Effect of current density on the microstructure and corrosion behaviour of plasma electrolytic oxidation treated AM50 magnesium alloy

Plasma electrolytic oxidation (PEO) of an AM50 magnesium alloy was accomplished in a silicate-based electrolyte using a DC power source. Coatings were produced at three current densities, i.e. 15 mA cm⁻², 75 mA cm⁻², and 150 mA cm⁻² and were characterised for thickness, roughness, microstructural morphology, phase composition, and corrosion resistance. Even though the 15 min treated coatings produced at higher current density levels were thicker, they showed poor corrosion resistance when compared to that of the coatings obtained at 15 mA cm⁻². Short-term treatments (2 min and 5 min) at 150 mA cm⁻² yielded coatings of thickness and corrosion resistance comparable to that of the low current density coatings. The superior corrosion resistance of the low thickness coatings is attributed to the better pore morphology and compactness of the layer.     

Effect of pulse repetition rate and number of pulses in the analysis of polypropylene and high density polyethylene by nanosecond infrared laser induced breakdown spectroscopy

Pulse repetition rates and the number of laser pulses are among the most important parameters that do affect the analysis of solid materials by laser induced breakdown spectroscopy, and the knowledge of their effects is of fundamental importance for suggesting analytical strategies when dealing with laser ablation processes of polymers. In this contribution, the influence of these parameters in the ablated mass and in the features of craters was evaluated in polypropylene and high density polyethylene plates containing pigment-based PbCrO₄. Surface characterization and craters profile were carried out by perfilometry and scanning electron microscopy. Area, volume and profile of craters were obtained using Taylor Map software. A laser induced breakdown spectroscopy system consisted of a Q-Switched Nd:YAG laser (1064 nm, 5 ns) and an Echelle spectrometer equipped with ICCD detector were used. The evaluated operating conditions consisted of 10, 25 and 50 laser pulses at 1, 5 and 10 Hz, 250 mJ/pulse (85 J cm⁻²), 2 μs delay time and 6 μs integration time gate. Differences in the topographical features among craters of both polymers were observed. The decrease in the repetition rate resulted in irregular craters and formation of edges, especially in polypropylene sample. The differences in the topographical features and ablated masses were attributed to the influence of the degree of crystallinity, crystalline melting temperature and glass transition temperature in the ablation process of the high density polyethylene and polypropylene. It was also observed that the intensities of chromium and lead emission signals obtained at 10 Hz were two times higher than at 5 Hz by keeping the number of laser pulses constant.     

Large aperture tapered fiber phase conjugate mirror in MOPA laser systems with high repetition rate and high pulse energy

A large aperture tapered fused silica fiber phase conjugate mirror with a maximum 50.7% stimulated Brillouin scattering (SBS) reflectivity is presented, which is operated with 400 Hz pulse repetition rate and 36.5 mJ input pulse energy. To the best of our knowledge, it is the first time that over 50% SBS reflectivity is achieved by using solid-state phase conjugate mirror under such high pulse repetition rate and high pulse energy. With much higher pulse repetition rate of 500 and 1000 Hz, the maximum SBS reflectivity is 41.2% and 33.3%, respectively. A single-longitudinal-mode Nd:YAG laser is experimentally studied with master oscillator power amplifier (MOPA) scheme using such a tapered fiber as a phase conjugate mirror. A 101 mJ pulse energy is achieved at 400 Hz repetition rate, with a pulse width of 6 ns and a M² factor of less than 2. The corresponding peak power reaches 16.8 MW.     

Thermal behavior and catalytic activity in naphthalene destruction of Ce-, Zr- and Mn-containing oxide layers on titanium

The present paper is devoted to studies of the composition and surface structure, including those after annealing at high temperatures, and catalytic activity in the reaction of naphthalene destruction of Ce-, Zr- and Mn-containing oxide layers on titanium obtained by means of the plasma electrolytic oxidation (PEO) method. The composition and structure of the obtained systems were investigated using the methods of X-ray phase and energy dispersive analysis and scanning electron microscopy (SEM). It was demonstrated that Ce- and Zr- containing structures had relatively high thermal stability: their element and phase compositions and surface structure underwent virtually no changes after annealing in the temperature range 600-800 °C. Annealing of Ce- and Zr-containing coatings in the temperature range 850-900 °C resulted in substantial changes of their surface composition and structure: a relatively homogeneous and porous surface becomes coated by large pole-like crystals. The catalytic studies showed rather high activity of Ce- and Zr-containing coatings in the reaction of naphthalene destruction at temperatures up to 850 °C. Mn-containing structures of the type MnO_x + SiO₂ + TiO₂/Ti have a well-developed surface coated by “nano-whiskers”. The phase composition and surface structure of manganese-containing layers changes dramatically in the course of thermal treatment. After annealing above 600 °C nano-whiskers vanish with formation of molten structures on the surface. The Mn-containing oxide systems demonstrated lower conversion degrees than the Ce- and Zr-containing coatings, which can be attributed to substantial surface modification and formation of molten manganese silicates at high temperatures.     

