Surface nitriding of Ti–6Al–4V alloy with a high power CO2 laser

Surface nitriding of a Ti–6Al–4V alloy by laser melting in a flow of nitrogen gas has been investigated, with the aim of increasing surface hardness and hence improving related properties such as wear and erosion resistance. The effect of the scanning speed, nitrogen dilution, and nitrogen flow rate on microstructure, microhardness, and cracking of the nitrided layers was studied. Optical, scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction (XRD) were used to reveal the microstructure and to identify the phases formed. It is shown that smooth, deep, and crack-free nitride layers of a surface hardness ranging between 500 and 800 HV can be obtained by controlling the processing parameters. Cracks are present in the sample processed at slow scanning speed and high laser power. Dilution of the nitrogen gas with argon gas leads to a crack-free nitride layer at the expense of a reduction in surface hardness. Slow scanning speeds lead to the formation of a deep and hard surface layer, and increasing the nitrogen flow rate results in a rough surface with a slight increase in hardness.     

Laser/sol–gel synthesis: a novel method for depositing nanostructured TiN coatings in non-vacuum conditions

In this work results of experiments on the in situ production of titanium nitride by the reaction of titania sol–gel with a nitrogenous admixture under laser irradiation are reported. A diode laser beam at different powers and traverse speeds was applied to the mixture placed on EN43 mild steel and 316L stainless steel substrates. Composite coatings of titanium nitride and titanium oxide with a hardness of 17–21 GPa have been achieved by this new method. Surface morphology and microstructure of the deposited coatings and substrate surface layers were examined using optical microscopy, scanning electron microscopy, and field-emission gun scanning electron microscopy. Chemical composition was determined by energy-dispersive X-ray analysis. The phases were identified by X-ray diffraction. Results of microhardness and nanohardness at the top surface were evaluated. PACS 81.15.Fg; 81.20.Fw; 81.05.-t     

Formation of charged defects during the nitridation of a metal particle

A model explaining and predicting generation of a temporal electric potential during nitridation of a single metal pellet has been developed. The model takes into account the kinetics of defects formation and assumes that the rate of the chemical reaction can be described by the shrinking-core process. The model simulations have shown that time scale of the generated electric potential depends on both the initial nitride shell thickness and heat removal from the particle surface. At thin initial shell and low rate of heat removal the maximum of the surface electric potential is attained before the temperature and surface nitrogen concentration have reached their maximums but after the maximum of nitridation has appeared. Quasi-neutral distributions of metal vacancies and electron holes are formed at the maximum temperature. At thick initial shell and/or high rates of heat removal from the particle surface the potential maximum may be observed much later: after the maximum temperature has been achieved. Correspondingly, non-equilibrium concentrations of the charged defects exist till the end of nitridation. In contrast to oxidation the nitrogen adsorption rate constants (the activation energy and pre-exponent) have negligible effect on the surface potential form and amplitude. At the ignition limit the rate of nitridation is proportional to the power of −1/2 for the ambient nitrogen pressure in the proposed scheme of defects formation. Metal vacancies and electron holes are the main charged defects in nitrides during nitrogen combustion. The nitride formation is limited by transfer of the vacancies in nitride.     

Low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation

The low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation has been studied. Two fabrication methods are presented. One is photoenhanced direct nitridation of a silicon surface with NH₃ for very thin gate insulators, and the other is photo-enhanced deposition of silicon nitride films with Si₂H₆ and NH₃ gases for stable passivation films. The ArF excimer laser irradiation dissociates the NH3 gas producing NH and NH₂ radicals which proved effective in instigating the nitridation reaction. The quality of both films has been much improved and the growth temperature has been lowered by using laser irradiation. These photo-enhanced processes seem to be promising ULSI techniques because they do not depend on high temperatures and are free from possible reactor contamination.     

