Ceramic gold alloys seminar Presented by, Jose “Paco” Cortes-Botello, D.D.S. University of Texas Health Science Center San Antonio Assistant Professor American Prosthodontic Society Membership Committee Chair and Executive Council Dr. Jose "Paco" Cortes-Botello 1 Overview. • • • • • • • Introduction. History. Physical properties. Chemical properties. Classification. Literature Review. Summary. Dr. Jose "Paco" Cortes-Botello 2 Introduction. Dr. Jose "Paco" Cortes-Botello 3 Metallurgy. • Science and technology of metals and alloys. • Process metallurgy: extraction and refining. • Physical metallurgy: physical properties. • Mechanical metallurgy: with the response of metals to applied forces. Dr. Jose "Paco" Cortes-Botello 4 Alloy. • Metallic material formed by the combination of 2 or more metals; or 1 or more metals with a nonmetal. • Au and Pd are soluble in each other. • Cu and Ag are not. Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 5 Why alloys? • Enhance: – Physical properties. – Chemical properties. – Biological properties. • Steel: is an alloy of carbon in iron. • Stainless steel: steel plus chromium and nickel. Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 6 History. Dr. Jose "Paco" Cortes-Botello 7 History. • Before 1975, 3 distinct alloy groups. • Alloys for full-cast restorations. • Alloys for metal-ceramic restorations. • Alloys for removable partial denture frameworks. Wataha, JPD 2002;87:4, 351-363. Eastman Dental Dispensary Building, 1950. Dr. Jose "Paco" Cortes-Botello 8 History. Alloys for metal-ceramic restorations. • Require melting ranges (MR) that could stand porcelain application. (870ºC-1370ºC) • Higher content of Pd MR. • Ag was avoided greening porcelain. Alloys for RPD frameworks. • Added 0.5-1% C to increase hardness and strength. • Formation of carbides. Wataha, Dr. Jose "Paco" Cortes-Botello JPD 2002;87:4, 351-363. 9 History. • Au 1969 $35/oz, 1980 $800/oz, November 2005 $495/oz * • Pd 1980 $150/oz, 2000 $1000/oz, November 2005 $267/oz * $1,200 $1,000 $800 Au $600 Pd $400 $200 $0 1969 1980 2000 2005 *www.kitco.com Dr. Jose "Paco" Cortes-Botello 10 Precious or Noble? • Precious refers to specific group of 8 elements: Au, Ag, Pt, Pd, Rh, Ru, Ir, Os. • Noble refers to zero based electrode, elements below hydrogen. Includes all the precious metals. Goldfogel and Nielsen. JPD 1982;48:3, 340-343. Dr. Jose "Paco" Cortes-Botello 11 Precious or Noble? • Nobility is the free energy of chemical reactions corrosion. • Inertness is referred to the tendency of the metals not to form oxides of sulfides. • Passivity, “partially nobility” is the inertness provided by a thin oxide or sulfide tenacious, transparent and completely insoluble layer in the surface of the metal. Goldfogel and Nielsen. JPD 1982;48:3, 340-343. Dr. Jose "Paco" Cortes-Botello 12 Physical properties. Dr. Jose "Paco" Cortes-Botello 13 Physical properties. • N = kg (m/s²) • Pa = N/m² = kg (m/s²) / m² • Kg/mm² – A newton is the amount of force required to accelerate a mass of one kilogram at a rate of one meter per second squared. – A pascal is the unit of pressure = one Newton per square metre. – 1 megapascal (MPa) = 1 000 000 Pa = 1 N/mm² – Unit of Vickers's Hardness. Dr. Jose "Paco" Cortes-Botello 14 Yield strength. • The stress required to permanently deform an alloy a standard amount (0.2%); to go from elastic to plastic deformation. (MPa) • Elongation: the amount of permanent deformation an alloy can endure before tensile fracture. Stiffness or rigidity (%) Elongation Yield strength Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 15 Elastic modulus. • Young's modulus, modulus of elasticity or tensile modulus. • Is a measure of the stiffness of a given material, defined as the limit for elastic deformation. (MPa) Elastic Modulus Dr. Jose "Paco" Cortes-Botello 16 Hardness. • Resistance to wear. Vickers hardness. (kg/mm²) • Must be enough to resist occlusal forces but not excessive to wear opposing teeth. • Enamel hardness = 340 kg/mm² M-90 $58,000 * NEWAGE, INC. * www.hardnesstesters.com Dr. Jose "Paco" Cortes-BotelloWataha, JPD 2002;87:4, 351-363. 17 Hardness. • • Diamond is a transparent crystal of pure carbon consisting of tetrahedrally bonded carbon atoms. Aggregated diamond nanorods (Natalia Dubrovinskaia, at the University of Bayreuth, Germany in 2005). Carat Cost per carat Total cost US$ 0.5 (50 points) $3000 $1500 1.0 $6500 $6500 1.5 $8500 $12,750 2.0 $13,000 $26,000 3.0 $17,000 $51,000 5.0 $23,000 $115,000 Unit cell of a diamond 1 carat = 200mg Dr. Jose "Paco" Cortes-Botello 18 Grain size. • Molten alloy cools forming microscopic crystals (grains) and spaces between them called grain boundaries. • • • • Smaller the grain, higher tensile strength. Grain size does not affect hardness. Iridium 50ppm to refine Au. Ruthenium 0.5% to refine Pd. • Optimal Grain size 30µm. High noble alloy, etched (100x) Grain size = 10µm Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 19 Phase structure or microstructure. • Single Phase. • Multiple Phase. Homogeneous. Elements soluble. Au, Pd, Cu. Less corrosion. Easier to manipulate. Heterogeneous. Not completely soluble. Au, Pt. Higher corrosion. Can be etched. 