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FUNCTIONS OF A METALLURGICAL LABORATORY Determination of Microstructure Microstructure is evaluated by using standard metallographic techniques including sectioning, mounting, polishing, chemical etching, and inverted optical microscopy in bright field or polarized light as necessary. When required, the analysis is supplemented by scanning electron microscopy. Heat Treatment Heat treatment is checked by coupled microstructural evaluation and hardness measurements, and supplemented by electrical conductivity measurements when necessary. Type and level of Inclusions Inclusions are checked by using appropriate metallographic sections to analyze inclusion type and amount (volume fraction or length). When required, composition of the inclusions is checked by EDS. Plating/Coating Characterisation and thickness are checked using an appropriate metallographic section that includes a representative plated or coated surface. Plating or coating thickness is measured on the metallographically prepared section using a calibrated digital measurement system. Composition is analyzed by a combination of scanning electron microscopy and energy dispersive spectroscopy. Grain Size Grain structure is revealed by appropriate chemical etchants and measured by comparison using a microscope eyepiece equipped with the standard ASTM grain size grid. When necessary (e.g. for very fine or coarse grain sizes outside the range of the grid), standard stereological measurements are performed. Grain Flow Grain flow is determined by using a section(s) of appropriate size and orientation. The section is prepared using standard metallographic techniques, and chemically etched to reveal the grain structure and deformation patterns. The grain flow is
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analysed with respect to the component geometry and photographically recorded using either an inverted optical metallograph or macro level highresolution digital imaging. Decarburization Decarburization is checked by using appropriate metallographic sections that include a representative portion of the component surface. Chemical etching is used to reveal the presence of decarburization. If decarburization is detected, the depth is measured using a calibrated digital image analysis system and compared with the requirements. In addition, if the decarburized layer is of sufficient depth, microhardness measurements are used as a confirmatory test. Retained Austenite Retained austenite is revealed by special chemical etching of standard metallographic sections. Microstructural estimation of retained austenite content is performed by standard stereological volume fraction counts. If the retained austenite content is found to exceed 3% by volume, X-ray diffraction is used as a confirmatory test and the results provided for comparison. Case Hardening Case hardening is checked by using an appropriate metallographic section that includes a representative portion of the component surface. The case is revealed by an appropriate chemical etchant and measured by a microhardness scan from the surface to the interior. Typically, the case depth is reported as the distance from the surface at which the hardness is HRC 50.
Sectioning of a metallographic
sample must be performed carefully to avoid altering or destroying the structure of interest otherwise the results would be misleading as shown in Fig. 2. Alterations in the microstructure of the specimen can be produced Figure 2. Cutting damage (top) and a by deformation and the creation burr after sectioning of an annealed and further development of cracks titanium specimen (mod. Wecks and breakouts. Due to heat reagent, 100X, polarized light plus generation, recrystallization, local sensitive tint). tempering, and in extreme cases, partial melting may occur. These problems can be minimized by the use of generous amounts of inert lubricants and coolants (water, oil, compressed air, etc.). The sectioning techniques are summarized in Fig. 1.1 and arranged according to the different sectioning mechanisms. When sectioning with a torch or by normal mechanical sawing, cutting, sand blasting, or cleaving, care must be taken to cut sufficiently far from the area of interest to avoid harmful effects.
