Field-emission Environmental Scanning Electron Microscopy Research Articles

Synthesis of phosphate hydrogels with excellent swelling behavior prepared by ascorbic acid -mediated ARGET ATRP

This manuscript explores the synthesis of hydrogels through reversible deactivation radical polymerization (RDRP) methods, specifically, activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) and Cu0-mediated ATRP. These techniques are known to offer improved control over polymer network structures due to their slow polymerization kinetics. However, these methods have historically been challenging to apply to stimuli-responsive polymers, such as those with acidic or basic moieties. In this study, the direct synthesis of poly(2-(methacryloyloxy) ethyl phosphate) (PMOEP), a phosphate-pendant hydrogel, was investigated in aqueous media by both ascorbic acid (AsA)-mediated ARGET ATRP and Cu0-mediated ATRP. 2-(methacryloyloxy) ethyl phosphate (MOEP) was utilized as the active monomer with tris(2-pyridylmethyl) amine (TPMA) as the ligand. A unique feature of this work is that the diene moiety inherently present in the commercial monomer, bis[2-(methacryloyloxy) ethyl] phosphate (BMOEP), served as the crosslinking agent to obtain the novel PMOEP hydrogel. Formulations were tuned to optimize the swelling characteristics of the hydrogels, with the restriction that the hydrogels should swell homogeneously without fracture. Importantly, using AsA as the reducing agent in the ARGET ATRP reaction resulted in improved homogeneity and enhanced swelling properties of the hydrogel. Furthermore, tuning the target degree of polymerization (Dp) ([monomer]:[initiator]) had a significant impact on swelling characteristics. Specifically, PMOEP hydrogels synthesized via ARGET ATRP with a target Dp of 300 and 1 mM CuII catalyst demonstrated outstanding water absorption capacity of more than 2500% (relative to the dry mass) in phosphate buffer solution (PBS) at pH 7.4 and over 6000% in pure water. The morphology of these hydrogels was imaged using field emission environmental scanning electron microscopy (FE-ESEM) and the chemical composition was examined using Fourier transform infrared (FTIR) spectroscopy. Furthermore, nuclear magnetic resonance (NMR) analysis was performed to investigate the conversion rate of monomer during Cu0-mediated ATRP. To the authors’ knowledge, the synthesis of a 100% phosphate-pendant hydrogel using AsA-mediated ARGET ATRP and an internal phosphodiester crosslinking moiety without dilution or comonomer, has not been reported previously. This facile method for synthesizing and controlling phosphate-based hydrogel properties also provides an opportunity to include additional functional groups and holds significant promise for applications in biomedical engineering, agriculture, and membrane separations.

Radiosensitization of Nasopharyngeal Carcinoma by Graphene Oxide Nanosheets to Reduce Bcl-2 Level.

There are many treatments for nasopharyngeal carcinoma (NPC), but none of them are very effective. Radiotherapy is used extensively in NPC treatment, but radioresistance is a major problem. Graphene oxide (GO) has been previously studied in cancer treatment, and this study is aimed to explore its role in radiosensitization of NPC. Therefore, graphene oxide nanosheets were prepared, and the relationship between GO and radioresistance was explored. The GO nanosheets were synthesized by a modified Hummers' method. The morphologies of the GO nanosheets were characterized by field-emission environmental scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The morphological changes and radiosensitivity of C666-1 and HK-1 cells with or without the GO nanosheets were observed by an inverted fluorescence microscopy and laser scanning confocal microscopy (LSCM). Colony formation assay and Western Blot were applied for analysis of NPC radiosensitivity. The as-synthesized GO nanosheets have lateral dimensions (sizes ∼1 μm) and exhibit a thin wrinkled two-dimensional lamellar structure with slight folds and crimped edges (thickness values ∼1 nm). C666-1 cells with the GO was significantly changed the morphology of cells postirradiation. The full field of view visualized by a microscope showed the shadow of dead cells or cell debris. The synthesized graphene oxide nanosheets inhibited cell proliferation, promoted cell apoptosis, and inhibited the expression of Bcl-2 in C666-1 and HK-1 cells but increased the level of Bax. The GO nanosheets could affect the cell apoptosis and reduce the pro-survival protein Bcl-2 related to the intrinsic mitochondrial pathway. The GO nanosheets could enhance radiosensitivity, which might be a radioactive material in NPC cells.

