Oxygen plasma functionalization of poly(p-phenilene sulphide)

Surface effects during plasma activation of poly(p-phenilene sulphide)—PPS have been studied. Samples that were exposed to weakly ionized highly dissociated oxygen plasma created an inductively coupled radiofrequency discharge with the power of 100 W. The electron density and temperature were measured with a double Langmuir probe and were 4 × 10¹⁵ m⁻³ and 3 eV, respectively, while the neutral atom density was measured with a fiber optics catalytic probe and was 4 × 10²¹ m⁻³. The surface tension was determined by measuring the contact angle of deionized water, while the appearance of surface functional groups was detected by XPS. The surface tension of untreated PPS was 7 × 10⁻³ N/m or/and increased to 7 × 10⁻² N/m in few seconds of plasma treatment. It remained fairly constant for longer plasma treatments. The XPS survey spectrum showed little oxygen on untreated samples, but its concentration increased to about 20 at.% in few seconds. Detailed high resolution XPS C 1s peak showed that the carbon was left fairly stable during plasma treatment. The main functional groups formed were rather sulphate in sulphite groups, as determined from high resolution S 2p peak. Namely, a strong transition from sulphide to sulphate state of sulfur was observed. The spontaneous deactivation of the polymer surface was measured as well. The deactivation was fairly logarithmic with the characteristic decay time of several hours.     

Short-time plasma surface modification of HDPE powder in a Plasma Downer Reactor - process, wettability improvement and ageing effects

The effectiveness of improving the wettability of HDPE powders within less than 0.1 s by plasma surface modification in a Plasma Downer Reactor is investigated. A correlation is revealed between the XPS results (O/C-ratio) and the wettability (contact angle, polar surface tension by capillary rise method). The O₂-content in the plasma feed gas has been adjusted for best wettability properties. XPS results indicate the formation of CO and COOH functional groups on the powder surface. The O/C-ratio increased from 0.0 (no oxygen on the non-treated powder) up to 0.15 for the plasma treated HDPE powder surface. With pure O₂-plasma treatment, a water contact angle reduction from >90° (no water penetration into the untreated PE powder) down to 65° was achieved. The total surface free energy increased from 31.2 to 45 mN/m. Ageing of treated powders occurs and proceeds mostly within the first 7 days of storage. Contact angle measurements and O1s/O2s intensity ratio data support that ageing is mainly a diffusion-controlled process. Nevertheless, XPS results show the presence of oxygen functional groups even after 40 days, which explains why the powder is still dispersible in water without any addition of surfactants.     

The water/graphitic-carbon interaction energy

The water/graphitic-carbon interaction energy was obtained for a sample having a water surface site adsorption density of 13.3 μmol m⁻². The interaction energy was determined from the spreading pressure of water, its surface tension and the water contact angle and using a formula obtained by the combination of the Young equation with a general equation of pair interaction. The values obtained for contact angles 42° and 86° are 7.63 and 7.18 kJ mol⁻¹ of water are similar to the water binding energies obtained from molecular dynamic simulations of water droplets on a graphite surface: 6.7-8.33 kJ mol⁻¹.     

Studies on surface graft polymerization of acrylic acid onto PTFE film by remote argon plasma initiation

The graft polymerization of acrylic acid (AAc) was carried out onto poly(tetrafluoroethylene) (PTFE) films that had been pretreated with remote argon plasma and subsequently exposed to oxygen to create peroxides. Peroxides are known to be the species responsible for initiating the graft polymerization when PTFE reacts with AAc. We chose different parameters of remote plasma treatment to get the optimum condition for introducing maximum peroxides (2.87 × 10⁻¹¹ mol/cm²) on the surface. The influence of grafted reaction conditions on the grafting degree was investigated. The maximum grafting degree was 25.2 μg/cm². The surface microstructures and compositions of the AAc grafted PTFE film were characterized with the water contact angle meter, Fourier-transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Contact angle measurements revealed that the water contact angle decreased from 108° to 41° and the surface free energy increased from 22.1 × 10⁻⁵ to 62.1 × 10⁻⁵ N cm⁻¹ by the grafting of the AAc chains. The hydrophilicity of the PTFE film surface was greatly enhanced. The time-dependent activity of the grafted surface was better than that of the plasma treated film.     

