Metakaolin-based inorganic polymer composite: Effects of fine aggregate composition and structure on porosity evolution,microstructure and mechanical properties

This paper examines the phase transformation, pore evolution, microstructural and mechanical changes that occur in inorganic polymer cement (IPC) in the presence of three different grade of fine aggregates (ф < 100 μm) of ladle slag, nepheline syenite and quartz sand. Experimental results indicate that polycondensation was enhanced in nepheline syenite based specimens, compared to quartz sand, due to the increase in HMAS phases in relation to the dissolution and interaction of amorphous/disordered fraction of aggregates. HCS and HCAS with HMAS phases were identified in the ladle slag based specimens. The formation of these new phases reduced both the cumulative pore volume and pores size. The apparent increase in volume of capillary pores in ladle slag based specimens was explained by the residual bubbles from the carbonates included in raw slag. The flexural strength of the inorganic polymer cement increases from 4 MPa to 4.2, 4.8 and 6.8 MPa with the addition of 20 wt% of quartz sand, nepheline syenite and ladle slag respectively. These values increase significantly between 28 and 180 days of curing (9.1 MPa for ladle slag and 10.0 MPa for nepheline syenite). It was concluded that fines can be used to remove the HM and poorly bounded alumina oligomers in metakaolin based inorganic polymer matrices and improve the interfacial zone for the design of an optimum grade and high-performance composites.     

Effect of annealing temperature on the microstructure and photoluminescence of low resistivity Si/SiN/TaN thin films using magnetron sputtering

A lot of studies have been devoted to the porous Si, erbium-doped Si and Si-embedded in dielectric matrix of SiO or SiN together with long-time conventional furnace annealing. Besides, it is noted that these Si nanostructured films were highly resistive and non-conducting. In this paper, we have investigated the effect of annealing temperature on the microstructure and photoluminescence of low-resistivity Si/SiN/TaN nanocomposite thin films which are deposited by magnetron sputtering and followed by rapid thermal annealing (RTA). All samples are of luminescence and staying low resistivity at about 1462–2162 μΩ cm which increases with increasing annealing temperatures. The asymmetric broad photoluminescence (PL) peak covered the wavelengths of 400–700 nm. The wide visible PL spectra can be deconvoluted into three bands of blue (~ 455 nm), green-yellow (~ 525 nm), and orange emissions (~ 665 nm), which correspond to the emission origins from unsatisfied states in imperfections of interface between the Si:O and SiN:O, located states related to the mixed SiO or SiN bonds in SiN:O layer and nc-Si embedded in SiN:O matrix. The detailed mechanism of broad visible PL was investigated in terms of microstructure and bonding configuration evolution. The relationship between the annealing temperature, microstructure and PL behavior of Si/SiN/TaN multilayer films is discussed and established.     

Phase constitutions of MoSiN anti-oxidation multi-layer coatings on CC composites by fused slurry

To improve the oxidation resistance of MoSi fused slurry coating fabricated in vacuum, MoSiN multi-layer coatings were synthesized on C/C composites in nitrogen atmosphere by fused slurry using same Mo and Si element powders. The phase compositions and microstructures were characterized by X-ray diffractometry (XRD), optical microscopy (OM), scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS). The results indicate that the MoSiN coating contains SiC inner layer and MoSi₂/Si main layer, which was similar with MoSi coating. Additionally, a thin outer layer with nano-filiform morphology has been found on the coating surface, which consists of SiC, Si₃N₄, AlN, Al₂O₃ and sialon phase. Oxidation experiments show that the MoSiN multi-layer coating exhibits excellent oxidation resistance at 1400 °C and anti-oxidizing potential ability at 1450 °C.     

Synthesis,crystal structure,luminescent properties and photo degradation of mer-tris(8-Hydroxy-quinolinato-N,O)-indium(iii) hydrate 0.5 methanol solvate

