Fabrication and anti-frosting performance of super hydrophobic coating based on modified nano-sized calcium carbonate and ordinary polyacrylate

Nano-sized calcium carbonate (CaCO₃) particles were modified by heptadecafluorodecyl trimethoxysilane under acidic water condition. An ordinary polyacrylate prepared via radical copolymerization of methyl methacrylate, butyl acrylate, acrylic acid and β-hydroxyethyl methacrylate was used as the binder to form hydrophobic coatings with the modified CaCO₃. Super hydrophobic coating with water contact angle of 155° was obtained from modified CaCO₃ and the polyacrylate at their weight ratio of 8/2 by a simple procedure. Based on surface analysis by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), the super hydrophobicity can be attributed to both the surface microstructure and surface enrichment of fluoroalkyl chains. Due to a low water sliding angle, carbon black powder on super hydrophobic surface was easily removed by rolling water droplet. Furthermore, the anti-frosting performance of different surfaces was investigated, which indicated that the frost formed on superhydrophobic surface was greatly retarded compared with that on bare copper surface. The surface kept super hydrophobicity even after freezing-thawing treatment for 10 times.     

Fabrication and tribological properties of super-hydrophobic surfaces based on porous silicon

In the present work, super-hydrophobic surfaces based on porous silicon (PS) were constructed by the self-assembled molecular films and their tribological properties were investigated. A simple chemical etching approach was developed to fabricate PS with the certain rough microstructure surface, which can be observed by the environmental scanning electron microscopy (ESEM). The hydrocarbon and fluorocarbon alkylsilane molecular films were self-assembled on PS, which was confirmed by the X-ray photoelectron spectroscopy (XPS) measurement. In contrast to PS, the alkylsilane molecular films modified PS (mPS) were super-hydrophobic since the apparent water contact angle (CA) exceeded 160°. The tribological properties of PS and the mPS were investigated by a ball-on-disk tribometer during the processes of different sliding velocities and normal loads. The experimental results showed that the alkylsilane molecular films could decrease the friction coefficient. Due to the difference of chain structure and functional groups, the fluorinated alkylsilane films are better candidates for improving the hydrophobicity and lubricating characteristics of PS comparing to the non-fluorinated ones. The carbon chain length of alkylsilane molecules self-assembling on the Si or PS substrates could have little effects on the hydrophobic properties and the tribology performances.     

Molecular dynamics simulation of wetting on modified amorphous silica surface

The microscopic wetting of water on amorphous silica surfaces has been investigated by molecular dynamics simulation. Different degrees of surface hydroxylation/silanization were considered. It was observed that the hydrophobicity becomes enhanced with an increase in the degree of surface silanization. A continuous transformation from hydrophilicity to hydrophobicity can be attained for the amorphous silica surfaces through surface modification. From the simulation result, the contact angle can exceed 90° when surface silanization percentage is above 50%, showing a hydrophobic character. It is also found that when the percentage of surface silanization is above 70% on the amorphous silica surface, the water contact angle almost remains unchanged (110–120°). This phenomenon is a little different from the wetting behavior on smooth quartz plates in previous experimental report. This change in the wettability on modified amorphous silica surfaces can be interpreted in terms of the interaction between water molecules and the silica surfaces.     

Effects of ultrasound pretreatment with different frequencies and working modes on the enzymolysis and the structure characterization of rice protein

