Designation: E340 − 00 (Reapproved 2006)

Standard Test Method for

Macroetching Metals and Alloys1
This standard is issued under the fixed designation E340; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope and ferrite banding, coring, inclusions, and depth of carburiza-

1.1 These test procedures describe the methods of mac- tion or decarburization. The information provided about varia-
roetching metals and alloys to reveal their macrostructure. tions in chemical composition is strictly qualitative but the
location of extremes in segregation will be shown. Chemical
1.2 The values stated in inch-pound units are to be regarded
analyses or other means of determining the chemical compo-
as the standard. The SI equivalents of inch-pound units may be
sition would have to be performed to determine the extent of
approximate.
variation. Macroetching will also show the presence of discon-
1.3 This standard does not purport to address all of the tinuities and voids, such as seams, laps, porosity, flakes, bursts,
safety concerns, if any, associated with its use. It is the extrusion rupture, cracks, etc.
responsibility of the user of this standard to establish appro-
3.1.3 Other applications of macroetching in the fabrication
priate safety and health practices and determine the applica-
of metals are the study of weld structure, definition of weld
bility of regulatory limitations prior to use. For specific
warning statements, see 6.2, 7.1, 8.1.3, 8.2.1, 8.8.3, 8.10.1.1, penetration, dilution of filler metal by base metals, entrapment
and 8.13.2. of flux, porosity, and cracks in weld and heat affected zones,
etc. It is also used in the heat-treating shop to determine
2. Referenced Documents location of hard or soft spots, tong marks, quenching cracks,
case depth in shallow-hardening steels, case depth in carbur-
2.1 ASTM Standards:2
E3 Guide for Preparation of Metallographic Specimens ization of dies, effectiveness of stop-off coatings in carburiza-
E381 Method of Macroetch Testing Steel Bars, Billets, tion, etc. In the machine shop, it can be used for the
Blooms, and Forgings determination of grinding cracks in tools and dies.
3.1.4 Macroetching is used extensively for quality control in
3. Significance and Use the steel industry, to determine the tone of a heat in billets with
3.1 Applications of Macroetching: respect to inclusions, segregation, and structure. Forge shops,
3.1.1 Macroetching is used to reveal the heterogeneity of in addition, use macroetching to reveal flow lines in setting up
metals and alloys. Metallographic specimens and chemical the best forging practice, die design, and metal flow. For an
analyses will provide the necessary detailed information about example of the use of macroetching in the steel forging
specific localities but they cannot give data about variation industry see Method E381. Forging shops and foundries also
from one place to another unless an inordinate number of use macroetching to determine the presence of internal faults
specimens are taken. and surface defects. The copper industry uses macroetching for
3.1.2 Macroetching, on the other hand, will provide infor- control of surface porosity in wire bar. In the aluminum
mation on variations in (1) structure, such as grain size, flow industry, macroetching is used to evaluate extrusions as well as
lines, columnar structure, dendrites, etc.; (2) variations in the other products such as forgings, sheets, etc. Defects such as
chemical composition as evidenced by segregation, carbide coring, cracks, and porthole die welds are identified.

1
4. Sampling
This test method is under the jurisdiction of ASTM Committee E04 on
Metallography and is the direct responsibility of Subcommittee E04.01 on Specimen 4.1 As in any method of examination, sampling is very
Preparation.
important. When macroetching is used to solve a problem, the
Current edition approved Oct. 1, 2006. Published October 2006. Originally
approved in 1968. Last previous edition approved in 2000 as E340 – 00´1. DOI: problem itself largely dictates the source of the sample as to the
10.1520/E0340-00R06. location on the work piece and the stage of manufacture; for
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or example, when looking for pipe, the sample should represent
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on the top of the ingot, or when looking for bursts or flakes, the
the ASTM website. sample should be taken as soon after hot working as possible.

