ELSEVIER

Metallographic Preparation of Soft

Materials: Lead Alloys
K. H. Ednie
Materials and Manufacturing Processes Department, Advanced Vehicle Systems Development,
Lucas Industries, Solihull, West Midlands B90 4JJ, United Kingdom

Metallographic preparation of lead and its alloys is notoriously difficult due to the low
hardness of the material and its tendency to pick up and embed abrasive particles readily.
Working with component parts for lead acid batteries at Lucas Advanced Vehicle Systems
Development, the odd shapes and sizes, such as connector posts and intercell welds, do not
lend themselves to microtoming or electropolishing. Vibratory polishing had been used in
the past but this method could take up to 6 days to produce an acceptable microsection. Us-
ing semiautomatic polishing equipment had proved more successful, but again long peri-
ods of time were taken to produce satisfatory results with all the problems of lubricant and
abrasive dosing. Tests on newer, commercially available pads and abrasives provided by
various manufacturers have been carried out, but it was found that a combination of ma-
chining, polishing with diamond, and final polishing with alumina gave the best results. The
use of automatic polishing equipment made the preparation easier with both contrarotation
and complementary rotation directions. Lubricants and abrasives recommended by the met-
allographic consumable suppliers for soft materials were not suitable for the easily stained and
oxidized lead alloys. This report lays out the steps taken to produce the stated optimized
procedure and shows some unusual structures that have been revealed in components
taken from batteries undergoing testing, one of which had suffered explosive damage.
0 ElsezTier Science Inc., 1996

INTRODUCTION any deformation of the samples incurred

For many years, Lucas Industries, latterly
in partnership with the Japanese company,
Yuasa, has manufactured lead acid batter-
ies for automotive applications. Tradition-
ally, metallography has always played a
significant role in the understanding and
investigation of the principles and mecha-
nisms involved in battery construction. How-
ever, the alloys used in the lead acid batter-
ies have hardnesses of around 7-21HVa,oas
(butter straight from a refrigerator might be
only a little softer), which makes the prepa-
ration especially difficult. Failed batteries
also had to be examined for any corrosion
products or microstructural changes. This
presented a requirement that the chosen
preparation method had to guarantee that
243
MATERIALS CHARACTERIZATION 36:243-255 (1996)
0 Elsevier Science Inc., 1996
655 Avenue of the Americas, New York, NY 10010
during sectioning was removed and would
not provide spurious information. Many
metallographic techniques have been evalu-
ated in order to obtain satisfactory speci-
mens. Innovations in pad, lubricant, or
abrasive technology that the consumable
manufacturers have incorporated in their
product ranges have also been tested. Prep-
aration of the various components of bat-
teries for microstructural examination has
always been fraught with pitfalls for the
unwary, especially as the intercell welds
and connector posts have such large and
convoluted shapes. Figure 1 shows com-
mon car-battery parts requiring metallo-
graphic preparation and their correspond-
ing sections.
Normal preparation routes for soft mate-
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244 K. H. Ednie

FIG. 1. Examples of components that have been sectioned.

rials are not suitable for lead alloys, as bide paper and polishing on short nap pads
these easily pick up diamond particles. At- down to */&m diamond, frequently left the
tempts to use recommended routes for soft sample peppered with particles. Figure 2 is
materials, such as grinding on silicon car- a scanning electron micrograph of a con-

