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\babel@toc {english}{}\relax
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\contentsline {xpart}{Chapters}{2}{part.1}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Introduction}{2}{chapter.1}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Materials and Experimental Test Procedure}{16}{chapter.2}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Results and Analysis}{22}{chapter.3}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Discussion}{29}{chapter.4}%
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\contentsline {xchapter}{Conclusions}{32}{chapter.5}%
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\contentsline {xpart}{Weird hanger-ons}{34}{part.2}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Erosion particles}{34}{chapter.6}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Reasons for why CE is less in seawater}{35}{chapter.7}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Residual Stress and why it's important}{36}{chapter.8}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Why HIP is better than cast}{37}{chapter.9}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Equiaxed grains - why HIP is better than cast}{38}{chapter.10}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Describing SEM images (light gray, dark, light)}{39}{chapter.11}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Stellite 1}{40}{chapter.12}%
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\contentsline {xchapter}{Parametric studies on Stellite}{41}{chapter.13}%
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\babel@toc {english}{}\relax
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\contentsline {xpart}{Chapters}{2}{part.1}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Introduction}{2}{chapter.1}%
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\contentsline {table}{\numberline {1.2}{\ignorespaces Cr3C2}}{9}{table.caption.6}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Materials and Experimental Test Procedure}{16}{chapter.2}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Results and Analysis}{22}{chapter.3}%
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\contentsline {table}{\numberline {3.1}{\ignorespaces Microhardness HV\textsubscript {0.01} of Al0.1CoCrFeNi HEA \blx@tocontentsinit {0}\cite {nairExceptionallyHighCavitation2018a}}}{27}{table.caption.7}%
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\contentsline {table}{\numberline {3.2}{\ignorespaces Microhardness HV\textsubscript {0.01} of 316LSS \blx@tocontentsinit {0}\cite {nairExceptionallyHighCavitation2018a}}}{28}{table.caption.8}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Discussion}{29}{chapter.4}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Conclusions}{32}{chapter.5}%
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\contentsline {xpart}{Weird hanger-ons}{34}{part.2}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Erosion particles}{34}{chapter.6}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Reasons for why CE is less in seawater}{35}{chapter.7}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Residual Stress and why it's important}{36}{chapter.8}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Why HIP is better than cast}{37}{chapter.9}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Equiaxed grains - why HIP is better than cast}{38}{chapter.10}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Describing SEM images (light gray, dark, light)}{39}{chapter.11}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Stellite 1}{40}{chapter.12}%
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\addvspace {10\p@ }
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\contentsline {xchapter}{Parametric studies on Stellite}{41}{chapter.13}%
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {1.1}Cavitation\hfill {}\textsc {ignore}}{\reset@font\mtcSfont 2}{section.1.1}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {1.2}Comparison to Literature}{\reset@font\mtcSfont 13}{section.1.2}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.1}Experimental determination of SFE}{\reset@font\mtcSfont 16}{section.2.1}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.2}Electrochemical measurement}{\reset@font\mtcSfont 17}{section.2.2}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.3}Experimental electrochemical - polarize electrode to -1.5 to remove oxides}{\reset@font\mtcSfont 18}{section.2.3}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.4}Description of constant phase element}{\reset@font\mtcSfont 18}{section.2.4}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.5}Other stuff}{\reset@font\mtcSfont 18}{section.2.5}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.6}Stellite 1}{\reset@font\mtcSfont 20}{section.2.6}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.7}Stellites}{\reset@font\mtcSfont 21}{section.2.7}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.8}Objectives and Scope of the Research Work}{\reset@font\mtcSfont 21}{section.2.8}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.9}Thesis Outline}{\reset@font\mtcSfont 21}{section.2.9}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.10}Literature Survey}{\reset@font\mtcSfont 21}{section.2.10}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.11}Cavitation Tests}{\reset@font\mtcSfont 21}{section.2.11}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {2.12}Charpy impact energy}{\reset@font\mtcSfont 21}{section.2.12}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {3.1}Microstructure and Phase Analysis}{\reset@font\mtcSfont 22}{section.3.1}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {3.2}Microstructure and Phase Analysis}{\reset@font\mtcSfont 22}{section.3.2}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {3.3}Electrochemical corrosion tests}{\reset@font\mtcSfont 26}{section.3.3}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {3.4}Strain hardening}{\reset@font\mtcSfont 26}{section.3.4}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {4.1}Experimental Test Procedure}{\reset@font\mtcSfont 29}{section.4.1}}
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{\reset@font\mtcSSfont\mtc@string\contentsline{subsection}{\noexpand \leavevmode \numberline {4.1.1}Hardness Tests}{\reset@font\mtcSSfont 29}{subsection.4.1.1}}
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{\reset@font\mtcSSfont\mtc@string\contentsline{subsection}{\noexpand \leavevmode \numberline {4.1.2}Cavitation}{\reset@font\mtcSSfont 29}{subsection.4.1.2}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {4.2}Relationships between cavitation erosion resistance and mechanical properties}{\reset@font\mtcSfont 29}{section.4.2}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {4.3}Influence of vibratory amplitude}{\reset@font\mtcSfont 29}{section.4.3}}
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{\reset@font\mtcSfont\mtc@string\contentsline{section}{\noexpand \leavevmode \numberline {4.4}Correlative empirical methods}{\reset@font\mtcSfont 30}{section.4.4}}
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Stellites are a family of cobalt-base superalloys used in aggresive service environments due to retention of strength, wear resistance, and oxidation resistance at high temperature \cite{ahmedStructurePropertyRelationships2014, shinEffectMolybdenumMicrostructure2003}. First developed in the early 1900s \cite{hasanBasicsStellitesMachining2016}, stellites became critical to components used in medical implants & tools, machine tools, and nuclear components, with new variations on the original CoCrWC and CoCrMoC alloys seeing expanding use in sectors like oil & gas and chemical processing \cite{malayogluComparingPerformanceHIPed2003, ahmedStructurePropertyRelationships2014, raghuRecentDevelopmentsWear1997}.
