Cryogenic Processing of Biomaterials for Improved Surface Integrity and Product Sustainability

S. Yang1, Z. Pu1, D.A. Puleo2, O.W. Dillon, Jr.1, I.S. Jawahir1

1

Department of Mechanical Engineering, University of Kentucky, Lexington, USA

2

Center for Biomedical Engineering, University of Kentucky, Lexington, USA

Abstract Improved functional performance and longer service life of biomedical products offer great sustainability benefits. Surface integrity, which can be modified by severe plastic deformation (SPD) processes, affects the functional performance of materials. Two SPD processes burnishing and machining were studied under cryogenic conditions. Cryogenic burnishing of a Co-Cr-Mo biomedical alloy using a novel burnishing tool led to significant grain refinement and 80% greater surface microhardness relative to the bulk. Cryogenic burnishing of AZ31 Mg alloy led to a more than 2 mm thick SPD surface layer with remarkably refined microstructure (grains <300 nm), where hardness was increased 95%. The SPD layer formed on AZ31 Mg alloy after cryogenic machining was about 60% harder than the bulk material. Furthermore, this layer enhanced corrosion resistance during incubation in simulated body fluid. The present results demonstrate significant surface and subsurface property improvement due to cryogenic processes of both alloys, thus providing improved sustainability. Keywords: Sustainable manufacturing, Microstructure, Cryogenic burnishing, Cryogenic machining, Co-Cr-Mo, AZ31 Mg

1 INTRODUCTION Improved functional performance and longer service life of products, especially biomedical devices, offer great societal and environmental benefits. Surface integrity plays a crucial role in the functional performance of such products. Severe plastic deformation (SPD) processes have been extensively reported for modifying surface region properties by creating ultrafine or nano-sized grains and grain size gradients in the surface region of many products. These nano-grained materials are due to the high strain/strain rate involved in the processing. Much evidence has shown that SPD induced nano-sized/ultrafine grained materials possess appealing properties compared with their coarse-grained counterparts. Wang et al. [1] fabricated a nanocrystalline surface layer on a low carbon steel plate via SPD process; improvements of wear resistance in parts with the nanocrystalline surface layer were demonstrated. Karimpoor et al. [2] also found that nanocrystalline cobalt exhibits unusual mechanical properties compared to coarse-grained cobalt. Nanocrystalline surface layers generated by SPD process on Cu, steels and Mg alloy with emphasis on reciprocating sliding wear behavior [3] showed improved wear resistances compared to the surfaces with normal sized grains. Burnishing and machining are two SPD processes where the strain and strain-rate are usually high [4]. Significant grain refinement has been reported on the processed surface layers. Altenberger et al. [5] created nanocrystalline surface layers on AISI 304 stainless steel from deep rolling. Their results showed that this nanocrystalline surface region remain stable against cyclic loading, even at high stress amplitudes, and impede dislocation movement and slip band

formation. Nalla et al. [6] conducted deep rolling on Ti-6Al-4V alloy; nanoscale grains were found on surface layers, which are believed to play a critical role in the enhancement of fatigue life. Nikitin and his co-workers [7] studied deep rolled austenitic stainless steel AISI 304 and Ti6Al4V alloy; their results show that deep rolling induced nanocrystalline regions are stable during short time annealing. Isothermal fatigue in the low cycle fatigue regime at high stress amplitudes does not alter the nanocrystalline region up to 600c. Hot rolled AZ31 Mg samples were reported to have a marked reduction in biodegradation rate compared with squeeze cast samples [8]. The reduction was attributed to grain refinement from 450 m to 20 m in average diameter. Prevey and co-workers [9-11] showed that low plasticity burnishing can provide a layer of compressive residual stress with sufficient depth to effectively increase the fatigue life of many materials. Iglesias et al. [12] also showed that wear rates of nanostructured copper and titanium specimens created by large strain extrusion machining are significantly lower than that of their coarse-grained counterparts. Nanocrystallized grains of 5-20 nm were reported on the top of the white layer of AISI 52100 steel after machining [13]. Nanocrystalline layers with grain size about 45 nm were shown to form on the cryogenically machined surface of AZ31 Mg alloy [14]; in vitro corrosion tests proved that the nano-sized layer improved the corrosion resistance of this alloy. However, due to the heat generated during SPD processing, refined grains often grow under the high temperatures created. Cryogenic SPD, where liquid nitrogen is applied during processing, has been reported to successfully introduce thicker surface layers consisting of ultrafine/nanograined structures. By using surface mechanical grinding

