251

Chapter 4f

The analysis of non-ferrous metals by atomic absorption spectrometry

F. J. BAN0
Linksfield Laboratories Ltd., Chalon Way, St. Helens, Merseyside
(G t. Britain)

I. INTRODUCTION

Atomic absorption spectrometry has been applied to the analysis of over

sixty elements. The technique combines speed, simplicity and versatility and
has been applied to a very wide range of non-ferrous metal analyses. This
review presents a cross section of applications. For the majority of appli-
cations flame atomisation is employed but where sensitivity is inadequate
using direct aspiration of the sample solution a number of methods using
a preconcentration stage have been described. Non-flame atomisation
methods have been extensively applied to the analysis of ultra-trace levels of
impurities in non-ferrous metals. The application of electrothermal atom-
isation, particularly to nickel-based alloys has enabled the determination
of sub-part per million levels of impurities to be carried out in a fraction
of the time required for the chemical separation and flame atomisation
techniques.

11. DETERMINATION OF IMPURITIES IN ALLOYS BASED ON

VARIOUS NON-FERROUS .METALS

A. Aluminium

The analysis of aluminium alloys by atomic absorption was one of the

earliest applications of the technique to non-ferrous metal analysis. Wallace
[l] has described the determination of magnesium in aluminium alloys
using an airpropane flame. Because of the strong interference of aluminium
on magnesium in low temperature flames, 8-hydroxyquinoline was used as
a releasing agent. The use of the nitrous oxideacetylene flame by Wilson
[ 21 eliminated the interference of aluminium on magnesium.
Aluminium alloys may be dissolved using the following procedure. Weigh
1.000 g of sample into a PTFE beaker in a cooling bath. Add 20 ml of con-
centrated hydrochloric acid dropwise, allowing the reaction to subside
between additions. (Note that the reaction is vigorous and the beaker should
be cooled during the addition of acid.) Agld 4 ml hydrofluoric acid and allow
t o stand for ten minutes, taking care that the temperature does not exceed
50-60"C. Add 4ml of nitric acid dropwise, again taking care t o cool the

References p . 259
252
TABLE 1
STANDARD CONDITIONS FOR THE ANALYSIS OF ALUMINIUM ALLOYS

Analyte Wavelength Flame Notes

(nm)

Aluminium 231.3 nitrous oxide/ Aluminium is ionised in the nitrous

acetylene oxidelacetylene flame ;add 2000
mg I-’ potassium to the sample
s o h tion
Magnesium 285.2 nitrous oxide/
acetylene
Copper 324.1 airtacetylene
Iron 312.0 nitrous oxidel
acetylene
Tin 224.6 nitrous oxide/
acetylene
Zinc 213.9 airlacetylene At the 213.9 nm wavelength non-
atomic species absorb strongly;
background correction is therefore
necessary
Silicon 251.6 nitrous oxide/ At the 217.0nm wavelength non-
acetylene atomic species absorb strongly;
background correction is therefore
necessary

mixture during the reaction. Cool and add 0.5 g A.R. boric acid t o complex
the excess fluorides. Transfer to a 100ml volumetric flask and make up
to volume with distilled water. Standard conditions for the analysis of
aluminium alloys are shown in Table 1.
Table 2 shows results obtained by Campbell [ 31 for the determination of
silicon in aluminium alloys. In this procedure the sample was dissolved in 20%
sodium hydroxide/hydrogen peroxide. After dissolution the solution was
treated with a mixture of nitric and hydrochloric acids and diluted to volume.

B. Cobalt

Welcher etal. 141 have described the analysis of cobalt-based alloys.

Cobalt alloys may be dissolved according t o the following procedure. Weigh
0.5000 g of sample into a PTFE beaker. Add 2 ml of water, 10 ml of concen-
trated hydrochloric acid and 5ml of concentrated nitric acid. Warm the
mixture for approximately thirty minutes. Add 2ml of concentrated nitric
acid and 5ml of concentrated hydrochloric acid and reheat for a further
thirty minutes. Cool, add 5ml of hydrofluoric acid and fume to dryness.
Add 5ml of concentrated nitric acid and heat for ten minutes. Repeat with
a further 5 ml of nitric acid. Add 1 0 ml of hydrochloric acid and reheat to
boiling, cool and dilute to 100ml. Standard conditions for the analysis of
cobalt alloys are shown in Table 3.
 253
TABLE 2
DETERMINATION OF SILICON IN ALUMINIUM ALLOYS

