High CEC generation and surface modification in mica and vermiculite minerals

Montmorillonite layered silicate has been commonly used to reinforce polymer matrices. Due to its swelling in water, organic modification of the mineral surface is easily achieved which makes the surface compatible with polymers. Other minerals like mica and vermiculite though can also lead to high aspect ratio platelets in nanocomposites, but they do not swell in water owing to much stronger electrostatic forces of attraction holding their platelets together (layer charge density >0.5?eq?·?mol^?1 in comparison with 0.25–0.5?eq?·?mol^?1 for montmorillonite). In current study, milling, delamination and cation exchange processing of mica and vermiculite minerals has been reported to explore their potential as reinforcement materials. Wet grinding and subsequent sieving of the coarse minerals led to fine-sized particles suitable to perform chemical delamination in water. The delamination process resulted in Li-mica and Na-vermiculite with enhanced access to the interlayer cations, thus, higher CEC. Successful surface modification of the delaminated minerals with alkyl ammonium ions could be achieved which resulted in significant enhancements in their basal plane spacing. Peak degradation temperatures of 260°C were measured for C18 and 2C18 modified vermiculite, whereas 300°C and 275°C were observed respectively for C18 and 2C18 modified mica minerals which make them suitable for compounding with polymers at high temperature.     

Surface modification of layered silicates. I. Factors affecting thermal stability

The resistance of modification molecules bound to montmorillonite platelet surfaces towards structural damage at high temperature is a major parameter guiding the formation of optimal interface between the filler and polymer phases in a nanocomposite material. As nanocomposites are generated by melt-blending of modified mineral and polymer, it is necessary to quantify the thermal resistance of the filler surface modification at the compounding conditions because different modifications differ in chain length, chemical structure, chain density, and thermal performance. A number of different alkyl ammonium modifications were exchanged on the montmorillonites with cation exchange capacities in the range 680–900?µequiv.?g^?1 and their thermal behaviour was characterised using high resolution thermogravimetric analysis. Quantitative comparisons between different modified minerals were achieved by comparing temperature at 10% weight loss as well peak degradation temperature. Various factors affecting thermal stability, such as length and density (or number) of alkyl chains in the modification, presence of excess modification molecules on the filler surface, the chemical structure of the surface modifications, etc. were studied. The TGA findings were also correlated with X-ray diffraction of the modified platelets.     

The Effect of Solid Sheet Fillers on Poly-p-Oxybenzoate Polymerization,Crystallization and Structure

The effect of added mineral sheet fillers (mica, montmorillonite, talc, graphite and kaolin) on the polymerization of acetoxybenzoic acid was investigated. The fillers exert a weak catalytic effect without affecting the structure and orientation of the polymer, the only exception being mica which can result in an epitaxial orientation.     

Polystyrene-Based Composites with Aluminosilicate Inclusions of Different Shapes

Technical Physics - Samples of composites based on polystyrene with addition of halloysite nanotubes, mica, and montmorillonite aluminosilicates are obtained and the influence of these fillers on...     

Anti-graffiti nanocomposite materials for surface protection of a very porous stone

The preservation of stone substrates from defacement induced by graffiti represents a very challenging task, which can be faced by applying suitable protective agents on the surface. Although different anti-graffiti materials have been developed, it is often found that their effectiveness is unsatisfactory, most of all when applied on very porous stones, e.g. Lecce stone. The aim of this work was to study the anti-graffiti behaviour of new nanocomposite materials obtained by dispersing montmorillonite nanoparticles (layered aluminosilicates with a high-aspect ratio) into a fluorinated polymer matrix (a fluorinated polyurethane based on perfluoropolyether blocks). Polymeric structure was modified by inducing a cross-linking process, in order to produce a durable anti-graffiti coating with enhanced barrier properties. Several composites were prepared using a naturally occurring and an organically modified montmorillonite clay (1, 3, and 5 % w/w concentrations). Materials were applied on Lecce stone specimens, and then their treated surfaces were soiled by a black ink permanent marker or by a black acrylic spray paint. Several repeated staining/cleaning cycles were performed in order to evaluate anti-graffiti effectiveness. Colorimetric measurements were selected to assess the anti-graffiti performance. It was found that the presence of 3 % w/w organically modified montmorillonite in the polymer coating is enough to induce a durable anti-graffiti effect when the stone surface is stained by acrylic paint. Less promising results are obtained when staining by permanent marker is considered as all the investigated treatments afford a reasonable protection from ink only for the first staining/cleaning cycle.     