G. Seliger et al. (eds.), Advances in Sustainable Manufacturing: Proceedings of the 8th Global Conference on Sustainable Manufacturing, DOI 10.1007/978-3-642-20183-7_26, Springer-Verlag Berlin Heidelberg 2011

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176 S. Yang et al. treatment at cryogenic temperatures, Li et al. [15] synthesized a gradient nano-micro-structure in the surface layer of bulk pure copper. The average grain sizes vary from about 22 nm in the topmost surface to sub-micrometers at 200 m deep. Ni et al. [16] also reported that by using cooling fluid during machining, grain size in the secondary deformation zone was reduced from 1.2 m to 360 nm. In the current study, two SPD processes burnishing and machining were studied at cryogenic conditions, where liquid nitrogen was applied so as to reduce the temperature rise created during and following processing. The effects of cooling conditions on microstructure and microhardness changes in two materials are reported herein. 2 2.1 EXPERIMENTAL Work materials surface region to cause grain refinement via SPD and possibly dynamic recrystallization (DRX). The processing conditions used for the burnishing experiments on Co-Cr-Mo and AZ31 Mg alloys are shown in Table 1. Co-Cr-Mo discs are burnished with and without liquid nitrogen for better study of the effects of cryogenic cooling. Table 1: Burnishing conditions for Co-Cr-Mo and AZ31 Mg alloys Material Co-CrMo AZ31 Mg Burnishing time 20 s 60 s Burnishing speed 100 m/min 100 m/min Feed rate 0.05 mm/rev 0.05 mm/rev Radial Force 230 N 240 N

Co-Cr-Mo alloy Cobalt-chromium-molybdenum (Co-Cr-Mo) alloy has good mechanical properties, wear resistance, and corrosion resistance, which combine to make it biocompatible [17, 18]. It has been extensively used in joint implants such as artificial hips and knees [19, 20]. BioDur Carpenter CCM alloy, which is a high nitrogen, low carbon wrought version of ASTM F75 Cast Alloy with an average initial hardness of 43 HRC is used as the work material in the burnishing experiments reported here. A Co-Cr-Mo alloy bar (50.8 mm diameter) is used to prepare disk samples which have a diameter of 50.8 mm and a thickness of 3 mm. AZ31 Mg alloy Magnesium alloys are emerging as a new class of biodegradable implant materials for internal bone fixation. They provide good temporary fixation and do not need to be surgically removed after healing occurs, providing relief to the patients and reducing the healthcare costs [14].The particular material studied was the commercial AZ31 B-O magnesium alloy. It was obtained in the form of a 3 mm thick sheet. Disc specimens (3 mm in thickness and 130 mm in diameter) were made from the sheet. 2.2 Processing

The application of liquid nitrogen is expected to effectively suppress grain growth after SPD processing and the occurrence of DRX within the surface region. Due to large strains, high strain-rates and lower temperatures, under the burnishing conditions used, the cryogenic SPD process introduces significant grain refinement to the material surface layer. Cavity for different diameter tools Nozzle for liquid nitrogen Fixed roller Work material

(a)