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 E340 − 00 (2006)
4.2 When macroetching is used as an inspection procedure, 4.5.5 Machined and Ground Parts—When looking for
sampling ought to be done in an early stage of manufacturing grinding cracks, etc., the surface itself is used as a sample.
so that if the material proves faulty, no wasteful unnecessary Because the machined or ground part is often the finished part,
work is done. However, the sample should not be taken so it may be undesirable to immerse the part in acid. In this case,
early that further working can introduce serious defects. In the other methods such as dye penetrant methods may be more
steel industry, for example, the sample is usually taken after desirable.
ingot breakdown and after most chances of bursts or flakes
occurring have passed. Billets or blooms going into small sizes 5. Preparation
are sampled after initial breakdown. Material going into 5.1 Sample preparation need not be elaborate. Any method
forging billets or die blocks is sampled near finish size. of presenting a smooth surface with a minimum amount of cold
Sampling may be done systematically or on a random basis. work will be satisfactory. Disks may be faced on a lathe or a
4.3 Samples may be cold cut from the source by any shaper. The usual procedure is to take a roughing cut, then a
convenient fashion; saws and abrasive cutoff wheels are finish cut. This will generate a smooth surface and remove cold
particularly effective. The use of torch cutting or hot cutting work from prior operations. Sharp tools are necessary to
should be used only when necessary to cut a sample from a produce a good specimen. Grinding is usually conducted in the
large piece. The sample then is sectioned well away from the same manner, using free-cutting wheels and light finishing
hot-cut surface. An example of permissible use of torch cutting cuts. When fine detail is required, the specimen should be
is the excising of a piece from a large plate and then cutting a ground down through the series of metallographic papers (see
sample for macroetching 4 to 5 in. (102 to 127 mm) away from Methods E3). Where necessary, details are given in the
the torch-cut edge. tabulation of procedures.
4.4 Some common methods of sampling, listed by source, 5.2 After surface preparation, the sample is cleaned care-
are as follows: fully with suitable solvents. Any grease, oil, or other residue
4.5 Billets, Blooms, and Hot-Rolled Products—Disks are will produce uneven attack. Once cleaned, care should be taken
usually cut from these products near the end. Samples cut too not to touch the sample surface or contaminate it in any way.
close to the end, however, may have false structures because of
fish-tailing. Disks from large blooms are sometimes cut into 6. Solutions
smaller pieces for ease in handling. 6.1 The solutions used for macroetching are given in the
4.5.1 Forgings and Extrusions—Disks cut transverse to the tables listed under each alloy. In most cases a good grade of
long dimension will show flakes, bursts, etc. Forgings may also reagent should be used but need not be chemically pure or of
be cut parallel to the long dimension to show flow lines. In analytical quality. The so-called technical grades are usually
complicated forgings, some thought will have to be given to satisfactory. The solution should be clean and clear, free of
the proper method of cutting so as to show flow lines. suspended particles, scum, etc.
Macroetching of an unprepared specimen will show surface 6.2 Caution must be observed in mixing. Many of the
defects such as shuts, flats, seams, etc. In extrusions, coring etchants are strong acids. In all cases, the various chemicals
and coarse grain are more commonly found in the back end of should be added slowly to the water or solvent while stirring.
the extrusion. In the cases where hydrofluoric acid is used, the solution
4.5.2 Sheets and Plates—A sufficiently large sample should should be mixed and used in polyethylene vessels.
be taken when looking for surface defects. An ideal length (Warning—Hydrofluoric acid should not be allowed to contact
would be the circumference of the last roll, but this may be the skin since it can cause painful serious ulcers if not washed
inconveniently long. Several samples totaling some given off immediately.)
fraction of the circumference can be used; however, there is
always a chance then that a defect arising from faulty rolls 7. Procedure
would not be detected. When seeking information on lamina-
tions, a transverse section is used. In many cases, however, to 7.1 Many of the solutions are aggressive and may give off
reduce the size of the specimen, only a section out of the center irritating and corrosive fumes. Etching should be done in a
of the plate may be taken. well-ventilated room, preferably under a fume hood. The
4.5.3 Weldments—A disk cut perpendicular to the direction solution should be mixed and placed in a corrosion resistant
of welding will show weld penetration, heat affected zone, tray or dish and brought to the operating temperature. The
structure, etc. Careful preparation is usually rewarded with specimen or specimens should be placed in a tray of stainless
highly detailed structures giving a large amount of information. steel screen or on some non-reactive support. Glass rods often
Welds involving dissimilar metals will produce problems in are placed on the bottom of the acid container and the
etching. The best method is to etch the least corrosion-resistant specimens laid directly on the rods. When etching is com-
portion first and the more resistant portion afterwards. Occa- pleted, remove the specimens from the dish taking great care
sionally an intermediary etchant may be required. The bound- not to touch the etched surface. When desmutting is required,
aries between etched and unetched portion will give an idea of dip the specimen into a second solution. After rinsing the
weld penetration and dilution. specimen with hot water, blow dry with clean compressed air.
4.5.4 Castings—Cut the specimen to display the defect or 7.2 In the case of large specimens, such as ingot sections,
feature being sought. swabbing may be the only practical method of macroetching.

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 E340 − 00 (2006)
TABLE 1 Macroetchants for Aluminum and Aluminum Alloys
Alloy Composition Procedure Comments
All NaOH 10 g Immerse sample 5 to 15 min in solution heated to 60 Good general-purpose etchant, can be
H2 O 100 mL to 70°C (140 to 160°F). Rinse in water, and remove used on almost all aluminum alloys.
smut in strong HNO3 solution. Rinse and repeat Does not require fine grinding.
etching if necessary.

3XXX HCl (concentrated) 75 mL Mix fresh before using. Use at room temperature. May Used to develop grain structure. May be
4XXX HNO3 (concentrated) 25 mL be used as immersion etch or swabbed over diluted with 25 % water to slow down
5XXX HF (48 %) 5 mL specimen surface. Rinse specimen in warm water and etching. Does not require fine grinding.
6XXX dry.
High Si castings

High purity A1 HCl (concentrated) 45 mL Immerse specimen at room temperature until desired Tucker’s etch. General purpose etch for
1XXX HNO3 (concentrated) 15 mL contrast is developed. Rinse in warm water and dry. revealing microstructure of both cast and
3XXX HF (48 %) 15 mL wrought aluminum. Does not require fine
4XXX H2 O 25 mL grinding.
5XXX
6XXX

All except high Si HCl (concentrated) 15 mL Same as above. 1 + 2 Tucker’s. Same as above, but
castings HNO3 (concentrated) 5 mL slower acting.
HF (48 %) 5 mL
H2 O 75 mL

2XXX HCl (concentrated) 15 mL May be used as an immersion etch or swabbed over Flick’s reagent. Best results are obtained
High Cu alloys HF (48 %) 10 mL the specimen surface. When desired contrast is with a ground surface. 180 grit will
H2 O 90 mL obtained, rinse in water and remove deposits with suffice.
concentrated HNO3. Rinse in warm water and dry.

