucleation and nucleation ability of the filler surface.     

Study of the Interface Microstructures of CVD Diamond Films by TEM

 The characteristics of the interface microstructures between a CVD diamond film and the silicon substrate have been studied by transmission electron microscopy and electron energy loss spectroscopy. The investigations are performed on plan-view TEM specimens which were intentionally thinned only from the film surface side allowing the overall microstructural features of the interface to be studied. A prominent interfacial layer with amorphous-like features has been directly observed for CVD diamond films that shows a highly twinned defective diamond surface morphology. Similar interfacial layers have also been observed on films with a <100> growth texture but having the {100} crystal faces randomly oriented on the silicon substrate. These interfacial layers have been unambiguously identified as diamond phase carbon by both electron diffraction and electron energy loss spectroscopy. For the CVD diamond films that exhibit heteroepitaxial growth features, with the {100} crystal faces aligned crystallographically on the silicon substrate, such an interfacial layer was not observed. This is consistent with the expectation that the epitaxial growth of CVD diamond films requires diamond crystals to directly nucleate and grow on the substrate surface or on an epitaxial interface layer that has a small lattice misfit to both the substrate and the thin film material.     

Influence of fluid flow on the deposition of soluble surfactants through receding contact lines of volatile solvents

Soluble surfactants are often deposited from volatile solvents through moving contact lines. In this study, we demonstrate that altering the flow field near such a contact line fundamentally changes the deposited surfactant structure. At slow contact line speeds, the substrate emerges dry. A densely packed, tilted monolayer of surfactant is deposited along the solid-vapor interface from the rolling fluid motion at the contact line. At faster speeds, the substrate emerges with an evaporating thin film entrained on its surface. Surfactant is confined in the film in a constantly increasing concentration environment. Monodisperse crystalline islands nucleate and grow on the surface with sizes and shapes controlled by varying the deposition conditions. These results contrast with disordered deposits that result from evaporation at a pinned contact line. Our results suggest that dip-coating with control of dipping speed and evaporation rate may provide better control of deposition through contact lines of evaporating solvents.     

Determination of nucleating ability ofwood for non-isothermal crystallisation of polypropylene

Composites made from an isotactic polypropylene matrix and wood (pine or beech) have been prepared and tested. To improve adhesion between components, the wood modification was performed by esterification with maleic, propionic, crotonic, succinic and phthalic anhydrides. The surface of wood fillers was also modified by chemical treatment with NaOH as well as by extraction process. Non-isothermal crystallisation of polypropylene in wood composites is studied by DSC, and the basic parameters of crystallisation are determined. We discovered that the composites containing chemical treated wood fillers showed the tendency reduction the nucleation efficiency of polypropylene. The ability of wood filler to induce nucleation in polypropylene matrix is dependent on the kind of chemical modification of surface wood     

Investigations on nucleated polypropylene with using thermal analysis method

In the following essay the results of the research on nucleation of polypropylene obtained in PKN Orlen SA were presented. Both, organic (Millad 3988, ADK NA21) and non-organic (talc) mediums were used in the process. The main aim of the examination was to measure the influence of the above-mentioned mediums on the structure and physicochemical features of polypropylene. It has been proved that the organic nucleation mediums are more efficient as not only did polypropylene become more transparent, its structure more homogenous but his melting temperature increased as well. All those changes demonstrate that the nucleation process has taken place. The favourable changes in the polymer macrostructure were enabled by the process of nucleate molecules in the process heteronucleation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sonochemical activation calcium sulfate whisker with enhanced beta-nucleating ability for isotactic polypropylene

The crystalline morphology, structure, and the β-nucleating ability of ultrasound-activated calcium sulfate whisker (CSW)-filled isotactic polypropylene were investigated via X-ray diffraction (XRD), polar light microscopy (PLM), and differential scanning calorimetry (DSC). The XRD results revealed that ultrasound treated CSW (UCSW) could improve the β-nucleated ability, and resulted in enhancing the content of β-crystal form. The ultrasonic time was conducive to the improvement of the contents of β-crystal and reached the maximum value at ultrasonic 120 min. PLM and DSC results verified the enhanced nucleating ability of UCSW supported as β-nucleating agent. The scanning electron microscopy, energy dispersive spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy indicated the surface of CSW treated by ultrasound had been changed. The activity of the calcium ion was improved and the sulfuric acid layer appeared on the whisker surface had a significant effect on the iPP β-heterogeneous nucleation, and resulted in enhancing the content of β-crystal form.     