1000 x Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 20 Malleability. • The property of a metal to be deformed by compression loads without cracking or rupturing. Material will be suitable for forging or rolling into thin sheet. Brown and Curtis. Dent Mat 1992, 325-328. Dr. Jose "Paco" Cortes-Botello 21 Chemical Properties. Dr. Jose "Paco" Cortes-Botello 22 Corrosion. • Deterioration of the properties in a material due to reactions with its environment. (release elements). • Compromise physical properties. (strength and esthetics) • Biological irritation. (Biocompatibility) • Multiple phase alloys and non-noble elements risk. • Noble elements: Au, Pt, Pd, Ir, Rh, Os, Ru. Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 23 Oxidation. • High Au alloys have thinner, light color oxide. • Ag, Ni, Co alloys have thicker, darker oxide. • Thicker opaque layer, lower value in porcelain. • Thicker oxide Higher risk MC bonding failure. • Stress from occlusal loads oxide layer. • Recasting Au alloys, the oxide-forming elements are depleted from 1st casting and produce inadequate oxide layer. Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 24 Coefficient of thermal expansion. (CTE) • The ratio of change in length, area, or volume per degree to the corresponding value at a standard temperature. • P contracts , tensile stress. • P contracts , compressive stress. • P CTE < A CTE 0.5 x 10ˉ / ºC.6 • If P CTE <<<< A CTE, MC bonding will fail as a result of compressive stress. Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 25 Melting range. • The range of temperature (T) between: • Solidus T: lower T at which melting begins. • Liquidus T: higher T at which entire alloy is melted. • Porcelain must sinters 50 ºC < alloy’s solidus T. • Solder must have liquidus T 50ºC < alloy’s solidus T. Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 26 Classification. Dr. Jose "Paco" Cortes-Botello 27 ADA Classification, 1984. • • Composition. Physical properties. • Hardness • Yield strength • Elongation • Amount of Au and noble metals. • Corrosion. CLASS Composition wt %. ADA Hardness Clinical use Yield strength Elongation High Noble Au >40% Noble metal >60% I Soft Inlay <140 MPa 18% II Medium Inlay, onlay 140 - 200 18% Noble Noble metal >25% III Hard Full crown, short FPD 201 - 340 12% Base-metal Noble metal < 25% IV Extra Hard Long FPD RPD framework >340 10% Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 28 High noble. Subclass Clinical use Vickers hardness Kg/mm² Yield Strength MPa Au 85%, Pt Full cast, MC. 165 580 Au 52%, Pd, In, Ga Full cast, MC 280 385 Au 72%, Cu, Ag Full cast. 210 450 • Single phase (low corrosion). • Favorable manipulation (cut, finish and polish). • Light color oxide, easier to mask. • • Low strength. Higher Cost. Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 29 Noble. Subclass. Use Vickers hardness Kg/mm² Yield Strength, MPa Au, Pd, Cu, Ag Full cast. 250 690 Pd, Cu, Ga Full cast, MC, long span FPD. 280 580 Pd, Ag Full cast, MC. 275 620 • • • • Harder alloys. Higher strength. Thicker oxide layer. Lower cost. • • • Multiple phase. Higher corrosion, Cu, Ag. Manipulation is difficult. Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 30 Base-metal alloys. Subclass Use Vickers hardness Kg/mm² Yield Strength, MPa Ni, Cr, Be, C MC, RPD. 350 825 Ni, Cr Full cast, MC, RPD. 350 310 Co, Cr RPD 390 310 Ti MC, RPD. 400 • Hardest alloys. • Higher yield strength. • Lowest cost. • • • Multiple phase, higher corrosion. Highest melting ranges. (margin) Very difficult manipulation. Wataha, JPD 2002;87:4, 351-363. Dr. Jose "Paco" Cortes-Botello 31 Purpose Disadvantages Au Nobility Hardness Pd Nobility, Higher MR, Hardness Oxide, grayness. Ag Increases solubility of elements (single phase) Thick oxide, greening. Hardness Cu Increases strength Low solubility (multiple phase) Co Increases strength Low solubility Ga Oxide for porcelain bonding Low solubility In Oxide for porcelain bonding Low solubility Ni Hardness Carcinogenic, allergenic Cr Strength, hardness. Extremely reactive, oxides. Be Reduce MR Corrosion, carcinogenic Ru Refiner 0.5% High MP 2310 ºC Ir Refiner 50 ppm High MP 2410 ºC Zn Increase hardness Multiple phase Brown and Curtis. Dent Mat 1992, 325-328. Dr. Jose "Paco" Cortes-Botello 32 Casting. • (1) An object at or near finished shape obtained by solidification of a substance in a mold. • (2) Pouring molten metal into a mold to produce an object of desired shape. Dr. Jose "Paco" Cortes-Botello 