Dry sliding wear behaviour of magnesium oxide and zirconium oxide plasma electrolytic oxidation coated magnesium alloy

Two types of PEO coatings, one consisting of magnesium oxide (MgO) and the other comprising zirconium oxide (ZrO₂) as the main phase composition were produced on AM50 magnesium alloy from alkaline and acidic electrolytes, respectively. The ZrO₂ coating was found to be spongy and thicker with a higher roughness, whilst the relatively more compact MgO coating was having contrasting features. In the dry sliding oscillating wear tests under two different loads viz., 2 N and 5 N, the ZrO₂ coating exhibited a very poor wear resistance. The MgO coating showed an excellent resistance to sliding wear under 2 N load; however, the load bearing capacity of the coating was found to be insufficient to resist the wear damage under 5 N load. The higher specific wear rates of the MgO coating under 5 N load and that of the ZrO₂ coating under 2 N and 5 N loads were attributed to the poor load bearing capacity and a three-body-abrasive wear mechanism.     

Preparation and characterization of boron nitride coatings on carbon fibers from borazine by chemical vapor deposition

Boron nitride (BN) coatings were deposited on carbon fibers by chemical vapor deposition (CVD) using borazine as single source precursor. The deposited coatings were characterized by scanning electron microscopy (SEM), Auger electron spectroscopy (AES), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. The effect of temperatures on growth kinetics, morphology, composition and structure of the coatings was investigated. In the low temperature range of 900 °C-1000 °C, the growth rate increased with increasing temperature complying with Arrhenius law, and an apparent active energy of 72 kJ/mol was calculated. The coating surface was smooth and compact, and the coatings uniformly deposited on individual fibers of carbon fiber bundles. The growth was controlled by surface reaction. At 1000 °C, the deposition rate reached a maximum (2.5 μm/h). At the same time, the limiting step of the growth translated to be mass-transportation. Above 1100 °C, the growth rate decreased drastically due to the occurrence of gas-phase nucleation. Moreover, the coating surface became loose and rough. Composition and structure examinations revealed that stoichiometric BN coatings with turbostratic structure were obtained below 1000 °C, while hexagonal BN coatings were deposited above 1100 °C. A penetration of carbon element from the fibers to the coatings was observed.     

Effects of pulse electrodeposition parameters on the properties of Ni-TiO2 nanocomposite coatings

The aim of this study is to investigate the effects of pulse electrodeposition parameters on the properties of nickel-titania composite coatings electrodeposited from a nickel Watts type bath. The effects of average current density, frequency and duty cycle on the surface morphology, crystal size, preferred orientation of the deposits and the amount of embedded nano-TiO₂ particles in the composite coatings were investigated. The results represented the optimum amount of average current density (e.g., 4 A dm⁻²) for obtaining the highest volume percentage of the incorporated titania particles and subsequently the maximum microhardness. Moreover, by increasing the frequency up to 10 Hz while reducing the duty cycle to 10% at constant peak current density, the volume percentage of particles increased to about 7% which is almost twice as much the volume percentage as deposited particles in direct current method. According to the results the composite coating exhibited obviously [1 0 0] + [2 1 1] as preferred orientation at low pulse frequency and the diffraction intensity of the [2 1 1] fiber orientation is increased, probably due to the pH increase adjacent to the electrolyte/cathode interface at higher frequencies. Also, it has been found that by reduction in the duty cycle, more titania particles were incorporated in the composite coatings and this promoted the nickel crystals growth on [1 0 0] planes and consequently the coatings preferred orientation changed from the [2 1 1] to [1 0 0] + [2 1 1] planes.     