Tris-(8-hydroxyquinioline) aluminium (Alq₃) is widely used in organic light emitting diodes as an emission and electron transport layer. In this study the effect of solvent molecules, in the solid state crystal lattice, on the photoluminescence properties of synthesized mer-tris(8-Hydroxy-quinolinato-N, O)-indium(iii) hydrate 0.5 methanol solvate (mer-[In(qn)₃]⋅H₂O⋅0.5 CH₃OH) was studied. Single crystals were obtained through a recrystallization process and single crystal X-ray diffraction was performed to obtain the unit cell structure. The main absorption peaks were assigned to ligand centered electronic transitions, while the solid state photoluminescence excitation peak at 440 nm was assigned to the 0–0 vibronic state of In(qn)₃. Broad emission at 510 nm was observed and was ascribed to the relaxation of an excited electron from the S₁–S₀ level. A powder sample was annealed at 130 °C for 2 h. A decrease in intensity was observed and could possibly be assigned to a loss of solvent species. To study the photon degradation, the sample was irradiated with an UV lamp for ∼15 h. The emission data was collected and the change in photoluminescence intensity with time was monitored. High resolution X-ray photoelectron spectroscopy (XPS) scans of the O-1s peak revealed that after annealing the binding energy shifted to lower energies indicating a possible loss of the H₂O and CH₃OH present in the crystal. The O-1s peak of the degraded sample indicated the possible formation of CO (∼532.5 eV), COH and OCOH (∼530.5 eV) on the phenoxide ring.     

Effects of He (90%)/H2 (10%) plasma treatment on electric properties of low dielectric constant SiCOH films

In microelectronics industry, integration of the low dielectric constant (low-k) material films is a continuing issue due to the decreasing device feature size. To improve electric properties, various post-deposition treatments of the low-k material films can be used. In this work, we used room temperature treatment of He/H₂ plasma and investigated the effects of plasma treatment on the electrical properties of low-k SiOCH films. Plasma treatment time changed from 300 to 1800 s. After treatment, the dielectric constant was decreased from 2.9 to 2.48, and the thickness of the low-k SiCOH films changed by only ～5%. The leakage current densities of the low-k SiCOH films were decreased to ～10^?11 A/cm², with treatment time ≥600 s. The breakdown occurred only around 2 V for films plasma-treated for 600 and 900 s. However, for 1800 s treatment time, the breakdown voltage was enhanced dramatically and breakdown occurred at applied voltage higher than 40 V. The surface composition change of the films after treatment was investigated by X-ray photoelectron spectroscopy (XPS). As the plasma treatment time was increased, the intensities of CC/CH and CSi peaks were decreased while the intensities of SiO and CO peaks were increased. It is thought that increase of oxygen content of the SiCOH film, after plasma treatment, contributed to leakage current reduction and breakdown voltage increase.     

Fibroblast functionality on novel Ti30Ta nanotube array

In this study, the mechanical substrate and topographical surface properties of anodized Ti30Ta alloy were investigated using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS) and contact angle measurement. The anodization process was performed in an electrolyte solution containing HF (48%) and H₂SO₄ (98%) in the volumetric ratios 1:9 with the addition of 5% dimethyl sulfoxide (DMSO) at 15 V, 25 V and 35 V for 20 and 40 min, producing a nanotube architecture when anodized at 35 V for 40 min. Human dermal fibroblasts (HDF, neonatal) were utilized to evaluate the biocompatibility of Ti30Ta nanotubes and Ti30Ta alloy after 1 and 3 days of culture. Cellular adhesion, proliferation, viability, cytoskeletal organization and morphology were investigated using fluorescence microscope imaging, biochemical assay and SEM imaging respectively. The results presented identify altered material properties and improved cellular interaction on Ti30Ta nanotubes as compared to Ti30 Ta alloy.     

Optical properties of TiO2 and disperse red-19 composite

Characteristic absorption and photoluminescence (PL) of TiO₂ and disperse red-19 (DR-19) composite have been investigated. Two step synthetic processes were employed to incorporate the DR-19 to the TiO₂ sol–gel. Firstly, urethane bonds between the DR-19 (OH) and 3-isocyanatopropyl triethoxysilane (ICPTES, NCO) were fabricated (ICPDR) prior incorporation to the TiO₂ sol–gel. Secondary, hydrolysis of the ethoxy group from the ICPDR and condensation reaction between silanol groups from ICPDR and TiO₂ sol–gel were performed by adding ICPDR to the TiO₂ sol–gel and aged for several days at room temperature (ICPDRTiO₂). There was no absorption peak shift with increasing the DR-19 concentration in methanol. However, UV–visible absorption band was shifted toward red approximately 0.09 eV for the ICPDRTiO₂ film, which indicated the formation of dimmer or more aggregates. The PL peaks of ICPDRTiO₂ were red-shifted compared with DR-19 in methanol (0.12 eV) and ICPDR film (0.09 eV). The relatively large emission peak shift toward red could be due to the fluorescence resonance energy transfer (FRET) between DR-19 and TiO₂ in ICPDRTiO₂ matrix.     