Saturate a large wad of cotton held in stainless steel or nickel are required. If fine detail is required, the machined surface
tongs with the etchant and sweep over the surface of the should be ground using silicon carbide paper lubricated with
specimen. An effort should be made to wet the entire surface as water or kerosine.
soon as possible. After the initial wetting, keep the swab 8.1.3 Several of the solutions used in macroetching react
saturated with solution and frequently sweep over the surface vigorously with the metal and can overheat the specimen. In
of the specimen to renew the solution. When the structure has these cases the specimen is periodically removed from the
been suitably developed, rinse the specimen, either with a swab solution, cooled in running water, and reimmersed in the
saturated with water, or better still, by pouring water over the etchant. This procedure is repeated until the desired degree of
specimen. After rinsing with hot water, blow the specimen dry etching is obtained.
with compressed air. Details of the procedure not discussed 8.1.4 Macroetchants for Aluminum and Aluminum Alloys
here are covered in the sections for the various metals and their (Table 1).
alloys.
8.2 Beryllium:
7.3 The times given in individual tabulations are only 8.2.1 While beryllium in the massive form is not dangerous,
intended as guides. In fact, the progress of etching should be beryllium and its compounds in the finely divided state are
closely watched and etching stopped when the preferred extremely poisonous. (Warning—Before starting any work
structural details have been revealed. Specimens should be involving beryllium, a review of hazards and plans for han-
etched to develop structure. Generally, a light etch is better dling should be made. A number of references on beryllium are
than a heavy etch; overetching can often lead to misinterpre- available. Particular mention may be made of“ Toxicity of
tation. The actual time to develop a structure properly may be Beryllium” ASD-TR-62-7-667, prepared by the Kettering
quite different from the one suggested. Laboratory for the Air Force.)
8.2.1.1 Generally speaking, beryllium and its alloys have
8. Specific Preparation Procedures and Recommended given difficulty in obtaining good macroetched specimens.
Solutions First, beryllium is a rather brittle metal and sectioning can be
8.1 Aluminum: difficult. Cut-off wheels with the designation C46FR70 have
8.1.1 The specimens can be cut using common cutting tools, been the most successful. Secondly, beryllium does not grind
hack saws, band saws, shears, abrasive cutoff wheels, etc. All easily; hence, specimens should be as small as possible to
these methods will cause cold work at the surface and will minimize grinding time. Grinding has been most successful
generate heat. The temperature rise can be enough to cause with the entire sequence of wet silicon carbide papers.
changes in structure. For these reasons sharp tools and gener- 8.2.1.2 The etching of fine grained metal may not always be
ous lubrication are necessary for sectioning. entirely successful, and further preparation will be required.
8.1.2 The cold-worked surface should be removed by ma- Rough polishing with 15 µm Al2 O3 suspended in water is
chining the surface. Again sharp tools and copious lubrication performed on a low-nap cloth. Light pressure and frequent

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TABLE 2 Macroetchants for Beryllium and Beryllium Alloys
Metal Composition Procedure Comments
Be HCl 10 mL Either swab or immerse at room temperature for a few Works best on coarse grained Be.
NH4 Cl 4g minutes, rinse in water and dry.
H2 O 90 mL

Be HCl 10 mL As above. An alternative when No. 1 does not work. Fine-grained

NH4 Cl 2g metal may not give good results in either case.
Picric acid 2g
H2 O 90 mL

change of cutting direction produce the best results. If further the specimen. For inspection purposes, finishing on a 120-grit
polishing is required, 1-µm green Cr2 O3 in tap water on wheel will be sufficient.
synthetic suede works best. 8.5.1.1 When the maximum amount of detail is required, as
8.2.2 Macroetchants for Beryllium and Beryllium Alloys— in weldments, polishing the specimen with the series of
(Table 2). metallographic papers gives the best results. When examining
8.3 Cobalt and Cobalt Alloys: for surface defects, the surface itself should be etched directly
8.3.1 Many of the cobalt-base high-temperature alloys can without much preparation. The only preparation that is advis-
be etched using the same procedures as those for iron- and able is to brush off the loose scale and then to give the
nickel-base high-temperature alloys. Other cobalt alloys, such specimen a light grinding pass with very coarse abrasive to
as the stellites used as machine tools, require special treatment. break through the adherent scale. When etching in 1 + 1 HCl
8.3.1.1 The cobalt-base alloys, as a group, are not easily for example, this scale will be removed, exposing the surface
machined. The specimens should be sectioned with abrasive underneath. If care has been exercised in the grinding opera-
cutoff wheels and ground on wet silicon carbide papers. tions, the grinding scratches will not interfere with examina-
Because of the rapid work-hardening characteristics of these tion.
alloys, fresh paper and copious cooling should be used. 8.5.1.2 The most commonly used solutions for macroetch-
8.3.2 Macroetchants for Cobalt and Cobalt Alloys (Table 3). ing iron and steel are Solution Nos. 1 and 3 in Table 5.
8.5.1.3 Electrolytic etching using a solution of 3 to 6 %
8.4 Copper and Copper Alloys: concentrated HCl in water at room temperature may be used.
8.4.1 These metals are usually macroetched to bring out the The specimen is immersed in the solution, placed in a carriage,
general structure of wire bar and billets as well as variations in and passed over a cathodic bar at a current of 40 A/in. of
grain size in extrusions and forgings. specimen width. After etching, the specimen is cleaned by
8.4.1.1 Specimens may be sectioned using common cutting using a vegetable fiber brush and a 10 % sodium citrate
tools. To minimize cold working the tools should be kept sharp. solution. The specimen finally is air dried.
8.4.1.2 Good results can be obtained by machining a smooth
8.5.2 Forgings—In addition to the examination for internal
surface in two stages, the first being a heavy cut to remove the
structure, surface defects, and structure, closed-die forgings are
cold work from sectioning and the second a fine cut with a
often sectioned to show flow lines. Etching for flow lines
V-shaped tool to remove the remaining cold work. Grinding
requires extremely careful preparation to provide a smooth
through the series of metallographic papers will give more
surface with a minimum of cold work. Long pieces such as
detailed results. The degree of grinding depends upon the
crank shafts are awkward to handle and are best prepared on a
amount of detail required. The etching solutions listed in Table
grinding machine using successively finer grinding wheels.
4 are simple to prepare and their use requires no special
Sectioning into shorter lengths may be advisable. The speci-
technique.
men should be heavily etched in 1 + 1 HCl or 20 % H2 SO4.
NOTE 1—It should be pointed out that heavy etching often will remove Contrast can often be increased by wiping the surface lightly
the effect of cold work but at the expense of producing a rough surface. If with very fine metallographic paper after etching. Examination
the specimen is then given light regrinding to remove the rough etched
for structure, defects, etc. is carried out in the same fashion as
surface, the second etch will provide good results.
hotmill products.
8.4.2 Macroetchants for Copper and Copper Alloys—(Table 8.5.3 Special Tests for Segregation—There are a number of
4). etchants containing copper salts which will reveal segregation.
8.5 Iron and Steel: Careful specimen preparation through the metallographic pa-
8.5.1 Macroetching has been most highly developed and is pers is required. Very careful cleaning after grinding is ex-
used extensively in the iron and steel industries. In hot-mill tremely important. When a specimen is immersed in this type
products such as bars, billets, sheet, and plate, the disk cut with of solution, copper plates out onto the specimen by a replace-
a parting tool is prepared by facing on a lathe or by grinding. ment reaction. The rate of deposition depends on the compo-
In facing, the first cut is moderately heavy with a sharp tool. sition of the steel and the copper plating will cover the
The second facing is a light cut with a V-shaped tool run at high segregated regions. Sometimes the specimen can be left in a
speed. Specimens produced in this manner are adequate for little longer than recommended and then rubbed lightly with
general inspection. A better though slower method is to grind metallographic papers to increase contrast.