Electrospun Coaxial Fibers to Optimize the Release of Poorly Water-Soluble Drug.

In a drug delivery system, the physicochemical properties of the polymeric matrix have a positive impact on the bioavailability of poorly water-soluble drugs. In this work, monolithic F1 fibers and coaxial F2 fibers were successfully prepared using polyvinylpyrrolidone as the main polymer matrix for drug loading and the poorly water-soluble curcumin (Cur) as a model drug. The hydrophobic poly (3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV) was designed as a blank layer to change the hydrophilicity of the fiber and restrain the drug dissolution rate. The curved linear morphology without beads of F1 fibers and the straight linear morphology with few spindles of F2 fibers were characterized using field-emission environmental scanning electron microscopy. The amorphous forms of the drug and its good compatibility with polymeric matrix were verified by X-ray diffraction and attenuated total reflectance Fourier transformed infrared spectroscopy. Surface wettability and drug dissolution data showed that the weaker hydrophilicity F2 fibers (31.42° ± 3.07°) had 24 h for Cur dissolution, which was much longer than the better hydrophilic F1 fibers (15.31° ± 2.79°) that dissolved the drug in 4 h.

Characterization of ground parenchyma cells in Moso bamboo (Phyllostachys edulis–Poaceae)

Summary Ground parenchyma cells play a crucial role in the growth and the mechanical properties of bamboo plants. Investigation of the morphology of ground parenchyma cells is essential for understanding the physiological functions and mechanical properties of these cells. This study aimed to characterize the anatomical structure of bamboo ground parenchyma cells and provide a qualitative and quantitative basis for the more effective utilization of bamboo. To do this, the morphology of ground parenchyma cells in Moso bamboo (Phyllostachys edulis) was studied using light microscopy and field-emission environmental scanning electron microscopy. Results show that various geometric shapes of ground parenchyma cells were observed, including nearly circular, square, long, oval, and irregular shapes. Cell walls of both long and short parenchyma cells exhibited primary wall thickening and secondary wall thickening, resulting in a primary pit field and simple pits. Most long cells were strip-shaped (L/W = 2.52), while most short cells were short and wide (L/W = 0.59). The proportion of long cells was 11 times greater than that of short cells. Most long cells were filled with starch grains, and some short cells also occasionally had starch grains. These findings allowed the first construction of the three-dimensional structure of parenchyma cells.

Selenium speciation in watermelon by g-C3N4 enrichment combined with capillary electrophoresis-inductively coupled plasma-mass spectrometry

