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.     

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.     

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.     

Laser diffusion nitriding of Ti-6Al-4V for improving hardness and wear resistance

Owing to poor tribological properties, titanium (Ti) alloys are usually surface-treated to enhance their surface properties. Laser surface nitriding, among others, is a common method employed to increase hardness and wear resistance for Ti alloys. Conventional laser nitriding involves surface melting of Ti alloys in a nitrogen atmosphere. This inevitably results in a roughened surface and post-treatment might be required. The present study aims at laser diffusion nitriding Ti alloys without surface melting via carefully selecting the laser processing parameters. The nitrided surface was characterized by X-ray diffractometry (XRD), optical microscopy (OM), scanning-electron microscopy (SEM), and profilometry. The nitride layer formed was about 1.62 μm upon repeated passes. The change in surface roughness resulting from laser diffusion nitriding was only minimal. Nanoindentation measurements revealed that the hardness of the nitride layer was around 11.3 GPa, being about 2.3 times that of Ti-6Al-4V. Ball-on-slab sliding wear test recorded a reduction in wear volume by about 8 times. The results of the present work thus demonstrate the feasibility of diffusion nitriding of Ti-6Al-4V by laser treatment for enhancing its surface properties and performance.     

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.     

Excimer laser decoating of chromium titanium aluminium nitride to facilitate re-use of cutting tools

This work reports on the technical feasibility and establishment of a process window for removing chromium titanium aluminium nitride (CrTiAlN) coating from steel substrates by laser irradiation. CrTiAlN coating has high hardness and oxidation resistance, with applications for use with cutting tools. The motivation for removing such coatings is to facilitate re-use of tooling by enabling regrinding or reshaping of a worn tool and hence promote sustainable material usage. In this work, laser decoating was performed using an excimer laser. The effect of laser fluence, number of pulses, frequency, scanning speed and laser beam overlap on the decoating performance was investigated in detail. The minimum threshold laser fluence for removing the CrTiAlN coating was lower than that of the steel substrate and this factor is beneficial in controlling the decoating process. Successful laser removal of CrTiAlN coating without noticeable damage to the steel substrate was demonstrated.     

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.     

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     

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     

Removal of doped poly(methylmetacrylate) from tungsten and titanium substrates by femto- and nanosecond laser cleaning

The influence of different laser pulse lengths on the removal of a polymer layer from metal substrates was investigated. As model systems, doped poly(methylmetacrylate) (PMMA) on titanium and tungsten substrates were selected.The ablation threshold and irradiation spot morphology of titanium and tungsten were compared for femtosecond (fs) and nanosecond (ns) laser irradiation and different pulse numbers. Nanosecond laser treatment resulted in a non-homogeneous surface morphology for both titanium and tungsten substrates. Femtosecond irradiation of tungsten revealed a homogeneous ablation spot with little changes in the surface morphology. For titanium, the formation of columnar structures within the irradiation spot was observed.Two different dopant concentrations were used for PMMA to achieve an equal linear absorption coefficient for the femto- and nanosecond laser wavelengths of 790 and 1064 nm. The best results were achieved for the removal of doped PMMA by femtosecond laser irradiation, where only a minimal modification of the metal surface was detected. In the case of nanosecond laser exposure, a pronounced change of the structure was observed, suggesting that damage-free cleaning of the selected metal may only be possible using femtosecond laser pulses. Different experimental parameters, such as laser fluence, pulse repetition rate and sample speed were also investigated to optimize the cleaning quality of doped PMMA from tungsten substrates with femtosecond laser pulses.     

Thermal stability of titanium nitride coatings prepared by the mixing technology with laser and plasma

Titanium samples were treated by the mixing technology with laser and plasma (LPN) using different laser power densities. These nitrided samples were then annealed at 473 K, 673 K, 873 K, and 1073 K for 2 h in vacuum, respectively. The samples before and after annealing were characterized at room temperature and compared in terms of microstructure. X-ray diffraction and cross-sectional optical microscopy studies showed that the layer structure of the titanium nitride coating is preserved after annealing at 1073 K when the coating is formed using a laser power density of 8.0 × 10⁵ W/cm². Therefore, titanium nitride coatings produced by LPN demonstrate excellent thermal stability and are potential candidates for high temperature tribological applications.     