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# A better introduction than most in malayogluCharacterisationPassiveFilm2005
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# The compositional roots of contemporary cobalt-base superalloys stem from the early 1900s when patents covering the cobalt–chromium and cobalt–chromium–tungsten system were issued. Consequently, the Stellite alloys of E. Haynes became important industrial materials for cutlery, machine tools and wear-resistant hardfacing applications [1,2]. The cobalt–chromium–molybdenum casting alloy Vitallium was developed in the 1930s for dental prosthetics, and derivative HS-21 soon became an important material for turbocharger and gas turbine applications during the 1940s. Similarly, wrought cobalt–nickel–chromium alloy S816 was used extensively for both gas turbine blades and vanes during this period. Another key alloy, invented in about 1943 by R.H.
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*** Principal Alloying Philosophy and Classification :ignore_heading:
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# Introduce the main alloying elements (Co, Cr, W, Mo, C) and their fundamental roles.
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@ -800,20 +796,8 @@ $$ 6C + 23Cr \rightarrow Cr23C6 $$
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# https://www.sciencedirect.com/science/article/pii/S0921509315306481?via%3Dihub#bib33
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# Fig. 10 illustrates the images of SEM elemental mapping analysis taken from the sample sintered at 1275 °C in order to determine the distributions of the elements inside the material. It is seen in the SEM image that abundantly discrete precipitates with block morphology formed at the grain boundaries. A significant decrease was observed in the amount of Co element forming the matrix in regions where these precipitates were located. Co based superalloys generally gain their strength from the solid solution hardening and the carbide precipitates [14]. Considering that the main strengthening phase is the carbides, it can be asserted that Cr is the most significant alloying element for Co based superalloys because Cr is not only a predominant carbide former but also contributes to the solid solution hardening [23], [36]. In addition, another significant role of Cr is to increase the corrosion and oxidation resistance of the alloy [23]. When the SEM elemental mapping analysis was examined, the Cr element exhibited a serious clustering in the precipitates seen in the microstructure. The fact that C element also had high amounts in these regions where Cr exhibits clustering signified that these precipitates were the carbides formed by Cr. The carbides formed by Cr in Co based superalloys are the carbides of M3C2, M7C3, and M23C6. It is indicated that M3C2 among them is a type of carbide seen in previous superalloys with a low rate of Cr. The M7C3 carbide also consists of low Cr–C alloy rates. This carbide forms more in intragranular regions and sometimes intergranular regions. Being a metastable carbide M7C3 transforms into the carbide of M23C6 with heat treatment or under high temperature service conditions [3], [23]. It is indicated that the M23C6 type carbides can precipitate as both the primary and the secondary carbides in Co based alloys containing a high level of Cr [23]. It is known that this carbide generally forms at the grain boundaries of the multi-crystalline materials and provides the grain boundary strength and the fracture resistance required for long service conditions when found as discontinuous precipitates [13]. The Cr ratio of the Stellite 6 powder used in the present study is 30.3 wt%, which is considerably high. The SEM images of Fig. 10 shows that all of the carbides formed at the grain boundaries. In addition, it was thought that since all the precipitates in the SEM images had approximately the same size and morphology, they were the same phase. All these explanations indicated that these precipitates seen in the microstructure were M23C6 type carbides formed by Cr. In the literature, it is reported that Co, W or Mo can substitute for a little amount of Cr in the M23C6 type carbides [23]. In a study conducted by Rosalbino and Scavino [5], it was found that the M23C6 carbide contained 69.6% Cr, 16% Co, 6.3% W, 2.3% Si, 1.8% Fe, and 1.3% Ni [5]. In the images of the elemental mapping analysis, Mn, Si, and O elements, along with Cr and C, were higher in amount in the regions having carbide precipitates when compared to the matrix. Additionally, it was observed that even though presence of Co, W, Ni, and Fe elements exhibited a decrease in these regions, these elements had low amounts inside the carbides.