33 Literature review. Dr. Jose "Paco" Cortes-Botello 34 Corrosion. Dr. Jose "Paco" Cortes-Botello 35 Corrosion of Pd alloys. • • • • • Corrosion resistance. Effect of preoxidation on their corrosion resistance. Cytotoxicity. Biocompatibility. Element analysis. Syverud et al. Dental Materials 2001;17:7-13. Dr. Jose "Paco" Cortes-Botello 36 Materials and methods. • • • • Scanning Electronic Microscopy (SEM) Element analysis Immersion test Cell culture test (mice fibroblasts) 32mm 10mm 1.5mm x9 x9 { a) *Preoxidize. b) -0.1mm. c) -0.2mm. *preoxidize 1010ºC, 5min. Syverud et al. Dental Materials 2001;17:7-13. Dr. Jose "Paco" Cortes-Botello 37 Corrosion. • Immersion Test: • Solution Lactic Acid and NaCl 0.1mM. • 7 days at 37ºC. • Ph = 2.3 • Ph = 7 Results are presented in µg/cm² Dr. Jose "Paco" Cortes-Botello 38 SEM and element analysis. Option (Cu) • As casting. IS85 • No visible oxidation. 200 x • After preoxidation. 26 x b 200 x 4000 x Dr. Jose "Paco" Cortes-Botello Syverud et al. Dental Materials 2001;17:7-13. 39 Cytotoxicity. Syverud et al. Dental Materials 2001;17:7-13. Dr. Jose "Paco" Cortes-Botello 40 Conclusions. • Manufacturer's information is accurate. • Specimens from both alloys, with oxide films from preoxidation, significantly released more ions. • Pd-Cu alloy (Option) showed higher oxidation and corrosion. • Pd Cu (1:2) was the most toxic combination. • Cu was most toxic element and released element. Syverud et al. Dental Materials 2001;17:7-13. Dr. Jose "Paco" Cortes-Botello 41 Corrosion behavior of Pd and Au alloys. • Pd alloys have been used as an alternative to Au alloys because of their physical properties and lower cost. • Concerns about Pd corrosion remains. • Purpose: • To measure the corrosion resistance of Pd alloys. • To compare their corrosion behavior with Au alloys. Sun et al. JPD 2002;87:1, 86-93. Dr. Jose "Paco" Cortes-Botello 42 Materials and methods. • 10 Disk specimens (1.2 x 0.13 cm), 2 groups: • As cast. • Heat treated, firing cycle – Vita porcelain Alloy Liberty Composition Pd 76%, Cu, Ga Freedom Plus Pd 78%, Cu, Ga • Tested under 5 different solutions: • 0.9% NaCl (human body fluid) • 0.09% NaCl (human saliva) • Fusayama solution (artificial saliva) • N2-deaerated 0.09% NaCl. • N2-deaarated Fusayama solution. Legacy Pd 85%, Ga Olympia Au 52%, Pd 38.5% Dr. Jose "Paco" Cortes-Botello Sun et al. JPD 2002;87:1, 86-93. 43 Results. • The open circuit potential (OCP) and polarization resistance (PR) were designated as the corrosion resistance. • The great similarity in corrosion behavior for the high Pd and Au-Pd alloys was attributed to their predominant Pd content. Sun et al. JPD 2002;87:1, 86-93. Dr. Jose "Paco" Cortes-Botello 44 Results. Sun et al. JPD 2002;87:1, 86-93. Dr. Jose "Paco" Cortes-Botello 45 Conclusions. • In vitro, corrosion resistance of the 3 high Pd alloys in simulated body fluid and oral environments were comparable to Au-Pd alloy. • There were no significant differences among the 4 Heat Treated alloys tested in oral environments. • 3 High Pd alloys showed passivity through a surface oxide film formation in simulated body fluids and oral environments. Corrosion occurred by dissolution of less noble elements. Sun et al. JPD 2002;87:1, 86-93. Dr. Jose "Paco" Cortes-Botello 46 Recasting alloys. Dr. Jose "Paco" Cortes-Botello 47 Effect of recasting on the cytotoxicity. • Recasting common practice in many laboratories to reduce costs. • Ni-Cr and Co-Cr alloys have been used as a substitute for noble and high noble alloys. • To determine if recasting of base metal alloys: • Affect their cytotoxicity. • Affect their element release. Hiyasat and Darmani. JPD 2005;93:2, 158-163. Dr. Jose "Paco" Cortes-Botello 48 Materials and methods. • • • • Cell culture cytotoxicity. Spectrophotometry to measure element release. 5 base metal alloys. 12 Disk specimens per alloy (3 x 5mm) divided in 3 groups. • 100% New Metal. • 50% Recast. • 100% Recast. Alloy Composition Remanium CS Ni 61%, Cr 26%, Mo Wiron 99 Ni 65%, Cr 23%, Mo Wirobond C Co 65%, Cr 26%, Mo CB Soft Ni 72%, Cr, Cu Thermobond Cu 87%, Al, Fe Hiyasat and Darmani. JPD 2005;93:2, 158-163. Dr. Jose "Paco" Cortes-Botello 49 Results. • Cytotoxicity: mouse fibroblasts were incubated with specimens for 3 days, 37ºC. • Cell activity = SDH formation. Alloy Comp. Remanium CS Ni, Cr, Mo Wiron 99 Ni, Cr, Mo Wirobond C Co, Cr, Mo CB Soft Ni, Cr, Cu Thermobond Cu , Al, Fe Cr, Mo Oxide. Less corrosion by passivation. Hiyasat and Darmani. JPD 2005;93:2, 158-163. Dr. Jose "Paco" Cortes-Botello 50 Element release in parts per billion. Alloy Ni Remanium Ni, Cr New. 50% R 100% R 132 206 218 Wiron 99 Ni, Cr New. 50% R 100% R 214 246 264 Wirobond C Co, Cr New. 50% R 100% R CB Soft New. 50% R 100% R Ni, Cr, Cu Thermobond Cu, Al, Fe New. 50% R 100% R Cr Co Cu Al Fe 56 74 193 22 1520 6560 21 61 