Biocompatibility of polypropylene non-woven fabric membrane via UV-induced graft polymerization of 2-acrylamido-2-methylpropane sulfonic acid

This work described the graft polymerization of a sulfonic acid terminated monomer, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), onto the surface of polypropylene non-woven (NWF PP) membrane by O₂ plasma pretreatment and UV-induced photografting method. The chemical structure and composition of the modified surfaces were analyzed by FTIR-ATR and XPS, respectively. The wettability was investigated by water contact angle and equilibrium water adsorption. And the biocompatibility of the modified NWF PP membranes was evaluated by protein adsorption and platelet adhesion. It was found that the graft density increased with prolonging UV irradiation time and increasing AMPS concentration; the water contact angles of the membranes decreased from 124° to 26° with the increasing grafting density of poly(AMPS) from 0 to 884.2 μg cm⁻², while the equilibrium water adsorption raised from 5 wt% to 75 wt%; the protein absorption was effectively suppressed with the introduction of poly(AMPS) even at the low grafting density (132.4 μg cm⁻²); the number of platelets adhering to the modified membrane was dramatically reduced when compared with that on its virgin surface. These results indicated that surface modification of NWF PP membrane with AMPS was a facile approach to construct biocompatible surface.     

Organic modification of TEOS based silica aerogels using hexadecyltrimethoxysilane as a hydrophobic reagent

The experimental results on the synthesis and characterization of tetraethoxysilane (TEOS) based hydrophobic silica aerogels using hexadecyltrimethoxysilane (HDTMS) as a hydrophobic reagent by two step sol-gel process, are described. The molar ratio of tetraethoxysilane (TEOS), methanol (MeOH), acidic water (0.001 M, oxalic acid) and basic water (10 M, NH₄OH) was kept constant at 1:55:3.25:1.25 and the molar ratio of HDTMS/TEOS (M) was varied from 0 to 28.5 × 10⁻². The organic modification was confirmed by infrared spectroscopic studies, and the hydrophobicity of the aerogels was tested by the contact angle measurements. The maximum contact angle of 152° was obtained for M = 22.8 × 10⁻². The aerogels retained the hydrophobicity up to a temperature of 240 °C and above this temperature the aerogels became hydrophilic. The aerogels were characterized by the thermal conductivity, density, contact angle measurements, optical transmission and scanning electron micrographs.     

Field electron emission improvement of ZnO nanorod arrays after Ar plasma treatment

Vertically well-aligned single crystal ZnO nanorod arrays were synthesized and enhanced field electron emission was achieved after radio-frequency (rf) Ar plasma treatment. With Ar plasma treatment for 30 min, flat tops of the as-grown ZnO nanorods have been etched into sharp tips without damaging ZnO nanorod geometrical morphologies and crystallinity. After the Ar ion bombardment, the emission current density increases from 2 to 20 μA cm⁻² at 9.0 V μm⁻¹ with a decrease in turn-on voltage from 7.1 to 4.8 V μm⁻¹ at a current density of 1 μA cm⁻², which demonstrates that the field emission of the as-grown ZnO nanorods has been efficiently enhanced. The scanning electron microscopy (SEM) results, in conjunction with the results of transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence observation, are used to investigate the mechanisms of the field emission enhancement. It is believed that the enhancements can be mainly attributed to the sharpening of rod tops, and the decrease of electrostatic screening effect.     

Topological and chemical investigation on super-hydrophobicity of PTFE surface caused by ion irradiation

Super-hydrophobic PTFE surfaces were obtained by irradiation of 200 keV Xe⁺ ion with the fluence of 6.2×10¹³ ions/cm². The contact angle of water on such surface is as large as 161±3°. SEM and XPS were used to investigate how the topological and chemical changes affect the wettability of the irradiated surface. Needle like structures at nanometer scale caused by irradiation are considered to be the reason of the super-hydrophobicity. The formation of oxygen containing group and defluorination effect on the treated surface are inferred to have negative contribution to the hydrophobic optimization of PTFE surface.     