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TABLE 3 Macroetchants for Cobalt and Cobalt Alloys
Alloy Composition Procedure Comments
49Co-49Fe-V HCl 50 mL Immerse specimen in hot solution (140 to 180°F) for General structure,
Some Co-Cr alloys H2 O 50 mL 30 to 60 min. Rinse in hot water and dry. porosity.

25Cr-10Ni-8W HCl 50 mL Swab until desired contrast is obtained then rinse in Grain size, general
21Cr-20Ni- HNO3 10 mL warm water and dry. structure.
3W-3Mo-1Cb FeCl3 10 g
H2 O 100 mL

18Cr-10Ni-14W CuCl2 ·2NH4 Cl·2H2 O 2g As above. As above.

FeCl3 5g
HNO3 5 mL
HCl 50 mL
H2 O 80 m

TABLE 4 Macroetchants for Copper and Copper Alloys

Alloys Composition Procedure Comments
Cu and all brasses HNO3 10 mL Immerse specimen in solution at room temperature Emphasize grains and cracks.
H2 O 90 mL for a few minutes. Rinse in water and dry.

Cu and all brasses HNO3 50 mL As above. Brings out grain contrast, pits result
H2 O 50 mL unless agitated. Aluminum bronzes may
form smut which can be removed by brief
immersion in concentrated HNO3.

Cu and all brasses HCl 30 mL As above. Good grain contrast.

FeCl3 10 g
H2 O or ethanol 120 mL

Cu, high Cu alloys, K2 Cr2 O7 sat 2g Immerse specimen in solution at room temperature Emphasizes grain boundaries and oxide
phosphorus, tin soln of NaCl for 15 to 30 min then swab with fresh solution. inclusions.
bronzes H2 SO3 Rinse in warm water and dry.
H2 O

All HNO3 50 mL Immerse specimen in solution at room temperature. Brilliant deep etch.
AgNO3 5g Rinse in warm water and dry.
H2 O 50 mL

Brass 20 % acetic acid 20 mL As above. Strain lines.

5 % chromic acid 10 mL
10 % FeCl3 in H2 O 5 mL

Silicon brass or bronze CrO3 40 g Immerse specimen in solution at room temperature,

NH4 Cl 7.5 g rinse in warm water and dry.
HNO3 (concentrated) 50 mL
H2 SO4 (concentrated) 8 mL
H2 O 100 mL

8.5.4 Macroetchants for Iron and Steel (Table 5). and Marble’s reagent are the recommended etchants. All three
8.6 Stainless Steels and High-Temperature Alloys: of these require very careful specimen preparation.
8.6.1 These alloys are generally more susceptible to cold 8.6.2 Macroetchants for Stainless Steels and High-
working of the surface than are the lower alloy grades of steel. Temperature Alloys (Table 6).
The best method of preparation is to grind the specimens as
8.7 Lead and Lead Alloys:
described for iron and steel. A smut tends to form on the
surface of the steel when immersed in 1 + 1 HCl. This can be 8.7.1 Lead and its alloys are among the most difficult metals
prevented by adding a small quantity of HNO3 to the etching to prepare for macroetching. They are not only very soft and
bath. It can also be removed by scrubbing the specimen with a cold work easily, but they (pure lead especially) recrystallize
vegetable fiber brush under running warm water or by immer- readily at temperatures which can be easily achieved in
sion in warm 20 % HNO3. Scrubbing will provide a higher careless preparation.
contrast for detection of segregation and inclusions. The 8.7.2 For best results in the macroetching of lead, all
desmutting either by the addition of HNO3 to the etching bath surfaces other than that to be examined must be masked from
or by the secondary rinse in HNO3 will provide a brighter the macroetch by the use of several coats of a plastic spray. The
surface which is suitable for determination of grain size and surface to be examined should be filed prior to etching. Three
structure. High-alloy stainless steels and austenitic high- 14-in. (360-mm) files, (seeNote 2), are usually required and
temperature alloys because of their extreme corrosion resis- used in the following order: (1) aluminum, Type A, (2) hand
tance often will give trouble in etching. Aqua regia, HCl-H2 O2, smooth, and (3) hand-finishing smooth.