54 13 60 28 28 109 269 323 546 435 471 501 Mo 21 116 15 433 539 602 7457 10,650 17,848 Hiyasat and Darmani. JPD 2005;93:2, 158-163. Dr. Jose "Paco" Cortes-Botello 51 Conclusions. • Recasting of alloys at 50% and 100% as previously cast metal significantly increased cytotoxicity of base metal alloys tested. • Element release increased proportionally with the percentage of recast alloy. • Cu was the most cytotoxic and the most affected by recasting. • Cr was not released in detectable amounts. Hiyasat and Darmani. JPD 2005;93:2, 158-163. Dr. Jose "Paco" Cortes-Botello 52 Marginal accuracy. Dr. Jose "Paco" Cortes-Botello 53 Marginal fit of gold inlay castings. • 10 gold inlays mounted with contact points. • Clinically evaluated inlays by sight, explorer and roentgenograms by 10 faculty of University of Washington. • Least acceptable margin = 39 µm. • Gingival margins accepted = 119 µm. • Margins visually accessible were rejected = 26 µm. • Gold margins may be closed up to 2 µm. Dr. Jose "Paco"Christensen. Cortes-Botello JPD 1966;16:2, 297-305.54 Wilhelm Conrad Roentgen, 1895. First X-ray, 1896. Michael Pu, 1896. E. Haschek, 1896. Dr. Jose "Paco"www.xray.hmc.psu.edu/rci/ss1/ss1_2.html Cortes-Botello 55 Evaluation of alternative alloys. • • • To evaluate the marginal fit of castings made of alternative alloys. 9 alloys: 2 full crowns and 2 ¾ crowns per alloy, shoulder preparation. Evaluated by 10 faculty of the University of Michigan. 1. 2. 3. 4. Margins completely covered Margins clinically acceptable, may need burnishing. Questionable margins, may not be closed. Clinically unacceptable. Dr. Jose "Paco" Cortes-Botello 56 Results. Alloy Composition Total rating Rank B-2 Au, High noble 58 1 Forticast Au 50%, Pd, Ag 59 2 Paliney CB Au 15%, Pd 20% 80 3 Alborium Au 15%, Pd 20% 100 4 Albacast 27% Pd, Ag 104 5 Aurolite CB 27% Pd, Ag 112 6 Howmedica Ni-Cr 128 7 Jelenko Exp Ni-Cr 124 8 • 40 = perfect score. •160 = worst. Nitkin and Asgar. JADA 1976;93, 622-629. Dr. Jose "Paco" Cortes-Botello 57 Conclusions. • Castings from type III gold alloy showed the best marginal accuracy. There was no significant difference with Au 50% gold alloy castings. • Castings from Ni-Cr alloys were tight on dies and presented the highest marginal discrepancies. Margins were usually incomplete. • Savings on lower cost alloy will be offset by the extra labor in grinding and adjusting alloys. Nitkin and Asgar. JADA 1976;93, 622-629. Dr. Jose "Paco" Cortes-Botello 58 Semiprecious vs nonprecious alloys. • In vitro study. • Marginal accuracy • Clinical 18 month follow up study. • • • • Gingival Irritation Tooth sensitivity Tarnish and corrosion Abrasion Alloy Comp Harmony Au 74%, Ag 12%, Cu 9% Minigold Au 40%, Ag 47%, Cu 8% WLW Pd 25%, Ag 71% Litecast Ni 63%, Cr 20%, Co 15% Landesman et al. JPD 1981;46:2, 161-166. Dr. Jose "Paco" Cortes-Botello 59 In vitro study. • 2 Inlays, 2 onlays and 2 crowns for each alloy. • Visually inspected 25 X binocular and SEM. • No significant differences in marginal accuracy. Inlay Crown Die Die High Au alloy x 60 Pd-Ag alloy x 60 Landesman et al. JPD 1981;46:2, 161-166. Dr. Jose "Paco" Cortes-Botello 60 Clinical study. • Evaluation at 3, 6, 12 and 18 months. • Index range = 1 - 4 Alloy Gingival Irritation Sensitivity Abrasion Harmony n=37 18 48% 37 100% 36 97% 29 78% 1.5 Minigold n=18 6 33% 18 100% 18 100% 12 67% 1.75 WLW n=22 11 50% 20 90% 20 90% 6 27% 2.5 Litecast n=7 Corrosion Tarnish 2 6 6 1 28% 85% 85% 14% Table shows number of restorations and percentage free of defects. Mixed Rank 4 Landesman et al. JPD 1981;46:2, 161-166. Dr. Jose "Paco" Cortes-Botello 61 Conclusions. • No significant differences were found in marginal fit among the tested alloys in the in vitro study. • High noble alloy (Au 74%, Ag 12%, Cu 9%) showed significant less corrosion and tarnish. • No significant differences were found among the 4 alloys regarding gingival irritation, abrasion or sensitivity. Landesman et al. JPD 1981;46:2, 161-166. Dr. Jose "Paco" Cortes-Botello 62 Marginal fit of base metal alloys. • • • • • 3 different investments. 5 base metal alloys. 1 gold alloy (control). Full crown: tapered 10º and beveled shoulder. 90 specimens; 5 castings per alloy and investment. Evaluated with microscope at X3 magnification. • Oversized. • Adequate. • Undersized. Vermilyea et al. JPD 1983;50:5,651-4. Dr. Jose "Paco" Cortes-Botello 63 Results. Hi Temp (immersed in 100ºF water) Neoloy (bench cure) 100 100 90 90 80 80 70 70 60 Adequate 50 40 60 % 50 Adequate Undersized. 40 Undersized. Oversized 30 Oversized 30 20 20 10 0 10 A 0 A B C D E B C D E F Alloy F Ceramigold 2 (immersed in 100ºF water) Base metal alloys A, B, C, D, E. 100 90 (Biobond, Ceramalloy II, Unibond, Biocast, Neobond II) 80 70 60 Adequate 50 Undersized. 40 Oversized 30 High noble gold alloy F. (Olympia). 