Mullins Effect and Crack Growth in Natural Rubber Vulcanizates during Heat Aging and Cyclic Loading

The effect of thermal aging and cyclic loading on mechanical properties and development of cracks in natural rubber vulcanizates was studied. After aging at 70oC and 110oC vulcanizates were subjected to cyclic loading. At a certain number of loading cycles, the samples were conducted in a tension test. At the aging condition of 70oC, the static tensile properties of material stay almost unchanged even after 88 aged hours and 8000 loading cycles. On the contrary, the dynamic fatigue resistance of vulcanizates decreases with increasing aging time. These results are attributed to the post-curing and the development of microcracks that might be caused by Mullins effect: in the case of static loading, the strain-induced crystallization may prevent cracks growth, but in the case of cyclic loading the strain-induced crystallization does not occur, so cracks develop without hindrance. However, at 110oC both static properties and dynamic fatigue resistance of material reduced dramatically because at high temperature the heat degradation exceeds both post-curing and strain-induced crystallization. Crack formation and propagation were examined by a digital optical microscope in the progress of cyclic loading. Results showed that natural rubber vulcanizate filled with carbon black has the best crack growth resistance (CGR) while the addition of modified and unmodified silica reduces CGR of materials. Moreover, the vulcanizate with unmodified silica has the lowest CGR.

Removing free-floating oil from water using cationic polymers/surfactant-modified silica

The purpose of this work was to evaluate the efficiency of oil sorption of silica particles modified by three different types of cationic polymers and a cationic surfactant. Low-molecular-weight polyethyleneimine (LPEI), high-molecular-weight polyethyleneimine (HPEI), polydiallyldimethylammonium chloride (PDM), and cetyltrimethylammonium bromide (CTAB) were used to modify the silica particles and then compared their performances for oil removal. The scanning electron microscope and zeta potential measurements were used to analyze the surface characteristics of unmodified and modified silica particles. Adsorptions of motor oil and palm oil on the modified silica particles have been investigated under various parameters such as the silica particle size, the oil concentration, the polymer/surfactant concentrations, and the pH. The results have shown that the modified silica particles enhanced the oil sorption ability by approximately 10–20 times depending on the size of silica particles, pH, and the type of polymer/surfactant used when compared with the unmodified silica particles. The highest palm oil adsorption values of LPEI-silica, HPEI-silica, PDM-silica, CTAB-silica, and unmodified silica were 2.40, 2.10, 1.95, 1.50, and 0.15 g/gsilica, respectively. Moreover, the oil sorption of the modified silica particles was increased by approximately 30–50% for the smallest-sized silica particles.

Multiple Intermolecular Interaction to Improve the Abrasion Resistance and Wet Skid Resistance of Eucommia Ulmoides Gum/Styrene Butadiene Rubber Composite

A rubber composite was prepared by using methyltriethoxysilane (MTES) to modify silica (SiO2) and epoxidized eucommia ulmoides gum (EEUG) as rubber additives to endow silica with excellent dispersion and interfacial compatibility under the action of processing shear. The results showed that compared with the unmodified silica-reinforced rubber composite (SiO2/EUG/SBR), the bound rubber content of MTES-SiO2/EEUG/EUG/SBR was increased by 184%, and its tensile strength, modulus at 100% strain, modulus at 300% strain, and tear strength increased by 42.1%, 88.5%, 130.8%, and 39.9%, respectively. The Akron abrasion volume of the MTES-SiO2/EEUG/EUG/SBR composite decreased by 50.9%, and the wet friction coefficient increased by 43.2%. The wear resistance and wet skid resistance of the rubber composite were significantly improved.

Unmodified Silica Nanoparticles Enhance Mechanical Properties and Welding Ability of Epoxy Thermosets with Tunable Vitrimer Matrix

Epoxy/silica thermosets with tunable matrix (vitrimers) were prepared by thermal curing of diglycidyl ether of bisphenol A (DGEBA) in the presence of a hardener—4-methylhexahydrophthalic anhydride (MHHPA), a transesterification catalyst—zinc acetylacetonate (ZAA), and 10–15 nm spherical silica nanoparticles. The properties of the resulting material were studied by tensile testing, thermomechanical and dynamic mechanical analysis. It is shown that at room temperature the introduction of 5–10 wt% of silica nanoparticles in the vitrimer matrix strengthens the material leading to the increase of the elastic modulus by 44% and the tensile stress by 25%. Simultaneously, nanoparticles enhance the dimensional stability of the material since they reduce the coefficient of thermal expansion. At the same time, the transesterification catalyst provides the thermoset with the welding ability at heating, when the chain exchange reactions are accelerated. For the first time, it was shown that the silica nanoparticles strengthen welding joints in vitrimers, which is extremely important, since it allows to repeatedly use products made of thermosets and heal defects in them. Such materials hold great promise for use in durable protective coatings, adhesives, sealants and many other applications.