Selenium is one of the essential trace elements in the human body, and it plays a critical role in human health. In this work, 2.0 g melamine was placed in an alumina crucible, which was heated in a box-type resistance furnace for 2 h at 600 ℃, at the heating rate of 3 ℃/min, and then cooled to room temperature. After cooling, yellow graphite phase carbon nitride (g-C3N4) nanosheets were obtained. Subsequently, 500 mg of the nanosheets was dispersed in 50 mL water with ultrasonication for 10 h in order to remove the residual un-exfoliated g-C3N4 nanoparticles and large-sized nanosheets. The obtained suspension was centrifuged at about 10000 r/min, followed by drying at 60 ℃ to produce g-C3N4. The prepared g-C3N4 was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), and field emission-environmental scanning electron microscopy (SEM) analyses. Given that the selenium content in actual samples is very low, high sensitivity, and accuracy are imperative for selenium detection. The combination of capillary electrophoresis (CE) with inductively coupled plasma-mass spectrometry (ICP-MS) can greatly improve the sensitivity, accuracy, and speed of the analysis. A novel method based on CE-ICP-MS was established for the determination of selenourea (SeUr), L-selenocystine (SeCys2), DL-selenomethionine (SeMet), selenite (Se(Ⅳ)), selenate (Se(Ⅵ)), and selenoethionine (SeEt) in watermelon. The selenium species in watermelon were extracted by ultrasonication with pepsin as an extractant and g-C3N4 enrichment. The enrichment factor of g-C3N4 ranged from 12 to 29. Six selenium species were completely separated within 11 min in a 100-cm-long capillary with 100 μm internal diameter, at an applied voltage of 22 kV, using a buffer solution of 8 mmol/L NaH2PO4-12 mmol/L H3BO3-0.2 mmol/L cetyl trimethyl ammonium bromide (CTAB; pH 9.2). The interference in the selenium detection was eliminated using a dynamic reaction cell with CH4. The linear correlation coefficients of all the selenium species were greater than 0.9995. Under the optimal conditions, the limits of detection (3 σ, σ for standard deviation, as Se) for SeUr, SeCys2, SeMet, Se(Ⅳ), Se(Ⅵ), and SeEt were 6.2, 30, 11, 8.2, 48, and 5.5 ng/L, respectively. The linear range (as Se) for SeUr, SeCys2, SeMet, Se(Ⅳ), Se(Ⅵ), and SeEt were 0.017-20 μg/L, 0.091-50 μg/L, 0.032-40 μg/L, 0.023-60 μg/L, 0.015-75 μg/L, and 0.015-30 μg/L, respectively. The recoveries ranged from 96.0% to 106%, and the relative standard deviations (RSDs; n=5) were less than 3%. The developed method is simple, rapid, and sensitive, and it is also suitable for the detection of selenium species in other food and environmental samples.

Ultrastructure of parenchyma cell wall in bamboo (Phyllostachys edulis) culms

Parenchyma cell wall structure plays a crucial role in the growth and the mechanical properties of bamboo plants, with the secondary cell wall providing strength and rigidity. However, little is known about the ultrastructure of the parenchyma cell wall. The aim of this study was to characterize the anatomical structure of the parenchyma cell wall and determine how it contributes to great mechanical superiority of bamboo culm. We investigated the ultrastructure of the parenchyma cell wall using transmission electron microscopy and field-emission environmental scanning electron microscopy. The key results show that the secondary cell walls of ground and vascular parenchyma cells exhibited tight-loose (light-dark) alternating layers. The pit membrane of the ground parenchyma cells contained numerous pores, and that of vascular parenchyma cells contained some plasmodesmata. Secondary cell walls of most bamboo parenchyma cells contained seven sub-layers, with a maximum of eleven sub-layers of ground parenchyma cells and nine sub-layers of vascular parenchyma cells. The average thickness of ground parenchyma cell wall sub-layers was higher than that in vascular parenchyma cells. The pit membrane thickness of ground parenchyma cells was also higher than that of vascular parenchyma cells, but the diameter of the ground parenchyma cells was smaller than that of the vascular parenchyma cells. The extremely high flexibility of moso bamboo stem could be the consequence of the presence of secondary cell walls in parenchyma cells, and its ultrastructure.

Development of Non-reactive F-Free Mold Fluxes for High Aluminum Steels: Non-isothermal Crystallization Kinetics for Devitrification

It is necessary to study crystallization from glass (devitrification) for non-reactive F-free CaO-Al2O3 based mold fluxes; this is especially important for the development of mold fluxes for continuous casting of high aluminum steels. To the knowledge of the authors, there is no report in the literature regarding devitrification of F-free mold fluxes based on the CaO-Al2O3-B2O3-Na2O-Li2O system. Therefore, crystallization kinetics for particular compositions in this system, with different w(CaO)/w(Al2O3) ratios, was investigated by Differential Scanning Calorimeter, Field-Emission Environmental Scanning Electron Microscopy / Energy Dispersive Spectroscopy, and X-ray Diffraction techniques. The first crystal, which precipitates during heating from glass, is Ca12Al14O33, followed by CaO. For the first crystal, which precipitates as plate-like (2-dimensional), it was found that, when using the Matusita–Sakka model, agreement between the calculated Avrami parameters and the micrographs obtained from electron microscope was reached. In the same way, agreement was found for the second event—CaO precipitation—which grows 2-dimensionally or 3-dimensionally, depending on the w(CaO)/w(Al2O3) ratio. The most important event (in terms of energy liberated and amount of crystals) is Ca12Al14O33 precipitation. For this event, the effective activation energy for crystallization, EG, decreases with the increase of w(CaO)/w(Al2O3) ratio. The activation energy for crystallization reflects the energy barrier for crystallization. Thus, it can be concluded that mold fluxes crystallization during heating is enhanced when increasing the w(CaO)/w(Al2O3) ratio, for constant contents of B2O3, Na2O, and Li2O.