Effect of mercerization of flax fibers on wheat flour/flax fiber biocomposite with respect to thermal and tensile properties

New composites materials, 100% ecofriendly based on modified wheat flour as matrix and flax fiber as fillers have been obtained by means of an extrusion process. The wheat flour matrix contains non-toxic plasticizers and is mixed well with natural fibers. One sample series without specific fiber surface treatment and a second series with a mercerization surface treatment have been prepared. The content of fillers varies from 0% w/w to 20% w/w. In this work the performances of these new composites in term of thermal stability, mechanical behaviours are compared and discussed in regard to the fiber treatment efficiency and composition. We observe an interesting behaviour: the efficiency is found the best for a fiber composition close to 10% w/w.     

Preparation and Properties of Polyethylene Terephthalate (PET)/Near Infrared Reflective Pigment (NIR) Composites

A near infrared reflective (NIR, nickel antimony titanium yellow rutile) pigment filler was incorporated into a polyethylene terephthalate (PET) matrix via a melt blending approach to increase the infrared reflection of PET and limit the thermal heat accumulation in light of environmental and energy conservation concerns. Two different types of surface modifiers, polyethylene glycol (PEG) and cetyltrimethylammonium bromide (CTAB), were used to modify the NIR surface, as NIR–PEG and NIR–CTAB fillers, to investigate the surface modification effect. Fourier transform infrared spectroscopy (FTIR), a Zetasizer, and electron spectroscopy for chemical analysis (ESCA) results suggested a successful adsorption of the organic modifiers onto the NIR surface. Thermogravimetric analysis indicated a higher adsorption degree for the CTAB modifier than the PEG modifier due to the electronic interaction between CTAB and NIR. The thermal crystallization temperature (T_c) for neat NIR-filled samples decreased with increasing NIR content within the PET matrix at first, up to 9°C, but then tended to increase again up to a measurable difference of 6°C with respect to pure PEG, indicating the promotion of the crystallization kinetics of the neat NIR within the PET matrix. On the other hand, a decrease in T_c for all NIR-CTAB or NIR-PEG loadings was found, with the depression close to 10°C for all NIR-CTAB samples regardless of the loading. CTAB modified NIR gave the highest improvement in tensile strength and strain at break in comparison with NIR and NIR-PEG filled samples. The near infrared reflection values of modified PET were higher than those of neat PET. The reflection values appeared to be the highest for some concentrations of the NIR-CTAB filled samples, but were of similar orders of magnitude with those for NIR or NIR-PEG filled samples.     

显微红外光谱法研究聚乙烯复合材料光氧化的深度分布

采用显微红外光谱法结合表面形貌分析研究了分别填充碳酸钙、绢英粉、云母、高岭土和硅藻土的高密度聚乙烯(HDPE)的自然光氧化随深度的分布。研究结果表明无机填料对HDPE光氧化的深度分布有很大的影响。填充碳酸钙的HDPE从表面到内部都没有明显氧化发生。而填充绢英粉、云母、高岭土和硅藻土的HDPE从表面到内部羰基指数逐渐减小,氧化深度都在150 μm以上。HDPE复合材料沿深度方向的氧化情况与其断面裂纹的产生情况吻合。结合无机填料的紫外吸收特性讨论了它们对HDPE光氧化的影响机理。     

Intercalative polymerization of cyclic esters in layered silicates: thermal vs. catalytic activation

Poly(ε-caprolactone) layered silicate nanocomposites were synthesized by in situ intercalative ring-opening polymerization (ROP) of ε-caprolactone. The polymerization was promoted by thermal or catalytic initiation starting from either non-modified natural sodium-montmorillonite (MMT-Na) or montmorillonite modified by different ammonium cations bearing either non-functional alkyl chains or chains terminated by carboxylic acid or hydroxyl functions. The resulting compositions were analyzed by small-angle X-ray diffraction and transmission electron microscopy. The clay dispersion depended on the structure of the alkyl ammonium. Exfoliated nanocomposites were formed when hydroxyl-containing alkyl ammonium was used; otherwise, partially intercalated/partially exfoliated structures were observed. Moreover, owing to the inherent catalytic properties of the montmorillonite surface, it was also possible to prepare intercalated nanocomposites by in situ polymerization of ε-caprolactone in presence of non-modified montmorillonite-Na (MMT-Na) without any added catalyst.     