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*** Introduction to Hot Isostatic Pressing :ignore_heading:
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# malayogluCharacterisationPassiveFilm2005
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# Hot isostatic pressing (HIPing) is rapidly becoming an industry standard as a processing method. Due to increasingly complex engineering shape specifications, higher demands on quality and lowering costs, HIPing has matured to a stage where it is recognized universally and is used on an industrial scale. HIPing requires a high-pressure vessel and consists of applying high isostatic pressure, using an inert gas, to the surface of the piece being processed or on the surface of a can filled with powder. A resistance heater inside the pressure vessel provides the necessary heat for the treatment.
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# malayogluCharacterisationPassiveFilm2005
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# Hypoeutectic vs hpereutectic alloys
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# The microstructures of Stellite alloys vary considerably with composition, manufacturing process and post treatment. They may either be in the form of hypoeutectic structure consisting of a Co-rich solid solution surrounded by eutectic carbides, or of the hypereutectic type containing large idiomorphic primary chromium-rich carbides and a eutectic [1].
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*** The Influence of Processing on Microstructure and Properties :ignore_heading:
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# COMMENTS
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# Contrast the microstructures resulting from different manufacturing routes (e.g., casting vs. Hot Isostatic Pressing - HIPing).
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# Explain how processing parameters control critical features like carbide size, morphology, and distribution, which in turn dictate the alloy's performance.
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@ -891,9 +875,6 @@ Stellite 6 \cite{yuInfluenceManufacturingProcess2008}
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**** Role of HIPing vs as Cast :ignore_heading:
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# Generated
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# Hot isostatic pressing (HIP) significantly changes the microstructure of cobalt-based alloys compared to conventional casting, producing refined structures with different carbide forms and improved mechanical properties. Cast alloys show coarse hypoeutectic or hypereutectic dendritic microstructures with interconnected three-dimensional eutectic carbide networks measuring 5-20 μm, whereas HIPed alloys exhibit much finer microstructures with discrete, uniformly distributed carbides measuring only 1-5 μm. This change from interconnected carbide networks to separate particles occurs alongside improved phase distribution, with HIP processing promoting the formation of specific carbides such as Cr₇C₃ in Stellite 4 while preventing the formation of others like Co₆W₆C in Stellite 6, and achieving complete density through metallurgical bonding that removes casting defects such as porosity. The refined microstructure of HIPed alloys provides better crack stopping mechanisms, resulting in impact toughness improvements of an order of magnitude and enhanced contact fatigue performance, as cracks must move through discrete carbide-matrix boundaries rather than spreading quickly along continuous brittle networks present in cast materials, while maintaining similar hardness and wear resistance properties.
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As well as the corrosion behaviour being of interest, Malayoglu and Neville [16] conducted a comparative study on the erosion-corrosion performance of both HIPed and investment cast Stellite 6® in 3.5% NaCl solution as a function of temperature and the level of erosive particle loading. They found that in all cases, the HIPed Stellite 6® exhibited the higher erosioncorrosion resistance, which they attributed to the fact that the carbides are not interconnected in the HIPed material whereas eutectic and dendritic carbides in the cast structure form a network of interconnected material. Furthermore, the mean free path between carbides is much smaller in the HIPed material and as such the material responded homogenously to 4 erosion-corrosion. Another study comparing the erosion-corrosion behaviour of a range of HIPed and weld-deposited Stellite alloys in a nitric acid environment demonstrated that the HIPed alloys generally exhibited a lower mass loss which was again attributed to the finer microstructure [17].
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A similar conclusion was also reached by Neville and Malayoglu [18] who attributed the superior corrosion resistance of HIPed Stellite 6 to its microstructure with equiaxed carbides and an absence of areas of chromium-depleted matrix material, due to reduced segregation.
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@ -902,32 +883,6 @@ A similar conclusion was also reached by Neville and Malayoglu [18] who attribu
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# Contrary to this, in the case of HIPed microstructure, the primary dendrites formed on the alloy powder Fig. 2 a , and the carbides in the powder particles Fig. 3 a promoted carbide growth due to the diffusion of carbon and other elemental species within and across the individual powder particle boundaries. As this diffusion process is time, temperature, and pressure dependent during HIPing, and the HIPing temperature 1200° C in this investigation was lower than the melting point of the powder, carbide growth was sluggish when compared with casting. Hence the size of individual carbide particles was much smaller than the cast counterpart. Although not reported in Sec. 3, authors also found that re-HIPing the HIPed alloy under similar conditions as were reported earlier in Sec. 2.1 did not substantially increase the average carbide size, indicating that carbide growth was more dependent on temperature than time during the HIPing process.