Ion-induced self-organized ripple patterns on graphite and diamond surfaces

In order to investigate the allotropic effect on ripple pattern formation, highly oriented pyrolytic graphite (HOPG) and single crystalline diamond were irradiated with 10-200 keV Xe⁺ at an incident angle of 60° with respective to the surface normal. The irradiation fluence was 2 × 10¹⁷ cm⁻² for all irradiations. Ripple patterns were observed on both HOPG and diamond surfaces. However, large differences in ripple wavelengths, amplitudes and surface roughnesses between HOPG and diamond were recognized. The reason for these differences is discussed.     

Fabrication of a superhydrophobic ZnO nanorod array film on cotton fabrics via a wet chemical route and hydrophobic modification

A superhydrophobic ZnO nanorod array film on cotton substrate was fabricated via a wet chemical route and subsequent modification with a layer of n-dodecyltrimethoxysilane (DTMS). The as-obtained cotton sample was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), scanning probe microscope (SPM) and X-ray photoelectron spectroscopy (XPS), respectively. The wettability of the cotton fabric sample was also studied by contact angle measurements. The modified cotton fabrics exhibited superhydrophobicity with a contact angle of 161° for 8 μL water droplet and a roll-off angle of 9° for 40 μL water droplet. It was shown that the proper surface roughness and the lower surface energy both played important roles in creating the superhydrophobic surface, in which the Cassie state dominated.     

Characterization of Ti6Al4V implant surface treated by Nd:YAG laser and emery paper for orthopaedic applications

A more noble and biocompatible Ti alloy was achieved at fluence of 140 J cm⁻² where the implant indicated a higher degree of hardness (825HV), higher corrosion resistance (−0.21 V) and highest hydrophilicity (i.e. θ_c = 37°) compared with 70° of the control sample. These values corresponded to 58 and 39 mN m⁻¹ of surface tension respectively. The laser treated samples at 140 J cm⁻² showed higher wettability characteristics than mechanically roughened surface. Cell growth and their spreading condition in a specific area were analyzed by SEM and Image J Program software. Clearly, more cells were attached (1.2 × 10⁵) to and spread (488 μm²) over the surface at 140 J cm⁻² than in any other condition. Pathologically, the treated samples indicated no sign of infection.     

Wettability of ZnO: A comparison of reactively sputtered; thermally oxidized and vacuum annealed coatings

We have studied the wettability of sputter deposited ZnO, thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings. The X-ray diffraction patterns showed the formation of hexagonal-wurtzite structure of ZnO, which was further confirmed by micro-Raman spectroscopy data. The X-ray photoelectron spectroscopy data indicated that the sputter deposited ZnO coatings were more stoichiometric than thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings. The wettability measurements indicated that water contact angles of 158.5° and 155.2° with sliding angles of 2° and 4° were achieved for thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings, respectively. The superhydrophobicity observed in thermally oxidized Zn-ZnO and vacuum annealed coatings is attributed to the nanorod cluster like morphology along with the presence of high fraction of micron scale air pockets. The water droplet on such surfaces is mostly in contact with air pockets rather than solid surface, leading to high contact angle. Whereas, the sputter deposited ZnO coatings exhibited a maximum water contact angle of 110.3°. This is because the sputter deposited ZnO coatings exhibited a densely packed nanograin-like microstructure without any air pockets. The work of adhesion of water was very low for thermally oxidized Zn-ZnO (5.06 mJ/m²) and vacuum annealed ZnO coatings (6.71 mJ/m²) when compared to reactively sputtered ZnO coatings (90.41 mJ/m²). The apparent surface free energy (SFE) for these coatings was calculated using Neumann method and the SFE values for sputter deposited ZnO, thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings were 32.95, 23.21 and 18.78 mJ/m², respectively.     

Surface modification of Sylgard 184 polydimethylsiloxane by 254 nm excimer radiation and characterization by contact angle goniometry, infrared spectroscopy, atomic force and scanning electron microscopy

The modification of polydimethylsiloxane (PDMS) by narrow band 254 nm excimer radiation under a nitrogen atmosphere was characterized by contact angle goniometry, attenuated total reflectance infrared spectroscopy, atomic force and scanning electron microscopy. UV irradiation results in the formation of the carboxylic acids that influences the wettability of the surface. Continued exposure results in the formation of an inorganic surface (SiO_x (1 < x < 2)) which hinders the ability to continually increase the wettability. The continuity of this inorganic layer is disrupted by the formation of surface cracks. These results have implications in the fabrication and chemical modification of microfluidic or micro-electro-mechanical systems.     