Effects of solvent polarity on mutual styrene grafting onto polypropylene by electron beam irradiation

Radiation induced mutual grafting of styrene onto polypropylene has been carried using several grafting solutions with different organic solvents and polarity levels. In the mixture of styrene and protic polar solvents high grafting yields were obtained. This behavior suggests that grafting process does not have dependence on swelling of the substrate, something that is expected when a non-polar substrate and a non-polar media are in contact. In this case, the grafting yield may be related to the free radical generation at protic polar solvent; these reactive specimens start the reaction on substrate surface to allow the accessibility of monomer species to active sites. Some reaction mechanisms are proposed.     

Effects of surface chemical composition on the early growth stages of alpha-sexithienyl films on silicon oxide substrates

In organic field effect transistors, charge transport is confined to a narrow region next to the organic/dielectric interface. It is thus extremely important to determine the morphology and the molecular arrangement of the organic films at their early growth stages. On a substrate of technological interest, such as thermally grown silicon oxide, it has been recently found that alpha-sexithienyl aggregates made of flat-lying molecules can simultaneously nucleate besides islands made of molecules standing vertical. In this paper, we investigate the effects due to variations in surface chemical composition on alpha-sexithienyl ultrathin film formation. Flat-lying molecules are no longer detected when Si-OH groups present at the surface are chemically removed but also when the Si-OH or Si-H group density is maximized. This gives evidence that variations in the surface chemical composition can largely affect the nucleation and growth processes of organic/dielectric interfaces. We hypothesize that isolated OH groups can interact with alpha-sexithienyl molecules and anchor them down flat with respect to the surface.     

Substrate effect on the formation of hydrogels with heterogeneous network structure

It was found that when an aqueous solution of vinyl monomers is polymerized on a hydrophobic substrate, obvious heterogeneity occurs in the region of the interface. This substrate effect was observed on polytetrafluroethylene (Teflon), polypropylene (PP), polyethylene (PE), polystyrene (PS), and polyvinylchloride (PVC), but not on hydrophilic substrates. Compared with synthesis on hydrophilic surfaces, the surfaces of hydrogels synthesized on a hydrophobic substrate exhibit a larger degree of swelling, a lower surface coefficient of friction and elastic modulus, weaker interfacial adhesion, and reduced interaction with biological cells. This substrate effect has been observed for many types of aqueous monomer solutions. It was found that the above properties are related to the loosely cross-linked architecture, containing some graft-like polymer chains, that is formed on the gel surface when the gel is prepared on a hydrophobic substrate. To understand the mechanism of the substrate effect, two novel optical methods, electric speckle pattern interferometry (ESPI) and real-time laser sheet refraction (RT-LSR), were developed. It was found that oxygen trapped in the composite interface between the monomer solution and rough hydrophobic substrates played an important role in the substrate effect.     

A study of transcrystallinity in polypropylene in the presence of wood irradiated with gamma rays

The interest in lignocellulosic composites has been growing in recent years because of their specific properties. In this study, a new technique of wood treatment using γ-irradiation was used. This research focuses on the influence of the gamma irradiation on the chemical composition of wood and on the nucleation ability of polypropylene matrice. The inner morphology of the transcrystalline layer was investigated using hot stage optical microscopy. Differential scanning calorimetry was used to investigate the kinetic parameters of polypropylene crystallization in the presence of wood surface. The results showed that the gamma irradiation can decrease the content of the cellulose in the wood, but it has a slightly negative effect on the transcrystallization process of polypropylene. This treatment also affects the crystal conversion and the half-time of PP crystallization. These results suggested that the gamma irradiation of wood may play a useful role in changing the microstructure of the matrice near the wood. It was observed that the nucleation of the wood surface was selective, indicating that the chemical characteristics of the lignocellulosics might have influence on the polypropylene crystallization. A possible mechanism for the appearance of transcrystallinity involving chemical composition of lignocellulosic is also proposed.     

A study of surface changes of wood-polypropylene composites as the result of exterior weathering

Outdoor applications of composites raised questions about their durability. In this study, the effects of outdoor weathering on the properties of wood-polypropylene composites with and without pigments were examined. The composites were placed outdoors for one year, and their colour changes were evaluated after 1, 3, 6, 9 and 12 months of weathering. The weathering resulted in considerable colour fading of the composites. Composites containing darker colour pigments had better colour stability. Scanning electron microscopy analysis revealed that surface cracks caused by weathering in a wood-polypropylene composite having a higher polypropylene content were less abundant, and the deterioration of the surface layer was lower compared to composites containing less polymer. Measurements of melting temperatures by differential scanning calorimetry gave a consistent picture of polypropylene degradation in the surface layer. After weathering, a decrease in Charpy impact strength was found for composites characterised by higher moisture absorption.     