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Fig. 1.1 Methods of metallographic specimen sectioning The most widely used sectioning device is the abrasive cutoff machine, ranging from units using thin diamond-rimmed wafering blades to those using wheels that are more than 1.5 mm ( in.) thick, 30 to 45 cm (12 to 18 in.) in diameter, containing silicon carbide particles Depending on the type of material to be sectioned, cutting wheels of different compositions should be used, and their selection is dictated by hardness and ductility of the material to be cut. Table 1.1 Materials Steel, ferrous materials, hardened steels High-alloy steels Cutting wheel: abrasive/binder Al2O3 (corundum)/bakelite Cubic boron nitride (CBN)/bakelite Silicon carbide (SiC)/bakelite Diamond/bakelite
Nonferrous metals, hardmetals Hard and tough materials, cermets, ceramics Hard and brittle materials, ceramics, Diamond/metal minerals
Conducting Mould: If analysis requires using SEM during characterisation, then a copper containing thermosetting material used. Grinding is generally considered the most important step in specimen preparation. Care must be taken to minimize mechanical surface damage. Grinding is performed by the abrasion of the specimen surface against water-lubricated abrasive wheels (assuming water does not adversely affect the metal). Grinding develops a flat surface with a minimum depth of deformed metal and usually is accomplished by using progressively finer abrasive grits on the grinding wheels. A typical sequence might begin with 120- or 180-grit papers and proceed to 240, 320, 400, and 600 grits. Scratches and damage to the specimen surface from each grit must be removed by the next finer grinding step. The surface damage remaining on the specimen after grinding must be removed by polishing. If this disturbed or deformed metal at the surface is not removed, microstructural observations may be obscured (Fig. 2).
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Fig. 2 The effect of disturbed metal on the metallographic appearance of a plain carbon steel. (a) A layer of disturbed metal--an artifact structure caused by grinding damage--covers the polished surface. (b) The layer of disturbed metal is removed, and the structure is revealed to be lamellar pearlite. Etched using picral. 1000
Fig. 3 The effect of improper polishing on AISI 1010 steel. (a) "Comet tails" from improper polishing. (b) The same material polished correctly, exhibiting small manganese sulfide inclusions
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Figure 14. SiC grit particle (arrow) embedded in a 6061-T6 aluminum weldment (500X, aqueous 0.5% HF).
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Kallings Reagent
40 ml Distilled water 2 grams Copper chloride (CuCl2) 40 ml Hydrochloric acid 40-80 ml Ethanol (85%) or Methanol (95%) 50 ml Acetic acid 50 ml Nitric acid
Immerse or swab for few seconds to a few minutes Swab Immersion or swab etching for a few seconds Immerse or Use fresh swab for seconds to minutes Do not let etchant crystallize or dry explosive
50 ml Distilled Water 50 ml Hydrochloric acid 10 grams Copper sulfate Murakami 100 ml Distilled Water 10 grams K3Fe(CN)8 Reagent 10 grams NaOH or KOH
Picral
Wrought Stainless steel, tungsten alloys, silver alloys, SiC, B4C Iron and Seconds to steel, minutes tin alloys
Vilella's Reagent
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Figure 38. Grain structure of annealed CP titanium revealed by heat tinting on a hot plate (100X, polarized light plus sensitive tint).
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of lower energy. The result is that the grain boundary edge will become rounded so that it can be evaluated by optical or electron microscope techniques. Depending upon the ceramic material, the atmospheric condition of the furnace may need to be controlled. For example, etching silicon nitride will require either a vacuum or an inert atmosphere of nitrogen or argon to prevent oxidation of the surface to silicon dioxide.
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Tint Etching
Tint etchants have been developed to color etch many metals and alloys -cast irons, steels, stainless steels, nickel base alloys, copper base alloys, molybdenum, tungsten, lead, tin, and zinc. Limited success has been obtained with tint etching of aluminum and titanium alloys. A selected list of etchants is given in Table I; additional information can be obtained in Ref 1 and 2. The most widely applicable tint etchant is that developed by Klemm which colors ferrite in steels, reveals overheating or burning in steels, and develops the grain structure of copper and many copper alloys, as well as those of lead, tin, and zinc.
Fig. 1-- Examples of brasses tint etched using Klemm's I reagent. A: cold worked and annealed alpha brass (70 Cu-30 Zn). B, C, and D are alpha-beta brass (60 Cu-40 Zn) heat treated via three different methods. B: 940 F (505 C), water quench. C: 1200 F (650 C), water quench. D: 1550 F (845 C), air cool. Original magnification: 100X
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Beraha's tint etch for Al alloys. Pre-etch with10% aq NaOH followed by 50% aq HNO3. Rinse in water, dip immediately into tint etch for 1-5 s. Rinse and dry. Colors matrix grains, outlines second phase particles. Tint etch of Lienard and Pacque: colors CuAl2 violet. Immerse about 2 min.
