Probing nano-scale phase separation at atomic resolution

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Probing nano-scale phase separation at atomic resolution within #-type Ti - Mn alloy; a potential candidate for biomedical implants Pritam Banerjee, Chiranjit Roy, Mohamed A.-H. Gepreel, Amit Ranjan, Soumya basu, and Somnath Bhattacharyya ACS Biomater. Sci. Eng., Just Accepted Manuscript • DOI: 10.1021/ acsbiomaterials.9b00808 • Publication Date (Web): 28 Aug 2019 Downloaded from pubs.acs.org on August 31, 2019

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ACS Biomaterials Science & Engineering

Probing nano-scale phase separation at atomic resolution within β-type Ti - Mn alloy; a potential candidate for biomedical implants

Pritam Banerjee1‡, Chiranjit Roy1‡, Mohamed A.-H. Gepreel2, Amit Ranjan3, Soumya Basu3, Somnath Bhattacharyya1*

1

Department of Metallurgical and Materials Engineering, Indian Institute of Technology

Madras, Chennai 600036, India 2 Department

of Materials Science and Engineering, Egypt–Japan University of Science and

Technology, New Borg El-Arab City, Alexandria 21934, Egypt 3

Cancer and Translational Research Laboratory, Dr. D. Y. Patil Biotechnology and

Bioinformatics Institute, Dr. D. Y. Patil Vidyapeeth, Tathawade, Pune 411033, India

*

Corresponding author: [email protected]

‡

Equally contributed as first authors

Abstract Biocompatible β-type Ti alloys with high ultimate tensile strength (UTS) and Yield strength are potential candidates for certain orthopaedic and cardiovascular implants. Aiming for these applications, Ti alloy with 14 wt% Mn (Ti – 14 Mn) as β-stabilizer was processed through thermo-mechanical treatment along with solutionizing and quenching followed by 95% cold rolling which resulted in ultra-high UTS and Yield strength. MTT assay with different cell lines suggests efficient cell growth on alloy surface without compromising biocompatibility. Cell adhesion and spreading assay show that cells are not only able to attach to the alloy surface but also able to spread and grow with normal morphology which projects this material a potential candidate for biomedical application. Previous studies on binary β-type Ti alloy systems treated with the above-mentioned processing route confirm the presence of 1 ACS Paragon Plus Environment

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nano-scale phase separation, which enhances its mechanical properties. To discover the same phenomena in the alloy of the present study, bright field and high-resolution Transmission Electron microscopy(HRTEM) imaging were performed and nano-scale contrast-modulated lamella regions were observed. Geometrical Phase analysis (GPA) on complex valued exit wave, reconstructed using focal series HRTEM images demonstrates that the lamella is a result of d-spacing modulation. Ab-initio calculation indicates that d-spacing modulation with the same crystal structure occurs due to composition modulation and was proved by Scanning Transmission Electron Microscopy (STEM) imaging coupled with quantitative Energy Dispersive X ray Spectroscopy (EDXS). Correlating contrast, strain and composition modulation confirms nano-scale phase separation which is the first report of this phenomenon in Ti-Mn alloy system.

Keywords : Ti-Mn alloy; Phase separation; Biocompatibility; Scanning/ Transmission Electron microscopy; Density Functional Theory

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1. Introduction In the last few decades, a lot of research has been done in the biomedical sector to replace commonly used metallic materials like SUS316L stainless steel and Co–Cr–Mo alloys with other alloys of superior properties and biocompatibility 1. SUS316L stainless steel contains Ni which can damage the body’s immune system and can also hamper magnetic resonance imaging (MRI) diagnosis due to its Ferromagnetic property 2. Similarly, Co-Cr-Mo alloys contain Co and Cr both of which have allergenic behaviour that is harmful to the human body 1.