FIG. 2. Scanning electron micrograph of a battery connector microsection showing embedded diamond particles.
Preparation of Lead Alloys
FIG. 3. Surface finish obtained on a lathe.
nectar that was prepared using the normal
soft material route showing embedded par-
ticles.
PREPARATION TECHNIQUES
CONSIDERED AND TESTED
SECTIONING
Cutting of the lead components to reach the
correct position for polishing has proved
especially difficult. The friable nature of
some of the materials, such as the active
pastes, and corrosion products meant that
complete plates or components had to be
encapsulated before any sectioning was
carried out. A recent task was to mount half
of a complete car battery in epoxy resin be-
fore the relevant sections could be cut and
remounted for preparation. The microsec-
tions were cut close to the relevant position
by using either a manual or an automatic
machine with an abrasive wheel for nonfer-
rous materials. A band saw even with a
245
fine-toothed blade, was found to be unsuit-
able as too much damage was caused to the
sample surface and the encapsulating ma-
terial.
Microtoming has been considered but,
again, any oxides or paste present, because
of their friable nature, would be easily bro-
ken up and lost. This latter requirement
precipitated a need to find a technique that
would prepare both the soft lead alloys and
the friable but relatively harder pastes and
oxides.
Other types of cutting, such as using dia-
mond wheels, jigsaws, and other grades of
abrasive wheels were tested for surface fin-
ish, but most that provided a fine cut also
produced large amounts of deformation by
clogging and smearing the soft lead. Water-
jet equipment and wire saws have not been
surveyed as to their suitability. Any tech-
nique chosen would also have to leave the
encapsulating media undamaged.
Facing off the sample surface on a small
bench-top lathe was found to yield a sur-
face finish with much less deformation.
246
FIG. 4. Connector sample: ground finish from PlZOO-grit silicon carbide paper.
Figure 3 shows the surface finish obtained
on a battery-strap sample prepared using a
small bench-top lathe. The final cut had to
be very small (less than 0.2mm), traversing
the sample at a relatively slow speed
(lOmm/minute linearly). The rotational
speed was 740 revolutions per minute
(rpm). The slow cutting speed meant that a
lubricant or cutting fluid was unnecessary.
This type of cut also appeared not to dam-
age the mounting media severely.
ENCAPSULATING
Choice of an encapsulant for several of the
preparation techniques was found to be
critical. Hot mounting would have modi-
fied the microstructure as recrystallization
can occur at temperatures of less than 40°C
so cold set resins were required. The intri-
cate shapes and friable pastes meant that
vacuum impregnation had to be used. This
negated the use of faster-setting resins that
also produce significant amounts of heat
during polymerization. The material cho-
sen needed to be polished back at a similar
K. H. Ednie
rate to the encapsulated component with
the abrasives suitable for the sample prepa-
ration. A medium could not be located that
satisfied all of the criteria, so materials at
hand were selected. The epoxy resin and
hardener used were Cieby-Gigy MY753
and HY971, respectively (8-12 h setting).
These materials had a viscosity suitable for
vacuum impregnation.
GRINDING
Grinding the microsections on silicon car-
bide papers seemed to cause significant
pickup of diamond particles at the first pol-
ishing stage. Trials showed that the dia-
mond particles were prone to embed only
if the previous preparation step left a
rough, smeared surface such as that re-
maining after grinding. A diamond polish-
ing step was, however, considered neces-
sary as a large amount of stock removal
was required in order to eliminate any de-
formation from previous stages. Scanning
electron microscope (SEM) examination
showed that the surface left after grinding
Preparation of Lead Alloys 247

FIG. 5. Connector post sample: ground finish from P4000-grit silicon carbide paper.

FIG. 6. Scanning electron micrograph of PlZOO-grit silicon carbide paper.