Surface modification on polyethylene terephthalate films with 2-methacryloyloxyethyl phosphorylcholine

In this study, the surface of polyethylene terephthalate (PET) was modified to improve the protein and cell adhesion behavior with low temperature ammonia plasma treatment followed by 2-methacryloyloxyethyl phosphorylcholine (MPC) grafting. The x-ray photoelectron spectroscopy (XPS) results showed that the COO^?, NCO and POH groups were successfully incorporated onto the sample surface after MPC grafting. Furthermore, formation of new bonds, N and NH on the sample surface grafted with MPC was recorded by Fourier transform infrared spectroscopy (FTIR). A large number of spherical particles at submicron to nanometer scale were also observed on the surface by atomic force microscopy (AFM). The cell adhesion experiments on PET film surfaces were evaluated and the highly hydrophilic surfaces could not promote cell adhesion and spreading. All results achieved in this study have clearly indicated that the method combining low temperature ammonia plasma treatment and MPC grafting is an effective way of producing a suitably hydrophilic PET surface with the capability of weakening the protein adsorption greatly.     

Nanoparticles of the giant dielectric material,calcium copper titanate from a sol–gel technique

The precursor of CaCu₃Ti₄O₁₂ (CCTO) nano particles have been successfully synthesized by sol–gel method at 90 °C. The dried precursor powder was milled and then calcined at 450 °C, 550 °C, 650 °C, 800 °C, 850 °C and 950 °C for 3 h. The phase formation of CCTO was analyzed by step by step using FTIR and XRD. Particle size and shape were evaluated by AFM. The XRD results of the powder calcined at 800 °C indicated the formation of CCTO phase. AFM studies showed that average particle size of the CCTO powder range 90–120 nm. The absorption bands corresponding to vibrations of CaO, CuO and TiOTi were observed at 606, 525 and 463 cm^? 1 using FTIR. The samples sintered at 1040 °C showed the densities as high as 96% of theoretical density. The grain sizes of sintered pellets were determined by FE-SEM. The dielectric properties of prepared samples were studied by LCR meter.     

Luminescence at 1.53 μm for a new Er3+-doped transparent oxyfluoride glass ceramic

Transparent 45SiO₂25Al₂O₃5CaO10NaF15CaF₂ glass ceramics doped with different levels of Er³⁺ were prepared. The spherical CaF₂ nanocrystals with 10–20 nm in size were verified to be homogeneously embedded among the glassy matrix. Room temperature absorption and emission spectra corresponding to ⁴I_13/2 ↔ ⁴I_15/2 transitions of Er³⁺ ions in precursor glasses and glass ceramics, respectively had been measured. For glass ceramics, with increasing of Er³⁺ content from 0.1 to 2.0 mol%, the FWHM values of the emission bands increased from 42 to 71 nm; meanwhile, the lifetime of ⁴I_13/2 level slightly reduced. However, both the values of FWHM and lifetime were larger than those of precursor glasses due to the change of ligand field of Er³⁺ ions.     

Sol–gel synthesis of tantalum oxide and phosphonic acid-modified carbon nanotubes composite coatings on titanium surfaces

Carbon nanotubes used as fillers in composite materials are more and more appreciated for the outstanding range of accessible properties and functionalities they generate in numerous domains of nanotechnologies. In the framework of biological and medical sciences, and particularly for orthopedic applications and devices (prostheses, implants, surgical instruments, …), titanium substrates covered by tantalum oxide/carbon nanotube composite coatings have proved to constitute interesting and successful platforms for the conception of solid and biocompatible biomaterials inducing the osseous regeneration processes (hydroxyapatite growth, osteoblasts attachment). This paper describes an original strategy for the conception of resistant and homogeneous tantalum oxide/carbon nanotubes layers on titanium through the introduction of carbon nanotubes functionalized by phosphonic acid moieties (P(O)(OH)₂). Strong covalent CP bonds are specifically inserted on their external sidewalls with a ratio of two phosphonic groups per anchoring point. Experimental results highlight the stronger “tantalum capture agent” effect of phosphonic-modified nanotubes during the sol–gel formation process of the deposits compared to nanotubes bearing oxidized functions (OH, CO, C(O)OH). Particular attention is also paid to the relative impact of the rate of functionalization and the dispersion degree of the carbon nanotubes in the coatings, as well as their wrapping level by the tantalum oxide matrix material. The resulting effect on the in vitro growth of hydroxyapatite is also evaluated to confirm the primary osseous bioactivity of those materials. Chemical, structural and morphological features of the different composite deposits described herein are assessed by X-ray photoelectron spectroscopy (XPS), scanning (SEM) and transmission (TEM) electronic microscopies, energy dispersive X-rays analysis (EDX) and peeling tests.     

