ANALYTICAL SCIENCES JUNE 1998, VOL.

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1998 The Japan Society for Analytical Chemistry

617

Notes

Determination of Inclusions in Molten Aluminum Alloy by X-Ray

Diffractometry after Selective Dissolution
Masaaki IWATSUKI*, Shintaro NISHIDA* and Teruo KITAMURA**
*Department of Applied Chemistry and Biotechnology, Faculty of Engineering, Yamanashi University,
Takeda, Kofu 4008511, Japan
**Research and Development Department, Showa Aluminum Corporation,
Kaisan-cho, Sakai, Osaka 5908576, Japan
Keywords Inclusion, aluminum alloy, X-ray diffractometry, selective dissolution, glass cloth filter

Inclusions in aluminum alloy can markedly affect the

quality of the alloy. Therefore, several techniques of
the treatment for cleaning of the molten aluminum
alloy have been developed: e.g., chlorination, flux
treatment, gas bubbling1, filtration2 and the combination of the last two techniques. The evaluation of these
cleaning processes and the analysis of inclusions are of
supreme importance. Therefore, several methods, e.g.,
filtration3,4, centrifugation5,6, electric resistance7,8, ultrasonic inspection9, etching or dyeing for microscopy10
and selective dissolution11, have been investigated for
such evaluation. However, these methods can give
only qualitative information or total mass concentration
of inclusions, but no quantitative evaluation of individual compounds. Inclusions in molten aluminum alloy
depend on its composition, used scrap, used cleaning
process and its operational conditions, etc. Problems
due to inclusions may be found by a user later on.
Although simple and rapid methods for quantitative
determination of individual compounds of inclusions
are necessary for avoiding troubles due to inclusions
and also for evaluating the used cleaning process, such
methods are not found in the literature.
Glass cloth filters are used before casting for the
removal of inclusions in molten aluminum alloy. This
filter is replaced with a new one for each casting. The
inclusions collected on the filters without any additional apparatus will reflect the overall efficiency of the
metal cleaning processes used and must have information on their sources. In the present report, an X-ray
diffraction (XRD) method with selective dissolution of
metallic aluminum has been developed for the determination of inclusions collected on the filters, and successfully applied to the determination of spinel
(MgAl2O4), periclase (MgO) and aluminum carbide,
which were detected in an aluminum-magnesium alloy.

called spout socks, which were located at the inlet of

a mold during casting of the aluminum-magnesium
5052 alloy, as shown in Fig. 1. The material collected
by the filter was cut to the size smaller than 3 mm with
a nipper for the homogenization and ease of chemical
treatment.
The following standard powders were used for recovery tests and the preparation of standard samples for the
XRD determination: Spinel powder of 99.9% purity
(Taimei Chemical, Nagano, Japan; aggregates of about
1 mm particles, mainly 5 10 mm); periclase fine powder (1 15 mm, mainly 5 10 mm) which was prepared
by pulverizing and sieving through a 20 mm sieve from
100 200 mesh powder of 99% purity prepared by
fusion (Soekawa Chemical, Tokyo, Japan); aluminum
carbide powder of 98% purity (Soekawa Chemical;
aggregates of <
= 1 mm particles, mainly 5 10 mm).
Reagents used for selective dissolution were of analytical-reagent grade.
Hydrophilized poly(tetrafluoroethylene) membrane
filters (Millipore, Omnipore JH, 0.45 mm in pore size,
25 mm in diameter) were used for filtering off the
residue after the selective dissolution and as a support

Experimental
Samples, reagents and filters
Samples were collected on glass cloth filters, so-

Fig. 1

Schematic diagram of mounting of glass cloth filters.

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ANALYTICAL SCIENCES JUNE 1998, VOL. 14

for XRD measurements.

Apparatus
A Rigaku X-ray diffractometer with a copper tube
and nickel filter was operated at 35 kV and 16 mA. A
thin-layer specimen was inserted between a standard
aluminum holder of 50351.5 mm with a square aperture of 2016 mm and a thin aluminum plate of
35280.4 mm with a round hole of 23 mm in diameter.
Recommended procedures
In order to remove metallic aluminum, 0.8 g of the
sample is weighed out into a 200-ml beaker, 75 ml of
methanol is added and the mixture is heated to 35C on
a hot plate. After 2.0 ml of bromine is added, the
resulting solution is agitated by ultrasonication and
kept at 35 45C. After 15 min, additional 1.0 ml of
bromine is added, and the resulting solution is treated
in the same manner. Forty-five minutes after the first
addition of bromine, the residue is filtered off through a
membrane filter and washed with methanol until the
bromine color disappears.
Integrated intensities of strong and non-overlapping
diffraction lines of the compounds in the residue, e.g.,
(4 0 0) or (4 4 0) diffraction of spinel, (2 0 0) or (2 2 0)

of periclase, (0 0 15 ) of aluminum carbide, etc., are

measured. The amounts of the compounds are determined from working curves, which are obtained by the
same measurements of the standard samples prepared
by filtrating the suspensions containing different
amounts between 0 and 1 or 2 mg of their standard
powders in methanol through the membrane filters.