248
FIG. 7. Scanning electron micrograph
on P1200grit paper had undergone signifi-
cant deformation and had left ridges. Fig-
ure 4 shows the surface finish of a sec-
tioned connector post after grinding for 60
s on a P1200-grit silicon carbide paper at
250rpm.
The finer P4000-grit paper left the surface
with some rough areas and other areas that
appeared smooth. Figure 5 is the same con-
nector post sample after grinding first on
I’1200 silicon carbide paper for 60s and
then for the same period on I’4000 grit. It
was concluded that the grit at first cut the
sample surface but then became clogged
and smeared loose material over areas of
the microsection. The lubricant used for
grinding was a recirculated cutting fluid/
inhibitor diluted with water. SEM examina-
tion of the silicon carbide papers showed
that a significant quantity of binder was
present on the I’1200 paper with only a
small number of particles raised above the
surface (Fig. 6). Very few particles from the
silicon carbide papers were observed em-
bedded in the as-ground samples. If the
K. H. Ednie
of P4000-grit silicon carbide paper.
surface was relatively smooth, very few, if
any, particles were embedded.
Figure 7, a scanning electron micrograph
of the P4000-grit silicon carbide paper,
shows a significant quantity of particles
with much less binder present. It was
thought that this lack of binder encouraged
the pickup of material, leading to smearing.
POLISHING
Electropolishing was found to produce
good results on the lead alloys without
pastes or corrosion products. The tech-
nique has been used to investigate the mi-
crostructures of the bulk-cast or wrought-
lead alloy components. However, it was
unsuitable for microsections of components
exhibiting porosity where severe edge
rounding was observed.
Electropolishing also proved totally un-
suitable when plane sections of freshly
made plates, including the active pastes,
were required in order to investigate the
formation of crystals and the path of corro-
Preparation of Lead Alloys
FIG. 8. Scanning electron micrograph of loose diamond particles on the surface of the fibers of a chemotextile
sion/oxidation in the grids. The plates con-
sist of a lead grid in to which a paste is
pressed. The paste formulation depends on
whether the plate is positive or negative
and has to hold its shape throughout the
reactions occurring during charging and
discharging of the battery. These samples
were to be examined both optically and by
using scanning electron microscopy analy-
sis; therefore, a flat section with no pickup
from the polishing media was required.
Vibratory polishing using a long nap
Selvyt cloth and alumina slurry was tested.
The samples needed to be encapsulated
and then sectioned close to the area of in-
terest prior to polishing. This technique
proved adequate with respect to the fin-
ished microsections, but preparation times
were of the order of 3-6 days, creating prob-
lems with keeping the slurry moist and
stretching and rucking of the polishing cloth.
The first step of any polishing procedure
is to remove gross deformation from the cut-
ting process and to keep the mounting me-
dia and sample at the same level. This step
249
pad.
can be repeated as many times as neces-
sary. Polishing using a chemotextile cloth
and 6pm diamond was tried, but attempts
to polish by hand led to long polishing
times and required some form of automa-
tion in order to become viable.
Bench-top polishing machines with semi-
automatic features such as individual
weights and a lubricant feed were used.
These also proved suitable for the final alu-
mina polishing stages. The rotation of the
samples and the pads was effectively in one
direction only, which introduced polishing
artifacts like swathes of embedded particles
or pitting.
Acquisition of an automatic system
(Struers Abramatic) gave the facility for us-
ing both contrarotation and complemen-
tary rotation. Loading on the samples was
adjustabIe and the lubricant and abrasive
dosing allowed for less operator interfer-
ence. It was also noted that the system de-
creased the time needed for the first step of
the preparation, because the stock removal
was increased by the use of contrarotation.
 K. H. Ednie

FIG. 9. Sample faced off on a lathe and subsequently polished to a 0.05km finish

PC9ishing of samples, both by hand and It was thought the ridges remaining irI the
auto)matically, after grinding them on sili- sample surface gathered up the loose dia-
con carbide papers showed a considerable mond grit present on the pad (Fig. 8). Fur-
amc xrnt of pickup of the diamond particles. ther polishing with the same or similar 1pad

FIG. 10. Copper-graphite brush microsection.

Preparation of Lead Alloys 251

FIG. 11. Unreacted paste material

did I-rot remove the impressed particles, embedded diamond particles. Figun 3 9
even though the polishing time was ex- shows a corroded grid sample that was cut
tends :d. on a lathe and subsequently polished t‘0 a
PO1 ishing of the sample machined on the 0.05km finish. Note also that the oxicde/
lathe on this system showed no evidence of paste has been kept intact.

FIG. 12. Connector-annealed structure leading to a creep failure.

252 K. H. Ednie

FIG. 13. As-cast structure of connector.

Changing the abrasives used, for in-
stance, larger particle sizes of alumina in-
stead of diamond or silica for the final polish-
ing stage, was unsuccessful. The alumina, in
a water-based lubricant, washed easily from
the pads, and the stock removal rate was sig-
nificantly lower than that of the diamond.
Collodial silica suspensions adhered to the
polished surface and induced severe stain-
ing that could not be removed without rub-
bing and scratching the surface of the sample.
Pads for the final polishing stages, both
long and short naps, were tested, but the
material itself scratched the lead rather

FIG. 14. Corrosion of battery grid.

Preparation of Lead Alloys 253

FIG.15.Porosity in a poor intercell weld

than allowing the abrasive to polish the rounding of the sample edges, but this was
surface. Using water as a lubricant affected one instance where it was detrimental to
the adhesive on most of the pads, causing the finish of the samples. Many of the latest
additional difficulties of the pads moving pad materials, abrasives, and lubricants
or lifting. The Selvyt cloth used for these have been tested on the lead samples. Al-
preparations was not self-adhesive and though most are highly suitable for the
was held on the disc with clamps. preparation such as alu-
of the soft alloys,
Manufacturers tend to reduce the length minium and copper, none could replace the
of the nap on newer pads so as to stop ones chosen initially.