Nanoparticles of Iron Nitride Encapsulated in Nitrogen-Doped Carbon Bulk Derived from Polyaniline/Fe2O3 Blends and Its Electrochemical Performance

Iron nitride nanoparticles encapsulated in nitrogen-doped carbon bulk is fabricated by a simple costep nitridation of Fe₂O₃ and carbonization of polyaniline. The microstructure and elemental composition of the materials are analyzed by transmission electron microscope, scanning electron microscope, X-ray diffraction, and X-ray photoelectron spectroscopy. The pore size distribution and specific surface area of the materials are identified using nitrogen adsorption and desorption method. The results illustrate that iron nitride nanoparticles with 5–20 nm in size are uniformly dispersed in the carbon bulk. The presence of carbon bulk effectively prevents the agglomeration of iron nitride nanoparticles, making the electrochemical performance of iron nitride nanoparticles/carbon nitride composite nanomaterials superior to that of pure iron nitride nanomaterials. At a current density of 0.5 A g⁻¹, the specific capacitance (257.5 F g⁻¹) of the iron nitride nanoparticles/nitrogen-doped carbon bulk is much higher than that (119.5 F g⁻¹) of pure iron nitride.     

Excimer laser surface treatment of aluminum alloy in nitrogen

The excimer laser nitriding process reported is developed to enhance the mechanical and chemical properties of aluminum alloys. An excimer laser beam is focused onto the alloy surface in a cell containing 1-bar nitrogen gas. A vapor plasma expands from the surface and a shock wave dissociates and ionizes nitrogen. It is assumed that nitrogen from plasma in contact with the surface penetrates to some depth. Thus it is necessary to work with a sufficient laser fluence to create the plasma, but this fluence must be limited to prevent laser-induced surface roughness. The nitrogen-concentration profiles are determined from Rutherford backscattering spectroscopy and scanning electron microscopy coupled to energy-dispersive X-ray analysis. Crystalline quality is evidenced by an X-ray diffraction technique. Transmission electron microscopy gives the in-depth microstructure. Fretting coefficient measurements exhibit a lowering for some experimental conditions. The polycrystalline nitride layer obtained is several micrometers thick and composed of a pure AlN (columnar microstructure) top layer (200–500 nm thick) standing on an AlN (grains) in alloy diffusion layer. From the heat conduction equation calculation it is shown that a 308-nm laser wavelength would be better to increase the nitride thickness, as it corresponds to a weaker reflectance R value for aluminum. Received: 17 October 2000 / Accepted: 19 October 2000 / Published online: 23 May 2001     

CO2 laser gas assisted nitriding of Ti-6Al-4V alloy

Laser gas assisted nitriding of Ti-6Al-4V alloy is carried out and nitride compounds formed and their concentration in the surface vicinity are examined. SEM, XRD and XPS are accommodated to examine the nitride layer characteristics. Microhardness across the nitride layer is measured. Temperature field and nitrogen distribution due to laser irradiation pulse is predicted. It is found that the nitride layer appears like golden color; however, it becomes dark gold color once the laser power irradiation is increased. The δ-TiN and ?-TiN are dominant phases in the surface vicinity. The needle like dendrite structure replace with the feathery like structure in the surface region due to high nitrogen concentration. No porous or microcracks are observed in the nitrided layer, except at high power irradiation, in this case, elongated cracks are observed in the surface region where the nitrogen concentration is considerably high.     

Surface hardening of titanium by pulsed Nd:YAG laser irradiation at 1064- and 532-nm wavelengths in nitrogen atmosphere

The surface hardness of titanium modified by laser irradiation at different wavelengths in nitrogen atmosphere was investigated. Further, surface characteristics such as morphology, chemical state, and chemical composition in the depth direction were also studied. The size and depth of the craters observed in the laser-irradiated spots increased monotonically with an increase in the laser power. Furthermore, the crater formed by the 532-nm laser was deeper than that formed by the 1064-nm laser for the same laser power. Laser power beyond a certain threshold value was required to obtain a titanium nitride layer. When the laser power exceeds the threshold value, a titanium nitride layer of a few tens of nanometers in thickness was formed on the substrate, whereas a titanium oxide layer containing small amounts of nitrogen was formed when the laser power is below the threshold value. Thus, it was shown that laser irradiation using appropriate laser parameters can successfully harden a titanium substrate, and the actual hardness of the titanium nitride layer, measured by nanoindentation, was approximately five times that of an untreated titanium surface.     