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**** Corrosion of HIPed materials :ignore_heading:
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Corrosion performance studies have demonstrated the superiority of HIPed materials.
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Malayoglu and Neville evaluated HIPed versus as-cast Stellite 6 in 3.5% NaCl solution under varying temperature and erosive particle loading conditions, with their findings of superior erosion-corrosion resistance in HIPed materials at temperatures up to 90C attributed to homogeneous material response.
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Additional investigations in nitric acid environments confirmed reduced mass loss in HIPed alloys [17], with enhanced corrosion resistance attributed to equiaxed carbides and absence of chromium-depleted matrix regions due to reduced segregation [18].
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Pitting corrosion
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Chromium-rich carbides (M3C2, M7C3) M23C6) and refractory-element-rich carbides (M6C and MC).
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# Mohamed et al. studied the localised corrosion behaviour of Stellite 6 alloy produced by two different processing methods; HIPing and wet powder pouring. They concluded that the HIPed alloy showed a higher resistance to corrosion and explained it in relation to the processing parameters and the beneficial change in microstructure.
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*** Corrosion Resistance of passive film :ignore_heading:
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The susceptibility of passivating metals to loccalized corrosion is dependent on the passive film's physical and chemical structure and ability to resist breakdown and to repassivate once corrosion has initiated.
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Malayoglu and Neville \cite{malayogluCharacterisationPassiveFilm2005} find that Stellite 6 shows a multilayer passive film, where the outer surface consists primarily of Cr(OH)3 / Cr2O3 and WO2 , and the inner layer consists of Cr(OH)3 / Cr2O3, metallic Cr & W, and WO3, with no evidence of Cl- ion content, unlike that reported for stainless steels.
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# Talk about the oxide film being removed by those wacky experimentalists with the BLR machine and potentiostats recording OCP.
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*** Stellite 1 in Literature Review :ignore_heading:
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@ -943,14 +898,6 @@ Malayoglu and Neville \cite{malayogluCharacterisationPassiveFilm2005} find that
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Wong-Kian et al.16 showed that under erosion-corrosion conditions HIPed Stellite alloys 1, 6, and 21 had lower mass loss than the welded specimens of the same Stellites. They related their finding to the finer and homogeneous microstructure, which was obtained after HIPing. They also showed that wear resistance of the cobalt-based alloys is promoted by the harder complex carbides of chromium and tungsten, while corrosion resistance is enhanced by the presence of cobalt in the matrix.
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*** Comparison to Literature
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General Microstructure of Cast Alloys
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Stellite 4: Features a hypoeutectic microstructure consisting of Co-rich dendrites, a Cr-rich eutectic phase, and W-rich carbides.
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Stellite 6: Also has a hypoeutectic microstructure with Co-rich dendrites set in a lamellar eutectic of Cr-rich and W-rich carbides. The relatively large carbides suggest a slow cooling rate during casting.
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Stellite 20: Possesses a hypereutectic microstructure, characterized by large, primary blocky (idiomorphic) Cr-rich carbides surrounded by a dendritic CoCrW solid solution and eutectic phases.
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*** Fundamental Mechanisms of Corrosion and Cavitation Resistance :ignore_heading:
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#+BEGIN_COMMENT
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@ -1336,12 +1283,6 @@ Although both HIPed and cast specimens are observed to have OCPs drift towards l
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**** Polarization Tests
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# malayogluComparingPerformanceHIPed2003
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# It has been verified by a number of parameters that corrosion occurs at a higher rate on Cast Stellite than on HIPed Stellite even under the severe impingement conditions. The icorr values determined through in situ electrochemical measurements were consistently higher on the HIPed material. This is in accordance with the work of Mohamed et al. [7] in static chloride-containing solutions and with the work of the Malayoglu and Neville [20] where it was found that the crevice and pitting corrosion resistance is enhanced as a result of HIPing. In an attempt to fully understand
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# the role of corrosion in degradation of the Stellite materials the corrosion-related and mechanical damage have been isolated through application of cathodic protection. Through measurement of the mass loss with applied CP, the mechanical erosion damage (E) can be determined and the corrosion-related damage is then defined as: TWL-E. From Table 7 it can be seen that there is a substantial corrosion-related component of damage as a proportion of the total damage and it is therefore evident that corrosion as well as microstructure is important in the assessment of erosion–corrosion rates.
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*** Strain hardening
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# The present paper is a contribution to this subject. It presents a model of prediction of the erosion damage applicable to ductile materials only. Other limitations of the model will be pointed out along the presentation. The originality of this work lies in the fact that the proposed model is fully predictive and involves no parameters to be adjusted on the basis of experimental data. It is based upon the original work of Karimi and Leo @5#.
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