Laser controlled melting of pre-treated zirconia surface

Laser treatment of pre-prepared zirconia surface is carried out. The pre-prepared surface, prior to laser treatment, consists of 50 μm carbon film and 7% titanium carbide particles, which are imbedded in the carbon film. The microstructural and morphological changes in the laser treated surface layer are examined using optical and scanning electron microscopes, energy dispersive spectroscopy, and X-ray diffraction. The fracture toughness of the laser treated surface is measured and the residual stress formed at the surface vicinity is determined from the X-ray diffraction technique. It is found that the microhardness of the laser treated surface increased slightly due to the dense layer formed at the surface vicinity. However, the laser treatment process reduces the fracture toughness of the surface due to improved surface hardness and the residual stress formed in the surface vicinity.     

脉冲高能量密度等离子体法制备TiN薄膜及其摩擦磨损性能研究

利用脉冲高能量密度等离子体技术在室温条件下在45号钢基材上制备出了超硬耐磨TiN薄膜.利用XRD，XPS，AES，SEM等手段分析了薄膜的成分及显微组织结构，并测试了薄膜的硬度分布及摩擦磨损性能.结果表明：薄膜主要组成相为TiN，薄膜组织致密、均匀，与基材之间存在较宽的混合界面；薄膜硬度高，在干滑动磨损实验条件下具有优异的耐磨性及较低的摩擦系数. 关键词： 脉冲高能量密度等离子体 TiN膜 显微组织 耐磨性     

Laser synthesis of nitrides on the surface of refractory metals immersed in liquid nitrogen

In this paper we describe an approach for the formation of composite layers on the surface of refractory metals. We show that laser radiation on refractory metals (Ti, V, Zr, Mo, Hf, Ta, and W) immersed in liquid nitrogen can provide a chemical synthesis of nitride phases on the surface of metals. The metals were subjected to pulsed laser radiation with a wavelength of 1.06 μm. The power density ranged from 10⁴ to 10⁹ W cm⁻². The synthesis of nitrides began with the formation of Me_xN_y (x > y) phases with low contents of nitrogen. When the melting point was reached at the metal surface, the quantity of MeN phases increased sharply. Study of the melting zone showed that it contained a non-uniform distribution of nitride phases. The quantity of nitrides was a maximum on the surface and decreased with the increase of the depth of melting zone. Due to the high-cooling rates, titanium nitride crystallized in the form of columns. Maximum microhardness in the Ti surface layer was up to 20,000 MPa.     

光纤激光气体氮化钛合金发射光谱及等离子体研究

激光气体氮化工艺可在钛合金表面快速生成氮化层,提高钛合金表面硬度和耐磨性,促进钛合金应用.采用光纤激光气体氮化Ti-6Al-4V合金,为了明确氮化过程光谱发射区是否形成等离子体,采用探针法检测了光谱发射区导电性;为了研究工艺参数对光谱特性、光谱发射区温度及等离子数量的影响,采用光谱仪采集了氮化过程发射光谱,并采用高速摄...     

Laser controlled melting of pre-prepared inconel 718 alloy surface

Laser treatment of Inconel 718 alloy surface is carried out. The alloy surface is coated with a carbon layer containing 7% TiC particles prior to the laser treatment. The carbon coating provides increased absorption of the incident laser beam and holds TiC particles. The microstrutural and morphological changes in the laser treated region are examined using optical and scanning electron microscopes, energy dispersive spectroscopy, and X-ray diffraction. The microhardness of the surface is measured and the residual stress formed at the surface vicinity is determined from the XRD technique. It is found that partial dissolution of carbide particles takes place at the surface. The composition of fine grains at the surface vicinity, nitride compounds formed, and dissolution of Laves phase at the surface region enhances the hardness at the treated surface. In addition, laser treated surface is free from the micro-crack network and cavities.     