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TABLE 5 Macroetchants for Iron and Steel
Alloys Composition Procedure Comments
Plain and alloy steels, HCl (concentrated) 50 mL Immerse specimen in solution heated to 160 to General purpose.
high-speed and tool steels, H2 O 50 mL 180°F for 15 to 30 min. Desmut by vigorous
cutlery (12–14 % Cr) and scrubbing with vegetable fiber brush under
stainless steels running water. Stainless steels may be desmutted
by dipping in a warm 20 % HNO3 to give a bright
finish.

High-alloy steels HCl (concentrated) 50 mL Immerse specimen for 10 to 15 min in solution at Ratio HCl:HNO3 runs 2:1 to 3:1.
HNO3 (concentrated) 25 mL room temperature. Rinse in warm water and dry.
H2 O 25 mL

Plain and alloy steels, cutlery HCl (concentrated) 38 mL Immerse specimen for 15 to 45 min in solution Works well on 12 % Cr steel.
steels H2 SO4 (concentrated) 12 mL heated to 160 to 180°F. Rinse in warm water and
H2 O 50 mL dry.

High-alloy steels HNO3 (concentrated) 10 mL Immerse specimen in solution heated to 160 to Ratio HNO3-HF varies.
HF (48 %) 4 mL 180°F until desired etch is obtained and rinse in
H2 O 87 mL warm water and dry.
H2 O 87 mL
to
HNO3 (concentrated) 40 mL
HF (48 %) 10 mL
H2 O 50 mL

Stainless steels, high-alloy HCl (concentrated) 50 mL Mix HCl and water then heat to 160 to 170°F. Produces bright finish.
steels H2 O 50 mL Immerse specimen and add H2 O2 in several
H2 O2 (30 %) 20 mL parts. Do not mix. Make each subsequent
addition after foaming from previous addition has
stopped.

Austenitic stainless steels HCl (concentrated) sat 50 mL Immerse specimen in solution which may be Marble’s reagent. Light etch, good for
soln heated or not depending upon alloy. Time also structure.
CuSO4 in H2 O 25 mL depends on alloy. Rinse in warm water and dry.

Plain and low-alloy steels (NH4)2 S2 O8 (ammo- 10 g Swab solution at room temperature over Grain size, weldments.
nium persulfate) specimen. Rinse and dry.
H2 O 100 mL

Plain and alloy steels CuCl2 2.5 g Immerse in solution at room temperature until a Stead’s reagent. Salts dissolved in HCl
MgCl2 10 g coppery sheen appears. Rinse thoroughly and with minimum of hot water. To bring out
HCl (concentrated) 5 mL dry. P-rich areas and P banding.
Alcohol—up to 250 mL

Mild steel, Bessemer and high CuCl2 90 g The surface should be rubbed with cloth soaked Fry’s reagent. Before etching, sample
N2 steel HCl (concentrated) 120 mL in etching solution. Wash in alcohol or rinse in should be heated to 200 to 250°C (302
H2 O 100 mL HCl (1 + 1) after etching to prevent deposition of to 482°F) for 5 to 30 min depending on
copper. condition of steel. To show strain lines
due to cold work.

Plain and alloy steels CuCl2 45 g As above. Modified Fry’s reagent. Same as for
HCl (concentrated) 180 mL reagent No. 9 but modified by Wazau,
H2 O 100 mL may give more contrast specimen can
be washed in water without depositing
copper.

Stainless and high-Cr steels HCl 10 mL Immerse specimen in solution at room Vilella’s reagent.
Alcohol 100 mL temperature until desired contrast is obtained.
Picric acid 1g Rinse and dry.

Plain and alloy steels HCl (concentrated) 6 to 12 mL Electrolytic, 5 to 10 A per square inch, specimen Small specimens, <20 in.2 area.
H2 O 100 mL vertical, rinse, brush, and dry.

Plain and alloy steels HCl (concentrated) 6 mL Electrolytic, specimen moves past a cathode bar, For specimens over 20 in.2 area,
H2 O 100 mL 30 to 40 A per inch of specimen width, rinse, blooms, billets, and slabs.
HBO3 1g brush, and dry.

NOTE 2—Nicholson designations. Be sure to preserve the distinction a few short strokes of a brass file brush in the direction of the
between hand smooth and hand-finishing smooth. last cut of the file. The molybdate etch listed in Table 7 is used
8.7.3 The file is usually held in a fixture and the specimen is in the removal of worked metal and also to reveal the structure
drawn over the file proceeding from the point of the file to the of lead of low-alloy content. The preparation of the solution is
tang. Remove the filings after each pass of the specimen with of paramount importance.

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TABLE 6 Macroetchants for Stainless Steels and High-Temperature Alloys
Alloys Composition Procedure Comments
Stainless steels and iron- HCl (concentrated) 50 mL Immerse specimen in solution heated to General purpose.
base H2O 50 mL 160 to 180°F for 30 min. Desmut by
high-temperature alloys vigorous scrubbing with vegetable brush
under running water. Stainless steels may
be desmutted by dipping in warm 20 %
HNO3 to give bright finish. Dropwise or
slow addition of H2O is often effective in
accelerating etching.