Effects of duty ratio at low frequency on growth mechanism of micro-plasma oxidation ceramic coatings on Ti alloy

The aim of this work is to study the effects of duty ratio on the growth mechanism of the ceramic coatings on Ti-6Al-4V alloy prepared by pulsed single-polar MPO at 50 Hz in NaAlO₂ solution. The phase composition of the coatings was studied by X-ray diffraction, and the morphology and the element distribution in the coating were examined through scanning electron microscopy and energy dispersive spectroscopy. The thickness of the coatings was measured by eddy current coating thickness gauge. The corrosion resistance of the coated samples was examined by linear sweep voltammetry technique in 3.5% NaCl solution. The changes of the duty ratio (D) of the anode process led to the changes of the mode of the spark discharge during the pulsed single-polar MPO process, which further influenced the structure and the morphology of the ceramic coatings. The coatings prepared at D = 10% were composed of a large amount of Al₂TiO₅ and a little γ-Al₂O₃ while the coatings prepared at D = 45% were mainly composed of α-Al₂O₃ and γ-Al₂O₃. The coating thickness and the roughness were both increased with the increasing D due to the formation of Al₂O₃. The formation of Al₂TiO₅ resulted from the spark discharge due to the breakdown of the oxide film, while the formation of Al₂O₃ resulted from the spark discharge due to the breakdown of the vapor envelope. The ceramic coatings improved the corrosion resistance of Ti-6Al-4V alloy. And the surface morphology and the coating thickness determined the corrosion resistance of the coated samples prepared at D = 45% was better than that of the coated samples prepared at D = 10%.     

Structural, thermal and optical studies of mechanical alloyed Ga40Se60 mixture

A mixture of elemental Ga and Se with the nominal composition Ga₄₀Se₆₀ was submitted to the Mechanical alloying technique and their structural, thermal and optical properties were followed by X-ray diffraction, differential thermal analysis, photoacoustic spectroscopy, UV-VIS‐NIR absorbance spectroscopy and Raman spectroscopy techniques. After 10 h of milling the X-ray pattern showed monoclinic Ga₂Se₃ phase nucleation, which is in the nanometric form, and also a minority amorphous phase. The DSC results showed exothermic reactions between 430 and 720 K attributed to amorphous-crystalline phase transition and structural relaxation of Ga₂Se₃ phase. Based on this a small amount of the as-milled sample was annealed at 723 K. Its XRD pattern showed evidences of grain growth, reduction of the interfacial component, as well as, disappearance of the amorphous phase. The annealing process induced thermal diffusivity increasing, while the optical band gap energy and Raman profile remained practically unchanged.     

Effect of sintering temperature on mechanical behaviour and bioactivity of sol-gel synthesized bioglass-ceramics using rice husk ash as a silica source

Bioglass-ceramics with SiO₂-Na₂O-CaO composition was prepared by sol-gel method using rice husk ash as a silica source. Material was sintered at different temperatures ranging from 900 to 1050 °C for 2 h. Phase-formation behaviour, densification characteristics, and mechanical strength of glass-ceramics were investigated. The material sintered at 1000 °C showed a good mechanical strength. Mechanical properties were correlated with microstructural features. Both in vitro bioactivity and biodegradability of sintered material were investigated by incubating in simulated body fluid and Tris buffer solution, respectively. Scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction were used to investigate the surface deposition during body fluid incubation. Both bioactivity and degradability decreased with increase in sintering temperature.     

Electrochemically assisted co-deposition of calcium phosphate/collagen coatings on carbon/carbon composites

Calcium phosphate (CaP)/collagen coatings were prepared on the surface of carbon/carbon (C/C) composites by electrochemically assisted co-deposition technique. The effects of collagen concentration in the electrolyte on morphology, structure and composition of the coatings were systematically investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The adhesive strength of the coatings was also evaluated by scratch tests and tensile bond tests. It was demonstrated that the coatings of three-dimensional collagen network structure was formed on the C/C composites from the electrolyte containing collagen. The surface of the collagen network was covered by uniform CaP aggregates. The coatings were actually composites of CaP and collagen. Hydroxyapatite (HA) was a favorable composition in the coatings with the increase of the collagen concentration in the electrolyte. The formed collagen network increased the cohesive and adhesive strength of the coatings. The adhesive strength between the coatings and substrates increased as the collagen concentration in the electrolyte increased. The coatings prepared at the collagen concentration of 500 mg/L in the electrolyte were not scraped off until the applied load reached 32.0 ± 2.2 N and the average tensile adhesive strength of the coatings was 4.83 ± 0.71 MPa. After C/C coated with composite coatings (500 mg/L) being immersed in a 10⁻³ M Ca (OH)₂ solution at 30-33 °C for 96 h, nano-structured HA/collagen coatings similar to the natural human bone were obtained on the C/C.     