Burnishing Burnishing experiments were conducted on a Mazak CNC lathe along with ICEFLYTM cryogenic equipment. Liquid nitrogen as a cryogenic coolant was used. It has the advantages of better surface finish for workpieces, environmentally safer and healthier for the worker. A specially designed and fabricated burnishing tool, with a fixed burnishing roller which was used, is shown in Figure 1(a). The spherical cavity in the tool holder permits the use of rollers with different diameters. Figure 1(b) and (c) show the experiment setup used for cryogenic burnishing. The roller is spring loaded for approximate adjustment of the burnishing force. The forces developed during the processing were measured by a KISTLER 3-Component Tool Dynamometer. A M2/M7 high-speed tool steel roller with a diameter of 14.3 mm was chosen as the burnishing tool for the current experiments. The hardness and surface roughness of these rollers were measured and found to be 63 HRC and 0.01 m (Ra), respectively. The roller head is fixed in order to induce enough shear stress and strain to the

(b) (c) Figure 1: (a) Burnishing tool illustration; (b) application of liquid nitrogen during cryogenic burnishing; (c) experiment setup for cryogenic burnishing Machining A Mazak CNC lathe equipped with an Air Products liquid nitrogen delivery system is also used to conduct orthogonal turning of the AZ31 Mg discs. As shown in Figure 2, liquid nitrogen was sprayed on the machined surface from the clearance side of the cutting tool for what is being called cryogenic machining. The cutting tools used were Kennametal uncoated carbide C5/C6 inserts with 68 m edge radius. AZ31 Mg disc was cryogenically machined with 100 m/min cutting speed and 0.01 mm/rev feed rate. 2.3 Material characterization

Co-Cr-Mo alloy Metallurgical Co-Cr-Mo specimens were cut from the processed discs. After hot mounting, grinding, and polishing, the specimens were chemically etched (120 ml 37% hydrochloric acid + 12 g cupric chloride dehydrate,

Cryogenic Processing of Biomaterials for Improved Surface Integrity and Product Sustainability 177 crystalline + 10 ml R.O. Water) [21] for 15 s at 120 c to reveal their microstructures. Nozzle for liquid nitrogen burnished surface using different burnishing conditions is shown in Figure 3. The burnishing direction is parallel to the plane of the figures, and the grains shown are exactly at the edge of the burnished surfaces. Comparisons between the initial microstructure (Figure 3(a)) and the burnished ones (Figure 3(b) and (c)) show that the grains were elongated and more condensed in a thin layer near the surface of the workpiece, grain structures within this layer are not discernable. This layer of indiscernible grain structure was also reported in other materials after burnishing [6] [15], which is defined as the SPD layer. Nano-grains were not observed. When Wu et al. [22] conducted SMAT process on cobalt, a microstructural evolution in the deformed surface layer was observed, which contained recrystallized nanograins, subgrain subdivisions, elongated subgrains, grains with heavily twins, and equiaxed bulk grains with stacking faults sequentially from the depth of 15 m down to 180 m. This is in line with the present investigation. However, recrystallized nano-grains have not been induced by the currently used burnishing conditions. From Figure 3(b) and (c); it is clearly visible that the depth of the process-influenced layer from the cryogenic burnishing conditions is much larger than that from using dry conditions. This suggests that cryogenic cooling has substantial influence on the surface layer developed during SPD processing. During burnishing, the top surface layer is subjected to the most severe SPD state; the layers beneath the surface are subjected to less severe deformation conditions. For dry burnishing, the effects of plastic deformation on the subsurface layer are compromised by the large amount of heat generated during processing. This layer is hardened by plastic deformation and softened by heat simultaneously; the mechanical and thermal effects oppose each other and finally lead to minor or no influence on microstructure changes. On the other hand, liquid nitrogen application effectively suppresses the heating effect and increases the process influenced depth to a larger extent. As shown in Figure 3(a), a large amount of twinning is present within the initial grain interiors, which may be attributed to pre-existing residual stresses prior to burnishing. This has a substantial influence on the subsequent effects of burnishing.