20 10 Vermilyea et al. JPD 1983;50:5,651-4. 0 A B C D E F Dr. Jose "Paco" Cortes-Botello 64 Conclusions. • Significant differences in marginal fit between the control alloy and the 5 base metal alloys. • Marginal adaptation of base metal alloys was poor due to undersized castings. • Investment manufacturer’s instructions will require alterations to enhance the fit of base metal castings. Vermilyea et al. JPD 1983;50:5,651-4. Dr. Jose "Paco" Cortes-Botello 65 Marginal accuracy of dental alloys. • In vitro study: • To measure and compare marginal accuracy of complete metal crowns before and after cementation. • To measure cement interface. ALLOY COMPOSITION Harmony Au 74%, Ag 12%, Cu 9% W-3 Au 49%, Pd 40% Spirit II Plus Au 2%, Pd 80% Duracast Cu 80%, Al 12%, Fe, Ni Will Ceram Litecast Ni 65%, Cr 15%, Mo 14% Elektra Pd 25%, Ag 59%, Cu 15% Dr. Jose "Paco" Cortes-Botello Tjan et al. JPD 1991;66:157-164. 66 Materials and methods. • 10 crowns, 5º taper, flat occlusal surface and chamfer margin. • Marginal discrepancy (MD) measured at 12 points, before and after cemented with Zinc-phosphate cement. • 2 specimens (highest and lowest MD) from each alloy were embedded and sectioned to measure the thickness of the cement. 4 layers of die spacer Video microscope, Digimatic micrometers. 1 µm resolution. Dr. Jose "Paco" Cortes-Botello Tjan et al. JPD 1991;66:157-164. 67 Results. ALLOY COMPOSITION Marginal Gap b.c. Vertical discrepancy a.c. Cement Thickness Harmony Au 74%, Ag, Cu 9.7 11.6 22 W-3 Au 49%, Pd 40% 43 33 100 Spirit II Pd 80%, Au 45.8 6.6 45.5 Duracast Cu 80%, Al, Fe, Ni 45.2 60 145.5 Litecast Ni 65%, Cr 15%, 121.1 75 221.5 Elektra Pd 25%, Ag 59% 22.2 8 34.5 Results in µm. 140 120 100 80 µm M.G. 60 V.D. 40 20 0 Au Au, Pd Pd Cu Ni, Cr Ag Alloy Dr. Jose "Paco" Cortes-Botello Tjan et al. JPD 1991;66:157-164. 68 Conclusions. • • • • Type III gold alloy consistently produced most accurate marginal fit. Ag-Pd alloy produced the closest marginal fit to gold alloy. Ni-Cr alloy produced the poorest margins. Dimensions of the internal relief achieved by die spacer were inconsistent and unpredictable. Dr. Jose "Paco" Cortes-Botello Tjan et al. JPD 1991;66:157-164. 69 Marginal accuracy of new and recast alloys. • Many dental laboratories combine new metal with previously cast metal in ranges that vary from 100% new metal to 50%/50%. • Marginal accuracy is crucial for restoration success and longevity. • Purpose: to study the compositional stability and marginal accuracy of type III gold alloy. Dr. Jose "Paco" Cortes-Botello Ayad, JPD 2002; 87:2,162-6. 70 Materials and methods. • 60 cylindrical wax patterns, no spacer. • Type III alloy. Au 74%, Pd 4%, Ag 11.5%, 9.5% Cu • Group A. 100% new metal. • Group B. 50% new + 50% recast metal. • Group C. 100% recast metal. • Microscope x100. • X ray energy-dispersive spectroscopy. Dr. Jose "Paco" Cortes-Botello Ayad, JPD 2002; 87:2,162-6. 71 Materials and methods. • 4 pairs index indentations equal distances around circumference. • Indentation position (IP1) was determined. (98N) • After adjustment, castings were cemented (98N) with Panavia and indentation position was again determined (IP2). • Marginal discrepancy = IP1 - IP2. • Specimens were removed, cleaned, embedded in acrylic resin and axial cut for elemental analysis. Dr. Jose "Paco" Cortes-Botello Ayad, JPD 2002; 87:2,162-6. 72 Results. • Marginal discrepancy. – Less 25 µm for all groups. – Significant difference between 3 groups. • Composition analysis. – Au decreased significantly in recast metal. – Pd increased. Dr. Jose "Paco" Cortes-Botello Ayad, JPD 2002; 87:2,162-6. 73 Conclusions. • For gold alloy type III tested, composition of Au significantly reduces with recasting of alloy. • Marginal opening for all castings was less than 25µm. • Lowest marginal discrepancy was obtained with 100% new metal. • No clinically differences could be detected on the margins among the 3 groups. Dr. Jose "Paco" Cortes-Botello Ayad, JPD 2002; 87:2,162-6. 74 Physical properties. Dr. Jose "Paco" Cortes-Botello 75 Properties of Au-Pd alloys. • 6 crown specimens were tested as cast and 6 heat treatment. • Tensile strength • 12 discs (13mm x 3mm) • • • • • • • • Hardness Yield strength Elastic limit Elongation Alloy Composition Olympia Au 52%, Pd 38%, In, Ga JPW Au 49%, Pd 31%, Ag 14% Neydium Au 49%, Pd 31%, Ag 14% Instron Machine. Strain Gauge Extensometer. Vickers Metallograph. Spectrophotometry. Vermilyea et al. JPD 1980;44:3,294-9. Dr. Jose "Paco" Cortes-Botello 76 Results. Neydium Property JPW Olympia As cast Heat tx As cast Heat Tx As cast Heat Tx Tensile strength * 86 97 85 100 109 115 Yield strength * 61 71 56 77 73 79 Elastic limit * 46 57 44 58 65 69 Elongation % 6 8 7 6 13 20 199 218 187 214 213 225 Hardness DPN * Values x 1000 PSI Vermilyea et al. JPD 1980;44:3,294-9. Dr. Jose "Paco" Cortes-Botello 77 Results. Neydium Au 49%, Pd 31%, Ag 14% JPW Au 49%, Pd 31%, Ag 14% Olympia Au 52%, Pd 38%, In, Ga Vermilyea et al. JPD 1980;44:3,294-9. 