Physical and Mechanical Properties of Co Based Thin Films for Window
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Physical and Mechanical Properties of Co Based Thin Films for Window Targets in Accelerators Thesis submitted in partial fulfillment of the requirements for the degree of “DOCTOR OF PHILOSOPHY” by Shlomo Haroush 01/12/2016 Submitted to the Senate of Ben-Gurion University of the Negev Beer-Sheva Physical and Mechanical Properties of Co Based Thin Films for Window Targets in Accelerators Thesis submitted in partial fulfillment of the requirements for the degree of “DOCTOR OF PHILOSOPHY” by Shlomo Haroush May 2017 Submitted to the Senate of Ben-Gurion University of the Negev Beer-Sheva Physical and Mechanical Properties of Co Based Thin Films for Window Targets in Accelerators Thesis submitted in partial fulfillment of the requirements for the degree of “DOCTOR OF PHILOSOPHY” by Shlomo Haroush Submitted to the Senate of Ben-Gurion University of the Negev Approved by the advisors Prof. Roni Z. Shneck: ________________________ 01/05/2017 Prof. Yaniv Gelbstein: ________________________ 01/05/2017 Approved by the Dean of the Kreitman School of Advanced Graduate Studies: Prof. Michal Shapira: ____________________________ May 2017 Beer-Sheva This work was carried out under the supervision of Prof. Roni Z. Shneck Prof. Yaniv Gelbstein In the Department of Materials Engineering Faculty of Engineering Sciences Research Student's Affidavit when Submitting the Doctoral Thesis for Judgment I, Shlomo Haroush, whose signature appears below, hereby declare that: I have written this Thesis by myself, except for the help and guidance offered by my Thesis Advisors. The scientific materials included in this Thesis are products of my own research, culled from the period during which I was a research student. This Thesis incorporates research materials produced in cooperation with others, excluding the technical help commonly received during experimental work. Therefore, I am attaching another affidavit stating the contributions made by myself and the other participants in this research, which has been approved by them and submitted with their approval. Date: May 01, 2016 Student's name: Shlomo Haroush Signature: Acknowledgements I would like extend my gratitude to my supervisors: Prof. Roni Z. Shneck and Prof. Yaniv Gelbstein from the Department of Materials Engineering at BGU. Their advice, experience and emotional support guided me through this study were a treasure for me. Special thanks to Prof. Luisa Meshi, and Dr. Sergei Remennik from the Department of Materials Engineering at BGU, Dr. Volodia Ezersky from the Ilse Katz Inst. for Nano-Science and Technology, Dr. Elad Priel from Mechanical Engineering Department, Shamoon College, and Dr. Giora Kimel for their help in understanding the experimental results. Many thanks to my dear friends from the NRCN, Asher Turgeman, Mimon Cohen, Ofer Sabag, Yair George and Michal Gelbstein for their help in the mechanical testing and heat treatments. In memoriam to my late mother – Sabina and my late father - Ben-Zion To my wife Dganit and my children Dotan, Eyal and Or for their support and patience throughout this long period of time until accomplishing my PhD. Abstract The mechanical properties of high strength Co Based alloys have been intensively investigated. However, the hardening mechanisms due to cold work and, especially, after heat treatments are not fully understood because of the microstructural complexity and the interplay of several hardening mechanisms. This limited knowledge and understanding led us to investigate the HAVAR alloy in different metallurgical states. HAVAR is a corrosion resistant high strength Co based alloy. One of HAVAR‘s applications is as a thin foil "window" in a medical cyclotron for 18 H2O targets, used to produce fluorodeoxyglucose. During irradiation, the HAVAR window may be damaged due to radiation effects and exposure to high temperatures. These severe conditions degrade the mechanical properties up to total failure. Window failure during the fluorodeoxyglucose production is an unacceptable scenario, so that understanding the strengthening mechanism of HAVAR, especially due to heat treatment, is a very important issue. Thin foils having thicknesses of 200 m and below are commonly applied in the food industries and for shielding, vacuum chamber and medical applications, where for the latter, a HAVAR cyclotron window of 25 m is required for fluorodeoxyglucose production. The Small Punch Test technique is known as a promising mechanical testing method for thin foils thicker than 250 µm, in which a formulation correlating the measured parameters to standard tensile properties has previously been reported. The present work focused on understanding the correlation between mechanical properties and