Preparation of activated carbons from cherry stones by activation with potassium hydroxide

Using cherry stones, the preparation of activated carbon has been undertaken in the present study by chemical activation with potassium hydroxide. A series of KOH-activated products was prepared by varying the carbonisation temperature in the 400-900 °C range. Such products were characterised texturally by gas adsorption (N₂, −196 °C), mercury porosimetry, and helium and mercury density measurements. FT-IR spectroscopy was also applied. The carbons prepared as a rule are microporous and macroporous solids. The degree of development of surface area and porosity increases with increasing carbonisation temperature. For the carbon heated at 900 °C the specific surface area (BET) is 1624 m² g⁻¹, the micropore volume is 0.67 cm³ g⁻¹, the mesopore volume is 0.28 cm³ g⁻¹, and the macropore volume is 1.84 cm³ g⁻¹.     

Low-temperature oxidation of SiGe by liquid-phase deposition

Low-temperature silicon dioxide (SiO₂) films were grown on silicon germanium (SiGe) surfaces using the liquid-phase deposition (LPD) method. The growth solutions of LPD-SiO₂ are hydrofluorosilicic acid (H₂SiF₆) and boric acid (H₃BO₃). It was found that the growth rate increases with increasing temperature and concentration of H₃BO₃. The Auger electron spectroscopy profile shows that no pileup of Ge atoms occurs at the interface of SiO₂/SiGe after the LPD-SiO₂ growth. Al/LPD-SiO₂/p-SiGe MOS capacitors were prepared to determine capacitance-voltage (C-V) and current-voltage (I-V) characteristics. In our experiments, a low leakage current density of 8.69 × 10⁻⁹ A/cm² under a 2 MV/cm electric field was observed. Such a value is much smaller than those of plasma- and thermal-oxides as a result of no plasma damage and a lower growth temperature. Moreover, lower oxide charges and interface charge densities of 3.82 × 10¹⁰ cm⁻² and 1.12 × 10¹¹ eV⁻¹ cm⁻², respectively, were achieved in our LPD-SiO₂ compared to direct photochemical-vapor-deposition-SiO₂.     

Chemical synthesis of nanocrystalline SnO2 thin films for supercapacitor application

Nanocrystalline SnO₂ thin films were deposited by simple and inexpensive chemical route. The films were characterized for their structural, morphological, wettability and electrochemical properties using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy techniques (SEM), transmission electron microscopy (TEM), contact angle measurement, and cyclic voltammetry techniques. The XRD study revealed the deposited films were nanocrystalline with tetragonal rutile structure of SnO₂. The FT-IR studies confirmed the formation of SnO₂ with the characteristic vibrational mode of Sn-O. The SEM studies showed formation of loosely connected agglomerates with average size of 5-10 nm as observed from TEM studies. The surface wettability showed the hydrophilic nature of SnO₂ thin film (water contact angle 9°). The SnO₂ showed a maximum specific capacitance of 66 F g⁻¹ in 0.5 Na₂SO₄ electrolyte at 10 mV s⁻¹ scan rate.     

PdSi based ohmic contact on n-InP

The electrical and microstructural properties of the PdSi based ohmic contacts on n-InP are discussed in the research. A low specific contact resistance of 2.25 × 10⁻⁶ Ω cm² is obtained on Au/Si/Pd/n-InP contact after rapid thermal annealing (RTA) at 450 °C for 30 s. The low contact resistance can be maintained at the order of 10⁻⁶ Ω cm² even up to 500 °C annealing. From the Auger analysis, it is found that both the outdiffusion of In and the indiffusion of Si into the InP surface occurred at the ohmic contact sample. The formation of the Pd₃Si compound lowered the barrier of the contact. The reactions between Pd and InP of the contact, forming In vacancies, and leading the doping of Si to the InP contact interface.     

