Rapid Manufacturing of Complex-Structured Transparent Silica Glass Materials through a Hybridized Approach of Photo-Curing and Machining from Interparticle Photo-Cross-Linkable Suspensions.

The rapid manufacturing of transparent SiO2 glass components via a hybridized 3D structuring approach for photo-curing and green machining, followed by a fast debinding/sintering process (at a heating rate of 20 °C min-1), is reported to be based on the design of a new series of interparticle photo-cross-linkable suspensions. In these suspensions, small amounts of multifunctional acrylates and silane alkoxides with acryloyl groups (A-Si) are co-photo-polymerized and further reacted with SiO2 particles modified using functionalized polyethyleneimine to form hybridized interparticle networks. The addition of A-Si increases the interparticle cross-linking densities, leading to an improvement in the mechanical properties and green machinability of the photo-cured bodies. Furthermore, the A-Si component in the cross-links forms siloxane-based networks among SiO2 particles in situ during the debinding/sintering process, which increases the mechanical strength of the debinded bodies and successfully prevents structural collapses under rapid heating conditions. The study demonstrates that the photo-cured body from the newly designed suspensions can be green-machined into pillars, microfluids, and assembling blocks and can be sintered into highly transparent SiO2 glass components. Overall, this work provides new options for the time- and energy-effective processing of SiO2 glass materials with tailor-made 3D structures.

Operando observation of concentrated SiO2 suspensions by optical coherent tomography during flow curve measurements: The relationship between polymer dispersant structures and surface interactions.

HYPOTHESIS: Flow curve measurement is commonly used to characterize the flow behavior of concentrated suspensions. However, dynamic changes in the suspension inner microstructures under highly sheared conditions have not been correctly understood even though they strongly affect the measured shear stress. We hypothesize that the real particle dynamics during shearing could be effectively revealed by a systematic investigation that combines macroscopic flow curve measurements with operando microstructural observation employing an optical coherent tomography (OCT) apparatus and surface interaction measurements with the colloidal probe atomic force microscopy (AFM) method. EXPERIMENTS: The model system was spherical SiO2/toluene suspensions stabilized by polyethyleneimine (PEI) partially complexed with different fatty acids. Inner structures of the suspensions during flow curve measurements were observed by the OCT technique. The surface-surface interactions in toluene were analyzed using the colloidal probe AFM method. FINDINGS: Operando OCT observations revealed that during flow curve measurements, the suspensions can have completely different microscopic flow modes depending on the fatty acid species complexed to PEI and the solid concentrations. These microscopic flow modes could not be recognized using the typical flow curve measurements alone. The different flow modes can be explained by surface interactions measured by the colloidal probe AFM method.

Polymer Ligand Design and Surface Modification of Ag Nanowires toward Color-Tone-Tunable Transparent Conductive Films.

Ag nanowire suspensions are one of the indispensable materials in the design and fabrication of flexible transparent conductive films. Although the required properties of Ag nanowire films, such as their high transparency, low haze, low contact resistance, and suppression of yellowing, are strongly related to the nanowire surface phenomena, approaches for the surface modification of polyol-synthesized Ag nanowires have rarely been reported. Here, we report the design of a polymer ligand and surface modification of Ag nanowires with the designed polymer to obtain color-tunable transparent conductive films through a simple casting and drying process. In this approach, we synthesized a series of functional polymer ligands by partially grafting polyethyleneimine (PEI) with polyethylene glycol (PEG) chains (PEI-mPEG). The amine sites in PEI-mPEG were designed to act as adsorption sites as well as anchoring sites for an anionic blue dye for suppressing the yellow color tone of Ag nanowires. On the other hand, the PEG chains were designed to maintain the stability of the Ag nanowires in aqueous suspensions and to suppress corrosion of Ag nanowires, which is enhanced by the amine groups of PEI. The effect of the grafting ratio of PEG chains on PEI on the ligand-exchange behavior of the Ag nanowires, their dispersion stability in aqueous inks, and final film properties were investigated systematically. Furthermore, successful color tuning of the Ag nanowire film, without suppressing the conductive and optical properties, is demonstrated by loading anionic blue dye onto PEI-mPEG-modified Ag nanowires.

Multi-scale laser direct writing of conductive metal microstructures using a 405-nm blue laser.