Uncovering the ultrastructure of ramiform pits in the parenchyma cells of bamboo [Phyllostachys edulis (Carr.) J. Houz.

Abstract Pits are the main transverse channels of intercellular liquid transport in bamboo. Ramiform pits are a special type of simple pit with two or more branches. However, little is known about the morphology and physiological functions of ramiform pits. The anatomy of plants can provide important evidence for the role of cells. To better understand the ultrastructure and the structure-function relationship of ramiform pits, their characteristics need to be investigated. In this study, both qualitative and quantitative features of ramiform pits were studied using field-emission environmental scanning electron microscopy (FE-ESEM). The samples included the native structures and the replica structures obtained by resin castings. The results show that the ramiform pits have a diverse morphology that can be divided into main categories: type I (the primary branches) and type II (the secondary branches). The distribution of ramiform pits is different in ground parenchyma cells (GPCs) and vascular parenchyma cells (VPCs). The number, the pit aperture diameter and the pit canal length of ramiform pits in the VPCs were, respectively, greater (3-fold), larger (2–3-fold) and shorter (1.3-fold) than those in the GPCs.

Characterization of the pits in parenchyma cells of the moso bamboo [Phyllostachys edulis (Carr.) J. Houz.] culm

Abstract The pits on parenchyma cell walls facilitate transfer of liquids between adjacent cells in the bamboo. To better understand the structure-function relationship of the pits, the structural characteristics of the pits in bamboo parenchyma cells need to be investigated. In this study, the pit structures were studied by field-emission environmental scanning electron microscopy (SEM). The samples included the native structure and the replica structure via resin castings. The results showed that the parenchyma cells possessed various shapes and the pits were diverse. Parenchyma cells exposed both simple and bordered pits. Pitting between vascular parenchyma cells (VPCs) was similar to that of the metaxylem vessel. In particular, a branched pit structure was found for the first time in the parenchyma cell.

Strain Evolution in Cold-Warm Forged Steel Components Studied by Means of EBSD Technique.

Electron BackScatter Diffraction (EBSD) in conjunction with Field-Emission Environmental Scanning Electron Microscopy (FEG-ESEM) has been used to evaluate the microstructural and local plastic strain evolution in different alloys (AISI 1005, AISI 304L and Duplex 2205) deformed by a single-stage cold and warm forging process. The present work is aimed to describe the different behavior of the austenite and ferrite during plastic deformation as a function of different forging temperatures. Several topological EBSD maps have been measured on the deformed and undeformed states. Then, image quality factor, distributions of the grain size and misorientation have been analyzed in detail. In the austenitic stainless steel, the γ-phase has been found to harden more easily, then α-phase and γ-phase in AISI 1005 and in duplex stainless steel, sequentially. Compared to the high fraction of continuous dynamic recrystallized austenitic zones observed in stainless steels samples forged at low temperatures, the austenitic microstructure of samples forged at higher temperatures, 600–700 °C, has been found to be mainly characterized by large and elongated grains with some colonies of fine nearly-equiaxed grains attributed to discontinuous dynamic recrystallization.

Synthesis of birnessite with adjustable electron spin magnetic moments for the degradation of tetracycline under microwave induction

Manganese dioxides (MOs) are excellent microwave absorbing materials and have been used as substrates or catalysts for enhanced degradation of organic compounds. In this study, we extended our research on using birnessite (Birn), a type of MOs, for the degradation of tetracycline (TC) in aqueous solution under microwave induction (MI). The Birns were fabricated to achieve different ratios of Mn(II)/Mn(III)/Mn(IV) in the crystal structure. Their physical and chemical characteristics were determined by X-ray diffraction, field-emission environmental scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray absorption fine structure spectra, and a microwave network analyzer. Their removal of TC under MI was evaluated under different physicochemical conditions. Lower solution pH, higher MI power, and higher Mn(II) and Mn(III) in the structure resulted in more TC removal. And the Birns are regenerable. LC–MS analyses confirmed the presence of degradation intermediates. The better performances of TC removal by Birns under MI was attributed to the high magnetic spin moment of Mn(II) and Mn(III) in the structure that has higher MI response.