The effects of ultrasound pretreatment with different frequencies and working modes, including mono-frequency ultrasound (MFU), dual-frequency ultrasound (DFU) and tri-frequency ultrasound (TFU), on the degree of hydrolysis (DH) of rice protein (RP) and angiotensin-I-converting enzyme (ACE) inhibitory activity of RP hydrolysate were investigated. Ultraviolet–visible (UV) spectroscopy, fourier transform infrared (FTIR) spectroscopy, surface hydrophobicity and scanning electron microscopy (SEM) of RP pretreated with ultrasound were measured. The results showed that ultrasound pretreatment did not increase DH of RP significantly (p > 0.05). However, all the ultrasound pretreatment increased the ACE inhibitory activity of RP hydrolysate significantly (p < 0.05). The MFU of 20 kHz showed higher ACE inhibitory activity compared to that of other MFU. The ACE inhibitory activity of sequential DFU was higher than that of simultaneous with the same frequency combination. Sequential TFU of 20/35/50 kHz produced the highest increase in ACE inhibitory activity in contrast with other ultrasound frequencies and working modes. All the results under ultrasound pretreatment showed that ultrasound frequencies and working modes were of great effect on the ACE inhibitory activity of RP. The changes in UV–Vis spectra and surface hydrophobicity indicated the unfolding of protein and exposure of hydrophobic groups by ultrasound. The FTIR analysis showed that all the ultrasound pretreatment with different frequencies and working modes decreased α-helix, β-turn content and increased β-sheet, random coil content of RP. The SEM results indicated that ultrasound pretreatment resulted in the deformation of RP. In conclusion, the frequency selection of ultrasound pretreatment of RP is essential for the preparation of ACE inhibitory peptide.     

Surface hydrophobic modification of ultra-fine aluminum silicate by mechanically grinding and heating

Highly hydrophobic ultra-fine aluminum silicate can be obtained by mechanically grinding and heating both aluminum silicate particles and octadecoic acid. The results showed that the organic modifier was adsorbed on the surface of aluminum silicate particles where a little new organic group was generated, and the hydrophobicity of ultra-fine aluminum silicate powder was enhanced. Grafting reaction was mainly carried out in heating process. Due to both grinding and heating, the modifier spread on the surface of particle completely and bonded with Si to form Si-O-C, and with Al to form acyl alumina in bidentate coordination. As a result, a highly hydrophobic layer was formed on the powder surface. However, it was unsuitable for heating temperature to exceed 180 °C, or else the layer would be destroyed. All the above points represent a useful effort for surface-grafting modification of powder particles. In this study, a novel method as a reference was provided on the surface-grafting modification of powder particles.     

镍改性ZSM-5催化剂及其SCR催化性能

采用液态离子交换法制备了不同负载量的镍改性ZSM-5分子筛催化剂,并考察了上述催化剂的微观结构和物理化学特性及其在NH3-SCR反应中的催化性能。结果表明:在负载量<10.9%时镍在分子筛中具有高度的分散性,而随着镍负载量的进一步增加,分子筛表面开始出现较大的NiO颗粒;镍元素只以+2价存在于分子筛催化剂中;在NH₃-SCR反应中,镍负载量低于14.9%时,增加镍负载量将提高催化剂的低温活性;当反应温度超过300℃时,高温催化中心开始起作用,但随镍负载量的增加,高温活性开始下降时的温度逐渐降低。     

Effect mechanism of ultrasound pretreatment on fibrillation Kinetics,physicochemical properties and structure characteristics of soy protein isolate nanofibrils

Self-assembly of soy proteins into nanofibrils is gradually considered as an effective method to improve their technical and functional properties. Ultrasound is a non-thermal, non-toxic and environmentally friendly technology that can modulate the formation of protein nanofibrils through controlled structural modification. In this research, the effect of ultrasound pretreatment on soy protein isolate nanofibrils (SPIN) was evaluated by fibrillation kinetics, physicochemical properties and structure characteristics. The results showed that the optimum ultrasound condition (20% amplitude, 15 min, 5 s on-time and 5 s off-time) could increase the formation rate of SPIN by 38.66%. Ultrasound reduced the average particle size of SPIN from 191.90 ± 5.40 nm to 151.83 ± 3.27 nm. Ultrasound could increase the surface hydrophobicity to 1547.67 in the initial stage of nanofibrils formation, and extend the duration of surface hydrophobicity increased, indicating ultrasound could expose more binding sites, creating more beneficial conditions for nanofibrils formation. Ultrasound could change the secondary and tertiary structure of SPIN. The reduction of α-helix content of ultrasound-pretreated soy protein isolate nanofibrils (USPIN) was 12.1% (versus 5.3% for SPIN) and the increase of β-sheet content was 5.9% (versus 3.5% for SPIN) during fibrillation. Ultrasound could accelerate the formation of SPIN by promoting the unfolding of SPI, exposure of hydrophobic groups and formation of β-sheets. Microscopic images revealed that USPIN generated a curlier and looser shape. And ultrasound reduced the zeta potential, free sulfhydryl groups content and viscosity of SPIN. SDS-PAGE results showed that ultrasound could promote the conversion of SPI into low molecular weight peptides, providing building blocks for the nanofibrils formation. The results indicated that ultrasound pretreatment could be a promising technology to accelerate SPIN formation and promote its application in food industry, but further research is needed for the improvement of the functional properties of SPIN.     