Moreover, higher Young’s Modulus of both these materials also limit their application in

the biomedical field. To meet the requirements of the biomedical sector, novel β-type Ti alloys have been developed by introducing β-stabilisers such as V, Cr, Fe, Al, Nb, Mo, Zr, Ta, W, and Mn, etc. These β-type Ti alloys have now been widely used because of their good biocompatibility, excellent corrosion and wear resistance, low-to-moderate Young’s Modulus and low cytotoxicity 3. But there is a limitation in the biomedical sector in case of Nb, Zr or Ta elements due to its market unavailability with higher cost and melting point4. Similarly, V and Al-containing alloys with satisfactory mechanical properties also have limited application in the biomedical sector because of their toxicity 5. Recently, a β type Ti alloy containing Mn addition is emerging as a potential candidate for the biomedical sector because of its low cost, availability of Mn, biocompatibility, and excellent mechanical properties 6. Although some reviewer has mentioned that high quantity of Mn for a longer culturing time can affect the immune system of a human body7 8 but several recent studies indicate that the incorporation of manganese in orthopeadic implants with care9 improves bio responses and cell adhesions by activating integrins10. In a very different study, Dey et al in 2013 have designed an Mn-chelate which showed anti-tumor activity in drug resistant tumor cells but is non-toxic in vivo 11 . β-type Ti alloys find their application in biomedical implants such as spine bearings disks, pacemaker case, cardiac valves, middle ear implants, dental screws, bone fracture fixations etc. 12. To be useful for the above mentioned biomedical applications, the alloy must exhibit good biocompatibility with very high ultimate tensile strength (UTS). It is well known that thermomechanical processing can affect the mechanical properties of alloys by optimizing several parameters like temperature, strain and strain rate etc. which finally result in optimization of microstructure

13,14.

In β-type Ti alloy systems, a remarkable amount of strength is observed

after thermo-mechanical treatment along with solution treatment and quenching followed by cold rolling due to the enhancement of dislocation density, reduction of grain size and porosity, 3 ACS Paragon Plus Environment


the formation of a deformation-induced ω phase

15

and more significantly due to nano-scale

phase separation 16. A. Biesiekierski et al. reported the occurrence of nano-scaled dual cubic spinodal reinforcement in Ti-Zr-Ta alloys to result in extremely high yield strength of 1.4 GPa without compromising biocompatibility17. Phase separation phenomenon was also observed in β-Ti–Nb–Zr–Ta alloy having a suitable combination of yield strength and low Young’s modulus for orthopaedic implant examined by C.R.M. Afonso et al.18. Yang and Zhang also studied phase separation and its effect on mechanical properties of biocompatible 50Ti–30Zr– 10Ta–10Nb (at.%) alloy19. Phase separation was also reported in other binary β-Ti alloy systems such as Ti-V20, Ti-Mo21 and Ti-Cr22. Therefore it can be concluded from the previously reported results that phase separation improves mechanical properties of the alloys for biomedical implant applications without effecting the biocompatibility. In present work, Ti -14 Mn alloy after thermo-mechanical treatment exhibited an exceptionally high tensile strength which is among the highest UTS reported for Ti alloys23. To propose this alloy a potential candidate for certain biomedical orthopaedic and cardiovascular implants due to its extraordinary mechanical properties, biocompatibility studies were performed and results were compared that with CP-Ti. To probe the reason behind this excellent mechanical property, the micro-structural analysis was performed using Transmission Electron Microscope (TEM). Conventional bright field imaging reveals the presence of nano-scale contrast modulated lamella in the beta matrix, which is the key feature of phase separation. Best of our knowledge, there is no report available so far which claims the presence of phase separation in the Ti – Mn alloy system. To prove the phase separation phenomenon occurred in Ti-Mn system, atomic scale structural and compositional characterization was done using advanced transmission electron microscopy techniques and results were validated using density functional theory calculations.