TiN growth on Si by hybrid radical beam PLD

High-quality (good crystallinity and stoichiometry) titanium nitride (TiN) thin films were grown on Si(100) substrates by pulsed laser deposition (PLD) using a high-purity titanium target (99.99%) and nitrogen radical beam. The crystallinity, chemical composition, and depth profiles of the grown films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Rutherford backscattering spectroscopy (RBS), respectively. The XRD pattern indicated that the preferred growth of TiN(200) with an orientation parallel to the Si(100) direction was obtained and the nitrogen radical drastically improved crystallinity compared with that grown in ambient nitrogen gas. RBS spectra indicated that the combination of PLD and the nitrogen radical beam suppressed silicidation at the interface between the Si substrate and TiN thin film during growth. The XPS analysis revealed that this method achieved the synthesis of stoichiometric TiN films.     

Numerical modeling and experimental investigation of TiC formation on titanium surface pre-coated by graphite under pulsed laser irradiation

A model for carbonization of titanium surface by pulsed Nd:YAG laser was developed. The Ti substrate was covered with a relatively thick graphite layer prior to be processed under the laser beam. The experiments were performed at 15 J pulse energy with various pulse durations and overlapping factor to validate the results obtained from the numerical calculations. The model results such as temperature gradient, surface temperature, and the cooling rate were correlated with the micro-hardness of the alloyed layer. Higher pulse durations and overlapping factors which lead to the heat input increasing will result in significant rising in the micro-hardness values. The hardness values of the processed layer partially containing TiC, increased up to 10 times of the Ti substrate.     

Formation of titanium carbide layer by laser alloying with a light-transmitting resin

The weight reduction of mechanical components is becoming increasingly important, especially in the transportation industry, as fuel efficiency continues to improve. Titanium and titanium alloys are recognized for their outstanding potential as lightweight materials with high specific strength. Yet they also have poor tribological properties that preclude their use for sliding parts. Improved tribological properties of titanium would expand the application of titanium into different fields.Laser alloying is an effective process for improving surface properties such as wear resistance. The process has numerous advantages over conventional surface modification techniques. Many researchers have reported the usefulness of laser alloying as a technique to improve the wear resistance of titanium. The process has an important flaw, however, as defects such as cracks or voids tend to appear in the laser-alloyed zone.Our group performed a novel laser-alloying process using a light-transmitting resin as a source for the carbon element. We laser alloyed a surface layer of pure titanium pre-coated with polymethyl methacrylate (PMMA) and investigated the microstructure and wear properties. A laser-alloyed zone was formed by a reaction between the molten titanium and thermal decomposition products of PMMA at the interface between the substrate and PMMA. The cracks could be eliminated from the laser-alloyed zone by optimizing the laser alloying conditions. The surface of the laser-alloyed zone was covered with a titanium carbide layer and exhibited a superior sliding property and wear resistance against WC-Co.     

Adjusting chemical bonding of hard amorphous CSixNy thin films by N*-plasma-assisted pulsed laser deposition

Hard amorphous carbon silicon nitride thin films have been grown by pulsed laser deposition (PLD) of various carbon silicon nitride targets by using an additional nitrogen RF plasma source on [100] oriented silicon substrates at room temperature. The influence of the number of laser shots per target site on the growth rate and film surface morphology was studied. Up to about 30 at. % nitrogen and up to 20 at. % silicon were found in the films by Rutherford backscattering spectroscopy (RBS) and X-ray photoelectron spectroscopy (XPS). The XPS of the films showed a clear correlation of binding energy to the variation of PLD parameters. The films show a universal hardness value up to 23 GPa (reference value for silicon substrate 14 GPa) in dependence on target composition and PLD parameters. The results emphasise the possibility of variation of chemical bonding and corresponding properties, such as nanohardness, of amorphous CSi_xN_y thin films by the plasma-assisted PLD process.