Nanoscale pore morphology and distribution of lacustrine shale reservoirs: Examples from the Upper Triassic Yanchang Formation, Ordos Basin

Pore structure plays an important role in the gas storage and flow capacity of shale gas reservoirs. Field-emission environmental scanning electron microscopy (FE-SEM) in combination with low-pressure carbon dioxide gas adsorption (CO2GA), nitrogen gas adsorption (N2GA), and high-pressure mercury intrusion (HPMI) were used to study the nanostructure pore morphology and pore-size distributions (PSDs) of lacustrine shale from the Upper Triassic Yanchang Formation, Ordos Basin. Results show that the pores in the shale reservoirs are generally nanoscale and can be classified into four types: organic, interparticle, intraparticle, and microfracture. The interparticle pores between clay particles and organic-matter pores develop most often, l with pore sizes that vary from several to more than 100 nm. Mercury porosimetry analysis shows total porosities ranging between 1.93 and 7.68%, with a mean value of 5.27%. The BET surface areas as determined by N2 adsorption in the nine samples range from 10 to 20 m2/g and the CO2 equivalent surface areas (<2 nm) vary from 18 to 71 m2/g. Together, the HPMI, N2GA, and CO2GA curves indicate that the pore volumes are mainly due to pores <100 nm in size. In contrast, however, most of the specific surface areas are provided by the micropores. The total organic carbon (TOC) and clay minerals are the primary controls of the structures of nanoscale pores (especially micropores and mesopores). Micropores are predominantly determined by the content of the TOC, and mesopores are possibly related to the content of clay minerals, particularly the illite-montmorillonite mixed-layer content.

Strength of interactions between immobilized dye molecules and sol–gel matrices

In this paper we present a new theory to re-examine the immobilization technique of dye doped sol-gel films, define the strength and types of possible bonds between the immobilized molecule and sol-gel glass, and show that the immobilized molecule is not free inside the pores as was previously thought. Immobilizing three different pH sensitive dyes with different size and functional groups inside the same sol-gel films revealed important information about the nature of the interaction between the doped molecule and the sol-gel matrix. The samples were characterized by means of ultraviolet-visible spectrophotometer (UV-VIS), thermal gravimetric analysis (TGA), mercury porosimetry (MP), nuclear magnetic resonance spectroscopy ((29)Si NMR) and field-emission environmental scanning electron microscopy (ESEM-FEG). It was found that the doped molecule itself has a great effect on the strength and types of the bonds. A number of factors were identified, such as number and types of the functional groups, overall charge, size, pK(a) and number of the silanol groups which surround the immobilized molecule. These results were confirmed by the successful immobilization of bromocresol green (BCG) after a completely polymerized sol-gel was made. The sol-gel consisted of 50% tetraethoxysilane (TEOS) and 50% methyltriethoxysilane (MTEOS) (w/w). Moreover, the effect of the immobilized molecule on the structure of the sol-gel was studied by means of a leaky waveguide (LW) mode for doped films made before and after polymerization of the sol-gel.

Simple and convenient preparation of Au–Pt core-shell nanoparticles on surface via a seed growth method

Au–Pt core-shell nanoparticles were prepared on glass surface by a seed growth method. Gold nanoparticles were used as seeds and ascorbic acid–H2PtCl6 solutions as growth solutions to deposit Pt shell on the surface of gold nanoparticles. These core-shell nanoparticles and their growth process were examined by UV–Vis spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy and field-emission environmental scanning electron microscopy and the results indicated that the deposition speed was fast and nanoparticles with obvious core-shell structure could be obtained after 2 min. Moreover, this seed growth method for preparation of the core-shell nanoparticles is simple and convenient compared with other seed growth methods with NH4OH as a mild reductant. In addition, electrochemical experiments indicated that these Au–Pt core-shell nanoparticles had similar electrochemical properties to those of the bulk Pt electrode.