78 Dr. Jose "Paco" Cortes-Botello Results. Au 49%, Pd 31%, Ag 14% A Au 49%, Pd 31%, Ag 14% B Au 52%, Pd 38%, In, Ga C Heat treatment. 5 min at 1800 ºF Magnification 450 X Vermilyea et al. JPD 1980;44:3,294-9. 79 Dr. Jose "Paco" Cortes-Botello Conclusions • Hardness, tensile and yield strength of the Au-Pd alloy and Au-Pd-Ag alloys were comparable. • 3 alloys presented homogenized structures due to their similar grain size and configuration. • Values for Au-Pd alloy were significantly higher. • Alloys with Ag were affected by increase temperature. Vermilyea et al. JPD 1980;44:3,294-9. Dr. Jose "Paco" Cortes-Botello 80 Microstructure and hardness of Pd alloys. • Pd alloys have good mechanical properties and lower cost than Au alloys. • Pd-Ga alloys are hard alloys difficult to manipulate by technicians and dentists. • Purpose: Compare the Vickers hardness and microstructure of 4 palladium based alloys for metal ceramic restorations. Vermilyea et al. J of Prosthodontics, 1996;5:4, 288-294. Dr. Jose "Paco" Cortes-Botello 81 Materials and methods. • 20 central incisor copings were cast for each alloy. • Microstructure: Scanning Electron Microscope (SEM). • Vickers hardness: M-400 Loading Machine: • 1-kg/30s load (ADA Specification no. 5) Alloy. Composition. Freedom Pd 76%, Cu 10% Ga 7%, In 7% Legacy XT Pd 75%, Ga 6%, Ag 10%, In 6% Accu-Star Pd 75%, Ag 6% Ga 6%, In 6% Super-Star Pd 60%, Ag 28%, In 6% Vermilyea et al. J of Prosthodontics, 1996;5:4, 288-294. Dr. Jose "Paco" Cortes-Botello 82 Results. Vickers Hardness. Alloy. Manufacturer Information. As cast. After Heat Tx. Vickers H. Yield strength Pd, Cu, Ga 345 332 360 779 Pd , Ga, Ag 249 230 240 483 Pd, Ag, Ga 261 240 260 517 Pd, Ag 263 219 280 655 • Tested as cast and after firing cycle: • • • • 1 oxidation. 1 opaque. 2 body. 1 glaze. Vermilyea et al. J of Prosthodontics, 1996;5:4, 288-294. Dr. Jose "Paco" Cortes-Botello 83 SEM Results. • As Cast. After Firing Cycle. • Freedom • Pd, Cu, Ga • Legacy • Pd , Ga, Ag » Ru Vermilyea et al. J of Prosthodontics, 1996;5:4, 288-294. Dr. Jose "Paco" Cortes-Botello 84 SEM Results. • As Cast. After Firing Cycle. • Accu-Star • Pd, Ag, Ga • Super-Star • Pd, Ag Vermilyea et al. J of Prosthodontics, 1996;5:4, 288-294. Dr. Jose "Paco" Cortes-Botello 85 Conclusions. • After Porcelain Firing Cycle, differences in hardness were statistically significant (4%-8%) for Pd-Ga alloys. This differences have no clinical significance. • However a 13% decrease in the hardness of the Pd-Ag alloy (Super Star) might be of clinical importance. • Considerable homogenization of the as cast microstructure of the 4 alloys occurred with heat treatment. Vermilyea et al. J of Prosthodontics, 1996;5:4, 288-294. Dr. Jose "Paco" Cortes-Botello 86 Investments. Dr. Jose "Paco" Cortes-Botello 87 Casting ringless vs ring investment system. • Marginal accuracy is essential for longevity: • Less plaque accumulation. • Less leakage. • Improves esthetics. • Accuracy is affected: • • • • Preparation Impression Waxing Casting process Lombardas et al. JPD 2000;84:1, 25-31. Dr. Jose "Paco" Cortes-Botello 88 Materials and methods. • Metal die; 30 copings, high Pd alloy (Argedent 52SF): • 2.5 cm Ring, Whip Mix Hi Temp w/ Bego liner. • 3.0 cm “Ringless”, Bego Belavest. • 2.5 cm Ring, Bego Belavest. • Gap measured at 4 points w/optical microscope by a “blind” operator. Dr. Jose "Paco" Cortes-Botello 89 Results. 52% 38% 25% 48% • 1 die of each group was internally adjusted as a pilot study. All measurements ranged between 15-30 µm. Lombardas et al. JPD 2000;84:1, 25-31. Dr. Jose "Paco" Cortes-Botello 90 Conclusions. • Ringless group’s vertical margin discrepancies significantly lower than that for the 2 ring groups. • Metal ring restricts setting and thermal expansion of the investment, which is necessary to compensate metal shrinkage due to solidification. • Ringless technique is clinically acceptable. • Ring techniques are well documented and should not be abandoned. Lombardas et al. JPD 2000;84:1, 25-31. Dr. Jose "Paco" Cortes-Botello 91 Temperature and distortion. Dr. Jose "Paco" Cortes-Botello 92 Temperature distortion in high Pd alloys. • Multiple variables affect the marginal fit of a cast preventing it to fit accurately, leading to bacterial plaque accumulation, caries, and gingival inflammation. • Evaluate the distortion produced by simulated porcelain firings in 9 Pd alloys. • Measure overall distortion. • Which part of the heat treatment produces more distortion. • Effect of an occlusal mesiodistal transverse groove in cast. Papazoglou et al. JPD 2001;85:2,133-140. Dr. Jose "Paco" Cortes-Botello 93 Material and methods. ALLOY COMPOSITION Option Pd 78%, Cu, Ga, Au Spartan Plus Pd 79%, Cu, Ga, Au Liberty Pd 76%, Cu, Ga, Sn, Au Freedom Plus Pd 78%, Cu, Ga, In, Au Protocol Pd 75%, Ga, In, Ag, Au Legacy XT Pd 75%, Ga, In, Ag, Au Jelenko No. 1 Pd 78%, Ga, In, Sn, Ag Superstar Pd 60%, Ag, In, Sn Olympia Au 51%, Pd 38%, Ga, In Papazoglou et al. JPD 2001;85:2,133-140. Dr. Jose "Paco" Cortes-Botello 94 Materials and methods. 