Sample A.A. Chemical % Relative error

1 12.93 13.10 1.3

2 13.86 13.79 0.2
3 13.20 13.40 1.5
4 18.35 18.28 0.4
5 14.12 14.05 0.5
6 11.15 11.07 0.7
7 11.55 11.64 0.8
8 13.23 13.41 1.3
9 10.99 11.07 0.7
10 11.66 11.64 0.2
11 12.30 12.18 1 .o
12 17.59 17.50 0.5
13 17.41 17.55 0.2
14 17.67 17.80 0.7

TABLE 3
INSTRUMENTAL PARAMETERS FOR THE ANALYSIS OF COBALT-BASED
ALLOYS

Analyte Wavelength Flame Notes

(nm)
Cobalt 304.4 nitrous oxide/ High levels of chromium can lead to
acetylene interference in the presence of
hydrochloric acid; the use of the
nitrous oxide/acetylene flame
avoids this interference.
Chromium 520.8 nitrous oxide/
acetylene
Iron 386.0 nitrous oxide/ The use of the nitrous oxide/
acetylene acetylene flame is recommended in
order to eliminate interference

C. Copper

The analysis of copper-based alloys by atomic absorption has been

described by Johns and Price [ 51.
For the sample preparation, weigh 0.5000g of sample into a 250ml
beaker and add 20ml of a mixed acid solution containing 250ml of con-
centrated hydrochloric acid, 250 ml of concentrated nitric acid and 500 ml
of water per litre of solution. Warm gently until dissolution is complete, cool
and transfer the solution to a 100 ml volumetric flask. Make up to the mark.
Instrumental conditions for the analysis of copper alloys are shown in
Table 4.

References p . 259
2 54
TABLE 4
INSTRUMENTAL PARAMETERS FOR THE ANALYSIS OF COPPER-BASEDALLOYS

Analyte Wavelength Flame Notes

(nm)

Aluminium 209.3 nitrous oxide/

acetylene
Antimony 217.6 airlacetylene
Arsenic 193.7 airlacetylene
Copper 327.4 airlacety lene For the determination of major
alloying elements the use of
Class A volumetric glassware is
recommended
Iron 372.0 airlacetylene
Lead 283.3 airlacety lene
Manganese 403.1 airlacetylene
Nickel 352.5 airlacety lene
Silicon 251.6 nitrous oxidel
acetylene
Tin 286.3 nitrous oxide/
acetylene
Zinc 213.9 airlacetylene

Results obtained for four samples of BCS copper alloys are shown in
Table 5. All the results indicate good agreement with certified values. The
results obtained for copper indicate that in favourable cases it is possible to
obtain satisfactory results for major alloying components. The excellent
results which can be obtained for the analysis of large percentage amounts
of copper is further confirmed by the work of Sattur [6], whose results for
five copper-based alloys are shown in Table 6.

D. Lead

A major problem in the analysis of lead-based alloys is the selection of a

suitable solvent mixture. Price [ 71 has described a method based on hydro-
bromic acid/bromine. The disadvantage of this method is that the solvent mix-
ture is unpleasant t o handle and precipitation often occurs on dilution. Hwang
[S) has described a method for the analysis of trace and minor elements in
lead/tin solders using a solvent mixture of fluoboric acid and nitric acid.
For fluoboric acid preparation, to 200ml 40% w/v hydrofluoric acid at
10°C, add, in small quantities, 75g boric acid. Allow t o dissolve and store
in a polythene bottle. This reagent should be prepared freshly each day.
Weigh 1.OOOg of finely divided sample into a 250ml beaker and cover
with a watch glass. Add 40 ml of water, 6 ml of fluoboric acid and 12 ml of
concentrated nitric acid. Warm the solution gently. Agitating the solution
using a magnetic stirrer will aid dissolution. Cool to room temperature. Add
5 ml of 1%tartaric acid solution. Dilute to 100 ml with water.
P

TABLE 5
RESULTS FOR FOUR SAMPLES OF BCS COPPER ALLOYS
BCS No. Aluminium Antimony Arsenic Copper Iron Lead Manganese Nickel Silicon Tin Zinc
- ~ ~ ~ _ _ _ ~ ~ _ _
Cert. Obt. Cert. Obt. Cert. Obt. Cert. Obt. Cert. Obt. Cert. Obt. Cert. Obt. Cert. Obt. Cert. Obt. Cert. Obt. Cert. Obt.

