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Scripta Materialia 68 (2013) 471474 www.elsevier.com/locate/scriptamat

A novel proposal to manipulate the properties of titanium parts by laser surface alloying
c and R. Carama J.B. Fogagnolo,a, A.V. Rodrigues,a M.S.F. Lima,b V. Amigo
a

UNICAMP University of Campinas, School of Mechanical Engineering, Rua Mendeleiev 200, 13083-860 Campinas, SP, Brazil b IEAv Instituto de Estudos Avanc ados, 12228-970 Sa o Jose dos Campos, SP, Brazil c ` cnica de Vale ` ncia, Spain a de Materiales, Universitat Polite Instituto de Tecnolog
Received 19 September 2012; revised 13 November 2012; accepted 16 November 2012 Available online 29 November 2012

A novel proposal is presented to increase the fatigue strength of titanium parts by applying a less rigid coating, which is expected to lower the tensile stresses at the surface and delay the onset of fatigue cracking. Niobium was introduced into the surface layer by laser surface alloying and, depending on the process parameters, b and a00 phases were obtained, resulting in a reduction of approximately 30% in Youngs modulus and a more than 100% increase in hardness. 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Surface alloying; Titanium alloys; Fatigue; Nanoindentation

Titanium and its alloys exhibit high specic strength, low elastic modulus and excellent corrosion resistance, which make them very attractive for a number of industrial sectors [1]. Furthermore, they are interesting materials for use in orthopedic and dental implants, because they are biocompatible and enable osseointegration, i.e. the rm anchoring of a surgical implant by the growth of bone around it. In addition, the low Youngs modulus of titanium-based materials when compared with stainless steel and CoCr alloys reduces the undesirable stress-shielding phenomenon [2]. Several surface treatments can enhance the performance of titanium and its alloys for aeronautical and biomaterial applications. The main objective of surface modication is the improvement of wear and corrosion resistance [3,4]. In the specic case of biomaterial applications, bioactive layers [5] serve to increase the materials biocompatibility, and osseointegration can be enhanced by producing greater surface roughness or even porosity [6]. However, coatings aimed at increasing biocompatibility or wear resistance usually reduce the materials fatigue strength [7] by introducing defects, which act as stress concentrators. Even the residual stresses produced at the coatingsubstrate interface can be deleterious to

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fatigue strength. The decrease in fatigue strength is the critical aspect involved in porous coatings [8]. Surface treatments such as shot peening [9] and laser peening [10] are designed specically to increase fatigue strength by producing residual compressive stresses [11], which increase the resistance to crack nucleation, thereby increasing fatigue life. However, such surface treatments are usually counterproductive to the enhancement of osseointegration and biocompatibility. One alternative for enhancing fatigue strength which has rarely been attempted is the use of a coating material with a lower Youngs modulus. Kralya and coauthors [12] applied hard coatings on titanium alloys to increase their wear resistance and reported a decrease in fatigue strength. However, using a more exible coating (molybdenum applied by plasma thermal spraying), they reported increased fatigue strength, which was attributed to the lower Youngs modulus and higher hardness of the surface layer, with a consequent delay in the onset of fatigue cracking. This paper presents the results of a study involving surface modication to increase the fatigue strength of titanium by obtaining parts with a less rigid surface layer covering a more rigid core. Since the core and surface should deform equally under elastic deformation, lower stresses should be produced at the surface, delaying the onset of surface fatigue cracking and thereby increasing the materials fatigue strength. The Youngs modulus of the high-temperature Ti-b phase with a

1359-6462/$ - see front matter 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.scriptamat.2012.11.016