硅烷类外给电子体的取代基变化对丙烯聚合影响的研究

合成了2种新型硅烷化合物双环己基二甲氧基硅烷(Donor-H)、双哌啶二甲氧基硅烷(Donor-Py),将其与工业化的环己基甲基二甲氧基硅烷(Donor-C)分别作为外给电子体,用于MgCl2负载的Ziegler-Natta催化剂催化丙烯聚合,通过DSC、GPC、SSA和13C-NMR等分析手段研究了3种外给电子体取代基的变化对催化剂的催化活性、氢调敏感性、聚丙烯的等规度、分子量分布、结晶能力、等规序列分布的影响.结果表明,随着外给电子体取代基体积的增大,外给电子体的给电子能力逐渐增强.与Donor-C相比,随着外给电子体取代基体积的增大,合成的具有较大取代基的Donor-H和Donor-Py用于丙烯聚合时都表现优异的催化性能,特别是新型含有N杂原子的氨基硅烷类Donor-Py为外给电子体的催化剂的催化活性和制备的聚丙烯的等规度最高,聚丙烯的熔融指数可调范围最宽,结晶能力更强.氨基硅烷类Donor-Py制备的聚丙烯SSA热分级后的高等规组分含量最多,可高达64.5%,聚丙烯等规序列长度最长,聚丙烯的等规序列分布最窄,而且13C-NMR结果也表明聚丙烯等规序列长度MSL最长,聚丙烯的分子链最规整.     

Interphase compatibilization of composites with immiscible blends as matrix: Glass beads filled nylon 6 / polypropylene blend-composite

The effect of a filler on the compatibility of an immiscible Nylon 6/polypropylene blend is studied. A compatibilized system with maleic anhydride grafted polypropylene is used as a reference. Dynamic mechanical analysis, differential scanning calorimetry and scanning electron microscopy measurements are performed for these two distinct systems containing treated and non-treated glass spheres. An improvement of the properties towards surface-induced compatibilization is observed when the filler surface is treated with a suitable silane coupling agent. Changes in the viscosity and main relaxations of the studied system are correlated with the presence of the filler and with its surface treatment. The crystallinity, adhesion and morphology behavior supports the rheological results. In this system, the filler takes not only the usual role of reinforcing material but also a new role as modifier of the interphase structure.     

Heterogeneous nucleation of crystallization of high polymers from the melt. I. Substrate-induced morphologies

Melt crystallization of isotactic polypropylene (iPP), poly(ethylene oxide), poly(butene-1), and polycaprolactone in contact with various substrates (mostly polymeric) has been studied by hot stage polarizing microscopy. Nucleating abilities of surfaces have been characterized qualitatively by examining the substrate-induced morphologies of the crystallizing polymer. These morphologies have been classified into three groups, depending on whether the substrate is very active (transcrystallinity), moderately active, or inactive as a nucleating agent. The morphologies observed are temperature-dependent, changing from transcrystalline to spherulitic upon increase of the crystallization temperature. At intermediate temperatures, mixed surface morphologies (transcrystalline plus spherulitic) are observed. The concentration of titanium and aluminum catalytic residues in isotactic polystyrene (iPS) samples can be reduced by two methods, i.e., (a) fractionating the polymer and (b) chelating Ti and Al with acetylacetone. The high nucleating ability of iPS samples in the crystallization of iPP has been shown to be due to the polymer (iPS) itself, and not to Ti and Al residues. Apart from iPS, other polymers (low energy surfaces) have also been found to induce transcrystallinity. From a survey of 43 substrate-crystallizing polymer pairs, conclusions have been drawn which are relevant to the following potential factors in heterogeneous nucleation processes: (a) chemical structure, (b) crystallographic unit cell type, (c) lattice parameters, (d) crystallinity of substrate, and (e) surface energy of substrate.     

Influence of individual ionic components on the agglomeration kinetics of silver nanoparticles

We demonstrate an original and powerful concept for elaborating spontaneous, high fidelity patterns of nanoporosity from nanoscale building blocks using patterned surface chemistry (i.e., "surface energy gating") to corral the growth of colloidal structures at a solid surface. Composite films consisting of polymethylsilsesquioxane nanoparticles uniformly dispersed in polypropylene glycol polymer were examined at temperatures beyond the decomposition of the polymer as a function of the substrate surface energy to clarify nanoparticulate ensemble behavior. The principle behind this colloidal assembly can be understood by taking into consideration the entropy and enthalpy dictating the mutual interactions between substrate surface, polymeric solvent, and dispersed colloids in the decomposition regime. The relevance of this research is shown by demonstrating how the principle of surface energy gating can be utilized to achieve spontaneous and controllable spatial patterns of nanoporous, high surface area thin films in a cost-effective and energy-efficient manner via brief thermal exposure. The simplicity and general nature of this methodology are further exemplified by showing the facility with which high-contrast fluorescent bioconjugate arrays can be prepared from nanoporous organosilicate patterns.