Cutting tool

Work material

Figure 2: Machining setup with the liquid nitrogen delivery system AZ31 Mg alloy Metallurgical AZ31 Mg samples were cut from the machined discs. After cold mounting, grinding and polishing, acetic picric solution was used as the etchant to reveal the grain structure as shown below. Characterization methods The materials microhardness and microstructure in the surface region were measured before and after the processing. Microindentation tests were undertaken for CoCr-Mo specimens by using a Vickers indenter on a CSM Micro-Combi Tester with 300 mN applied load. The hardness of AZ31 Mg alloy was measured by a CLARK Digital Micro hardness Tester (CM-700 AT) with 50 mN load and 15 s dwell time. Metallurgical analysis was conducted by using optical and scanning electron microscope (SEM). Chemical compositions were determined from energy dispersive spectroscopy (EDS). 3 3.1 RESULTS AND DISCUSSION Co-Cr-Mo alloy

SEM investigations were conducted to study the burnished workpieces deformed microstructures. A comparison between SEM photomicrographs of the initial surface and

(a)

(b)

(c)

Figure 3: SEM micrographs of Co-Cr-Mo discs before (a) and after burnishing: (b) dry, (c) cryogenic In order to characterize the hardness variation in the surface region of the processed Co-Cr-Mo workpieces, microhardness measurements were made. The minimum measurement depth from the surface is 5 m in order to avoid the edge softening effect. For each depth, at least three measurements were taken. The microhardness profiles shown in Figure 4 were averaged values from these measurements.

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Vy

V 0  kD 1/ 2

(1)

Figure 4:Subsurface microhardness profiles for cryogenic and dry burnished Co-Cr-Mo discs The measured microhardness of the virgin disk is 430 HV on average. Comparing to the initial workpiece hardness, an increase of up to 80% was achieved after cryogenic burnishing. With the same burnishing conditions, the application of liquid nitrogen led to higher hardness value and larger process-influenced depth comparing to dry burnishing. The general trend of the curves shows a gradual decrease in microhardness with distance below the surface until the bulk value is reached. Based on the well-known Hall-Petch relationship [23]:

between yield stress (y) and grain size (D) as well as the close interrelations among hardness, yield stress, and residual stresses, high hardness values often indicate fine grain size and large residual stresses. In other word, grain size and residual stresses collectively contribute to the hardness value. In our current work, microstructure changes due to different cooling conditions were only observed within 20 m depth from the surface. In contrast, microhardness differences were measured to the depth of 250 m. It is reasonable to state that the variations in microhardness were due to the different residual stresses being generated during processing. The residual stresses of the processed samples will be measured using X-ray diffraction techniques to validate this hypothesis. These results will be published later. Figure 5 shows the results of the EDS analysis. Measurements were taken on the processed surface and bulk of specimens. The higher oxygen amount on the surface is due the formation of chromium oxide during processing, which is believed to protect the surface from electrochemical degradation and improve corrosion resistance [24].

(a)

(b)

Figure 5: EDS results of Co-Cr-Mo discs from cryogenic burnishing: (a) bulk, (b) surface 3.2 AZ31 Mg alloy of about 8 m in which grain boundaries were no longer visible (at this magnification) was created by machining.

The initial microstructure of the AZ31 Mg disc is shown in Figure 6. There is no twinning in the bulk material since the as-received material is annealed. However, twinning is visible near the surface of the disc. This is due to the sample preparation in the machine shop where a turning operation is used as the final step in making the disc.

Figure 7: Microstructure of AZ31 Mg discs after cryogenic machining Figure 8(a) shows the microstructure after cryogenic burnishing, in which a 2 mm process-influenced layer was formed, which is similar to the machined surface. The grain structure in the burnished surface region (Figure 8(b)) was no longer discernable compared to the clearly defined microstructure prior to processing (Figure 5). The transition between the initial microstructure and the process-influenced microstructure can clearly be seen in Figure 8(c).