Iron-, cobalt-, and nickel- HCl (concentrated) 50 mL Immerse specimen in solution at room Ratio HCl + HNO3 runs 2 + 1 to
base HNO3 (concentrated) 25 mL temperature for 10 to 30 min. Rinse and 3+1
high-temperature alloys H2 O 25 mL dry.

Stainless steels and high- HNO3 10 mL Immerse specimen in solution heated to Ratio HNO3-HF varies.
temperature alloys HF (48 %) 3 mL 160 to 180°F until desired contrast is
H2 O 87 mL obtained. Rinse and dry.
to
HNO3 (concentrated) 40 mL
HF (48 %) 10 mL
H2 O 50 mL

Austenitic stainless steels I (NH4)2 SO4 15 g Combine I and II then add III. Immerse Lepito’s etch. I, mix fresh, grain
and H2 O 75 mL specimen in solution at room temperature structure.
nickel base alloys II FeCl3 250 g until desired contrast is obtained.
HCl 100 mL
(concentrated) 30 mL
III HNO3
(concentrated)

Austenitic stainless steels HCl (concentrated) 50 mL Mix HCl and water then heat, immerse
and H2 O 50 mL specimen and add H2 O2 in several parts.
high-temperature alloys H2 O2 (30 %) 20 mL Do not mix. Make each subsequent
addition after foaming from previous
addition has stopped.

Austenitic stainless steels HCl (concentrated) 50 mL Immerse specimens in solution which may Marble’s reagent. Light etch, good
and Sat soln of 25 mL be heated up to 170°F until desired for structures. Amount of CuSO4
high-temperature alloys CuSO4 in H2 O contrast is obtained. Rinse and dry. solution may be increased to 1 + 1
ratio for difficult alloys.

TABLE 7 Macroetchants for Lead and Lead Alloys

Alloy Composition Procedure Comments
Lead and lead A. H2 O 250 mL Add A to B and let precipitate redissolve. If B is added to A an
alloys NH4 OH (sp gr 0.90) 140 mL insoluble precipitate forms.
HNO3 (concentrated) 60 mL Add C to mixture of A and B after precipitate has redissolved.
Molybdic acid (85 %) 100 mL
B. H2 O 960 mL Swab surface of the specimen with mixed solution until desired
HNO3 (concentrated) 400 mL contrast is obtained. Rinse and dry.
C. Glacial acetic acid 100 mL

Antimonial lead A. Glacial acetic acid 30 mL Prepare surface on silk velvet wheel with Al2 O3 abrasive at 150
HNO3 (concentrated) 40 mL rpm. Etch with solution A at 42°C then repolish until bright. Reetch
H2 O 16 mL with B at room temperature for 1 to 2 h.
B. Glacial acetic acid 1 mL
H2 O 400 mL

A. HNO3 (concentrated) 80 mL Mix equal quantities of A and B immediately before use. Immerse Grain structure
H2 O 220 mL specimen in solution at room temperature until desired contrast is
B. (NH4)2 MoO4 45 g obtained. Rinse and dry.
H2 O

A. (NH4)2 MoO4 10 g Immerse specimen in solution at room temperature until desired Bright etch, grain
Citric acid 25 g contrast is obtained, then rinse and dry. structure, defects.
H2 O 100 mL

A. Acetic acid 75 mL Mix with strongest H2 O2 available to minimize water content. Chemical polish-etch.
H 2 O2 25 mL Immerse dry specimen in solution at room temperature until
desired contrast is obtained, then rinse and dry.

8.7.4 Macroetchants for Lead and Lead Alloys (Table 7). 8.8 Magnesium:

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TABLE 8 Macroetchants for Magnesium and Magnesium Alloys
Alloy Composition Procedure Comments
ZK60A Glacial acetic acid 5 mL Immerse specimen in solution at room temper- Flow lines in forgings.
H2 O ature for 1⁄2 to 8 min until desired contrast is
95 mL obtained. Desmut with 50 % HF (48 %) in
water. Rinse in rapidly flowing water and dry.

AZ61A Glacial acetic acid 10 mL As above but for 1⁄2 to 5 min. Grain size, surface casting defects.

AZ80A H2 O 90 mL

AZ31B Glacial acetic acid 20 mL As above but for 1⁄4 to 5 min. Flow pattern in forgings. Surface casting defects.
Glycolic acid may be substituted for acetic acid.
AZ61A NaNO3 5g
AZ80A H2 O 80 mL

AZ31B HNO3 (concentrated) 10 mL As above but for 1⁄2 to 5 min. Flow pattern in forgings. Internal defects in cast
H2 O 90 mL slabs and ingots.

Na2 Cr2 O7 180 g As above but rinse in hot water. General etch for defects in sand and die castings.
HNO3 (concentrated) 180 mL
H2 O to make 1000 mL

CrO3 280 g As above. Germination on sand cast surfaces. Surface

HNO3 (concentrated) 25 mL defects of die castings.
HF (48 %) 10 mL
H2 O to make 1000 mL

AZ61A 6 % picric acid in 100 mL As above for 1⁄2 to 3 min or may be swabbed. Grain size and flow patterns of both cast and
alcohol wrought forms. Requires fine finish (600 grit).
AZ80A 10 mL
H2 O 5 mL
Glacial acetic acid

AZ21 6 % picric acid in 70 mL As No. 7. Grain size. Specimen should be finished on 600-
alcohol grit paper.
AZ31 10 mL
H2 O 10 mL
Glacial acetic acid

ZK60A 6 % picric acid in 50 mL As No. 7. Flow pattern and grain size of homogeneous alloy.
alcohol 20 mL Increase water to increase strain contrast.
H2 O 20 mL Specimen should be finished on 600-grit paper.
Glacial acetic acid

4 % picric acid in 100 mL Immerse specimen in solution at room Segregation of intermetallic compounds and
alcohol 0.7 mL temperature repeatedly until desired stain is associated cracks. Specimen should be finished
H3 PO4 obtained, rinse and dry. on 600-grit paper.