Nitrogen plasma cleaning of Ge(1 0 0) surfaces

We propose a dry method of cleaning Ge(1 0 0) surfaces based on nitrogen plasma treatment. Our in situ Auger electron spectroscopy (AES) and low-energy electron diffraction (LEED) analyses demonstrate that surface contamination remaining after wet treatment was effectively removed by nitrogen radical irradiation at low substrate temperatures. The nitrogen plasma cleaned Ge(1 0 0) surface shows a well-ordered 2 × 1 reconstruction, which indicates the formation of a contamination-free Ge(1 0 0) surface with good crystallinity. We discuss the possible reaction mechanism considering how chemisorbed carbon impurities are removed by selective C-N bond formation and subsequent thermal desorption. These findings imply the advantage of plasma nitridation of Ge surfaces for fabricating nitride gate dielectrics, in which we can expect surface pre-cleaning at the initial stage of the plasma treatment.     

Comparison of surface films formed on titanium by pulsed Nd:YAG laser irradiation at different powers and wavelengths in nitrogen atmosphere

The nitridation of titanium (Ti) caused by a Q-switched Nd:YAG laser under nitrogen gas atmosphere was investigated in situ using X-ray photoelectron spectroscopy (XPS). A laser having a wavelength of 1064 nm and 532 nm (SHG mode) was irradiated on a titanium substrate in an atmosphere-controlled chamber, and the substrate was then transported to an XPS analysis chamber without exposing it to air. The characteristics of the surface layer strongly depend on the laser power. When the power is relatively low, a titanium dioxide layer containing a small amount of nitrogen is formed on the substrate. Laser irradiation beyond a certain laser power is required to obtain a stoichiometric titanium nitride (TiN) layer. A TiN layer and an oxynitride layer with a TiO_xN_y-like structure are formed as the topmost and the lower surface layer, respectively, when the laser power exceeds this threshold value. The threshold laser power strongly depends on the wavelength of the laser, and this threshold value for the 532-nm laser is quite lower than that for the 1064-nm laser.     

Surface treatment of titanium by Nd:YAG laser irradiation in the presence of nitrogen

This work presents the surface treatment of commercial titanium alloy by means of a Nd:YAG (1.064 7m) laser in the presence of nitrogen. The treated surface was characterised by using scanning electron microscopy, atomic force microscopy, X-ray diffraction, secondary ion mass spectrometry, UV-visible spectrophotometry and microindentation. Experimental results show the formation of a nitrogen-rich layer, 500 nm thick, with a surface morphology characterised by the presence of polygonal structures which suggest that melting occurred under the action of the laser. The ' phase of titanium nitride was identified, in addition to a nitrogen in !-titanium solid solution. The reflectance spectrum of the yellow-golden sample is similar to that of deposited titanium nitride thin films. The hardness of the treated surface was measured by microindentation and found to be 14 GPa, a value three times higher than that of the titanium alloy. In scratch tests the nitrided layer detached at a load of 0.9 N.     

X-ray photoelectron spectroscopic study on surface reaction on titanium by laser irradiation in nitrogen atmosphere

The surface reaction on titanium due to pulsed Nd:YAG laser irradiation in a nitrogen atmosphere was investigated using X-ray photoelectron spectroscopy (XPS). The laser, with a wavelength of 532 nm (SHG mode), was irradiated on a titanium substrate in an atmosphere-controlled chamber, and then the substrate was transported to an XPS analysis chamber without exposure to air. This in situ XPS technique makes it possible to clearly observe the intrinsic surface reaction. The characteristics of the surface layer strongly depend on the nitrogen gas pressure. When the pressure is 133 kPa, an oxynitride and a stoichiometric titanium nitride form the topmost and lower surface layers on the titanium substrate, respectively. However, only a nonstoichiometric titanium oxide layer containing a small amount of nitrogen is formed when the pressure is lower than 13.3 kPa. Repetition of laser shots promotes the formation of the oxide layer, but the formation is completed within a few laser shots. After the initial structure is formed, the chemical state of the surface layer is less influenced by the repetition of laser shots.     