5 copings for each alloy. 0.5mm thickness. 1 mm wide margin. Measures at 4 points at: As cast. Oxidized, 650 ºC to 1030 ºC. 2nd opaque from 600 ºC to 990 ºC. 2nd dentin from 600 ºC to 930 ºC. Marginal opening = d1 – d2. Papazoglou et al. JPD 2001;85:2,133-140. Dr. Jose "Paco" Cortes-Botello 95 Results. Marginal opening = d1 – d2. Oxidized 2nd Opaque 2nd Dentin Option -8 -4 -3 Spartan Plus -5 -3 -1 Liberty -4 6 16 Freedom Plus -7 -5 -2 Protocol -5 -7 -8 Legacy XT -4 -3 -2 Jelenko No. 1 -15 -13 -12 Superstar -19 -11 -12 Olympia -7 -24 -7 ALLOY Results in µm. Papazoglou et al. JPD 2001;85:2,133-140. Dr. Jose "Paco" Cortes-Botello 96 Results. • Vertical gap in µm after complete heat treatment. ALLOY Vertical gap. Mesiodistal. Vertical gap. Buccolingual. Option 0 21 Spartan Plus 25 6 Liberty 0 0 Freedom Plus 29 13 Protocol 0 55* Legacy XT 6 12 128* 84* Superstar 38 87* Olympia 24 52* Jelenko No. 1 *values greater than the 40µm Papazoglou et al. JPD 2001;85:2,133-140. Dr. Jose "Paco" Cortes-Botello 97 Conclusions. • Most of the selected high Pd alloys presented distortions not significantly different than those form the control Au-Pd alloy. • Greatest distortion occurred during oxidation heating cycle. • Mesiodistal groove did not prevent distortion for the 9 alloys. • Distortion values were low and there are several laboratory techniques to counteract it. Papazoglou et al. JPD 2001;85:2,133-140. Dr. Jose "Paco" Cortes-Botello 98 Solders. Dr. Jose "Paco" Cortes-Botello 99 Infrared vs torch-soldering. • Purpose of the study is to compare solder joints: • Bond strength. • Discoloration. • Fracture models. • 2 alloys: Olympia Au 52%, Pd 39%. Genesis Co 53%, Cr 27%. • Solder: Olympia Pre-solder Au 70%, Pd 10%, Ag 18%. Dominici et al. J of Prostho 1995;4:2, 101-110. Dr. Jose "Paco" Cortes-Botello 100 Materials and methods. • 10 pair of specimens for each alloy and solder method. • Soldered and re-soldered with the other method. • Torch Solder: 12 mm Length O2 flame at pressure of 34.5 MPa. • Infrared Soldering: Ney Infrared 1000 W Tungsten filament quartz lamp. 6 mm 3 mm 14mm 0.25 mm Dominici et al. J of Prostho 1995;4:2, 101-110. Dr. Jose "Paco" Cortes-Botello 101 Results. • Percentage of fracture and discolor for specimens. Au-Pd • Tensile strength. Co-Cr Torch Infrared Torch Infrared Cohesive Frac. 61% 79% 47% 18% No Discolor 39% 11% 18% 18% Discolor 1/3 28% 68% 70% 82% Discolor 2/3 33% 21% 12% 0 Voids, porosity 89% 32% 82% 12% Dominici et al. J of Prostho 1995;4:2, 101-110. Dr. Jose "Paco" Cortes-Botello 102 Results. • Au-Pd Infrared “free defect”. Au-Pd Torched “porosity”. Magnification 10X . Cr-Co Torched “porosity”. Cr-Co Torched “adhesive” and cohesive fracture. Dr. Jose "Paco" Cortes-Botello 103 Conclusions. • There were no significant differences between bond strength of Au-Pd and Co-Cr alloys when both had infrared heated joints or torch heated joints. • Entirely cohesive fractures were observed more frequently for Au-Pd specimens. • Infrared solder joints, for both alloys, showed significantly less porosity, voids and inclusions than torched heated joints, at 40 x magnification. Dominici et al. J of Prostho 1995;4:2, 101-110. Dr. Jose "Paco" Cortes-Botello 104 Solder between precious and nonprecious. • Photomicrographic evaluation of solder joints between precious and nonprecious alloys. • Solder joints between gold alloys and nonprecious metals. (Solder mr = 1370 ºF) • A chemical and physical union between solder and gold alloy. • Interface between the solder and nonprecious alloy lacked of chemical and physical union. Dr. Jose "Paco" Cortes-Botello Walters. JPD 1976;35:689-692. 105 Alloy and final color. Dr. Jose "Paco" Cortes-Botello 106 Spectrophotometric evaluation of alloys. • • • Purpose: To evaluate the influence of 4 types of alloys and 2 porcelains on the final color. 2 Porcelains: Vita Omega and Dentsply Ceramco. 