Facile synthesis of mesoporous ZSM-5 aided by sonication and its application for VOCs capture

Application of ultrasound power to the mother liquor is popular pretreatment for zeolite synthesis which offers a simple way of accelerating crystallization process and finetuning the properties of nanocrystalline zeolites. In this work, sonication-aided synthesis of mesoporous ZSM-5 at low temperature and ambient pressure was systematically studied, in an attempt to reach efficient and benign synthesis of zeolites with hierarchical pore structure, which has wide applications as catalysts and sorbents. The effects of sonication duration, power density, sonication temperature and seeding on the crystallization of ZSM-5 were investigated. The obtained samples were characterized by XRD, SEM, BET and VOCs capture. High quality mesoporous ZSM-5 can be obtained by a facile 5 d synthesis at 363 K, much faster than conventional hydrothermal synthesis. The reduced synthesis time was mainly attributed to the enhanced crystallization kinetics caused by the fragmentation of seeds and nuclei, while sonication radiation had little impact on the nucleation process. Compared with control sample, mesoporous ZSM-5 prepared by sonochemical method had higher surface area and mesoporosity which demonstrated improved adsorption performance for the capture of isopropanol.     

Effects of multi-frequency ultrasound pretreatment under low power density on the enzymolysis and the structure characterization of defatted wheat germ protein

The effects of ultrasonic frequency mode, power density, pretreatment time and other parameters under low power density on the degree of hydrolysis (DH) of defatted wheat germ protein (DWGP) and angiotensin-I-converting enzyme (ACE) inhibitory activity of DWGP hydrolysate were studied in this research. Ultraviolet–visible (UV–Vis) spectra, free sulfhydryl (SH), disulfide bond (SS), surface hydrophobicity and hydrophobic protein content of ultrasound-pretreated protein and hydrophobic amino acid (HAA) content of alcalase-hydrolysate of DWGP were measured under optimized ultrasonic condition. The ultrasonic frequency mode with dual-fixed frequency combination of 28/40 kHz showed higher ACE inhibitory activity of DWGP hydrolysate compared with that of other ultrasound frequency modes and all the ultrasonic frequency combinations involving in 28 kHz showed higher ACE inhibitory activity. Under the dual-fixed frequency ultrasound mode of 28/40 kHz, ultrasonic power density of 60 W/L, pretreatment time of 70 min, temperature of 60°C and substrate concentration of 60 g/L, the ACE inhibitory activity of DWGP hydrolysate was the highest with its value of 74.75% (increased by 62.30% compared to control). However, all the ultrasonic pretreatment did not increase the DH of DWGP significantly (p > 0.05). The changes in UV–Vis spectra, SH and SS groups, surface hydrophobicity and hydrophobic protein content indicated that the structure of DWGP unfolded after ultrasound pretreatment. The HAA content of hydrolysate from the pretreated DWGP increased significantly (p < 0.05). The results proved that ultrasound pretreatment loosed the protein structure and exposed more HAA residues of protein to be attacked easily by alcalase. This resulted in the increase in the HAA content which related to the ACE inhibitory activity.     

A novel approach for the preparation of organic-siloxane oligomers and the creation of hydrophobic surface

In this paper, poly(acrylate-g-siloxane) with novel comb-like structure was designed and prepared so as to create a strongly hydrophobic polymer surface. In order to achieve this goal, a series of organic-siloxane oligomers with different chain lengths and a double bond were firstly synthesized through the catalytic reforming and hydrosilylation reaction. Then, poly(acrylate-g-siloxane) was prepared by the copolymerization of the resulting oligomers with acrylate via emulsion polymerization. The as-synthesized oligomers were characterized by ¹H NMR and UV spectrometry, and the morphologies and surface chemical compositions of the dried membrane were investigated by FT-IR, XPS, as well as AFM. XPS analysis result shows that the chemical composition of the membrane's surface was rich in polysiloxane segments, which could be responsible for an increase of surface water repellency (the contact angle could reach 115° at a lower content of polysiloxane). A further investigation suggest that the side chain length of siloxane in the poly(acrylate-g-siloxane) was the dominant factor in influencing the hydrophobicity of the membrane’ surface. When the siloxane chain length reaches to eight, the membrane's surface could exhibit the strongest hydrophobicity.     