A multi-scale direct writing method for metal microstructures is proposed and demonstrated. In this study, metal structures were created in a gelatin matrix containing silver nitrate by photoreduction using a 405-nm blue laser. The influence of concentrations of materials in the sample solution was evaluated by measuring the conductivity of the fabricated microstructures. The fabrication line width could be controlled by changing the laser scanning speed. A network structure was also observed, which possibly helps in increasing the microstructure's conductivity. Finally, we demonstrated multi-scale drawing by using objective lenses with different numerical apertures. Our method can result in new possibilities for conductive metal direct writing.

[Characterization of Surface Interaction between Chitosan-modified Liposomes and Mucin Layer by Using CNT Probe AFM Method].

　In order to characterize the adhesion and deformation behavior between chitosan-modified liposomes and the mucin layer of the small intestine, mucin was coated on hydrophobic surface-modified carbon nanotube (CNT) probe of an atomic force microscope. The interaction between this mucin layer and the liposomes with or without chitosan modification in phosphoric acid buffer solution was determined by atomic force microscopy. The pH of the buffer solution was controlled at 2.8 and 7.0. The chitosan modification increased the attractive force between the liposomes and mucin layer during the separation process under both pH conditions. This result corresponded with that from a previous study about the liposome adhesion behavior on the surface of the small intestine of rats. By using the mucin-coated CNT probe, the long range and different types of attractive forces between the chitosan-modified liposomes and mucin layer was observed. Furthermore, the small-scaled deformation behavior change on the liposomal surfaces due to chitosan modification was also observed by the CNT probe. The detail deformation and adhesion behavior of the liposomes with or without chitosan modification was detected.

Toward continuous LC-MS analysis: surface modification of magnetic microparticles with TiO2 for phosphate adsorption.

Continuous liquid chromatography-mass spectrometry (LC-MS) analysis was successfully demonstrated by using magnetic TiO2/Fe3O4 microparticles at the desalination interface. The particles could be prepared easily even on a practical scale at sufficient quality for efficient phosphate adsorption. Not only phosphate but several biomolecules were adsorbed onto the particles in a non-specific manner. Such samples could still be detected effectively in MS because the removal of phosphate derived from the LC eluent enhanced sample ionization and resulted in a significant reduction of phosphate cluster ions.

Layer-by-layer surface modification of functional nanoparticles for dispersion in organic solvents.

In order to prepare SiO(2) nanoparticles that are dispersible in various organic solvents, an anionic surfactant 1, which branches into a hydrophobic chain and a hydrophilic chain, was adsorbed on to SiO(2) nanoparticles through a layer-by-layer surface modification route using polyethyleneimine (PEI). First, the relationship among the additive content of PEI, adsorbed content of PEI, and the redispersion stability of the SiO(2) nanoparticles in water was investigated. While almost the entire PEI was adsorbed when the additive PEI content was lower than 67 mg/g of SiO(2), the adsorbed content of PEI became saturated when the additive content was increased above 90 mg/g of SiO(2). SiO(2) nanoparticles that were saturated with PEI could be redispersed into water at sizes close to their primary particle size without the large-scale formation of aggregates. Next, the anionic surfactant 1 was adsorbed on the SiO(2) nanoparticles by using a SiO(2) aqueous suspension saturated with adsorbed PEI. It was found that the adsorbed content of 1 increased almost linearly as the additive content was increased when the additive condition was below 1400 mg/g of SiO(2). Furthermore, SiO(2) nanoparticles adsorbed with 80 mg/g of SiO(2) of PEI and 810 mg/g of SiO(2) of 1 could be dispersed into various organic solvents with different polarities. This layer-by-layer modification technique can also be applied to Ag nanoparticles in order to prepare Ag nanoparticles that can be dispersed in various organic solvents.

Surface modification and characterization for dispersion stability of inorganic nanometer-scaled particles in liquid media.

Inorganic nanoparticles are indispensable for science and technology as materials, pigments and cosmetics products. Improving the dispersion stability of nanoparticles in various liquids is essential for those applications. In this review, we discuss why it is difficult to control the stability of nanoparticles in liquids. We also overview the role of surface interaction between nanoparticles in their dispersion and characterization, e.g. by colloid probe atomic force microscopy (CP-AFM). Two types of surface modification concepts, post-synthesis and in situ modification, were investigated in many previous studies. Here, we focus on post-synthesis modification using adsorption of various kinds of polymer dispersants and surfactants on the particle surface, as well as surface chemical reactions of silane coupling agents. We discuss CP-AFM as a technique to analyze the surface interaction between nanoparticles and the effect of surface modification on the nanoparticle dispersion in liquids.

Anionic surfactant with hydrophobic and hydrophilic chains for nanoparticle dispersion and shape memory polymer nanocomposites.