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3.
Beraha`s tint etch for Fe, Ni, or Co base heat resistant alloys. Colors the matrix, carbides and nitrides unaffected. Immerse sample in solution at room temperature for 60-150 s. Move sample during etching. Start with lowest HCI concentration; if coloration does not result, increase HCI or etch longer.
4. 50 mL saturated aqueous sodium thiosulfate 3 1 g potassium metabisulfite 5. 50 mL saturated aqueous sodium thiosulfate 5 g potassium metabisulfite 5 mL saturated aqueous sodium thiosulfate 45 mL water 20 g potassium metabisulfite
Klemm's I tint etch. Good for many alloys. Immerse 3 min or more for beta brass, alpha-beta brass, and bronzes. Use 10-60 min for alpha brass. Use 40-100 s for coloring ferrite in steels, reveals P segregation and overheating. Longer time produces line etching of ferrite. Etch 30 s for zinc alloys. Klemm s II tint etch. Immerse 6 min or more for alpha brass. lmmerse 30-90 s for steels Reveals P segregation. Good for austenitic Mn alloys. Immerse 60-90 s for tin and its alloys. Klemms III tint etch. Immerse 3-5 min for bronze. Immerse 6-8 min for Monels. Beraha`s lead sulfide tint etch. Dissolve in order given. Allow each to dissolve before adding next (cannot get complete dissolution). Age in dark bottle at least 24 hr before using. Do not remove precipitate. When stock solution turns gray after prolonged storage, discard. Immerse in solution until surface is colored violet or blue. Excellent for copper and its alloys. To color MnS in steels, add 200 mg sodium nitrate (optional) to 100 mL solution; good for 30 min. Colors MnS white. Pre-etch with nital or picral. Beaujard and Tordeux`s tint etch for steels. Immerse 10-25 s Reveals grain boundaries and ferrite orientations. darkens asquenched martensite. Tint etch for lath or plate martensite. lmmerse 2 min (Benscoter et al). Darkens as-quenched martensite. Immerse about 20 s. Darkens as-quenched martensite. Immerse 1-15 s. Beraha`s tint etch for cast iron and steels. Add HNO3 to pH 2.5-4.0 (about 0.4 mL). Immerse 20-30 s for cast iron. Fe3P and Fe3C, 16
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8.
9.
10. 8-15 g sodium metabisulfite 100 mL water 11. 3-10 g potassium metabisulfite 100 mL water 12. 1 g sodium molybdate 100 mL water
yellow-orange; ferrite, white. For low carbon steei add 0.1 g NH4FHF, immerse 45-60 s. For medium carbon steel add 0.2 g NH4FHF. For high carbon steel add 0.3-0.4 g NH4FHF. Carbides, yellow-orange to violet; ferrite, white or yellow 13. 3 g potassium metabisulfite 10 g anhydrous sodium thiosulfate 100 mL water 14. 0.5-1.0 mL HCI 100 mL water 1 g potassium metabisulfite Beraha's tint etch for iron and steel. Immerse 1-15 min. Colors ferrite, martensite, pearlite, and bainite: sulfides are brightened Beraha's tint etch for irons, steels, tool steels. Agitate strongly during etching. then hold motionless until surface is colored; 10-60 s total time. Colors ferrite, martensite, pearlite, bainite. Reveals grain boundaries. Beraha`s tint etch for stainless steels. Immerse 30-120 s with agitation. Colors austenite. Beraha's tint etch for stainless steels. Before use, add 0.6-0.8 g potassium metabisultite (0.1-0.2 g for martensitic grades). Afer mixing, reagent is good for 2 hr. Use plastic tongs and beaker. Immerse 20-90 s, shake gently during etching. Colors matrix phases. Hasson's tint etch for Mo. Immerse without agitation for 40-50 s (do not exceed 70 s). FeCI3 can be dissolved in ethanol but etch is slower, 2-3 min. Colors vary with grain orientation. Tint etch for Mo alloys (Oak Ridge National Laboratory). Immerse 2 min, wash and dry. Swab removes colors, produces grain boundary attack. Weck's tint etch for alpha Ti. For pure Ti, immerse a few seconds, longer times for Ti alloys. Colors vary with grain orientation. Weck's tint etch for alpha Ti alloys. Immerse for a few seconds. Colors vary with grain orientation. Tint etch for W (Lehwald et al). Immerse at 55 C (130 F). Use 2 or 3 stages (view between etches) of 15, 10, and 10 min. Pre-etch with grain boundary etch.
