Metallography and Microstructures of Refractory Metals and Alloys, Metallography and Microstructures, Vol 9, ASM Handbook, ASM International,

2004, p. 877888

Metallography and Microstructures of Refractory Metals and Alloys

Introduction
REFRACTORY METALS and their alloys are prepared similarly for metallographic examination. Slight modifications in grinding, polishing, and etching times may be required for alloys, because they are generally harder than the unalloyed metals. Particular product forms, such as wire, may also necessitate special preparation techniques. Information on the properties and selection of refractory metals and their alloys can be found in Properties and Selection: Nonferrous Alloys and Special-Purpose Materials, Volume 2 of ASM Handbook. Powder production and powder metallurgy of refractory metals are described in Powder Metal Technologies and Applications, Volume 7 of ASM Handbook. This article focuses on the refractory metals of niobium, tantalum, molybdenum, tungsten, and rhenium. Other metals classified as refractory (i.e., zirconium, hafnium, and titanium) are discussed elsewhere in this Volume.

Metallography and Microstructures of Refractory Metals and Alloys, Metallography and Microstructures, Vol 9, ASM Handbook, ASM International, 2004, p. 877888
Metallography and Microstructures of Refractory Metals and Alloys

Niobium, Tantalum, Molybdenum, Tungsten and Their Alloys

Revised by Ann Kelly, Los Alamos National Laboratory This section describes procedures that can be applied to metallographic preparation of niobium (columbium), tantalum, molybdenum, tungsten, and their alloys. Alternate procedures that have been used for each of these materials are also described. Specific etchants for these metals and their alloys are listed in Table 1. Table 1 Etchants for metallographic specimens of refractory metals See also Table 2 for etchants suitable for refractory metals Etchant Composition Comments Etchants for niobium and tantalum and their alloys ASTM 66(a) 30 mL HF, 15 mL Swab 3 to 10 s or immerse for 2 min HNO3, 30 mL HCl (a) ASTM 158 10 mL HF, 10 mL Swab 5 to 15 s HNO3, 20 mL glycerol ASTM 159(a) 5 mL HF, 20 mL Swab 10 to 30 s HNO3, 50 mL acetic acid ASTM 161(a) 25 mL HNO3, 5 mL Immerse 5 to 120 s HF, 50 mL H2O ASTM 163(a) 30 mL H2SO4, 30 mL Immerse 5 to 60 s; use this solution for alternate etch and polishing.

HF, 35 drops 30% Adjust amount of H2O2 to obtain a reaction rate that will reveal the H2O2, 30 mL H2O microstructure after etching for approximately 2040 s. Swab 3 to 10 s; use fume hood ASTM 164 50 mL HNO3, 30 g NH4HF2 (ammonium bifluoride), 20 mL H2O Additional etchants for niobium and niobium alloys Immerse up to 5 min ASTM 160(a) 20 mL HF, 15 mL H2SO4, 5 mL HNO3, 50 mL H2O (a) ASTM 162B 10 mL HNO3, 10 mL Swab for 5 s; repeat if necessary HF, 30 mL lactic acid HNO3 + HF + 25 mL HNO3, 5 mL Immerse up to 2 min H2O HF, 50 mL H2O Swab specimen 1 to 3 min with solution A, acts as a chemical 50 mL lactic acid, 30 Solution A polishing agent and etchant; then swab 5 s with solution B; repeat if mL HNO3, 2 mL HF necessary; HF content in solution B controls etch speed 30 mL lactic acid, 10 mL HNO3, 10 mL HF Solution B Additional etchants for tantalum and tantalum alloys ASTM 177(a) 10 g NaOH, 100 mL Swab or immerse 5 to 15 s H2O ASTM 178(a) 20 mL HF, 20 mL Swab for 5 to 20 s HNO3, 60 mL lactic acid Solution C 10 mL HF, 10 mL Swab specimen 2 or more min using solution C for desired surface; HNO3, 30 mL lactic solution C is used as a chemical polish, though some etching will acid occur; if surface is not etched sufficiently, use solution D electrolytically at 0.08 to 0.16 V/cm2 (0.5 to 1 V/in.2) of specimen; Solution D 10 mL HF, 90 mL solution D should be mixed very slowly; use carbon cathode and H2SO4 platinum connection to specimen; discard solution D after 1 h; use fume hood (a) ASTM 164 50 mL HNO3, 30 g Swab 3 to 10 s; use fume hood NH4HF2, 20 mL H2O Etchants for tungsten and molybdenum and their alloys Murakami's 10 g K3Fe(CN)6 Swab 5 to 60 s; immersion will produce a stain etch; follow with reagent (potassium water rinse, alcohol rinse, dry (ASTM 98C) ferricyanide), 10 g KOH or NaOH, 100 mL H2O Murakami's 15 g K3Fe(CN)6, 2 g reagent NaOH, 100 mL H2O (modified) Murakami's 30 g K3Fe(CN)6, 10 g reagent NaOH, 200 mL H2O (modified A) ASTM 131(a) 5 mL H2SO4, 1 mL HF, Electrolytic at 50 to 60 V for 10 to 20 s 100 mL 95% methanol ASTM 132(a) 5 mL HF, 10 mL Swab with heavy pressure for 5 to 10 s; water rinse, alcohol rinse, HNO3, 30 mL lactic dry, then swab etch using ASTM 98C for 5 to 30 s acid ASTM 209(a) 15 mL HNO3, 3 mL Immerse for 5 to 60 s HF, 80 mL H2O Additional etchants for molybdenum and molybdenum alloys