Controlled assembly of DNA nanostructures on silanized silicon and mica surfaces for future molecular devices

In order to establish key technology for future molecular devices, we have explored the assembly behaviour of λ-deoxyribonucleic acid (DNA) molecules adsorbed on silanized mica and silanized oxide silicon surfaces by using atomic force microscopy (AFM). AFM experiments show that λ-DNA molecules can be hardly adsorbed on untreated mica and oxidized silicon surfaces, but can be strongly adsorbed onto aminosilanized mica and oxidized silicon surfaces. Importantly, DNA molecules can be assembled into linear DNA alignment, and can also self-assemble into various network structures on the silanized surfaces. Our experimental observations have demonstrated the feasibility of assembling DNA-based nanostructures by varying surface chemistry of substrates, and offer useful clues in constructing DNA-based nanodevices for nanoelectronics and biomolecular computation as well as quantum computation.     

Morphology of synthetic DOPA-eumelanin deposited on glass and mica substrates: An atomic force microscopy investigation

Bright field microscopy and atomic force microscopy techniques are used to investigate morphological properties of synthetic eumelanin, obtained by oxidation of l-DOPA solution, deposited on glass and mica substrates. Deposits of eumelanin are characterized by aggregates with different shape and size. On a micrometric scale, filamentous as well as granular structures are present on glass and mica substrates, with a larger density on the former than on the latter. On a nanometric scale, filamentous aggregates, several microns long and about 100 nm wide and high, and granular aggregates, ∼50 nm high and 100 nm wide, are found on both substrates, whereas point-like deposits less than 10 nm high and less than 50 nm wide are found on mica substrate. Dynamic light scattering measurements and atomic force microscopy images support the evidence that eumelanin presents only nanometric point-like aggregates in aqueous solution, whereas such nanoaggregates organize themselves according to granular and filamentous structures when deposition occurs, as a consequence of interactions with the substrate surface.     

On the surface temperature of substrates on a hotplate used for epitaxial growth

With the help of thin-film Au-constantan thermocouples the surface temperature of mica substrates on a hotplate was measured. The improvement of the thermal contact between the substrate and the hotplate by a thin layer of aquadag was verified and the influence of the mica thickness on its surface temperature was evaluated. The thin-film thermocouple proved useful for the investigation of the effect of radiant heat from the evaporation source on the temperature of the substrate surface.     

Solvent-Induced Crystallization of PS-b-PEO-b-PS Block Copolymer Films

Solvent-induced crystallization and dewetting behaviors of polystyrene-b-poly (ethylene oxide)-b-polystyrene (PS-b-PEO-b-PS) block copolymer films deposited on three different substrates, silicon, mica, and carbon-coated mica have been studied by atomic force microscope (AFM). When the common solvent dichloromethane was used for annealing, the films on all three of the substrates exhibited dewetting behavior; the dendritic crystallization patterns were found in the dewetted regions for the films on silicon and mica substrates, while for the films on carbon-coated mica, no crystallization pattern appeared. According to the observation of the crystallization patterns formed in the films with different initial thicknesses, it is shown that the width of the dendritic branches decreases with the increase of film thickness and solvent annealing time. When the PS-selective solvent toluene was used for annealing, the dewetting process was absent, and the crystallization patterns were observed on the surface of the films on all three kinds of substrates.     

各向异性堆叠结构环氧树脂复合材料的热防护性能

基于导热-隔热原理,通过在环氧树脂(Epon)中添加质量分数为5%,15%,25%的六方氮化硼(h-BN)作为填料制备环氧基散热层,质量分数为1%的膨胀蛭石(E-ver)作为填料制备环氧基隔热层,设计了宏观交替堆叠的环氧复合材料,并进行了热防护性能的研究。研究结果表明:具有各向异性结构的复合材料,顶部中心温度较传统材料的温度下降13~16℃,热延迟时间大大提升,并随着h-BN含量的增加,热性能得到明显改善。理论分析了该堆叠结构下复合材料"横向散热、纵向抑热"的机理。     

Microstructure and topography of vapor deposited,sputtered and annealed (111) palladium films

The microstructural effects of argon ion bombardment and thermal annealing on vapor deposited (111) Pd films on mica substrates have been studied. Sputtering resulted in surface roughening as well as in the formation of an amorphous phase and double positioned twins. In the higher fluence zones, relatively large blisters were formed. Moderate annealing of the sputtered film did not restore the original smoothness of the surface. The hillocks became larger while their density decreased.     

Influence of substrate temperature,deposition rate and surface conditions on the epitaxial growth of copper on mica

In this experimental investigation copper was deposited on mica substrates under UHV conditions. Both air-cleaved and vacuum-cleaved mica substrates were used. Evaporation rate and substrate temperature have been varied systematically over a wide range. The structure of the films was studied with X-ray methods (Laue-transmission photographs and rocking curves). It was observed that the polar orientation of the crystallites depends mainly on evaporation rate and substrate temperature. The azimuthal orientation, however, is strongly dependent upon the surface conditions of the substrate, i.e. a surface gas layer improves the azimuthal orientation significantly. On vacuum-cleaved substrates an improvement of the azimuthal orientation can only be achieved by high evaporation rates (> 2500 Å/s). These effects are explained by the dependence of the rotation jump frequency on the size of nuclei and clusters.     