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body-centered-cubic (bcc) structure is lower than that of the low-temperature Ti-a phase, which has a hexagonal close-packed structure. A less rigid surface can be produced on titanium components by introducing a sufcient amount of b-stabilizer element onto the surface to stabilize the Ti-b phase at room temperature. Therefore, we applied laser surface alloying to introduce niobium and produce titaniumniobium alloy on the surface of commercially pure titanium plates, obtaining single laser tracks, as the rst step of a more comprehensive research project. Depending on the process parameters, this procedure produced a harder phase with a lower Youngs modulus on the surface. Three-millimeter-thick sheets of commercial purity titanium (grade 2) were used as the substrate. Nb powder (99.8% Nb, supplied by CBMM, Brazil) with an average particle size of 36 lm was used as the alloying material. The substrate was previously sanded using 600-grit SiC sandpaper and cleaned ultrasonically in acetone. The niobium powder was rst mixed with acetone into a viscous slurry, which was then applied to the surface of the titanium sheets. After the acetone had dried, the result was a uniform layer of niobium powder about 150 lm thick, with sucient adherence to allow for manipulation. A ber laser operating at a wavelength of 1.08 lm was used to produce linear remelting tracks on the materials surface. Applying a Gaussian beam distribution mode, the defocused laser beam produced a spot diameter of 1.6 mm at the surface. A protective ux of 30 l min1 argon was used in the melting region to prevent oxidation. An xy table with computer numerical control moved the samples at a constant rate of 10 mm s1 under the laser beam. Laser powers of 200 and and 400 W were employed. For purposes of comparison, a titanium sheet without powder coating was also treated using a laser power of 300 W. The laser alloyed surface region was characterized in the direction parallel to the laser track by scanning electron microscopy (SEM), using the back-scattered electron mode. The hardness and Youngs modulus of the substrate and the laser track regions were determined by nanoindentation, using an Agilent Nano Indenter G200 (Agilent Technologies) with a previously calibrated diamond Berkovich tip, and applying the continuous stiness measurement method [13]. The analyzed areas were rst selected by optical microscopy. Three different regions (top, center and bottom) inside the track were analyzed and ve indentations were made in each region. All the indentations were programmed to reach a depth of 1000 nm under controlled displacement. Figure 1 shows a cross-section of the laser tracks observed by SEM in the longitudinal direction. A focal distance of 10 mm and a laser power of (a) 200 W and (b) 400 W were used. The lighter regions indicate the incorporation of niobium in the remelted zone. As expected, the higher the laser power, the larger the remelted zone. However, the laser power of 400 W tended to produce a track with keyhole characteristics, which is more suitable for the welding process than for surface modication. Because the thickness of the Nb powder layer deposited on the Ti sheet was almost constant, the larger the remelted zone the higher the dissolution of Nb. An

Figure 1. Cross-sections of laser tracks using a laser power of 200 (a) and 400 W (b).

EDS analysis indicated that, using 200 W, TiNb alloys with 25 and 29 mass% of Nb were formed on the bottom and upper parts, respectively. Increasing the laser power to 400 W resulted in TiNb alloys with lower Nb content (9 and 11 mass% of Nb) on the aforementioned parts. Hence, the dissolution of Nb on the Ti surface layer was strongly dependent on the laser power applied. Figure 2 shows the hardness and Youngs modulus as a function of the depth of the surface, measured by nanoindentation, of the Nb-alloyed tracks obtained with laser powers of 200 and 400 W, as well as the non-alloyed track obtained with 300 W laser power. Hardness was found to increase by more than 100%, independently of laser power and Nb alloying. The probable reasons for this are solid-solution strain hardening due to the introduction of interstitial (e.g. O) and substitutional site defects (e.g. Nb). Although x phase was not detected by SEM or X-ray diraction, it may nevertheless have been formed and, consequently, contributed to increasing the hardness in the alloyed tracks. With regard to the inuence of laser surface modication on Youngs modulus, dissimilar results were identied. In the non-alloyed track, only a minor tendency for an increased Youngs modulus of the substrate was found in response to laser treatment, probably due to the introduction of interstitial defects. The modication by Nb alloying did not alter Youngs modulus when using 400 W of laser power, but 200 W of laser power decreased it by about 30%. The decrease in Youngs modulus was related to the phases obtained at the surface due to the dissolution of Nb. Figure 3 shows the microstructures observed by SEM in the laser track alloyed with Nb, obtained with laser power of 200 (a) and 400 W (b). The application of 200 W of laser power resulted in needles of orthorhombic martensitic structures (a00 ) embedded in the bcc b phase (Fig. 3a), while the presence of the

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Figure 2. Hardness and Youngs modulus of the Nb-alloyed tracks obtained with laser powers of 200 and 400 W, and the non-alloyed track obtained with a laser power of 300 W, measured by nanoindentation in three regions (top, center and bottom) of the track and in the substrate.