the microstructure evolution during cold rolling and heat treatment of HAVAR. Furthermore, the research focused on the correlation between Small Punch Test results and the tensile mechanical properties of thin foils in the range of 100 to 200 µm. The Small Punch Test experiments were done using SS-316L foils, since these are much cheaper than HAVAR alloy foils. Research observations show that the annealed state of HAVAR alloy is a solid solution comprising an FCC structure, equiaxed grains, very low dislocation density and a low amount of annealing twins. During plastic deformation by rolling, up to 20% large twins form across the grains. As cold rolling increases (up to 44%) a variety of defects evolve, subdividing the large twins. These defects include dislocations, stacking faults, micro-twins and thin strain induced platelets. At higher degrees of deformation (85%), the matrix contains very high dislocation density, twins, micro-twins and fine grains, which form a mosaic-like structure. The overall changes in the microstructure are the hardening mechanisms responsible for the increase of the tensile yield stress from 400 MPa in the annealed state up to 1900 MPa at the 85% cold rolled state. Heat treatment following cold work, between 500°C and 700°C, invokes a secondary hardening mechanism that enhances the yield strength to above 2000 MPa and eliminates the ductility. This treatment did not disrupt the cold rolled microstructure, but added homogeneous precipitation of fine cubic M23C6 carbides of sub-nanometer size. This carbide precipitation is responsible for the enhanced strength. The alloy regains ductility by recrystallization, starting around 700°C. The precipitated particles were very fine therefore, electron diffraction could not detect their crystallographic structure. A set of cold rolling followed by heat treatments were done, from high temperature (900C) scale down to 500C using TEM images, electron diffraction and elemental analysis indicate that these particles are cubic (Cr,Co,Mo)23C6 carbides. The research observations demonstrated, by finite element analysis of thicknesses in the range 25 to 500 µm, that for foils thicker than 300µm thin plate bending equations, which were applied previously for thicker specimens, are still valid. On the other hand, for thinner specimens this theory fails to provide adequate correlation between the results of the Small Punch Test and tensile yield stress. For specimens thinner than 50 µm it was identified that equations derived from membrane solution should be employed rather than classical plate theory. For intermediate thickness values in the 50 to 300 µm range, a "transition zone" was identified between plate and membrane like mechanical responses. For the lower region of this "transition zone" (50 to 100 µm), an analytical expression correlating the measured Small Punch Test parameters and the tensile yield stress is currently proposed, facilitating a simple interpretation of the yield stress of foils in this thickness range from Small Punch Test measurements. It was also shown, using numerical analysis, that for specimens thinner than 50 µm, the classical “region I” of elastic bending does not exist and membrane stretching is dominant. Keywords: Co based alloy, HAVAR, Cold rolled, Heat treatment, Microstructure, Carbide, TEM, Thin foils, Mechanical properties, Small Punch Test, Finite Element Analysis Table of content 1. Background ...................................................................................................... 9 1.1. The element Cobalt (Co) ................................................................................... 9 1.1.1. Physical properties ............................................................................................... 9 1.1.2. Mechanical properties ........................................................................................ 10 1.2. Cobalt-based alloys .......................................................................................... 10 1.2.1. Wear-resistant alloys .......................................................................................... 11 1.2.2. High-temperature alloys ..................................................................................... 11 1.2.3. Corrosion resistant alloys ................................................................................... 12 1.3. The HAVAR alloy............................................................................................. 15 1.4. Small punch test ............................................................................................... 17 2. Research goals ............................................................................................... 23 2.1. Study of the mechanical properties of thin foils .............................................