Size-dependent magnetic properties of iron oxide nanoparticles

Uniform iron oxide nanoparticles in the size range from 10 to 24 nm and polydisperse 14 nm iron oxide particles were prepared by thermal decomposition of Fe(III) carboxylates in the presence of oleic acid and co-precipitation of Fe(II) and Fe(III) chlorides by ammonium hydroxide followed by oxidation, respectively. While the first method produced hydrophobic oleic acid coated particles, the second one formed hydrophilic, but uncoated, nanoparticles. To make the iron oxide particles water dispersible and colloidally stable, their surface was modified with poly(ethylene glycol) and sucrose, respectively. Size and size distribution of the nanoparticles was determined by transmission electron microscopy, dynamic light scattering and X-ray diffraction. Surface of the PEG-functionalized and sucrose-modified iron oxide particles was characterized by Fourier transform infrared (FT-IR) and Raman spectroscopy and thermogravimetric analysis (TGA). Magnetic properties were measured by means of vibration sample magnetometry and specific absorption rate in alternating magnetic fields was determined calorimetrically. It was found, that larger ferrimagnetic particles showed higher heating performance than smaller superparamagnetic ones. In the transition range between superparamagnetism and ferrimagnetism, samples with a broader size distribution provided higher heating power than narrow size distributed particles of comparable mean size. Here presented particles showed promising properties for a possible application in magnetic hyperthermia.     

Key factor affecting the structural and textural properties of ZSM-5/MCM-41 composite

ZSM-5/MCM-41 micro/mesoporous composite materials were synthesized by the hydrothermal technique with alkali-treated ZSM-5 zeolite as source of silica and aluminum and characterized by various physico-chemical techniques such as X-ray diffraction (XRD), nitrogen sorption at 77 K, transmission electronic microscopy (TEM), FTIR spectroscopy and NH₃ temperature programmed desorption (TPD) techniques. The effect of concentration of CTAB in the synthesis of these solids has been investigated, the mesopore volume, surface area and surface acidity decrease with increasing the concentration of CTAB. Increasing the CTAB concentration causes the recrystallization of zeolite ZSM-5 and it disadvantage the formation of mesoporous materials MCM-41. The catalytic activity of ZSM-5/MCM-41 materials has been evaluated in the Friedel–Crafts acylation of anisole with benzoyl chloride as alkylating agent. The results revealed the reaction to be influenced by surface area, pore volume and surface acidity.     

TMOS based water repellent silica thin films by co-precursor method using TMES as a hydrophobic agent

The present paper describes the room temperature synthesis of dip coated water repellent silica coatings on glass substrates using trimethylethoxysilane (TMES) as a co-precursor. Silica sol was prepared by keeping the molar ratio of tetramethoxysilane (TMOS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:29.27:2.09 respectively, with 0.5 M NH₄OH throughout the experiments and the TMES/TMOS molar ratio (M) was varied from 0 to 3.8. It was found that with an increase in M value, the roughness and hydrophobicity of the films increased, however the optical transmission decreased from 93% to 57% in the visible range. The hydrophobic silica films retained their hydrophobicity up to a temperature of 250 °C and above this temperature the films became hydrophilic. The hydrophobic silica thin films were characterized by taking into consideration the surface roughness studies, Fourier transform infrared (FT-IR) spectroscopy, percentage of optical transmission, scanning electron microscopy (SEM) and contact angle measurements.     