17912 2.20 58.7 1.02 0.35 0.87 0.56 0.04 0.71 35.3
2.22 58.5 1.02 0.35 0.86 0.56 0.044 0.70 35.8
2.15 59.0 1.01 0.36 0.87 0.56 0.04 0.72 35.7
18312 0.24 0.16 85.2 3.40 0.51 5.00 5.14
0.24 0.14 85.0 3.35 0.51 5.03 5.16
0.25 0.15 84.7 3.40 0.52 5.02 5.12
304 8.78 80.2 4.65 0.495 4.75 0.185 0.607
8.92 80.4 4.71 0.51 4.75 0.19 0.60
8.82 80.1 4.68 0.500 4.70 0.19 0.604
364 0.18 81.0 9.30 0.28 9.31 0.128
0.18 80.6 9.25 0.28 9.35 0.13
0.18 80.5 9.35 0.28 9.22 0.126
256
TABLE 6
RESULTS OBTAINED [ 6 ] FOR THE ANALYSIS OF FIVE COPPER-
BASED ALLOYS

Sample Type A.A. % cu

Cert. Value

NBS37d Brass 70.6 70.78

63c Bronze 80.7 80.48
124d Bronze 83.6 83.6
157 Cu-Ni-Zn( nickel silver) 71.3 72.14
164a Aluminium bronze 82.3 82.25

TABLE 7
INSTRUMENTAL PARAMETERS FOR THE ANALYSIS
OF LEAD-BASED ALLOYS

Analyte Wavelength Flame

(nm)

Aluminium 309.3 nitrous oxide/acetylene

Antimony 217.6 airlacety lene
Arsenic 193.7 air/acetylene
Bismuth 223.1 airlacetylene
Cadmium 228.8 air /acety le ne
Copper 324.8 airlacetylene
Gold 242.8 air/acetylene
Iron 248.3 airlacetylene
Lead 283.3 airlacetylene
Nickel 232.0 airlacetylene
Silver 328.1 airlacetylene
Tin 224.6 nitrous oxide/acetylene
Zinc 213.9 airlacetylene

Instrumental parameters for the analysis of lead-based alloys are shown

in Table 7 and results obtained by Hwang [ 81 for the analysis of impurities
in lead solder are shown in Table 8.

E. Nickel

Welcher and Kriege [91 have described a procedure for the analysis of the
major alloying elements in nickel alloys.
Prepare the sample by dissolving 1.000 g of turnings in a mixture of 10 ml
of hydrochloric acid and 10 ml of nitric acid. Heat gently until the cessation
of nitrogen dioxide fumes. Transfer to a PTFE beaker and add 5 m l of
hydrofluoric acid dropwise. Ensure that the solution temperature does not
exceed 3OoC. Transfer the solution to a plastic 100 ml volumetric flask and
make up to volume with water.
 257
TABLE 8
RESULTS OBTAINED [ 81 FOR THE ANALYSIS OF IMPURITLES IN LEAD SOLDER

Element Reported Found Element Reported Found

value @I value (%)

~
(%) (%I
Ag 0.019 0.019 cu 0.05 0.05
0.036 0.035 0.10 0.11
A1 0.05 0.05 Fe 0.006 0.004
0.07 0.03 0.016 0.014
As 0.019 0.018 Ni 0.0025 0.0025
0.031 0.032 0.033 0.032
Au 0.010 0.010 Sb 0.12 0.11
0.040 0.038 0.30 0.31
Bi 0.038 0.039 Zn 0.005 0.0008
0.089 0.094 0.0013 0.0020
Cd 0.0057 0.0059
0.010 0.010

Instrumental parameters for the analysis of nickel alloys are shown in

Table 9.

F. Zinc

To prepare the sample, dissolve 1,000 g of the sample in 10 ml of hydro-

chloric acid. Oxidise with 2ml of 1OOvol. (30% w/v) hydrogen peroxide.
Boil to destroy excess peroxide. Cool, transfer to a l00ml volumetric flask
and make up to volume with distilled water.
Instrumental parameters for the analysis of zinc alloys as shown in
Table 10,

111. ELECTROTHERMAL TECHNIQUES

The methods already described have illustrated the wide applicability of

flame atomisation techniques to the analysis of non-ferrous alloys. The
introduction of electrothermal atomisation has enabled the direct deter-
mination of subpart per million levels of impurities. The presence of very
low levels of lead, bismuth and other low melting point metals is known
t o have a deleterious effect on the metallurgical properties of nickel alloys.
Welcher et al. [lo] have described the direct determination of trace quan-
tities of lead, bismuth, selenium, tellurium and thallium in high-temperature
nickel alloys using electrothermal atomisation.