Nano-scale and surface precipitation of metallic particles in laser interference patterned noble metal-based thin films

Laser interference patterning (also known as “laser interference metallurgy”) is used to locally tailor the microstructure of oxide (Pd_0.25Pt_0.75O_x) and nitride (Cu₃N) thin films to induce a chemical decomposition, which is responsible for a decrease of electrical resistivity. This technique allows hereby a laser-induced chemical decomposition of as-deposited oxide and nitride films, resulting locally in a porous microstructure due to the simultaneous emission of gaseous nitrogen and oxygen. The process locally generates at the nanometer scale metal precipitatation of Pt or Cu in the oxide or nitride matrix. Thus, isolated metallic clusters with low resistivity coexist with a high resistivity phase, establishing a preferential electrical conduction path and giving the system a lower effective resistivity. The decomposition process is investigated by four-point probe method, X-ray diffraction, spectrophotometry, white light interference, scanning and transmission electron microscopies.     

Spontaneous N incorporation onto a Si(100) surface

Initial nitridation of the Si(100) surface is investigated using photoemission, ion-scattering and ab initio calculations. After dissociation of NO or NH3, nitrogen atoms are found to spontaneously form a stable, highly coordinated N[triple bond]Si(3) species even at room temperature. The majority of the N species is incorporated into the subsurface Si layers occupying an interstitial site, whose atomic structure and unique bonding mechanism is clarified through ab initio calculations. This unusual adsorption behavior elucidates the atomistic mechanism of initial silicon nitride formation on the surface and has important implication on the N-rich layer formation at the SiO(x)N(y)/Si interface.     

Pulsed laser deposition of hexagonal and cubic boron nitride films

Hexagonal and cubic boron nitride films are deposited by pulsed laser ablation from a boron nitride and a boron target using a KrF excimer laser. Hexagonal films are deposited in nitrogen as background gas or with nitrogen/argon ion bombardment at ion-to-arriving-target-atom (I/A) ratios at the substrate below 0.5. Nucleation of the cubic phase takes place exclusively with ion bombardment at I/A ratios above 1.0, which may be reduced down to 0.6 after the completion of the nucleation process. The influence of the parameters of the laser and ion beams on the properties of the hexagonal films are presented. The Vickers microhardness and the intrinsic stress of those films vary in wide ranges of 5 to 25 GPa and 1 to 16 GPa, respectively. Pulsed laser deposited hexagonal boron nitride films show good adhesion to silicon and stainless steel if they are deposited at I/A ratios below 0.5, and can be used as intermediate layers for improving the adhesion of cubic boron nitride films. So far, 0.5 7m thick, nearly phase-pure cubic boron nitride films with good adhesion have been deposited. The microstructural, mechanical, and optical properties of those layer systems are presented and discussed.     

Formation of nano-crystalline and amorphous phases on the surface of stainless steel by Nd:YAG pulsed laser irradiation

Thin surface layers consisting of nano-crystalline and amorphous phases on the surface of stainless steel have been attained under the Nd:YAG pulsed laser irradiation. The phases and microstructures were investigated by X-ray diffraction (XRD) and high resolution transmission electron microscope (HRTEM). The phase compositions of the surface determined by XRD were α-Fe (ferrite) and γ-Fe (austenite) or only γ-Fe in the near surface region on the bases of the different laser power densities. The nano-crystalline grains with sizes of 4-100 nm could result from high cooling rate and crystallization in amorphous region by homogeneous and heterogeneous nucleation. The formation of the amorphous phase was attributed to the higher cooling rates.     