An anionic surfactant comprising a hydrophilic poly(ethylene glycol) (PEG) chain, hydrophobic alkyl chain, and polymerizable vinyl group was synthesized as a capping agent of nanoparticles. TiO(2) nanoparticles modified by this surfactant were completely dispersible in various organic solvents with a wide range of polarities, such as nitriles, alcohols, ketones, and acetates. Furthermore, these particles were found to be dispersible in various polymers with different properties, such as thermosetting epoxy resins and radical polymerized poly(methylmethacrylate) (PMMA). A polymer composite of surface-modified TiO(2) nanoparticles in epoxy resins prepared by using the developed surfactant also possessed temperature-induced shape memory properties.

Rapid magnetic catch-and-release purification by hydrophobic interactions.

A reversible, conventional, and rapid purification method of hydrophobically tagged products using hydrophobic magnetic nanoparticles was developed. The reversible purification system entails simply controlling the polarity of solvents. First, for the catching procedure, poor solvents were added into a well-dispersed system of magnetic nanoparticles and tagged products. Once the poor solvents were added to the system, the products were recrystallized among the nanoparticles and the aggregation of magnetic nanoparticles occurred due to hydrophobic interactions. These aggregates with the products contained within them were able to be collected rapidly by magnets. Then, the releasing procedure can be easily performed by redispersing the collected aggregates into good solvents. The availability of this purification protocol was confirmed by using a hydrophobically tagged fluorescent model product. Furthermore, this rapid purification method was successfully applied to a peptide elongation reaction system which enabled the synthesis of peptides such as Leu-Enkephalin in high purity, in high yield, and in a short time.

Tuning the stability of TiO2 nanoparticles in various solvents by mixed silane alkoxides.

The surface of TiO(2) nanoparticles which were well dispersed into acidic aqueous solution was successfully modified by silane alkoxides without strong aggregate formations. By adding decyltrimethoxysilane (DTMS) as silane alkoxides into the TiO(2) aqueous solution which were carefully diluted with methanol, DTMS slowly attached onto the TiO(2) surface without rapid hydrolysis and condensation reaction among DTMS. Because of the hydrophobicity of DTMS, the dispersed TiO(2) nanoparticles slowly formed flocks as DTMS reacted on TiO(2). These flocks were able to be completely redispersed into nonpolar solvents even after they were collected by centrifugation and drying under vacuum as dry powder. Furthermore the surface of TiO(2) nanoparticles have been successfully tuned by combining silane alkoxides which contains hydrophobic and hydrophilic groups such as DTMS and 3-aminopropyltrimethoxysilane (APTMS), respectively, toward their complete redispersion into various solvents. While TiO(2) nanoparticles modified by DTMS were redispersible into toluene, those modified by mixed alkoxides of 50 mol % DTMS and 50 mol % APTMS were redispersible into a mixed solution of toluene and methanol. Further when they were modified by mixed alkoxides of 25 mol % DTMS and 75 mol % APTMS, they were redispersible into polar solvents such as methanol with a little addition of acids.

Direct measurement of interactions between stimulation-responsive drug delivery vehicles and artificial mucin layers by colloid probe atomic force microscopy.

A novel thermo- and pH-sensitive nanogel particle, which is a core-shell structured particle with a poly(N-isopropylacrylamide) (p(NIPAAm)) hydrogel core and a poly(ethylene glycol) monomethacrylate grafted poly(methacrylic acid) (p(MMA-g-EG)) shell, is of interest as a vehicle for the controlled release of peptide drugs. The interactions between such nanogel particles and artificial mucin layers during both approach and separation were successfully measured by using colloid probe atomic force microscopy (AFM) under various compression forces, scan velocities, and pH values. While the magnitudes of the compression forces and scan velocities did not affect the interactions during the approach process, the adhesive force during the separation process increased with these parameters. The pH values significantly influenced the interactions between the nanogel particles and a mucin layer. A large steric repulsive force and a long-range adhesive force were measured at neutral pH due to the swollen p(MMA-g-EG) shell. On the other hand, at low pH values, the steric repulsive force disappeared and a short-range adhesive force was detected, which resulted from the collapse of the shell layer. The nanogel particles possessed a pH response that was sufficient to protect the incorporated peptide drug under the harsh acidic conditions in the stomach and to effectively adhere to the mucin layer of the small intestine, where the pH is neutral. The relationships among the nanogel particle-mucin layer interactions, pH conditions, scan velocities, and compression forces were systemically investigated and discussed.

Effect of particle size on surface modification of silica nanoparticles by using silane coupling agents and their dispersion stability in methylethylketone.