10 specimens (10 x 1mm) per alloy: • 2 opaque layers A3. (0.2mm) • 2 dentin layers A3. (1.0mm) Alloy Composition Thermabond Ni, Cr Wirobond Co, Cr Cerapal-2 Pd, Cu V-Delta Au, Pd. Spectrophotometer: Datacolor Spectraflash 600 Kourtis et al. JPD 2004;92:5, 477-485. Dr. Jose "Paco" Cortes-Botello 107 CIE Lab color system. • Color difference ΔE > 3.7 visually unacceptable difference. • L* = lightness (value). • a* = red-green axis. • b* = yellow-blue axis. Kourtis et al. JPD 2004;92:5, 477-485. Dr. Jose "Paco" Cortes-Botello 108 Results. • • • • Vita Porcelain showed highest L* values for all alloys. Ceramco porcelain showed higher a* values. Au-Pd and Co-Cr, higher L* with both porcelains. Au-Pd with Vita porcelain showed higher b*. Kourtis et al. JPD 2004;92:5, 477-485. Dr. Jose "Paco" Cortes-Botello 109 Conclusions. • Type of alloy influenced the final color of the restorations. • Vita porcelain showed the highest L* values for all alloys. • Au-Pd and Co-Cr showed significant higher L* values. (brighter) • For all the alloys tested, Ceramco Porcelain was found to be more red. (higher a*) • Au-Pd and Pd-Cu were founded to be more yellow (higher b*) with both porcelains. Kourtis et al. JPD 2004;92:5, 477-485. Dr. Jose "Paco" Cortes-Botello 110 High Pd alloys effect on final color. • • • In vitro study to evaluate the final color difference of 9 high Pd alloys. 6 disk specimens (16mm x 1mm) per alloy. 2 groups: – Opaque porcelain (0.1mm) – Opaque porcelain (0.1mm) + Dentin porcelain (0.9mm) • Shade B1 Vita. CR 400 Chroma Meter, Konica. Alloy Composition Spartan Plus Pd 79%, Ga, Cu Liberty Pd 76%, Ga, Cu Freedom Plus Pd 78%, Ga, Cu Legacy Pd 85%, Ga IS 85 Pd 82%, Ga Protocol Pd 75%, Ga Legacy XT Pd 75%, Ga Jelenko No. 1 Pd 78%, Ga Super Star Pd 60%, Ag Olympia Au 52%, Pd 39% Stavridakis et al. JPD 2004;92:2, 170-8. Dr. Jose "Paco" Cortes-Botello 111 Results. Acceptability intraorally = 2.8 – 3.7 ΔE CIELAB units. Acceptability ideal conditions = 1.0 ΔE CIELAB units. Stavridakis et al. JPD 2004;92:2, 170-8. Dr. Jose "Paco" Cortes-Botello 112 Results. greenish darker Stavridakis et al. JPD 2004;92:2, 170-8. Dr. Jose "Paco" Cortes-Botello 113 Conclusions. • Pd-Cu-Ga alloys did not reliable reproduce the final color after firing cycle. Darker, greener and less yellow. • Opaque porcelain. (2.8 – 3.7 ΔE CIELAB units) • Dentin porcelain. ( > 1 ΔE CIELAB units) • Pd-Ag alloy, after firing cycle, showed Lighter, color differences after glaze cycle > 1 ΔE CIELAB units. • Color differences for all other Pd-Ga alloys and Au-Pd were not significant < 1 ΔE CIELAB units. Stavridakis et al. JPD 2004;92:2, 170-8. Dr. Jose "Paco" Cortes-Botello 114 Titanium. Dr. Jose "Paco" Cortes-Botello 115 Marginal fit comparison Au and Ti alloys. • Titanium: Biocompatibility. Corrosion resistance. Physical properties. Low density. (weight) Low cost. • • • • Special machines ($). High fusion temperature. Low detail reproducing capacity. Difficult to manipulate. • To compare the marginal fit, between implant frameworks made of Au and Ti alloys, before and after electroerosion. Sartori et al. JPD 2004;92:2,132-8. Dr. Jose "Paco" Cortes-Botello 116 Materials and methods. • 3 unit FPD frameworks were fabricated (n=10). Ti alloy. Au alloy. – Induction melting and centrifugal, Neutrodyn. – Gold cylinders. – – – – Electric arc melting, Argon atm. Injection metal with vacuum pressure. MR = 1668ºC. Plastic cylinders. 3 mm 3.75 mm 10 mm Master Screw, Brazil. Sartori et al. JPD 2004;92:2,132-8. 117 Dr. Jose "Paco" Cortes-Botello Materials and methods. • 12 measures per implant: B, L, D, M. • Passive fit, 1 screw tightened. – Tightened side. – Opposite side. • Both screws were tightened to 10 N. • Electroerosion, Electric Discharge TMT. Sartori et al. JPD 2004;92:2,132-8. Dr. Jose "Paco" Cortes-Botello 118 Results. Before Electroerosion After Electroerosion Alloy. Opposite Tightened Both Opposite Tightened Both Au 69 ± 25 12.8 ± 1.4 12.6 ± 3 35.7±8.2 8.3 ± 4.2 5.4 ± 2.3 Ti 94 ± 40 29.6 ± 4.4 30.1 ± 6 45.7±4.7 17 ± 5.3 16 ± 5.5 Results in µm Au, opposite, before electroerosion. Au, opposite, after electroerosion. Sartori et al. JPD 2004;92:2,132-8. Dr. Jose "Paco" Cortes-Botello 119 Conclusions. • Electroerosion procedure significantly reduced marginal gap for both alloys in all conditions. • Comparison between both alloys after electroerosion did not show significantly differences for the opposite side. • Au alloy showed the shortest marginal gaps in all conditions. Opposite Tightened Both Au before electroerosion 69 ± 25 12.8 ± 1.4 12.6 ± 3 Ti after electroerosion 45.7±4.7 17 ± 5.3 16 ± 5.5 Alloy Results in µm Sartori et al. JPD 2004;92:2,132-8. Dr. Jose "Paco" Cortes-Botello 120 Conclusions. Criteria for alloy selection. 1. 2. 3. 4. 5. 6. Know and understand alloy composition (allergies). Single phase. Avoid selection based on color. Keep track of the alloys used, name and manufacturer. Long-term clinical performance, and long term costs of restorations over short term costs. Clinical situations: esthetics, occlusion, space, curvature, length. Dr. Jose "Paco" Cortes-Botello 121 Conclusions. Use reliable, clinically proven products. Companies research and manufacture alloys. Tested alloys for element release and corrosion. Dental laboratory. As Prosthodontists, we are responsible for the safety and success or failure of our restorations. Dr. Jose "Paco" Cortes-Botello 122 THANK YOU Dr. Jose "Paco" Cortes-Botello 123