8.8.1 Features detected by macroetching are grain size, with Marble’s reagent or strong HNO3 solutions. The high-
segregation of intermetallic compounds, coring, cracks, poros- temperature alloys are difficult to etch. First of all, they are
ity, laps, germinations, surface burning, and tears. subject to cold-working problems, and secondly, the alloys are
8.8.2 Cast or wrought magnesium alloys are prepared in a extremely corrosion resistant. Best results have been obtained
similar manner to aluminum or copper and brass; however, a with aqua regia, modified Marble’s reagent, or HCl-H2 O2
final facing with a 0.005-in. (0.127-mm) radius V-shaped tool solutions.
fed at a rate of 0.002 to 0.003 in. (0.508 to 0.762 mm) is often 8.9.2 Macroetchants for Nickel and Nickel Alloys (Table 9).
sufficient. For some applications, the specimen may be finished 8.10 Noble Metals— Ag, Au, Ru, Rh, Pd, Os, Ir, and Pt:
on a 400-grit wet wheel. To resolve small detail, additional 8.10.1 These metals, in general, are soft and ductile. Be-
polishing with a water suspension of 600-grit Alundum or cause of their expense, usually specimens for macroetching
further with alpha alumina may be necessary. will be small and can be handled the same as microspecimens.
8.8.3 The finely divided magnesium as chips or swarf is Care should be used to avoid cold work. Well-lubricated
highly combustible and precautions against it catching fire metallographic papers are recommended. Some of the platinum
should be taken. group metals, notably osmium and rhodium, are more abrasion
8.8.4 Macroetchants for Magnesium and Magnesium resistant than their hardness would indicate and, therefore, will
Alloys—(Table 8). require long grinding time.
8.9 Nickel and Nickel Alloys: 8.10.1.1 Except for silver, all of these metals are corrosion
8.9.1 Nickel alloys cold work easily and their preparation is resistant and require the use of strong etchants. Etching should
not always easy. Grinding produces the best specimens. Low- be done under a fume hood, with the proper precautions for the
nickel and cobalt alloys of basically pure metal can be etched use of HF.

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TABLE 9 Macroetchants for Nickel and Nickel Alloys
Alloy Composition Procedure Comments
Ni CuSO4 10 g Immerse specimen in solution at room Marble’s reagent, for grain
HCl 50 mL temperature until desired contrast is structure.
H2 O 50 mL obtained. Rinse and dry.

Low-Ni alloys HNO3 20 mL Immerse specimen in solution at room Grain structure.

H2 O 10 mL temperature for 20 to 30 min, rinse and dry.
CuSO4 10 g

High-Ni alloys HNO3 50 mL As above. Porosity and flowlines.

(concentrated) 50 mL
H2 O

Alloys containing Cr, Fe, HNO3 50 mL Immerse specimen in hot solution. Rinse in Grain structure.
and Acetic acid 50 mL hot water and dry.
other elements

Acetic acid 50 mL Swab Lepito’s reagent II, etchant for

HNO3 50 mL nickel welds.

Sat soln of CuSO4 50 mL Swab etchant. Modified Marble’s reagent.

in H2 O

HCl 100 mL Mix HCl and water, then heat, immerse

H2 O 100 mL specimen, and add H2O2 in several parts.
H2 O2 (30 %) 40 mL Do not mix. Make subsequent additions
after foaming from the previous addition
has stopped.

8.10.2 Macroetchants for the Noble Metals (Table 10). Add an additional 200 mL of NH4 OH (sp gr 0.9) and dilute
8.11 Refractory Metals—Cr, Mo, W, V, Cb, and Ta: with water to make 1 L. Add 100 g of sulfur. Stir occasionally
8.11.1 The above six metals, the refractory metals, are over a period of 1 h, then filter and use.
found in Group V-B (V, Cb, Ta) and Group VI-B (Cr, Mo, W) 8.13 Titanium, Zirconium, Hafnium and Their Alloys:
of the periodic table. (Some tables list them as V-A and VI-A.) 8.13.1 Titanium, zirconium, and hafnium, the reactive met-
In general, these metals are soft and ductile in the pure state, als, are macroetched for general structure, grain size, and
but in the form usually encountered are hard and brittle. segregation of impurities. They require extreme care in prepa-
Consequently, these metals and their alloys must be carefully ration. Sharp tools and fresh grinding paper are required to
ground before macroetching. The abrasives must be of suffi- prevent cold work from blurring the structure. The best results
cient hardness, and particles on the laps must be sharp. Wet are obtained by grinding. These metals grind slowly and
silicon carbide papers have proved satisfactory provided they require sharp, fresh abrasives. The recommendations of grind-
are used with sufficient pressure to effectively cut the sample ing wheel manufacturers should be followed closely for rough
and are not used after they become dull or worn. Longer grinding. Silicon carbide papers, usually run wet, will give a
grinding times than would be expected from the hardness of fine finish. Papers should be discarded frequently to prevent
these metals and alloys are needed. The solutions listed in loading. Chemical polishing preparations, while relatively
Table 11 used for the metals specified will reveal defects, untried, may have decided advantages in handling these
general structure, grain size, and segregation. materials.
8.11.2 Macroetchants for the Refractory Metals (Table 11). 8.13.2 Solutions in Table 13 are not difficult to prepare but
8.12 Tin and Tin Alloys: involve the use of hydrofluoric acid. This acid can give
8.12.1 Tin and its alloys, like lead, are difficult to prepare. extremely serious, very painful burns. The HCl-HF solution
Because these metals cold work easily and recrystallize at requires desmutting. The specimen should be rinsed between
room temperature, false structures are easily produced. The etching and desmutting. (Table 13)
best method of preparation for macroetching is the same as for
8.14 Zinc and Zinc Alloys:
microetching. The specimen should be cut carefully and then
ground gently on lubricated silicon carbide paper. This may be 8.14.1 Zinc and its alloys cold work rapidly and recrystal-
followed by polishing with 6-µm diamond paste on a moder- lize at low temperatures, thus allowing false structures to form
ately nappy wheel. easily. Coarse-grained zinc and zinc alloys are more prone to
8.12.2 Precision cast tin-base bearing alloys may be etched cold work than some of the fine grained die-casting alloys. A
directly without preparation. good test for the presence of cold work, especially in coarse-
8.12.3 Macroetchant for Tin and Tin Alloys (Table 12). grained samples, is the appearance of twinning after etching.
8.12.4 Preparation of Ammonium Polysulfide—Pass H2 S 8.14.2 Samples should be cut with a sharp saw and ground
gas into 200 mL of NH4 OH (sp gr 0.9) until saturated. The on well-lubricated silicon carbide papers at slow speeds.
solution should be kept in an ice bath during this operation. 8.14.3 Macroetchants for Zinc and Zinc Alloys (Table 14).