Green synthesis of Au–Pd bimetallic nanoparticles: Single-step bioreduction method with plant extract

A facile and eco-friendly method for the preparation of Au–Pd bimetallic nanoparticles (~ 7 nm) has been developed based on simultaneous bioreduction of Au(III) and Pd(II) precursors with Cacumen Platycladi leaf extract in aqueous environment. The morphology, structure, and size were confirmed with the aid of transmission electron microscopy, selected area electron diffraction, UV–vis spectroscopy, X-ray diffraction, and energy dispersive X-ray spectroscopy. The results from Fourier transform infrared spectroscopy showed that the CO and CO groups in the plant extract played a critical role in capping the nanoparticles. Importantly, the process can be described as pure “green chemistry” technique since no additional synthetic reagents are used as reductants or stabilizers.     

Room temperature solid–solid reaction preparation of ironboron alloy nanoparticles and Mössbauer spectra

The amorphous ironboron alloy can be prepared very easily by a room temperature solid–solid reaction of the FeCl₃·6H₂O, CrCl₃·6H₂O and KBH₄ powders. The characterizations show that the product is mainly composed of amorphous ironboron alloy nanoparticles. ⁵⁷Fe Mossbauer spectra at 84 and 295 K show that there are three kinds of Fe-containing components in the sample. There are the superparamagnetic relaxation in Mössbauer spectra and the continuous distribution of internal magnetic field in the ironboron alloy.     

Effect of water content in sol on optical properties of hybrid sol–gel derived TiO2/SiO2/ormosil film

Sol–gel derived TiO₂/SiO₂/ormosil hybrid planar waveguides have been deposited on soda-lime glass slides and silicon substrates, films were heat treated at 150 °C for 2 h or dried at room temperature. Different amounts of water were added to sols to study their impacts on microstructures and optical properties of films. The samples were characterized by m-line spectroscopy, Fourier transform infrared spectroscopy (FT-IR), UV/VIS/NIR spectrophotometer (UV–vis), atomic force microscopy (AFM), thermal analysis instrument and scattering-detection method. The refractive index was found to have the largest value at the molar ratio H₂O/OR = 1 in sol (OR means OCH₃, OC₂H₅ and OC₄H₉ in the sol), whereas the thickest film appears at H₂O/OR = 1/2. The rms surface roughness of all the films is lower than 1.1 nm, and increases with the increase of water content in sol. Higher water content leads to higher attenuation of film.     

High contrast glasses for all-solid fibers fabrication

We present composition development of borosilicate glasses for fabrication of high refractive index contrast, all-solid photonic crystal fibers. An oxide system composed of SiO₂B₂O₃Al₂O₃Li₂ONa₂OK₂O was adjusted to match thermal properties of selected highly nonlinear, lead bismuth gallium silicate glass. A high difference of refractive index of 0.376 is achieved at a wavelength of 1550 nm. We proved experimentally that the developed pair of glasses enables to draw optical fibers, and we propose a design of a photonic crystal fiber structure for broadband supercontinuum generation.     

Degradation performance of biodegradable FeMnC(Pd) alloys

Biodegradable metals offer great potential in circumventing the long-term risks and side effects of medical implants. Austenitic FeMnCPd alloys feature a well-balanced combination of high strength and considerable ductility which make them attractive for use as degradable implant material. The focus of this study is the evaluation of the degradation performance of these alloys by means of immersion testing and electrochemical impedance spectroscopy in simulated body fluid. The FeMnCPd alloys are characterized by an increased degradation rate compared to pure Fe, as revealed by both techniques. Electrochemical measurements turned out to be a sensitive tool for investigating the degradation behavior. They not only show that the polarization resistance is a measure of corrosion tendency, but also provide information on the evolution of the degradation product layers. The mass loss data from immersion tests indicate a decreasing degradation rate for longer times due to the formation of degradation products on the sample surfaces. The results are discussed in detail in terms of the degradation mechanism of Fe-based alloys in physiological media.     

Whether do nano-particles act as nucleation sites for C-S-H gel growth during cement hydration?