15. 20 mL HCI 100 mL water 0.5-1 g potassium metabisulfite 16. Stock solution: 20 mL HCI 100 mL water 2.4 g NH4FHF 17. 40-60 mL FeCI3, solution (1300 g/L water) 25 mL HCI 75 mL ethanol 18. 70 mL water 20 mL H2O2 (30%) 10 mL H2SO4, 19. 5 g NH4FHF 100 mL water 20. 39 g NH4FHF 4 mL HCI 100 mL water 21. 94 mL 10% aqueous HCI 20 g Cr03
Footnotes 1. Additional tint etches are listed in Ref 1 and 2. 2. Whenever water is specified, use distilled water. 3. Maximum solubility of anhydrous sodium thiosulfate (Na2S2O3) is 50 g/100mL water at 20 C (70 F), while that of the crystal form (Na2S2O3. 5H2O) is 79.4 g/100mL water at 0 C (32 F) or 291.1g/100 mL water at 45 C (115 F).
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Figure 1 (above) shows the microstructure of cold worked and annealed alpha brass (Cu-30% Zn) and three examples of alpha-beta brass (Cu-40% Zn) heat treated in various ways to alter the grain size and amount and distribution of the phases. For the alpha brass sample (A), etching is very slow -- requiring nearly an hour. Tint etching has revealed all of the grains and the annealing twins. With ordinary chemical etchants it is very difficult to get such complete revelation of the grain structure.9
For the alpha-beta brass samples, the anodic beta phase is colored rather quickly, generally less than 5 min is required. The sample (B) heated to 940 F (505 C) and water quenched contains close to the minimum amount of beta (actually, ordered beta) that will form. Tint etching produces only a light yellowish color in all of the beta grains.
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Samples heated higher in the two phase region -- 1200 F (650 C) and water quenched -- contain more beta which is tinted with a variety of colors depending on orientation.
The third example -- heated into the all-beta region and air cooled -- shows three prior beta grains where the beta phase within each of these regions has the same color. Note that the coloring is very precise, no enlargement of the beta occurs, and all of the beta is revealed. None of these samples was pre-etched -- the attack polish produced enough relief to eliminate need for one. Figure 2 shows the microstructure of eutectic Al-33% Cu tint etched with the aqueous ammonium molybdate-ammonium chloride solution suggested by Lienard and Pacque.10 This sample was attack polished using a few mL of 0.5% aqueous HF added to colloidal silica in the Fini-Pol device. The CuAl2 phase is colored violet.
Figure 3 illustrates the use of Beraha's acidified aqueous sodium molybdate reagent to color the cathodic cementite in an Fe- 1% C, high purity alloy where the cementite in the pearlite is blue but the grain boundary cementite is violet.
Figure 4 shows the microstructure of solution annealed, austenitic Hadfield manganese steel. After polishing with colloidal silica, the sample was given a light pre-etch with 2% nital (3 s) and then etched 20 s with 20% aqueous sodium metabisulfite. This procedure is also effective for revealing the a + e structure of decarburized surfaces of the alloy.11 Tint etched samples can also be photographed in black and white and still produce superb results (see Fig. 5 and 6).