2. Material and Methods

Ti-Mn ingot of (100gm) was prepared by arc melting of elemental constituents (99.9% purity, The NILACO Corporation, Tokyo, Japan) under argon atmosphere while using electromagnetic stirrer during melting to assure good elemental mixing. The ingots were hot rolled at 850˚C for 40 % reduction in thickness. The hot rolled sample was solution-treated at


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900˚C followed by water quenching to room temperature. Further 95 % reduction in thickness was introduced by cold rolling, referred cold rolled hereafter. 2.1. X-ray diffraction The X-ray diffraction (XRD) pattern of the solution treated cold rolled sample was obtained using monochromatic Cu Kα radiation (λ = 1.54 Å) via X'pert Pro PANalytical machine having a step size of 0.005˚ and operating at 45 kV and 30 mA in a 2θ range of 20–80°. 2.2. Tensile test The Ultimate tensile stress (UTS) was measured by tensile testing of the cold rolled specimen using Shimadzu AGS-X universal testing machine with a crosshead speed to achieve an initial strain rate of 10 ―4 s-1. 2.3. Biocompatibility examination In vitro cytotoxicity assay as well as Cell adhesion and spreading assays were performed as the initial phase of the biocompatibility examination. Before performing biocompatibility experiments, the surfaces of the material examined were polished using emery papers up to 2400 grit size followed by mirror finish polishing with diamond paste. The polished samples were cleaned using deionized water with 70% ethanol and then sterilized in an autoclave at 120ºC temperature and 15 Psi pressure for 30 mins. 2.3.1. Cell Culture The osteosarcoma cells (MG-63) were maintained in Eagle's Minimum Essential Medium (Himedia, India), supplemented with heat-inactivated fetal bovine serum (FBS) to a final concentration of 10% (Gibco, USA). Mouse embryonic fibroblast (MEF), a primary cell line was maintained in Dulbecco's Modified Eagle's medium, supplemented with 15% FBS. F12K medium supplemented with 10% FBS was used to maintain Lung carcinoma A549 cells. Additional glutamine (2 mM) and 1% penicillin, streptomycin sulfate and amphotericin B were added to each medium. Cells were grown in plastic tissue culture flasks (Nunc, USA) in a 5% CO2 atmosphere at 37ºC (Galaxy 170 S incubator, Eppendorf). Exponentially growing cultures were used for all experiments. All experiments were repeated for three times. All the cell lines were procured from National Centre for Cell Sciences, India repository.



2.3.2. In vitro cytotoxicity assay To evaluate the cytotoxicity effect of the investigated material, MG-63, MEF and A549 cells were cultured individually on polished specimens. The specimens (Ti-CP alloy as positive control and Ti – 14 Mn alloy) were placed in 12 well polystyrene coated culture plates25. The cells were seeded at a density of 25,000 cells/per mL and cultured for 24h, 48h and 72h. The data generated were from three separate experiments, each performed in triplicate. Cell viability was determined using MTT assay, which was carried out as described previously 26 with slight modifications. After the completion of the incubation period, 3-[4,5-dimethylthiazol-2-yl]-2,5diphenyltetrazolimbromide (MTT) solution at a concentration of 5mg/mL was added to each culture well and the plate containing specimens was incubated for another 4 h in 5% CO2 atmosphere at 37ºC to form the formazan precipitates. The supernatant was aspirated and the cells (cells grown on alloy and without alloy) were trypsinized with 0.25% trypsin-EDTA for 1 min. Cells were centrifuged at 1000 rpm for 5 min and then formazan crystals inside cells were dissolved with 150 µL dimethyl sulfoxide for 10 min and transferred into a 96-well plate for optical density (OD) measurement. The optical density was determined at 540 nm using an enzyme-linked immunosorbent assay reader (BioTek-Epoch, USA). To provide statistical results comparison, standard deviation (SD) was calculated. 2.3.3. Cell adhesion and spreading assays Briefly, MG-63 cells were harvested and seeded at a cell density of 1.5 x 106 cells/ml in a complete medium on P35 mm culture dishes containing the metallic plates and were incubated for another 96 h. Cells were fixed in 4% paraformaldehyde and permeabilized with 0.5% Triton X-100 for 15 min and stained with 2 μg/mL Phalloidin-FITC staining solution made in PBS (containing 10% Methanol, 0.5% BSA in PBS) for 30 min at room temperature. Nuclei were stained with 5 μg/ml of 4',6'-diamidino-2phenylindoledihydrochloride (DAPI) in PBS for 5 min. Images were acquired at Venture Center, Pune, India using Leica SP8 Spectral Confocal laser scanning microscope at 20X magnification. 2.4. Transmission Electron Microscopy (TEM) studies Small 3mm disc pieces were punched from 140 μm thickness slice for TEM sample preparation. After that grinding followed by dimpling were done from both the sides to bring 6 ACS Paragon Plus Environment