In this study, three modelling experiments were designed to investigate whether nano-particles incorporated in the cement paste act as nucleation sites for CSH gel growth during cement hydration. The nano-particles with (nano-SiO₂) and without (nano-TiO₂) pozzolanic reactivity were used. In the first experiment, both the cement and nano-particles were dispersed in water to prepare dilute cement paste, in which the cement and nano-particles can contact each other. In the second one, the cement particles were laid inside a filter paper funnel and immersed in tap and ultrapure water with nano-particles dispersed, in order to separate the cement particles with nano-particles by using the filter paper. In the third one, large clinker particle was embedded in resin, surface-polished and then exposed upside down in ultrapure water with and without nano-particles dispersed. After hydration for 7 days, the hydration products in the paste or the nano-particle dispersion were observed by using TEM and the hydrated surface of the embedded clinkers were detected by using SEM. Based on the experimental results and the detailed discussions by using the classic nucleation theory, it was found that there may have no nucleus function of the nano-particles for the CSH gel precipitation during cement hydration, at least in the hydrating system with nano-silica and nano-TiO₂ addition. It was proposed to more reasonably explain the observations in the three modelling experiments by using the topochemical reaction instead of the through-solution mechanism for the CSH gel formation.     

The effects of the SiOSi segment presence in BAPP/BPDA polyimide system on morphology and hardness properties for opto-electronic application

Recent technological advances demanded incorporation of SiOSi segment into polyimides (PI)s to improve versatility in terms of processing, morphology and optoelectronic properties. In order to study the role of SiOSi segment in the morphology and hardness properties of PI, the SiOSi segment have been introduced into the PI backbone through the conventional copolymerization and in PI matrix through sol gel method. The PI series were characterized by Fourier transform infra-red (FT-IR), nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, solution viscosity and gel permeation chromatography (GPC). Scanning electron microscope (SEM) analysis suggested a microphase separation between the two components. FT-IR spectra confirmed the presence of silicone segment, as well as a complete imidization of PI series. Micrograph suggested a homogeneous phase between the PI and silicone segment for copolymerization series while sol gel technique revealed the inorganic particles were distributed homogenously in PI matrix. It was also found that the presence SiOSi segment in PI backbone and PI matrix influenced the opto-electronic properties.     

Formaldehyde on TiO2 anatase (1 0 1): A DFT study

The adsorptions of formaldehyde molecule on the stoichiometric anatase TiO₂ (1 0 1) surface have been studied by first principles calculations. Four types of adsorption have been investigated at 0.25 ML coverage. Two of them are chemical adsorptions and the other two are physical adsorptions. For the chemical adsorptions, C, O atoms in the formaldehyde molecule form two bonds with the O_2c/O_3c and Ti_5c on the anatase (1 0 1) surface. The CO bond in the formaldehyde molecule is elongated and a dioxymethylene structure forms in the two chemical adsorptions. The OTi_5c interaction can be found in the two physical adsorptions and it is the only contacting point at the interface. No serious internal distortion in the formaldehyde molecule can be found in the physical adsorptions. The LDOS and the difference of the charge density are calculated to investigate the interface bonds of the adsorption. As the adsorption coverage increase, the molecules on the surface repel each other and weaken the adsorptions. For example, the chemical adsorption may become physical adsorption at high coverage.     

Poly (hydroxyethyl methacrylate-glycidyl methacrylate) films modified with different functional groups: In vitro interactions with platelets and rat stem cells

Copolymerization of 2-hydroxyethylmethacrylate (HEMA) with glycidylmethacrylate (GMA) in the presence of α-α′-azoisobisbutyronitrile (AIBN) resulted in the formation of hydrogel films carrying reactive epoxy groups. Thirteen kinds of different molecules with pendant NH₂ group were used for modifications of the p(HEMA-GMA) films. The NH₂ group served as anchor binding site for immobilization of functional groups on the hydrogel film via direct epoxy ring opening reaction. The modified hydrogel films were characterized by FTIR, and contact angle studies. In addition, mechanical properties of the hydrogel films were studied, and modified hydrogel films showed improved mechanical properties compared with the non-modified film, but they are less elastic than the non-modified film. The biological activities of these films such as platelet adhesion, red blood cells hemolysis, and swelling behavior were studied. The effect of modified hydrogel films, including NH₂, (using different aliphatic CH₂ chain lengths) CH₃, SO₃H, aromatic groups with substituted OH and COOH groups, and amino acids were also investigated on the adhesion, morphology and survival of rat mesenchymal stem cells (MSCs). The MTT colorimetric assay reveals that the p(HEMA-GMA)-GA-AB, p(HEMA-GMA)-GA-Phe, p(HEMA-GMA)-GA-Trp, p(HEMA-GMA)-GA-Glu formulations have an excellent biocompatibility to promote the cell adhesion and growth. We anticipate that the fabricated p(HEMA-GMA) based hydrogel films with controllable surface chemistry and good stable swelling ratio may find extensive applications in future development of tissue engineering scaffold materials, and in various biotechnological areas.