Excimer laser processing of ZnO thin films prepared by the sol-gel process

ZnO thin films were prepared on soda-lime glass from a single spin-coating deposition of a sol-gel prepared with anhydrous zinc acetate [Zn(C₂H₃O₂)₂], monoethanolamine [H₂NC₂H₄OH] and isopropanol. The deposited films were dried at 50 and 300 °C. X-ray analysis showed that the films were amorphous. Laser annealing was performed using an excimer laser. The laser pulse repetition rate was 25 Hz with a pulse energy of 5.9 mJ, giving a fluence of 225 mJ cm⁻² on the ZnO film. Typically, five laser pulses per unit area of the film were used. After laser processing, the hexagonal wurtzite phase of zinc oxide was observed from X-ray diffraction pattern analysis. The thin films had a transparency of greater than 70% in the visible region. The optical band-gap energy was 3.454 eV. Scanning electron microscopy and profilometry analysis highlighted the change in morphology that occurred as a result of laser processing. This comparative study shows that our sol-gel processing route differs significantly from ZnO sol-gel films prepared by conventional furnace annealing which requires temperatures above 450 °C for the formation of crystalline ZnO.     

Injection-seeded Tm:YAG laser at room temperature

The solid-state, tunable, narrowband, high pulse energy and high reliability lasers are attractive source for LIDAR system. In this paper, we demonstrated a diode pumped injection-seeded 2 μm Tm:YAG laser. By inserting two F-P etalons into the laser cavity, linear-polarized single-frequency seed-laser was achieved at a wavelength of 2013 nm, with a maximum output power of 60 mW. Long-term and short-term frequency stability for the seed-laser were 1.27 × 10^− 7 and 97 Hz/μs, respectively. High power Q-switched laser was operated using a bowtie cavity, the bidirectional output of which was favorable for the injection-seeded. After injecting the seed-laser to the power-laser, single-frequency, nearly transform-limited pulsed 2 μm laser was obtained. As much as 2.0 mJ output energy was achieved at an operating repetition rate of 15 Hz, with a pulse width of 356.2 ns.     

Characterization of laser sealed coatings of yttria partially stabilized zirconia

The present paper reports an experimental investigation based on X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), and wavelength dispersive spectroscopy (WDS) analyses of phases formed after laser sealing of plasma sprayed coatings of 8.5 wt% yttria partially stabilized zirconia (YPSZ). X-ray diffraction and X-ray step-scanning analyses showed that the plasma sprayed and sealed coatings consisted mainly of t′ phase with a very small amount of monoclinic phase (m phase) in the plasma sprayed coatings. It was also found that the small amounts of m and cubic phases (c phase) present in the sealed coatings were dependent on laser processing specific energies (specific energy is equal to laser power/traverse speed x beam diameter). It was also found that rhombohedral (r) phase formed after laser sealing of coatings at higher specific energies. A direct relationship between c/a ratio of transformable tetragonal phase (t phase) produced by thermal treatment of sealed coatings and nontransformable tetragonal phase (t′ phase) and the amount of Yttria was obtained. A new equation was derived, which describes the relationship between Yttria concentration and the c/a ratio of tetragonal phases (t or t′).     

High-beam-quality, 5.1 J, 108 Hz diode-pumped Nd:YAG rod oscillator-amplifier laser system

A high efficiency, high beam quality diode-pumped Nd:YAG master oscillator power-amplifier (MOPA) laser with six amplifier stages is demonstrated. The oscillator with two-rod birefringence compensation was designed as a thermally determined near hemispherical resonator, which presents a pulse energy of 223 mJ with a beam quality value of M² = 1.29 at a repetition rate of 108 Hz. The MOPA system delivers a pulse energy of 5.1 J with a pulse width of 230 μs, a M² factor of 3.6 and an optical-to-optical efficiency of 38.5%. To the best of our knowledge, this is the highest pulse energy for a diode-pumped Nd:YAG rod laser operation with a high beam quality and a pulse width of hundreds of microseconds at a repetition rate of over 100 Hz.     