Tailoring Nanocomposite Membranes of Cellulose of Acetate/Silica Nanoparticles for Desalination

Herein, fabrication of cellulose acetate (CA) silica-based nanocomposite membranes via the dry-wet phase inversion procedure for the water desalination was investigated. The modified and unmodified silica nanoparticles (SNPs and MSNPs) were prepared by the sol-gel technique. The addition effect of the SNPs and MSNPs was investigated on the CA membranes properties and their performance for water separation. The CA nanocomposite membranes were characterized to study their structure, hydrophilicity, and morphology. The fabricated nanocomposite membranes showed hydrophilic surface properties. The performance of reverse osmosis (RO) membranes was measured using a crossflow RO unit. At 10 bar, The membrane with 10 mg of SNPs showed enhanced permeate water flux compared to the pristine CA membrane by 1.6 L/m 2 .hr. Increasing the SNPs in the nanocomposite membrane showed enhancement in the permeate water flux all over the operating pressure. The effect of MSNPs on the nanocomposites’ performance was lower than their counterpart in the case of adding SNPs. The membrane with 30 mg of MSNPs showed the highest permeate water flux among other nanocomposite membranes with a value of 35.7 L/m 2 .hr at 24 bar.

SORPTION OF BISMUTON (III) IONS FROM AQUEOUS SOLUTIONS BY SILICAS MODIFIED BY ORGANIC REAGENTS

In current paper, adsorbents based on silica L 40/100 modified with 4-(2-pyridylazo)resorcinol, 1-(2-pyrylazo)naphthol‑2, pyrocatechol violet and sodium N, N‑diethyldithiocarbamate were obtained. Adsorbents were modified by non-covalent immobilization of organic analytical reagents on the silica surface. It is noted that the preparation of such adsorbents is fast and easy to manufacture. The conditions of Bismuth (III) adsorption from dilute aqueous solutions by the proposed adsorbents are studied and optimized. The optimal values of the medium acidity for the effective Bismuth (III) preconcentration by the proposed adsorbents based on silica modified with organic analytical reagents have been established. It is shown that the use of modified silicas allows efficient (95–98%) removal of Bismuth (III) from dilute aqueous solutions. Under optimal adsorption conditions, the capacity of modified adsorbents is determined. It is established that the modification of silica leads to a significant (2–3 times) increase in the capacity of the obtained sorbents by Bismuth (III) in comparison with the unmodified silica, which is associated with the processes of complexation on the surface. The desorption of Bismuth (III) from the surface of unmodified and modified silicas by solutions of mineral acids has been studied. It is shown that Bi(III) is quantitatively desorbed from the surface of unmodified silicas by solutions of sulfuric and nitric acids, and in the case of modified silicas the degree of desorption is small and does not exceed 35%. The data obtained can then be used to develop a test system for determination of Bismuth (III) via corresponding colorimetric scales or for quantitative solid phase extraction and adsorption-spectroscopic quantification of Bismuth (III) in some real samples.

Hydrophilic interaction in solid-phase extraction of antisense oligonucleotides

The presented studies aimed to develop a new and simple extraction method based on hydrophilic interaction for antisense oligonucleotides with different modifications. For this purpose, solid-phase extraction cartridges with unmodified silica were used. All extraction steps were performed by utilizing water, acetonitrile, acetone or their mixtures. The results obtained show that a high content (95%) of organic solvent, used during sample loading, is critical to achieve a successful extraction, while elution with pure water allows effective oligonucleotides desorption. The recovery values were greater than 90% in the case of unmodified DNA, phosphorothioate, 2′-O-(2-methoxyethyl) and 2′-O-methyl oligonucleotides. For the mixture of phosphorothioate oligonucleotide and its two synthetic metabolites, the recovery values for the standard solutions were in the range of 70–75%, while for spiked human plasma, 45–50%. The developed method is simple, may be performed in a short time and requires simple solvents like water or acetonitrile/acetone, thus showing promise as an alternative to chaotropic salt-based or ion pair-based SPE methods.

Glycopolymer Grafted Silica Gel as Chromatographic Packing Materials

The modification of the surface of silica gel to prepare hydrophilic chromatographic fillers has recently become a research interest. Most researchers have grafted natural sugar-containing polymers onto chromatographic surfaces. The disadvantage of this approach is that the packing structure is singular and the application scope is limited. In this paper, we explore the innovative technique of grafting a sugar-containing polymer, 2-gluconamidoethyl methacrylamide (GAEMA), onto the surface of silica gel by atom transfer radical polymerization (ATRP). The SiO2-g-GAEMA with ATRP reaction time was characterized by Fourier infrared analysis, Thermogravimetric analysis (TGA), and elemental analysis. As the reaction time lengthened, the amount of GAEMA grafted on the surface of the silica gel gradually increased. The GAEMA is rich in amide bonds and hydroxyl groups and is a typical hydrophilic chromatography filler. Finally, SiO2-g-GAEMA (reaction time = 24 h) was chosen as the stationary phase of the chromatographic packing and evaluated with four polar compounds (uracil, cytosine, guanosine, and cytidine). Compared with unmodified silica gel, modified silica gel produces sharper peaks and better separation efficiency. This novel packing material may have a potential for application with highly isomerized sugar mixtures.