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Figure 5 (above)-- Tint etching of nickel base superalloys such as X750 using Beraha's reagent (right) can produce excellent color contrast development of twin and grain structures compared with that produced using standard reagents such as Kalling's No.2 etch (left). B&W photos clearly reveal color differences. 100X. Composition of Beraha's tint etchant: 100mL HCL, 50 mL H2O,1 g potassium metabisulfite, and 1 g ferric chloride.
Figure 6 (above)-- Beraha's lead sulfide etch will color sulfide inclusions white. Shown here is quenched and tempered AISI 41S50, pre-etched with 2% nital. Photomicrograph at left is of as-polished steel; one at right is of the tint etched sample. 500X
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Metallographic Analysis
Metallurgical analysis (metallography) of the microstructural provides the Material Engineers information varying from phase structure, grain size, solidification structure, casting voids, etc. Figure 2 shows an example of two cast iron structures. o Figure 2a shows a cast iron microstructure which has graphite flakes. Over time this materials will most likely fail under load. o On the other hand by adding some solidifying agents the cast iron can be made to form the more durable graphite nodules (Figure 2b). Analysis of a materials grain size provides valuable information regarding a materials physical hardness and ductility. Figure 3 shows the grain size of a tough pitch copper. Microstructural analysis can also provide very useful information about the types of phases that occur during cooling. Figure 4 shows the dendritic growth of the microstructure for an aluminumsilicon alloy which formed during solidification. The direction and size of these dendrites again relate to the materials strength and durability.
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Macroanalysis
Macrostructural characterization of metals and alloys is the detailed evaluation of large-scale inhomogeneities in composition, morphology, and/or density. These inhomogeneities may develop during processing such as casting, extrusion, forging, rolling, and welding or during service. Materials characterization by optical macrostructural examination can be divided into three categories. First, examination of the macrostructure of metallographically prepared sections of interest is used to evaluate such structural parameters as: Flow lines in wrought products Solidification structures in cast products Weld characteristics, including depth of penetration, fusion-zone size and number of passes, size of heat-affected zone and type and density of weld defects Size and distribution of large inclusions. Gas and shrinkage porosity in cast products Depth and uniformity of a hardened layer in a case-hardened product Second, characterization of the macrostructural features of fracture surfaces is used to identify such features as: Fracture initiation sites and changes in crack propagation process Third, characterization of surfaces and surface defects on parts and coupons such as: Estimations of surface roughness, grinding patterns, and honing angles Evaluation of coating integrity and uniformity Determination of extent and location of wear Estimation of plastic deformation associated with various mechanical processes Determination of the extent and form of corrosive attack; readily distinguishable types of attack include pitting, uniform, crevice, and erosion corrosion
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To obtain the macrograph, the aluminum ingot was sectioned, then ground and polished to produce a flat reflective surface. The polished section was then etched by immersion in a solution that attacked the various grain orientations at different rates.
The etched structure was examined using a low-power microscope. The structural elements visible in this macrograph are grains. The small grains near the bottom of the ingot appear relatively equiaxed. This region of small equiaxed grains is the chill zone. During casting, such macrostructural defects as gas or shrinkage porosity and center cracks can develop. Many of these defects can be characterized using macrostructural evaluation.
Fig. 5 Macrostructure of as-cast aluminum ingot. Transverse section shows outer chill zone and columnar grains that have grown perpendicularly to the mold faces. Etched using Tucker's
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Exampl-2: Flow Lines Figure 7 shows the flow lines show the direction of metal flow during processing and frequently represent paths for easy fracture. Fig. 7 Flow lines in a forged 4140 steel hook. Specimen was etched using 50% HCl. 0.5
Example 3: Case Hardening Fig. 8 Case-hardened layer in W1 tool steel. Specimens were austenitized at 800 C (1475 F), brine quenched, and tempered 2 h at 150 C (300 F). Black rings are hardened zones. Etched using 50% hot HCl. Approximately 0.5 Figure 8 shows the use of similar macroscopic techniques to illustrate the depth of case hardening in a tool steel;
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