Figure 6: Initial microstructure of AZ31 Mg discs before processing The microstructure obtained from cryogenic machining is shown in Figure 7. Significant changes in microstructure near the processed surface were found; a SPD surface layer

Cryogenic Processing of Biomaterials for Improved Surface Integrity and Product Sustainability 179

(a)

(b)

(c)

Figure 8: Microstructure of AZ31 Mg discs after cryogenic burnishing: (a) cryogenic burnishing; (b) surface layer in (a); (c) transition layer in (a) SEM investigations were undertaken for better study of the severe plastic deformed layer from burnishing. As shown in Figure 9, highly uniform grains were present in the burnished surface layers; the grain sizes are generally less than 500 nm, although grains less than 300 nm can be found close to the surface. Comparing to the 10 m grains before burnishing, the grain size on the burnished surface was more than 20 times smaller. experiments resulted in significant grain refinement in the surface region through burnishing-induced SPD. Microhardness in the SPD layer was increased up to 80% relative to the bulk value.

Figure 10: Subsurface microhardness profiles of AZ31 Mg discs before and after cryogenic processing Figure 9: SEM micrograph of AZ31 Mg disc surface region from cryogenic burnishing

Figure 10 shows the microhardness profiles of AZ31 Mg discs before and after cryogenic processing. The initial hardness of the material was measured to be about 50 HV. The hardness values near the surface on these three profiles (Figure 10) were increased to different extents. The increase of hardness on the edge of the initial disc is due to the disc preparation in the machine shop. Comparing to the bulk material, the measured hardness at about 15 m from the surfaces was increased about 60% during cryogenic machining and 95% by cryogenic burnishing, which indicate significant grain refinement based on the classical Hall-Petch equation (1). 4 SUMMARY

AZ31 Mg alloy was subjected to both cryogenic machining and burnishing processes. The cryogenic burnishing process led to a more than 2 mm thick surface layer with remarkably refined microstructures formed on the burnished surface. A 95% increase in hardness was obtained on the burnished surface, where grains less than 300 nm were observed under scanning electron microscopy. A SPD layer was shown to form on the surface of AZ31 Mg disc after cryogenic machining. The hardness of this layer was about 60% larger than the bulk material. It has been reported that the corrosion resistance of the AZ31 Mg alloy in simulated body fluid was enhanced due to the formation of this SPD layer [14][25]. The present results demonstrate that both cryogenic processes significantly modify the surface properties of CoCr-Mo and AZ31 Mg alloys and, therefore, may enhance their performances for improved sustainability. Systematic studies will be done to further investigate the influence of various processing conditions on microstructural changes of Co-Cr-Mo and AZ31 Mg alloys. Pin-on-disc wear testes will be conducted for studying the relationship

Two manufacturing processes machining and burnishing are shown to be viable SPD routes for introducing ultrafine or nano-sized grains into the surface region of Co-Cr-Mo and AZ31 Mg alloys. Cryogenic burnishing of Co-Cr-Mo alloy