The effect of particle size on the reactivity of hexyltrimethoxysilane (C6S) with the particle surface was studied by using silica nanoparticles (SNPs) with different diameters (30 or 200 nm). In case of 30-nm SNPs, a large amount of isolated silanol was observed. On the other hand, in the case of 200-nm SNPs, the amount of hydrogen bonded silanol and hydrogen bonded water molecules at the surface of the SNPs increased. Since the hydrogen bonded silanol and the hydrogen bonded water enhanced the reaction of C6S with SNPs, the chemisorbed C6S on 200-nm SNPs was larger than that on 30-nm SNPs. Furthermore, the effects of surface modification on the dispersion stability in MEK were studied using viscosity measurements and surface force measurements by the AFM colloid probe method. The viscosity of the dilute SNPs/MEK suspension did not change by the chemisorptions of C6S; however, the viscosity of dense suspension reduced effectively by surface modification. It was estimated that the suspension viscosity reduced effectively when the mean particle surface distance in the suspension was near to the distance where the repulsive force appeared by the surface force measurements using the colloid probe AFM.

Effect of surface interaction of silica nanoparticles modified by silane coupling agents on viscosity of methylethylketone suspension.

In order to control the viscosity of a dense silica methylethylketone (MEK) suspension, the surfaces of silica nanoparticles were modified by 3-glycidoxypropyltrimethoxysilane (GPS) or hexyltrimethoxysilane (C6S) in MEK with the addition of a small amount of pH-controlled water. First, the effect of water addition on the amount of chemisorbed coupling agent was investigated. pH-controlled water enhanced the reactivity of the coupling agent in MEK. The amount of chemisorbed coupling agent increased slightly with the addition of pH 3 water and increased remarkably with the addition of pH 12 water. Next, the effect of the organic functional groups of the coupling agent, pH of the additive water, and additive amount of coupling agent on surface interaction were determined by colloid probe AFM. The steric repulsive force between the silica nanoparticles increased due to water addition, particularly when the pH was maintained at 3. The viscosity of the silica MEK suspension reduced effectively when this repulsive force appeared; however, the optimum condition for reducing the suspension viscosity was dependent on the coupling agent species. The viscosity of the dense silica MEK suspension can be controlled by the addition of small amounts of pH-controlled water and the functional groups of the coupling agent.

Microstructure control of iron hydroxide nanoparticles using surfactants with different molecular structures.

To control the morphology and crystal phase of iron oxide nanoparticles within several 10 nm in diameter, a microbial-derived surfactant (MDS) with a high carboxyl-group density and relatively low molecular weight (about 650 g/mol) or an artificially synthesized polyacrylic acid sodium salt (PAA) was added into the raw material aqueous solution before iron oxide particle synthesis by the gel-sol method. While pseudo-cubic hematite particles with a diameter of 500 nm were prepared without surfactant addition, spherical iron hydroxide nanoparticles with a diameter of 20 nm were prepared by MDS addition. In contrast, needle-type iron hydroxide nanoparticles with a length of 100 nm along the long axis were prepared by PAA addition. Complex formation due to the interaction between COO- groups in each surfactant and Fe3+ ions, as well as the template role prior to the synthesis of iron oxide in raw aqueous solution, inhibited the phase transition from iron hydroxide to hematite. Furthermore, the morphology of the iron hydroxide nanoparticles depended on the molecular structure of the surfactants.

Preparation of agglomeration-free hematite particles coated with silica and their reduction behavior in hydrogen.

To prepare silica-coated hematite particles without agglomeration, the effects of solid fraction, ion content in solution, and designed layer thickness on agglomeration and dispersion behavior after silica coating were examined. Since the ion concentration remained high in suspension after the hematite particles were prepared, these particles formed aggregates by the compression of an electric double layer on the hematite and silica layer produced a solid bridge between primary hematite particles. Silica bridge formation and agglomeration were almost completely prevented by decreasing the ion concentration and solid fraction of the hematite particles. Furthermore, the effects of the silica-layer thickness and structure on the reduction of hematite to iron under hydrogen gas flow and the iron core stability under air were discussed. When the solid fraction was low in suspension to prevent agglomeration during coating, a densely packed structure of nanoparticles formed by heterogeneous nucleation was observed on the silica-layer surface. Since this structure could not completely prevent oxide diffusion, the layer thickness was increased to 40 nm to obtain a stable iron core under air. Although a dense uniform layer was produced at a high solid fraction during coating, its thickness was reduced to 20 nm to completely reduce hematite to iron.