Results and Discussion

Dissolution of metallic aluminum
It has been found that metallic aluminum in the filter

Fig. 3 X-Ray diffraction pattern of the residue after bromine

methanol treatment. AC: aluminum carbide; Sp: spinel; Pe:
periclase.

collection can be practically dissolved by the

brominemethanol treatment within 45 min by cutting it
to the size smaller than 3 mm and by adding divided
volumes of bromine twice under ultrasonication, as
shown in Fig. 2.
XRD qualitative analysis of the residue
Figure 3 shows the XRD pattern of the residue
obtained from a filter collection of a molten aluminum
alloy containing magnesium. Spinel, periclase and aluminum carbide were identified from the pattern.
Recovery tests
Standard powders of 3.0 mg each were treated separately in the same manner as the recommended procedure and the residues were weighed, as shown in Table
1. Recoveries of these powders on the bromine
methanol treatment were 94 96%, except for fine periclase powder whose recovery was 89%. This suggests
that very fine particles of periclase may be lost during
the treatment, but coarse particles which strongly affect
the quality of alloys can be recovered.
Working curves
Table 2 shows that linear working curves of spinel,
periclase and aluminum carbide were obtained with
good precisions.
Analysis of real samples
Spinel, periclase and aluminum carbide in the

Table 1 Recoveries of standard powders on bromine-methanol

treatment
Standard powder

Fig. 2

Relation between treatment time and residue.

Spinel
Periclase (100 200 mesh)
(fine)
Al4C3

n
5
4
4
5

Recovery, %
Av.

96.2
94.2
88.9
94.9

2.2
2.9
0.4
1.1

ANALYTICAL SCIENCES JUNE 1998, VOL. 14

Table 2

619

Working curves of spinel, periclase and aluminum carbide

Diffraction line

Equationa

Correlation factor

s(x)/mg

Spinel (4 0 0)
Periclase (2 0 0)
Al4C3 (0 0 15)

y=26.4x0.69
y=77.7x+5.7
y=10.3x0.12

0.996
0.995
0.997

0.013
0.029
0.012

a. y, integrated intensity /cpsdeg; x, content /mg.

Table 3 Determination of spinel, periclase and aluminum carbide in filter collection

Found/mg

Content,%(m/m)

Sample
taken/g

MgAl2O4

0.798
0.801
0.808
0.804
0.797 a

0.60
0.59
0.57
0.56
0.58

0.68
0.66
0.66
0.65
0.67

1.6
1.5
1.7
1.5
1.5

0.075
0.074
0.071
0.070
0.073

0.085
0.082
0.082
0.081
0.084

0.20
0.19
0.21
0.19
0.19

Av.
s

0.57
0.01

0.66
0.01

1.6
0.1

0.073
0.002

0.083
0.002

0.20
0.01

MgO Al4C3

MgAl2O4

MgO Al4C3

a. Standard powders of spinel and aluminum carbide of 0.50 mg

each were added and the corresponding values were subtracted
from the analytical results.

residues after the brominemethanol treatment of real

samples of about 0.8 g were repeatedly determined by
the present method. These compounds of 0.07, 0.08
and 0.20%(m/m), respectively, were found in the filter
collection, together with satisfactory results of a standard addition test, as shown in Table 3. Concentrations
of inclusions in the molten aluminum alloy can be calculated from these results by multiplying the ratio of
the total amount of the sample in the spout socks
against that of the molten aluminum passed through the
spout socks.

In summary, an X-ray diffractometric method has

been developed for the determination of inclusions,
e.g., spinel (MgAl2O4), periclase (MgO) and aluminum
carbide, which were collected on a glass cloth filter in
molten aluminum alloy just before casting. The proposed method can give useful data for the evaluations
of the quality of the obtained ingot and of the used
cleaning process.

References
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1993, 915.
2. J. E. Dore and J. C. Yarwood, Light Metals, 1977, 171.
3. N. J. Keegan and J. M. McCollum, Light Metals, 1992,
1085.
4. R. B. Blackburn, Aluminium, 56, 585 (1980).
5. F. R. Mollard, J. E. Dore and W. S. Peterson, Light Metals,
1972, 483.
6. C. J. Simensen, Metallurgical Trans., 12B, 733 (1981).
7. C. Dupuis and R. Dumont, Light Metals, 1993, 997.
8. J.-P. Martin and F. Painchaud, Light Metals, 1994, 915.
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(Received November 4, 1997)
(Accepted March 12, 1998)