Investigation on femtosecond laser irradiation energy in inducing hydrophobic polymer surfaces

This study investigates the use of ultrashort femtosecond laser pulses to induce hydrophobic properties on PMMA surfaces. The modification of surface wetting property exhibits a strong dependence on the amount of energy deposited on the PMMA surface. A simple equation has been deduced from the laser parameters to express the energy deposition. It was revealed that water contact angle (WCA) of more than 120°, with a maximum of around 125°, could be achieved when the total energy deposited per unit area on the PMMA surface ranged from 600 J/cm² to 900 J/cm² at an energy deposition rate of around 50 J/cm²/s. Beyond this range, WCA reduced with increasing amount of energy deposition. Furthermore, with higher energy deposition rate or higher laser fluence, total energy required to induce hydrophobic surfaces was reduced. Under different energy deposition, the quantity of polar groups or non-polar groups induced was responsible for the changes in WCA and thus the different surface hydrophobicity.     

Antibacterial activities of surface modified electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) fibrous membranes

Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) membrane, with its excellent chemical and mechanical properties, has good potential for broad applications. However, due to its hydrophobic nature, microbial colonization is commonly encountered. In this work, electrospun PVDF-HFP fibrous membranes were surface modified by poly(4-vinyl-N-alkylpyridinium bromide) to achieve antibacterial activities. The membranes were first subjected to plasma pretreatment followed by UV-induced surface graft copolymerization of 4-vinylpyridine (4VP) and quaternization of the grafted pyridine groups with hexylbromide. The chemical composition of the surface modified PVDF-HFP electrospun membranes was studied by X-ray photoelectron spectroscopy (XPS). The morphology and mechanical properties of pristine and surface modified PVDF-HFP fibrous membranes were characterized by scanning electron microscopy (SEM) and tensile test, respectively. The antibacterial activities of the modified electrospun PVDF-HFP fibrous membranes were assessed against Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli). The results showed that the PVDF-HFP fibrous membranes modified with quaternized pyridinium groups are highly effective against both bacteria with killing efficiency as high as 99.9999%.     

Ultrasonic pretreatment improves the gelation properties of low-salt Penaeus vannamei (Litopenaeus vannamei) surimi

The effects of different ultrasonic pretreatments (120–600 W, 20 min; 360 W, 10–30 min) on the gel properties of shrimp surimi were investigated. Gel properties and protein functional properties were analysed to clarify the mechanism of action of ultrasound. The gel strength, water holding capacity and surface hydrophobicity of shrimp surimi gel increased initially and then decreased with the increase in ultrasound power or time, but the change in total sulfhydryl content showed the opposite trend, which indicated that proper ultrasound pretreatment could improve the gel properties of shrimp surimi, expand the protein to a greater extent and expose more SH groups and hydrophobic groups. According to scanning electron microscopy observation, ultrasound made shrimp surimi gel form a denser gel network. Fourier transform infrared analysis indicated that the α-helix content in shrimp surimi gel decreased initially and then increased with the increase of in ultrasound power or time, whereas the change in β-sheet content showed the opposite trend. And the protein was the most stable in 360 W/20 min pretreatment. SDS-PAGE patterns showed that proper ultrasound inhibited the degradation of actin and troponin C. In addition, dynamic rheology illustrated that the G′ values of the ultrasonic pretreatment group were higher than that of the control group, indicating that ultrasound could improve the elasticity and stability of shrimp surimi gel. The results suggested that the shrimp surimi gel pretreated by 360 W/20 min ultrasound showed the best gel properties. Furthermore, the correlation between the indexes affecting the properties of the gel was analyzed. This study provides a new technical means to improve the gel properties of shrimp surimi.     

Ultrasound pretreatment prior to spray drying improve the flowability and water sorption properties of micellar casein concentrate

This research investigated the effect of ultrasound (US) pretreatment prior to spray drying on the powder flow and moisture sorption behaviour of micellar casein concentrate (MCC). MCC produced from skim milk microfiltration was sonicated at energy intensity of 0 (control), 47 J/mL (S-2000), 62 J/mL (S-3000) and 76 J/mL (S-4000). The results revealed that US pretreatment significantly increased the average particle size (D50) from 82.46 μm to 100.73 μm and reduced the surface fat content from 19.2% to 13.8%, resulting in decreased basic flow energy, cake energy and cohesion. Besides, the US treated samples showed relatively poor ability to acquire the moisture from the atmosphere than the control. Protein structure analysis showed that α-helix decreased with enhanced US power, while β-sheet and surface hydrophobicity increased, implying hydrophobic groups were exposed and water sorption rate was impeded. As a result, US pretreatment can improve the powder flow and potentially reduce the negative effect of cake formation at high humidity.     