Preparation of activated carbon from a renewable bio-plant of Euphorbia rigida by H2SO4 activation and its adsorption behavior in aqueous solutions

The use of activated carbon obtained from Euphorbia rigida for the removal of a basic textile dye, which is methylene blue, from aqueous solutions at various contact times, pHs and temperatures was investigated. The plant material was chemically modified with H₂SO₄. The surface area of chemically modified activated carbon was 741.2 m² g⁻¹. The surface characterization of both plant- and activated carbon was undertaken using FTIR spectroscopic technique. The adsorption process attains equilibrium within 60 min. The experimental data indicated that the adsorption isotherms are well described by the Langmuir equilibrium isotherm equation and the calculated adsorption capacity of activated carbon was 114.45 mg g⁻¹ at 40° C. The adsorption kinetics of methylene blue obeys the pseudo-second-order kinetic model and also followed by the intraparticle diffusion model up to 60 min. The thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated to estimate the nature of adsorption. The activation energy of the system was calculated as 55.51 kJ mol⁻¹. According to these results, prepared activated carbon could be used as a low-cost adsorbent to compare with the commercial activated carbon for the removal textile dyes from textile wastewater processes.     

Baking impact on photoelectrochemical cells performance of electrodeposited CdSe films

Cadmium selenide (CdSe) nanocrystalline thin films in the form of upright nanocones, perpendicular to substrate surface, are grown electrochemically onto a conducting and transparent indium-tin-oxide substrate at room temperature and impact of baking under oxygen flow on their structure, morphology, optical absorbance and dark-light photoelectrochemical cell performance is explored. Crystallinity improvement followed by enhancement in the surface roughness 11-19 nm and reduction in water contact angle from 60° to 22° (±0.2)° due to baking impact showed increase in crystallite size from 25 to 100 Å. Increase in current density from 0.07 to 5.61 mA/cm² after baking under oxygen flow has promoted the conversion efficiency to 0.5% from 0.007%.     

Chemical reaction of sputtered Cu film with PI modified by low energy reactive atomic beam

Polyimide (PMDA-ODA) surface was irradiated by low energy reactive atomic beam with energy 160-180 eV to enhance the adhesion with metal Cu film. O₂⁺ and N₂⁺ ions were irradiated at the fluence from 5 × 10¹⁵ to 1 × 10¹⁸ cm⁻². Wetting angle 78° of distilled deionized (DI) water for bare PI was greatly reduced down to 2-4° after critical ion flounce, and the surface energy was increased from 37 to 81.2 erg/cm. From the analysis of O 1s core-level XPS spectra, such improvement seemed to result from the increment of hydrophilic carbonyl oxygen content on modified PI surface. To see more carefully correlation of the peel strength with interfacial reaction between Cu and PI, flexible copper clad laminate with Cu (9 μm)/Cu (200 nm) on modified PI substrate (25 μm) was fabricated by successive sputtering and electroplating. Firstly, peel strength was measured by using t-test and it was largely increased from 0.2 to 0.5 kgf/cm for Ar⁺ only irradiated PI to 0.72-0.8 kgf/cm for O₂⁺ or N₂O⁺ irradiated PI. Chemical reaction at the interface was reasoned by analyzing C 1s, O 1s, N 1s, and Cu 2p core-level X-ray photoelectron spectroscopy over the as-cleaved Cu-side and PI side surface through depth profiling. From the C 1s spectra of cleaved Cu-side, by the electron transfer from Cu to carbonyl oxygen, carbonyl carbon atom became less positive and as a result shifted to lower binding energy not reaching the binding energy of C₂ and C₃. The binding energy shift of the peak C₄ as small as 1.7 eV indicates that carbonyl oxygen atoms were not completely broken. From the analysis of the O 1s spectra, it was found that new peak at 530.5 eV (O₃) was occurred and the increased area of the peak O₃ was almost the same with reduced area of the peak carbonyl oxygen peak O₁. Since there was no change in the relative intensity of ether oxygen (O₂) to carbonyl oxygen (O₁), and thus O₃ was believed to result from Cu oxide formation via a local bonding of Cu with carbonyl oxygen atoms. Moreover, from X-ray induced Auger emission spectra Cu LMM which was very sensitive to chemical bonding, Cu oxide or CuOC complex formation instead of CuNO complex was clearly identified by the observation of the peak at 570 eV at higher 2 eV than that of metal Cu. In conclusion, when Cu atoms were sputtered on modified PI by low energy ion beam irradiation, it can be suggested that two Cu atoms locally reacted with carbonyl oxygen in PMDA units and formed Cu⁺O⁻C complex linkage without being broken from carbon atoms and thus the chemically bound Cu was in the form of Cu₂O.