References p . 259
TABLE 9
INSTRUMENTAL PARAMETERS FOR THE ANALYSIS O F NICKEL-BASED ALLOYS

Analyte Wavelength Flame Notes

(nm)

Chromium 520.8 nitrous oxide/ Chromium is subject to interference

acetylene from nickel. It is advisable to adjust
the fuel flow until the absorbance
obtained from a 1500pgmI-'
chromium solution and a 1500 pg
ml-' chromium plus nickel at the
sample level produce the same
absorbance
Bismuth 223.1 airlacety lene Sample preparation. Dissolve
2.000 g of sample in 12 ml of
hydrochloric acid, 6 ml of nitric
acid and 20 ml of water in a PTFE
beaker. Evaporate the solution to
10-12 ml, cool, add 1ml of hydro-
fluoric acid dropwise and boil for
five minutes. Cool, add 5 ml of 1%
boric acid solution and dilute to
50 ml. Background correction using
a UV continuum source is advisable
for bismuth
Iron 386.0 nitrous oxide/ Nitrous oxidelacetylene flame is
acetylene recommended to avoid interference
Cobalt 304.4 nitrous oxide/
acety lene
Lead 217.0 airlacetylene Sample preparation as for
bismuth. Background correction
recommended
Silicon 251.6 nitrous oxide/
acetylene

The samples were dissolved by the following procedure. Dissolve 1.OOOg

of metal chips in 30ml of a 1:l:l mixture of nitric acid, hydrofluoric acid
and water in a PTFE beaker. When dissolution is complete, reduce the
volume to approximately 5ml by evaporation. Cool, add about 20ml of
water and heat to dissolve all salts. Cool, transfer to a 50ml plastic volu-
metric flask and dilute to the mark.
Prepare standards by making standard additions to previously character-
ised samples. Operating parameters and detection limits are shown in
Table 11. The results obtained by Welcher indicate that electrothermal
atomisation is capable of yielding a very rapid means of analysing trace
impurities in non-ferrous alloys. In many cases lengthy separations are not
necessary and the technique is clearly applicable to a wide range of alloys.
 259
TABLE 10
INSTRUMENTAL PARAMETERS FOR THE ANALYSIS OF ZINC-BASED ALLOYS
~ ~

Analyte Wavelength Flame Notes

(nm)
Aluminium 309.3 nitrous oxide/ Add 2000 pg ml-' potassium to
acetylene sample solutions to suppress
ionisation. Use a standard additions
procedure to avoid interference
from the zinc matrix
Magnesium 285.2 nitrous oxide/
acetylene
Iron 248.3 air/acetylene
Copper 327.4 nitrous oxide/ The nitrous oxide/acetylene flame
acetylene is used to minimise the effect of
the high zinclcopper ratio
Cadmium 228.8 airlacetylene
Lead 217.0 air/acetylene Background correction should be
used

TABLE 11
OPERATING PARAMETERS AND DETECTION LIMITS FOR THE ELECTRO-
THERMAL ATOMISATION TECHNIQUE OF WELCHER ET AL. [ 101

Element Lead Bismuth Tellurium Selenium Thallium

Wavelength (nm) 283.3 223.1 214.3 196.0 276.9

Spectral band width (nm) 0.7 0.2 0.7 0.7 0.7
Solution volume (PI) 50 20 50 50 50
Sample concentratio? (mg ml-' ) 20 20 20 20 4
Drying temperature ( C) 150 150 150 600 150
Drying time (s) 20 20 20 20 20
Char temperature (OC) 400 800 600 1000 500
Char time (s) 60 45 60 45 60
Atomisation temperature ("C) 2000 2 200 2200 2400 2000
Atomisation time (s) 5 5 5 5 5
Detection limit in sample (ppm) 0.1 0.1 0.2 0.1 0.1

REFERENCES
1 F. J. Wallace, Analyst, 88 (1963) 259.
2 L. Wilson, Anal. Chim. Acta, 40 (1969) 503.
3 D. E. Campbell, Anal. Chim. Acta, 46 (1969) 31.
4 G. G. Welcher and 0. H. Kriege, At. Absorpt. Newsl., 9 (1970) 61.
5 P. Johns and W. J. Price, Metallurgia, 81 (1970) 75.
6 T. W. Sattur, At. Absorpt. Newsl., 5 (1966) 37.
7 W. J. Price, Analytical Atomic Absorption Spectrometry, Heyden, London, 1972.
8 J. Y. Hwang and L. M. Sandonato, Anal. Chem., 42 (1970) 744.
9 G. G. Welcher and 0. H. Kriege, At. Absorpt. Newsl., 8 (1969) 97.
10 G. G. Welcher, 0. H. Kriege and J. Y. Marks, Anal. Chem., 46 (1974) 1227.