Transparent Superhydrophobic silica coatings on glass by sol-gel method

Wetting behavior of solid surfaces is a key concern in our daily life as well as in engineering and science. In the present study, we demonstrate a simple dip coating method for the preparation of Thermally stable, transparent superhydrophobic silica films on glass substrates at room temperature by sol-gel process. The coating alcosol was prepared by keeping the molar ratio of methyltriethoxysilane (MTES), trimethylmethoxysilane (TMMS), methanol (MeOH), water (H₂O) constant at 1:0.09:12.71:3.58, respectively with 13 M NH₄OH throughout the experiments and the films were prepared with different deposition time varied from 5 to 25 h. In order to improve the hydrophobicity of as deposited silica films, the films were derivatized with 10% trimethylchlorosilane (TMCS) as a silylating agent in hexane solvent for 24 h. Enhancement in wetting behavior was observed for surface derivatized silica films which showed a maximum static water contact angle (172°) and minimum sliding angle (2°) for 25 h of deposition time. The superhydrophobic silica films retained their superhydrophobicity up to a temperature of 550 °C. The silica films were characterized by field emission scanning electron microscopy (FE-SEM), surface profilometer, Fourier transform infrared (FT-IR) spectroscopy, thermo-gravimetric and differential thermal analysis (TG-DTA), percentage of optical transmission, water contact angle measurements. The imperviousness behavior of the films was tested with various acids.     

Magnetic structure and collective Jahn-Teller distortions in nanostructured particles of CuFe2O4

The aim of the present work is to compare the structural, the composition and chemical state of the surface and magnetic properties of different nanosized CuFe₂O₄ powders exhibiting collective Jahn-Teller effect. The samples under examination consist of edged nanosized particles (needle like) with average length 1300 ± 20 nm and diameter 300 ± 20 nm obtained after high temperature synthesis, and superparamagnetic (at room temperature) spherical particles (d = 6 ± 2 nm), obtained by soft chemistry techniques. The surface composition of the particles was investigated by X-ray photoelectron spectroscopy (XPS). Mössbauer spectroscopy (MöS), including at high magnetic field up to 5 T and 4.2 K, was used for characterization of cation distribution in the samples. The data yielded by the XPS and MöS analyses for spherical nanosized particles led us to the assumption for the existence of a Jahn-Teller effect gradient—from the B-sublattice on the surface to a compensation of the tetragonal distortion in the two sublattices in the core. The analysis of the contribution of the anisotropy energy in edged and spherical nanoparticles shows that it must be considered as an effective value reflecting the influence of the individual factors depending on the particle shape and surface.     

Melting and crystallization transitions in organically modified layered silicates studied with differential scanning calorimetry

Melting and crystallization behaviors of the monolayers in the surface modified layered silicates were studied with differential scanning calorimetry. The layered silicates with different layer charge densities were used for the purpose. The ammonium ions forming the monolayer were also varied according to their chemical architecture, chain length and number of chains in the molecular structure. The quality of surface modification of the mineral was quantified using high resolution thermo-gravimetric analysis. At an optimum combination of the cross-sectional area of the ions, chain length as well as chain density, ordered monolayers are formed on the surface which turn to disordered state at a temperature corresponding to the melting of the ordered structure. These transitions are reproducible in nature but may require longer cooling times to regenerate again. The heat flow to the modified mineral (corresponding to melt enthalpy) increased on increasing the chain length as well as chain density, however, the transition temperatures decreased with increasing chain density in the surface modification molecules. The modified minerals were also hygroscopic in nature with first heating cycles showing the evaporation of water, however, with increasing chain length and chain density in the surface modification, the extent of hydrophobicity of the minerals increased. The effect of chemical architecture was not significant as it seemed to be driven by the chain length and capability of the modification molecules to crystallize in general or on the processing conditions used.