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down the disc thickness to 10 to 15 micron, and finally double sided Ar ion-beam thinning was performed using Gatan Model 651 Precision Ion Polishing System (PIPS). Ion beam thinning was performed at a temperature of -160˚C, at small angles ( 0) means the system favours the formation of A-A and B-B bonds compared to A-B bonds results in A-rich and B-rich region44. In alloy systems with positive alloy formation energy, entropy contribution is small at low temperature hence Gibbs free energy curve shows a negative curvature in the middle of the phase diagram and the miscibility gap appears. As discussed in Fig. 5.4 of 44, if the interfacial energy effect due to composition gradient across the interface of the two phase region and coherence strain energy effect due to different size of constituent atoms are included in the chemical free energy term, then coherent miscibility gap forms44. Alloy composition that falls under coherent miscibility gap undergoes phase separation either by spinodal decomposition24 or nucleation and growth mechanism45. If the composition lies within the coherent spinodal region then phase separation occurs by spinodal decomposition without any activation energy barrier. If the alloy composition lies between coherent miscibility gap 18 ACS Paragon Plus Environment

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and coherent spinodal, then the alloy phase separates by nucleation and growth as shown in figure 5.41 of ref44. The phase separated (β1) and (β2) phases have coherent boundary across the interface, which is possible due to early-stage nucleation as discussed in ref 45 or due to spinodal decomposition24. For phase separation to occur, the supersaturated solid solution at high temperature needs to be quenched to room temperature. In Ti-Mn phase diagram46, the Ti-Mn solid solution having BCC crystal structure with higher Mn solubility is stable at high temperature. When the alloy is cooled slowly, below eutectoid temperature β-Ti phase transforms to α-Ti phase and TixMn1-x intermetallic phase. Whereas the high temperature β-Ti phase when quenched to room temperature after solution treatment, the supersaturated solid solution of beta phase is retained. The β-Ti phase is a non-equilibrium phase at room temperature, which tends to undergo phase separation to lower the system energy. Only incoherent equilibrium phases appear in the miscibility gap on an equilibrium phase diagram. Coherent miscibility gap containing coherent metastable phases results of phase separation does not appear in the equilibrium phase diagram as discussed in ref44. The phase separation phenomenon has been observed in Ti alloys such as Ti-V20, Ti-Mo21, Ti-Cr22 and other systems as well47 18 48. The solution treated cold rolled Ti – Mn alloy when examined in conventional TEM, contrast modulated lamella was observed which is the key feature of phase separation49. The contrast modulated lamella consist of alternating bright and dark region corresponds to the two phase region (β1) and (β2) phase respectively. Highresolution lattice images with the help of stereographic projection prove these lamella appear along direction, which is the elastically soft direction in the cubic system24. The streaking of the diffraction spots appeared in the power spectrum in figure 3(c) & figure 3(e) shows that there is variation in d-spacing across the two phase lamella. It means that β1 and β2 phase have the same crystal structure but the only difference in lattice parameter which is reported for other alloy systems as well50 18 21. Determination of strain variation within contrast modulated region using GPA on the reconstructed phase of exit wave also shows that these contrast modulated regions are alternate tensile (bright contrast) and compressive (dark contrast) region, therefore, an increased or decreased in d-spacing with same crystal structure is perpendicular to the length of lamella on the image plane. Ab-initio calculation outlines that by keeping the same crystal structure, increasing of Mn content reduces lattice parameter which indicates the compressive 19 ACS Paragon Plus Environment