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TABLE 10 Macroetchants for the Noble Metals
Metal Composition of Solution Condition of Use Comments and Use
Ag HNO3 10 mL RT, few minutes. Grain contrast.
Methyl alcohol 90 mL

Au HCl 66 mL Hot, few minutes. Grain contrast.

Pt alloys HNO3 34 mL
Pd alloys

Ru and alloys Lactic acid 50 mL RT, few minutes. Grain contrast.

Os and alloys HNO3 20 mL
Rh and alloys HF 30 mL

As above HCl 30 mL RT, few minutes. Grain contrast.

HNO3 15 mL
HF 30 mL

Pt and alloys Sat solution of 80 mL Electrolytic, 6V, few Grain contrast.

NaCl in H2 O minutes.
HCl 20 mL

TABLE 11 Macroetchants for the Refractory Metals

Metal Composition of Solution Temperature Time Comments
Mo, W, V, Cb, and Ta HCl (concentrated) 30 RT 5 to 20 min
HNO3 (concentrated) 15
HF (48 %) 30

Mo, W, and V HF (48 %) 15 RT 10 to 20 min

HNO3 (concentrated) 35
H2 O 75

W, V, Cb, and Ta HF (48 %) 10 RT 1 to 40 min Too fast for Mo, 1 to 5 s

HNO3 (concentrated) 30
Lactic acid (85 %) 50

Cr H2 SO4 10 Boiling 2 to 5 min

H2 O 90

TABLE 12 Macroetchant for Tin and Tin Alloys

Composition of Solution Procedure Comments
Saturated ammonium polysulfide Immerse specimens in full strength solution at room temperature for 20 to 30 min. Do not swab surface Grain structure
during etching.

9. Keywords
9.1 alloys; etchants; etching; macroetching; macroetchant;
macrostructure; metals

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TABLE 13 Macroetchants for Titanium, Zirconium, Hafnium and Their Alloys
Alloy Solution Composition Procedure Comments
Ti alloys HCl (concentrated) 20 mL Immerse specimen in solution heated to 120 to Desmut Ti, -13V-11 Cr-3A1, alloys. Others
HF (48 %) 40 mL 150°F for 20 to 30 min. Rinse. If smut forms do not normally need desmutting.
H2 O 40 mL immerse in 30 % H2 SO4 for 3 min. Rinse and
dry.

7A1-4Mo alloys HNO3 (concentrated) 42 mL As above.

HF (48 %) 8 mL
H2 O 50 mL

Zr, Hf, and low alloys H2 O2 (30 %) 45 mL Swab specimen with solution at room Should be used under a hood; chemical
HNO3 (concentrated) 45 mL temperature. Rinse 10 s after yellow fumes polishing solution.
HF (48 %) 10 mL form, then dry.

Zr, Hf, and high alloys H2 O 45 mL As above. As above.

HNO3 45 mL
HF 10 mL

1.5Sn-0.15Fe-0.10Cr, H2 O 70 mL As above. As above.

and Hf HNO3 (concentrated) 30 mL
HF (48 %) 5 mL

Iodide Ti H2 O2 (30 %) 60 mL Swab with solution at room temperatures until As above.

H2 O 30 mL desired contrast is obtained. Rinse in cold
HF (48 %) 10 mL water and dry.

TABLE 14 Macroetchants for Zinc and Zinc Alloys

Alloy Solution Composition Procedure Comments
Cu-free zinc alloys HCl (concentrated) 50 mL Immerse in solution for about 15 sec. Grain structure.
H2 O 50 mL Remove smut by wiping under running
water. Repeat until desired contrast is
obtained, then dry.

Zn alloys containing Cu CrO2 20 g Immerse in solution until good contrast is Grain structure.
Na2 SO4 1.5 g obtained. Rinse in running water and dry.
or Repeat if necessary.
Na2 SO4 ·10H2 O 3.4 g
H2 O 100 mL

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