Tuning the hydrophobicity of ZSM-5 zeolites by surface silanization using alkyltrichlorosilane

ZSM-5 zeolites were modified with alkyltrichlorosilanes of various chain lengths (octyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane and hexadecyltrichlorosilane) and characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Thermal gravimetric analysis (TGA) and contact angle measurements (CA). The results showed that a closely packed and hydrophobic layer was presented at the particles surface and the surface wetting property varied from hydrophilic to hydrophobic, even to superhydrophobic. It was interesting to notice that the hydrophobic properties of modified ZSM-5 particles could be tuned by varying the chain length of chlorosilane and changing the pretreatment temperature before silanization. With increasing the alkyl chain length of trichlorosilane, the hydrophobicity increased. However, with an increase in the pretreatment temperature, the hydrophobicity decreased. Moreover, the relationship between the wetting properties and thermal stability was also investigated, the results showed that the modified ZSM-5 particles possessed good hydrophobicity at a temperature below 250 °C in air. These modified ZSM-5 particles may be utilized for many potential applications, such as membrane fillers, selective adsorbents, catalysts, chromatographic supports and so on.     

Nucleation kinetics for gold deposited onto mica substrates

The nucleation behavior of gold deposited under ultra high vacuum conditions onto cleaved mica substrates has been measured over the temperature range 270–450 °C at impingement fluxes of 6 × 10¹³ and 8 × 10¹² atoms cm^?2sec^?1. A step-kinetic technique was used wherein separate substrate areas were exposed for successively longer times to the vapor beam from a thermal source. The deposits were examined in a high resolution electron microscope. For mica cleaved in situ in UHV, the variation in number density of nuclei with time of exposure to the atom beam revealed that nucleation occurred rapidly on preferred sites which were exhausted within the first few seconds of exposure. After the initial saturation, nucleation appeared to occur randomly over the rest of the surface. The number density of preferred sites increased with decreasing temperature indicating that a spectrum of preferred sites of varying degrees of potency were active. The random nucleation rates could by analyzed satisfactorily using the atomistic model for nucleation. A critical sized nucleus consisting of one atom is consistent with the data. The characteristic energy for nucleation (2ΔG_des ?ΔG_sd), was found to be 1.1 eV. Nucleation behavior on mica substrates cleaved in air did not indicate the presence of active preferred sites, but nucleation was more rapid.     

Effect of sonication conditions: Solvent,time, temperature and reactor type on the preparation of micron sized vermiculite particles

The effects of temperature, time, solvent and sonication conditions under air and Argon are described for the preparation of micron and sub-micron sized vermiculite particles in a double-jacketed Rosett-type or cylindrical reactor. The resulting materials were characterized via X-ray powder diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Fourier Transform Infrared (FTIR) Spectroscopy, BET surface area analysis, chemical analysis (elemental analysis), Thermogravimetry analysis (TGA) and Laser Granulometry. The sonicated vermiculites displayed modified particle morphologies and reduced sizes (observed by scanning electron microscopy and laser granulometry). Under the conditions used in this work, sub-micron sized particles were obtained after 5 h of sonication, whereas longer times promoted aggregation again. Laser granulometry data revealed also that the smallest particles were obtained at high temperature while it is generally accepted that the mechanical effects of ultrasound are optimum at low temperatures according to physical/chemical properties of the used solvent. X-ray diffraction results indicated a reduction of the crystallite size along the basal direction [0 0 1]; but structural changes were not observed. Sonication at different conditions also led to surface modifications of the vermiculite particles brought out by BET surface measurements and Infrared Spectroscopy. The results indicated clearly that the efficiency of ultrasound irradiation was significantly affected by different parameters such as temperature, solvent, type of gas and reactor type.     

Thermal etching of sodium chloride III. Etching of non-cubic surface

Previous work on the thermal etching of (100) surfaces of NaCl single crystals is extended to the other surface orientations by using polycrystalline samples. The results obtained with (110), (111), (520) and (144) surfaces are used to corroborate the correctness of the mechanisms proposed in a previous paper to explain the thermal etching in air of (100) surfaces; it is also shown that these mechanisms are only dependent on crystal structure and not on the surface orientation.When such surfaces were treated with wet silk, concentrated HC1, and Moran's reagent, a very different behaviour was observed for each orientation. The reactivity is very sensitive to crystallographic orientation, being very low in the case of the (144) surface.