Figure 3. SEM micrographs of microstructures in the laser track alloyed with Nb obtained with laser powers of 200 (a), and 400 W (b).

hexagonal martensite a0 phase predominated when using 400 W (Fig. 3b). The predominance of the bcc b phase in the 200 W laser track and the hexagonal a/a0 phase in

the 400 W laser track was conrmed by X-ray diraction (not shown here). Hon and coauthors [14], who worked with furnacecooled TiNb alloys with the Nb content ranging from 14 to 40 mass%, reported a decrease in Youngs modulus in response to increased Nb content, except in the range of 2634 mass% Nb, in which Youngs modulus increased. They correlated these results with the presence of a, b and x phases. Because Nb is a b-stabilizer element, the amount of b phase increases with increasing Nb content; also, since b phase has a lower Youngs modulus than a phase, its presence decreases Youngs modulus. The precipitation of x phase, which has a higher Youngs modulus, in alloys whose composition varies from 26 to 34 mass% Nb, may explain the increase in Youngs modulus observed in this range of Nb content. Increasing the cooling rate causes martensitic transformation. TiNb alloys with lower Nb content, which under slow cooling should form a + b phases, form hexagonal martensite a0 when cooled rapidly [15]. A higher Nb content should promote the formation of martensite a00 , with an orthorhombic crystal structure, instead of hexagonal martensite a0 [16]. An amount of 2530 mass% Nb (200 W laser track) was suciently high to stabilize a high volume fraction of bcc b phase. At a slow cooling rate, the bcc b phase should coexist with a low volume fraction of a phase, but at the higher cooling rates typical of laser surface alloying, martensitic transformation occurred and a00 was formed. The presence of these phases may explain the lower elastic modulus of the coating when compared with the titanium substrate. On the other hand, at a fur-

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nace cooling rate, an amount of about 10 mass% Nb (400 W laser track) should produce a + b, with lower volume fraction of b phase. However, at a high cooling rate, the martensitic transformations produced a0 , the Youngs modulus of which is closer to that of the substrate, i.e. closer to that of a phase. Accordingly, by controlling the process parameters, the amount of alloying element introduced into the surface of the substrate can be controlled and phases with lower stiness can be stabilized at the surface of titanium parts. These results simply conrm that the application of this process can produce a harder coating with lower stiness in titanium parts a decrease of about 30% in Youngs modulus compared with that of the substrate and this should be seen as the beginning of a new proposal for obtaining coatings specically designed to increase fatigue strength. However, many challenges must still be overcome to achieve this goal. First of all, more suitable process parameters must be used to produce tracks without keyhole characteristics. In addition, a continuous coating must be obtained without a signicant number of defects, such as pores, which can be strongly counterproductive, decreasing the fatigue strength. Also, the level of oxygen dissolved in the tracks must be better controlled. A protective ux applied on the melt region was not eective in preventing oxygen contamination. The use of better protection against oxygen, such as a sealed box with a high-purity inert atmosphere, should also be tried. Also, heat treatment could be used to improve the dispersion of the alloying element. Another approach is the analysis of residual stresses produced in the coating and at the interface with the substrate, which can play an additional role. During cooling, the b phase should be maintained in great part or even totally in the alloyed layer, while the thermally aected, non-alloyed underlying zone, which was transformed from a to b phase during heating, should undergo back-transformation from b to a. Considering that Nb has a minimum eect on the Ti b lattice parameter and a phase is denser than b phase, a contraction of approximately 8.1% is produced by the allotropic transformation from b to a phase. Thus, tensile and compressive stresses should appear in the substrate and coating, respectively. Additional studies are required to check and measure such residual stresses. Moreover, this surface modication involving a less rigid layer may also be employed as an intermediate coating upon which bioactive, porous or even hard coatings can be deposited, which opens up a wide eld of exploration.

In summary, a harder, less rigid surface layer is proposed to increase the fatigue strength of Ti parts. To this end, commercially pure Ti sheets were subjected to laser surface alloying with Nb powder to produce TiNb alloy in the surface layer. The application of low laser power produced surface tracks with sucient Nb content, i.e. between 25 and 29 mass%, to obtain the less rigid b and a00 phases. The hardness of the material increased by more than 100%, while Youngs modulus decreased by approximately 30%. However, further investigation is needed to determine the optimum process parameters that allow for the production of a continuous coating with few defects, as well as to characterize such coated parts in fatigue tests. The authors would like to thank the Sa o Paulo State Research Foundation (FAPESP, Brazil) for nancial support and Professor Conrado R.M. Afonso of the Structure Characterization Laboratory (LCE, Brazil).
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