Microstructures and coercivities of SmCox and Sm(Co,Cu)5 films prepared by magnetron sputtering

We have investigated the influence of composition and annealing conditions on the magnetic properties and microstructural features of SmCo_x films that were prepared by sputtering and subsequent annealing. A huge in-plane coercivity of 5.6 T was obtained from an optimally annealed Sm–Co film, which was attributed to the nanometer sized polycrystalline microstructure of the highly anisotropic SmCo₅ phase. Although a high density of planar defects were observed in the films that were annealed at high temperatures, they did not act as strong pinning sites for domain wall motion. The effect of Cu on [SmCo_4.5(9 nm)/Cu(xnm)]₁₀ multilayer thin films was also studied. An appropriate Cu content increased the coercivity.     

Microstructure, bonding strength and thermal shock resistance of ceramic coatings on steels prepared by plasma electrolytic oxidation

Ceramic coatings were successfully prepared on steel by plasma electrolytic oxidation (PEO) in aluminate electrolyte and silicate electrolyte, respectively. The microstructure of the coatings including surface morphology, phase and element composition were studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The bonding strength between the ceramic coating and the substrate was tested using different methods including tensile tests and shearing tests. The thermal shock resistance of the coatings was also evaluated. The results indicated that coatings obtained in both electrolytes were porous and coarse. The average diameters of the pores were below 10 μm. PEO coatings obtained in aluminate electrolyte were composed of Fe₃O₄ and FeAl₂O₄, while those obtained in silicate electrolyte were in a noncrystal state. PEO coatings obtained in aluminate electrolyte showed similar change trend of tensile strength and shearing strength with increasing treating time, namely, a relatively high values with middle time treating and low value with short and long time treating. The best coating was the samples treated with 30 min, whose tensile strength was 20.6 MPa and shearing strength was 16 MPa. The tensile strength and shearing strength of coatings obtained in silicate electrolyte were not strongly influenced by the treating time, the values of which were range in 14 ± 2 MPa and 11 ± 2 MPa, respectively. Coatings obtained in both electrolytes showed the best thermal shock resistance with middle time treating. Coatings obtained in silicate electrolyte show a little better thermal shock resistance than those obtained in aluminate electrolyte.     

Ni-Co-TiO2 nanocomposite coating prepared by pulse and pulse reversal methods using acetate bath

Ni-Co/nano TiO₂ (Ni-Co-TiO₂) composite coatings were prepared under pulse current and pulse reverse current methods using acetate bath. The microstructure and corrosion resistance of the coatings were characterized by means of XRD, SEM and EIS. Both the Ni-Co alloy and composite coatings exhibited single phase of Ni matrix with face centered cubic (fcc) crystal structure. The crystal orientation of the Ni-Co-TiO₂ composite coating was transformed from crystal face (2 0 0) to (1 1 1) compared with Ni-Co alloy coatings. The results showed that the microstructure and performances of the coatings were greatly affected by TiO₂ content on the deposits prepared by PC and PRC methods. The microhardness and corrosion resistance were enhanced in the optimum percentage of TiO₂ composite coatings. The PRC composite coatings were exhibited from compact surface, higher microhardness and good corrosion resistance compared with that of the PC composite coating.     

LD end pumped mode locked and cavity dumped Nd:YAP laser at 1.34 μm

We report a LD end pumped actively mode locked, passively Q switched and cavity dumped Nd:YAP laser at 1.34 μm. The dumped output pulse energy of 160 μJ is obtained at a repetition rate of 10 Hz. Passing through a LD end pumped, double-passed Nd:YAP amplifier the pulse energy is amplified to 1.44 mJ. The corresponding amplification factor is 9. Stimulated Raman scattering experiment is taken with a 9 mm long PbWO₄ Raman crystal. Maximum of 20% Raman conversion is reached.     

Effects of laser operating parameters on metals micromachining with ultrafast lasers

180 femtoseconds (1 kHz) and 10 picoseconds (1-50 kHz) ultrafast laser micro-structuring of the metals Ti alloy, Al and Cu have been studied for the purpose of industrial application. The effects of some key laser operating parameters were investigated. The evolution of surface morphology revealed that laser pulses overlap in a range around the spatial FWHM can help to achieve optimal residual surface roughness. While observed ablation rate (unit: μm³ per pulse) changed dramatically with repetition rate due to the combined effects of plasma absorption, residual thermal energy and phase transition, higher throughput can be achieved with higher repetition rate. This study also indicated that residual surface roughness is almost independent of repetition rate at 10 ps temporal pulse length. The ablation depth is approximately proportional to the number of overscan; however, machining accuracy deteriorates, especially for femtosecond laser processing and metals with low thermal conductivity and short electron-phonon coupling time.