Fouling autopsy of hollow-fibre MF membranes in wastewater reclamation

Fouling in membrane filtration processes is problematic but inevitable as it occurs with the retention of contaminants that accumulate on the membrane surface. The causes of fouling are often specific, depending upon feed water constituents, the membrane, and the operation regime. Therefore, it is desirable that a thorough investigation is performed on fouled membrane elements of the affected plant. This technique is known as “membrane autopsy”, which identifies the cause of poor membrane performance, and hence, gives the opportunity to rectify or mitigate the problem and improve future plant design. The cause of membrane fouling at a small water recycling plant using a hollow-fibre microfiltration system was investigated. A membrane autopsy protocol was developed for water recycling applications that consists of four major steps: (1) tensile testing to investigate the membrane mechanical integrity, (2) direct visual inspection, (3) membrane surface analysis using field-emission environmental scanning electron microscopy (as well as atomic force microscopy, although it is not used in this case) techniques, and (4) foulant constituent analysis. Results obtained from this study indicate that the membrane was fouled by a mixture of colloids and organic matters, enhanced by the presence of multivalent cations. Possible measures to mitigate fouling in this particular case have also been suggested.

Properties of chemically and mechanically isolated fibres of spruce (Picea abies [L.] Karst.). Part 1: Structural and chemical characterisation

Abstract Single fibres of spruce (Picea abies [L.] Karst.) were isolated both chemically and mechanically from a solid wood sample. Mechanical isolation was carried out using very fine tweezers to peel out fibres, thereby taking advantage of the low shear strength between them. Chemical isolation was achieved using hydrogen peroxide and glacial acetic acid. Fibres were examined with Fourier-transform infrared (FT-IR) microscopy, and field-emission environmental scanning electron microscopy (FE-ESEM) in low-Vacuum mode to compare the isolation techniques with respect to their influence on cell wall structure and polymer assembly. The chemical treatment led to degradation of lignin and hemicelluloses, significantly influencing the cell wall assembly and structure. The cell wall polymers of mechanically isolated fibres remained in their natural constitution. As expected, the peeling process caused separation of cell wall layers. Our examinations indicate that delamination predominately took place at the interface between the secondary cell wall and the compound middle lamella. However, fracture between the S1 and S2 layers was examined as well. With respect to fibre quality, it was of particular importance that transverse crack propagation in the secondary cell walls (S2) was not observed.

Regeneration of Bombyx mori silk by electrospinning. Part 3: characterization of electrospun nonwoven mat

Regenerated Bombyx mori silk fibroin in formic acid was electrospun and the morphological, chemical and mechanical properties of these nanofibers were examined by field emission environmental scanning electron microscopy (FESEM), Raman spectroscopy (RS), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and tensile testing. FESEM indicated that the average fiber diameter was less than 100nm and circular in cross section. This paper maps the silk fibroin molecular conformations of each step of the sample preparation and the electrospinning process. The secondary structural compositions (random and β-sheet) of the fibroin were determined by FTIR and RS. The crystallinity index of the electrospun fiber, calculated as the intensity ratio of 1624 (β-sheet) and 1663 (random) cm−1 FTIR bands was higher than that of the pristine fiber. Raman spectra of the amide I (1665cm−1, random) to amide III (1228cm−1, β-sheet) ratio of the electrospun fiber was less than that of the pristine fiber indicative of higher β-sheet content. The fiber crystallinity, determined by XRD, showed a lower value for the electrospun fiber. The electrospun fiber shows small but significant increases in the β-sheet content in comparison with the pristine fiber. Dissolution of fibroin in formic acid enhances β-sheet crystallization and may facilitate β-sheet formation in electrospun fiber. The electrospun random silk mat had a Young's modulus, ultimate tensile strength and strain of 515MPa, 7.25MPa and 3.2%, respectively.