Microstructure and wear resistance of composite layers on a ductile iron with multicarbide by laser surface alloying

Multicarbide reinforced metal matrix composite (MMC) layers on a ductile iron (QT600-3) were fabricated by laser surface alloying (LSA) using two types of laser: a 5 kW continuous wave (CW) CO₂ laser and a 400 W pulsed Nd:YAG laser, respectively. The research indicated that LSA of the ductile iron with multicarbide reinforced MMC layers demonstrates sound alloying layers free of cracks and porosities. The microstructure, phase structure and wear properties of MMC layers were investigated by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD), as well as dry sliding wear testing. The microstructure of the alloyed layer is composed of pre-eutectic austenite, ledeburite, spherical TiC, Cr₇C₃ and Cr₂₃C₆ with various morphologies. TiC particles are dispersed uniformly in the upper region of MMC layers. The average hardness of LSA layers by CO₂ laser and pulsed Nd:YAG laser is 859 HV_0.2 and 727 HV_0.2, respectively. The dry sliding wear testing shows the wear resistance of ductile iron is significantly improved after LSA with multicarbide.     

GaN nucleation on (0 0 0 1)-sapphire via ion-induced nitridation of gallium

The growth of epitaxial GaN films on (0 0 0 1)-sapphire has been investigated using X-ray photoelectron spectroscopy (XPS) and low energy electron diffraction (LEED). In order to investigate the mechanism of the growth in detail, we have focused on the nitridation of pre-deposited Ga layers (droplets) using ion beam-assisted molecular beam epitaxy (IBA-MBE). Comparative analysis of XPS core-level spectra and LEED patterns reveals, that nitride films nucleate as epitaxial GaN islands. The wetting of the surface by GaN proceeds via reactive spreading of metallic Ga, supplied from the droplets. The discussed growth model confirms, that excess of metallic Ga is beneficial for GaN nucleation.     

Effects of laser power density on the microstructure and microhardness of Ni–Al alloyed layer by pulsed laser irradiation

Laser alloying of Ni–P electroless deposited layer with aluminum substrate was carried out by Nd–YAG pulsed laser. The phase composition and microstructure of the alloyed layers produced by different laser power densities were identified by X-ray diffractionary (XRD), scanning electron microscope (SEM) accompanied by energy dispersion X-ray analysis (EDS) and transmission electron microscope (TEM). Furthermore, the surface roughness of the alloyed layers was characterised by confocal laser scanning microscope (CLSM). The results showed that the characteristic dendritic or lamellar microstructures were observed in the alloyed layers. The phase constituents of the alloyed zones were intermetallic compounds of nickel–aluminum NiAl, Al₃Ni and Al₃Ni₂, as well as some non-equilibrium phases and amorphous phases depending on the employed laser power density. As a result, the microhardness of the alloyed layer with Ni–P amorphous phases formed at laser power density 5.36×10⁹ W/m² reached to HV_0.1 390.     

Plasma nitridation of Ge(100) surface studied by scanning tunneling microscopy

The geometric and electronic structures of the surface species on Ge(100) after plasma nitridation were investigated in this study. An electron cyclotron resonance (ECR) plasma source was used to directly nitride Ge(100), and scanning tunneling microscopy and spectroscopy (STM/STS) were employed to study the structures of the nitrided surface. Nitridation at room temperature generated a large diversity of adsorbate sites on the surface containing N, O, and displaced Ge atoms, differentiated by annealing between 200 °C and 450 °C. Conversely, nitridation at 500 °C produced Ge–N adsorbate sites which formed ordered and disordered structures on the surface free from oxygen. Density functional theory (DFT) simulations were performed focusing on the ordered nitride structure, and the simulated surface structure showed a good correspondence with the STM data. DFT calculations also found an increase of density of states near the Fermi level on the ordered nitride structure, which is consistent with the Fermi level pinning observed in the STS results. The DFT results predict H-passivation can unpin the Fermi level of the nitrided surface by reducing the dangling bonds and the bond strain, but the residual plasma damage and the low nitridation rate in UHV are challenges to obtain complementary experimental results.