Table 1 Refined Procedure for the Preparation of Lead Alloy Microsections

Step Cloth Abrasive Lubricant Rotation Load Time

1 Sectioning/machining on lathe to position prior to polishing: final cut to be as fine as possible

2 Pan-W 6pm Diamond Methanol Alternating until 250N As long as

slurry based sample is flat necessary in
maximum steps
of 600 s

3 Selvyt 0.3t.i.m Weak solution Once each of 1OON 60 s each rotation

Alumina of detergent contrarotation
in water and complementary
rotation

4 Selvyt 0.05km Weak solution Once each of 1OON 60 s each rotation

Alumina of detergent contrarotation
in water and complementary
rotation
254 K. H. Ednie

Table 2 Modified Procedure for Brush and Paste Samples

Step Cloth/Pad Abrasive Lubricant Rotation Load Time

Silicon carbide From 120 to Water-based Alternate with 300N Between

papers 4000 grit cutting fluid each change 60 and 90 s
of grit size

Pan-W 3p.m Diamond Methanol Once each of 250N 300 s each

slurry based contrarotation and rotation
complementary
rotation

Pan-W lbm Diamond Methanol Once each of 250N 300 s each

slurry based contrarotation and rotation
complementary
rotation

Long napped 0.25pm Diamond Methanol Once each of 100N 300 s each
cloth paste based contrarotation and rotation
complementary
rotation

Final polishing of the samples after sec-
tioning was carried out using the following
technique:
Step 1: A chemotextile cloth (Pan-W) with
6pm diamond abrasive and a meth-
anol-based or kerosene-based lubri-
cant.
Step 2: Long napped pure cotton cloth
(Selvyt) with 0.3pm alumina (al-
pha) and water/detergent lubri-
cant.
Step 3: Selvyt cloth with 0.05F.m alumina
(gamma) and water/detergent lu-
bricant.
Through most of the trials, a copper-graph-
ite electrical brush sample from an alterna-
tor was included. This sample was a mix-
ture of a metal and friable material similar
to the battery components but also in-
cluded a hard phase. This component had
been almost as difficult to polish, with
much of the graphite being lost and the
hard-phase material pulled out. The brush
was found to be easily prepared using a
slightly modified “normal” route, mainly
because of using the P4000-grit paper. This
seemed to provide a step similar to lap-
ping, keeping the sample very flat but with
little disturbance to the material. This grit
size also allowed the first polishing step to
be 31_tm diamond instead of 6pm, which
shortened the preparation time. Figure 10
shows the copper-graphite brush microsec-
tion polished to r/4krnfinish.
Unreacted battery paste without the lead
grid material present was also sectioned
with good results by following this modi-
fied preparation route. The cross section
obtained of the crystal structure of the lead
oxide sulfate paste is shown in Fig. 11.
Figure 12 shows the microstructure of a
connector from a battery that had under-
gone prolonged and varied testing. The
battery had exploded after the connector
had failed. The etchant used for these lead
alloys was a modified Votes reagent (see
the Appendix). An investigation was car-
ried out in order to find the cause of failure.
The prolonged testing had modified the
microstructure so that the grains were equi-
axed and, therefore, very susceptible dur-
ing further testing to creep. Figure 13
shows the normal microstructure for an as-
cast connector. Figure 14 is from a small
area of a crossection of a corroded grid
strut. The battery had undergone testing in
an attempt to emulate potential failure
modes.
Figure 15 shows the porosity that can be
Preparation of Lead Alloys 255

present in an intercell weld when the pa-
rameters are set incorrectly. Some porosity
can be present without detrimental effects
to the life of the battery. Numerous sam-
ples were sectioned when new equipment
was installed and the conditions for good
welds had to be set.
Table 2 presents the modified route for the
copper-graphite brush and paste samples.
The author is grateful to Christopher Smith for
the original idea for the methods.
Appendix: Etching of Lead Alloys: Modified
Votes Reagent

SUMMARY 1Og Ammonium molybdate

2% Citric acid
The testing and evaluation of techniques
for the preparation of lead samples will be 1OOmL Water
ongoing. The types of material used in the 1mL Nitric acid
battery industry may change, but there will Swabbed using cotton wool for 5-10 s, washed in water,
always be a need for procedures to prepare methanol, or Propan- and acetone, and blown dry using
soft and/or friable samples. The procedure compressed air or nitrogen. Hot-air dryers were found to
encourage staining.
presented in Table 1 has been established
as suitable for the majority of the lead alloy
Received February 1996; accepted May 1996.
components prepared in this laboratory.