180 S. Yang et al. between microstructure and wear resistance of Co-Cr-Mo alloy. 5 ACKNOWLEDGMENTS We sincerely thank to Air Products and Chemicals for supplying the equipment for liquid nitrogen application and Dr. Fuqian Yang (Material Science Dept., Univ. of Kentucky) for providing the equipment for microhardness measurements. Additional thanks to our technicians Bill Young and Richard Anderson for their valuable help on conducting the experimental work. 6 [1] REFERENCES Wang, Z.B. et al., Effect of surface nanocrystallization on friction and wear properties in low carbon steel, 2003, Mater. Sci. Eng., 352:144-149. Karimpoor, A.A., Erb U., Aust, K.T. and Palumbo, G., High strength nanocrystalline cobalt with high tensile ductility, 2003, Scripta Material, 49: 651656. Shi, Y.N. and Han, Z., Tribological behaviors of nanostructured surface layer processed by means of surface mechanical attrition treatment, 2008, Key Eng. Mater., 384: 321-334. Swaminathan, S., Shankar, M.R., Lee, S., Hwang, J., King, A.H., Kezar, R.F., Rao, B.C., Brown, T.L., Chandrasekar, S., Compton, W.D., and Trumble, K.P., 2005, Large strain deformation and ultra-fine grained materials by machining, Mater. Sci. Eng. A, 410411: 358363. Altenberger I., Scholtes B., Martin U. and Oettel H., Cyclic deformation and near surface microstructures of shot peened or deep rolled austenitic stainless steel AISI 304, 1999, Mater. Sci. Eng. A, 264: 116. Nalla, R.K., Altenberger, I., Noster, U., Liu, G.Y., Scholtes, B., and Ritchie, R.O., On the influence of mechanical surface treatments-deep rolling and laser shock peening on the fatigue behavior of Ti-6Al-4V at ambient and elevated temperatures, 2003, Mater. Sci. Eng. A, 355: 216-230. Nikitin, I., Altenberger, I., Maier, H.J., Scholtes, B., 2005, Mechanical and thermal stability of mechanically induced near-surface nanostructures, Mater. Sci. Eng. A 403: 318327 Yang, L. and Zhang, E., 2009, Biocorrosion behavior of magnesium alloy in different simulated fluids for biomedical application, Mater. Sci. Eng. C, 29: 1691 1696. Prevey, P. and Cammett, J., 2001, Low cost corrosion damage mitigation and improved fatigue performance of low plasticity burnished 7075-T6, J. Mater. Eng. Perform. 10: 54855. [12] Iglesias, P., Bermudez, M.D., Moscoso, W., Rao, B.C., Shankar, M.R. and Chandrasekar, S., Friction and wear of nanostructured metals created by large strain extrusion machining, 2007, Wear, 263: 636642. [13] Ramesh, A., Melkote, S.N., Allard, L.F., Riester, L., Watkins, T.R., 2005, Analysis of white layers formed in hard turning of AISI 52100 steel, Mater. Sci. Eng. A, 390: 8897. [14] Pu, Z., Puleo, D.A., Dillon, Jr., O.W. and Jawahir, I.S., controlling the biodegradation rate of magnesium-based implants through surface nanocrystallization induced by cryogenic machining, 2011, TMS, in press. [15] Li, W.L., Tao, N.R. and Lu, K., Fabrication of a gradient nano-micro-structured surface layer on bulk copper by means of a surface mechanical grinding treatment, 2008, Scripta Material, 59: 546549. [16] Ni, H., Elmadagli M. and Alpas, A.T., Mechanical properties and microstructures of 1100 aluminum subjected to dry machining, 2004, Mater. Sci. Eng. A, 385: 267278. [17] Disegi, J.A., Kennedy, R.L. and Pilliar, R., Cobalt-based alloys for biomedical applications, 1999, Technology & Engineering, Book Chapter. [18] Hsu, H.C. and Lian, S.S., Wear properties of Co-Cr-MoN plasma-melted surgical implant alloys, 2003, J. Mater. Process. Technol., 138: 231-235. [19] Nasab, M.B. and Hassan M.R., Metallic biomaterials of knee and hip - A review, 2010, Trends Biomater. Artif. Organs, Vol. 24(1): 69-82. [20] Yamanaka, K., Mori, M., Kurosu, S, Matsumoto, H., and Chiba, A., Ultrafine grain refinement of biomedical Co29Cr-6Mo alloy during conventional hot-compression deformation, 2009, Metallurgical and Mater. Trans. A, 40: 1980-1994. [21] http://www.cartech.com/news.aspx?id=578, Feb. 2008. [22] Wu, X., Tao, N., Hong, Y., Liu, G., Xu, B. and Lu, J., Strain-induced grain refinement of cobalt during surface mechanical attrition treatment, 2005, J. Acta Mater, 53: 681-691. [23] Meyers, M. and Chawla, K., Mechanical behavior of materials, 2009, 2nd edition, Cambridge Univ. Press. [24] Hallab, N.J. and Jacobs, J.J., 2003, Orthopedic Implant Fretting Corrosion, Corrosion Reviews, Vol. 2 J, Nos. 23: 184-213. [25] Pu, Z., Puleo, D.A., Dillon, Jr., O.W. and Jawahir, I.S., 2010, Microstructural changes of AZ31 magnesium alloys induced by cryogenic machining and its influence on corrosion resistance in simulated body fluid for biomedical applications, MSEC2010, in press.

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