region should be of Mn rich and vice versa. Comparing with ABF-HRSTEM and HAADFHRSTEM images, it can be explained that bright contrast in ABF-HRSTEM becomes dark contrast in HAADF-HRSTEM and vice versa. Since contrast in HAADF-HRSTEM image governs by atomic number contrast, so, bright contrast in HAADF-HRSTEM image (dark contrast in ABF-HRSTEM image) indicates the presence of Mn-rich region, as Mn has higher atomic number than Ti. EDXS spot analysis quantitatively verified that the dark region in ABF-HRSTEM image contains more Mn than Ti and vice versa which is the compressive region in strain variation, hence exhibit smaller d-spacing. A similar observations were also reported for the V-Ti20, V-Ti-Cr51, Fe-Cr52 and Ti-Mo53 system where phase separation occurred. This result correlated well with ab initio calculation that Mn-rich structure has a smaller lattice parameter compared to the base Ti – 14 Mn alloy structure. DFT calculations also conclude that the Ti-Mn system has clustering tendency as system favours the formation of more number of Mn-Mn bonds in the system and Mn atom like to be surrounded by Mn atoms. Alloy formation energy is statistically related to the difference in electronegativity between atoms54. Lower is the electronegativity difference, higher is the alloy formation energy and vice-versa. Ti and Mn have an electronegativity difference of 0.01 similar to CuNi system which has positive alloy formation energy, clearly indicates that Ti-Mn could have positive alloy formation energy, which is responsible for clustering results in phase separation. Finally, it can be stated that the nano-scale contrast-strain-composition modulated lamella is nothing but the result of phase separation, where beta supersaturated solid solution of Ti-14 Mn is stable at high-temperature upon quenching after solution treatment, decomposes into two coherent phases like Mn-rich and Mn-lean as the system has a clustering tendency 55. The composition variation between two decomposed phases result in a change in lattice parameters with the same BCC crystal structure as of parent phase, therefore, introduces internal coherent elastic strain variation in the matrix. So, these coherency strain and nano-scale phase separation with severe cold rolling; both are responsible for ultra-high yield strength of this β-type Ti-Mn alloy via hardening mechanisms which were already established by cahn et al.42 where the yield strength or hardness varied with the amplitude of composition fluctuation56. Lastly, it is difficult to conclude whether the mechanism of phase separation is occurred due to spinodal decomposition or nucleation and growth mechanism without knowing the 20 ACS Paragon Plus Environment

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occurrence of the alloy composition within the coherent miscibility gap but the result from experimental and theoretical aspect clearly confirms that the feature is observed only due to phase separation.

5. Conclusion The β-type Ti – 14 Mn alloy of present study exhibits ultrahigh UTS, Yield strength and no cytotoxicity with very good cell adhesion and spreading behaviour which support to propose this alloy a potential candidate for certain biomedical orthopaedic and cardiovascular implants. Conventional bright field HRTEM imaging reveals the presence of contrastmodulated nano-lamella regions which were proved as the signature of nano-scale phase separation using power spectrums, strain mapping within lamellar region, ab-initio calculations, ABF-HRSTEM with HAADF-HRSTEM image comparison coupled with quantitative EDXS analysis. Supporting Information 

Tensile properties of different grade of biomaterials, change in lattice parameter with Mn concentration; and relation between energy of the system with minimum interatomic Mn-Mn atom distance in supercell and cytotoxicity test of CP-Ti alloy on different cell lines at different intervals of time.

Acknowledgments This work was supported by the International Bilateral Cooperation Division, Department of Science and Technology, Government of India [DST/INT/Egypt/P-12/2016, 2016] and Academy of Scientific Research and Technology (ASRT) of Egypt. Biocompatibility study was supported by DST Early Career Research Award (ECR/2016/000943), Department of Science and Technology, Government of India and Dr. D. Y. Patil Vidyapeeth’ seed grant [DPU/14/2016, dated 06/01/2016]. The authors express sincere gratitude to Prof. Rajarshi Banerjee, Department of Materials Science and Engineering, University of North Texas, USA for fruitful discussion on phase transformation in Ti alloy systems. Conflict of interest There is no conflict of interest. 21 ACS Paragon Plus Environment


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Probing nano-scale phase separation at atomic resolution within β-type Ti - Mn alloy; a potential candidate for biomedical implants

Pritam Banerjee, Chiranjit Roy, Mohamed A.-H. Gepreel, Amit Ranjan, Soumya Basu, Somnath Bhattacharyya

For Table of Contents Use Only


Page 28 of 28

Probing nano-scale phase separation at atomic resolution

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