Interaction of resin-modified glass-ionomer cements with moist dentine.

The objective of this study was to report on a novel phenomenon that occurs when resin-modified glass-ionomer cements (RMGICs) are bonded to moist human dentine. Dentine surfaces from extracted third molars were abraded with 180-grit SiC paper. Ten teeth were prepared for each of the two RMGICs tested (Fuji II LC, GC Corp. and Photac-Fil Quick, 3M ESPE). RMGIC buildups were made according to the manufacturers' instructions. After storage at 37 degrees C, 100% humidity for 24 h, the bonded specimens were cut occlusogingivally into 0.9 x 0.9 mm beams. Dentine surfaces bonded with the two RMGICs were examined along the fractured RMGIC/dentine interfaces. Additional beams fractured within the RMGICS and at 3 mm away from the interfaces were used as controls. The fractured beams were examined using scanning electron microscopy (SEM), field emission-environmental SEM (FE-ESEM) and transmission electron microscopy (TEM). SEM and FE-ESEM revealed numerous solid spherical bodies along the RMGIC/dentine interfaces. By contrast, no spherical bodies could be identified within the RMGIC fractured 3 mm distant from the bonded interface. TEM and energy dispersive X-ray analyses performed on carbon-coated ultrathin sections showed that these solid spherical bodies consisted of a thin aluminum and silicon-rich periphery and an amorphous hydrocarbon core within the air voids of the original resin matrix. The spherical bodies probably represent a continuation of GI reaction and poly(HEMA) hydrogel formation that results from water diffusion from the underlying moist dentine. Their existence provides evidence for the permeation of water through RMGIC/dentine interfaces.

Microfiltration of Polyoxyalkylene Metalworking Fluid Lubricant Additives Using Aluminum Oxide Membranes

Microfiltration is capable of reducing health hazards and environmental pollution associated with metalworking fluids (MWFs) by enabling recycling and microbial removal. This paper investigates chemical characteristics of MWFs that can lead to flux decline during microfiltration using aluminum oxide membranes by studying the family of polyoxyalkylene diblock copolymers comprised of ethylene oxide and propylene oxide. These copolymers are commonly used as lubricant additives in metalworking fluids and serve as a model for beginning to understand the relationship between metalworking fluid formulation and microfiltration flux. It is found that increasing the hydrophobic content of the copolymers can lead to reduced flux. Anionic modification and increasing molecular weight of the copolymers can also lead to reduced flux. Insufficient cleaning of anionic copolymers from the membrane leads to pH-dependent flux of deionized water during subsequent filtration. The pH-dependence of flux arises due to swelling caused by electrostatic repulsions between the aluminum oxide surface and anionic copolymers that remain adsorbed to the surface of the membrane. This swelling serves to resist permeate flow above the isoelectric point of aluminum oxide. This phenomenon is observed directly using Field Emission Environmental Scanning Electron Microscopy (FE-ESEM).

Ingredient-Wise Study of Flux Characteristics in the Ceramic Membrane Filtration of Uncontaminated Synthetic Metalworking Fluids, Part 2: Analysis of Underlying Mechanisms

Part 2 of this paper reveals the predominant mechanism of flux decline during microfiltration of the synthetic MWF described in Part 1 of this paper. An analysis of flux data obtained during the experimental investigation suggests that adsorptive interactions occur at the membrane surface. Field Emission Environmental Scanning Electron Microscopy (FE-ESEM) images of aluminum oxide membranes after MWF microfiltration illustrate that adsorption leads to a reduction in pore diameter that serves to reduce flux. The majority of the adsorption is accounted for by a single lubricant additive in the MWF formulation. FE-ESEM images also reveal that the mechanism of flux decline for the defoamer varies depending on the presence of lubricant additive in solution. In the absence of lubricant additive, the defoamer forms a cake layer at the membrane surface. In the presence of the lubricant additive, the defoamer adsorbs to the surface of the membrane with the lubricant additive to constrict pores. In contrast to the lubricant additive and defoamer, base fluid flux decline observed after specialty additive exposure cannot be accounted for by adsorption leading to pore constriction. [S1087-1357(00)01203-X]