Rapid Gravimetric Determination of Silicon in

Aluminum Alloys
PHILIP LI SAN1 and HENRY L. KATZ
Industrial Test Laboratory, Philadelphia Naval Shipyard, Philadelphia 12, Pa.

A rapid gravimetric method is described for the determination of silicon in

aluminum alloys for amounts exceeding 1.5%. An acid attack is employed using
phosphoric, nitric, and sulfuric acids. The silicon is oxidized by evaporation of
the solution, an excess of perchloric acid is added, and the silicic acid is dehydrated
by moderate boiling of the perchloric acid. The usual procedure of handling
dehydrated silicic acid is then followed. The precision and accuracy of the new
method are determined by a statistical study of the data.

INVESTIGATION was recently undertaken at this labo- addition of perchloric acid to the solution after the conversion of
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AN ratory to
L obtain a rapid and accurate gravimetric method silicon to silicic acid, followed by a moderate boiling of the per-
for the determination of silicon in aluminum alloys. Although chloric acid, appeared to solve the problem. Subsequent experi-
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many colorimetric procedures which have the necessary speed and
accuracy have appeared in the literature (7, 8, 9, 16), the control
of pH, temperature, and time was so critical as to render these
methods unsuccessful in the hands of routine analysts running
large numbers of determinations. This laboratory usually deter-
mines lower amounts of silicon (under 5%) spectrographically,
but the need still existéd for a rapid chemical procedure for de-
termining silicon contents of 5% and above.
Two gravimetric procedures have been used in this laboratory
for the determination of silicon in aluminum alloys. One is a
modified A.S.T.M. method (2), employing an alkali attack of the
aluminum alloy followed by a single evaporation with hydrogen
peroxide and a subsequent single dehydration with perchloric
acid; the other is the Alcoa procedure (1), similar to the A.S.T.M.
method but using a triple evaporation with hydrogen peroxide
followed by a double dehydration with a perchloric-sulfuric acid
mixture. Since the alkali attack common to both procedures is
tedious and time-consuming, efforts were directed toward evolv-
ing an accurate and rapid gravimetric method employing an acid
attack of the aluminum alloy.
Many papers have been published on the use of acid mixtures
(S, IS, 14,15,18,19) for attacking aluminum alloys in an attempt
to speed up the analysis. In general these procedures tend to
give low results which have been attributed to two factors—the
incomplete oxidation of silicon in the metal to silica and loss of
volatile silicon compounds, such as silicon hydride, incurred dur-
ing acid decomposition (4, 5, 17), indicating that the proper com-
bination of acids had not been attained. Fuchshuber, however,
proposed a method (6) using a mixture of phosphoric, nitric, and
sulfuric acids which, besides effectively dissolving the alloy with-
out any apparent loss of silicon by volatilization, oxidized all the
silicon present directly to silicic acid upon evaporation of the
solution. Hydrochloric acid was then added and the solution
evaporated again until the silicic acid was dehydrated. The main
objection to this procedure is that continuance of the dehydration
for as little as one minute longer than is necessary tends to cause
dissolution of silica in phosphoric acid. A later modification of
this method (11) introduced cobalt nitrate as a means of indicat-
ing exactly when the silicic acid was completely dehydrated. The
authors, however, have found that the change in color of the co-
balt nitrate is not so sharp as suggested and have experienced
difficulty in obtaining precise and accurate results.
EXPERIMENTAL
Investigations were undertaken by the authors to eliminate
the critical time factor inherent in the above procedures. The
ments showed that when sufficient perchloric acid was present,
the boiling time was not critical and could be extended from 5 to
15 minutes without causing a significant change in the silicon re-
sults. In the course of the investigation the authors confirmed
the lower limit on the percentage of silicon (1.5%) that could be
determined by means of a phosphoric, nitric, and sulfuric acid
mixture (11). Further observations on alloys containing up to
1% magnesium and more than 1.5% silicon showed no apparent
loss of silicon due to the possible presence of magnesium silicide.
To establish the fact that the acid mixture used in the proposed
method effected a complete oxidation of all the silicon present in
the alloy, four samples in duplicate (types 43, 355, 356, and 32)
were dissolved and the silicon was oxidized in the manner de-
scribed below. The solutions were then diluted and filtered, and
the amount of residue was determined. In practically every case
the residue was negligible and the greatest amount found repre-
sented less than 0.05% silicon.
The procedure finally evolved employs an acid attack of the
alloy by a phosphoric, nitric, and sulfuric acid mixture in a ratio
of 3-4-1, respectively. The solution is evaporated until the
silicon is completely oxidized, as evidenced by a clearing of the
solution. Perchloric acid is then added and the solution boiled
moderately. Gelatin is added to facilitate the filtration of the
silica (10) and the usual procedure for handling dehydrated silicic
acid is followed.
REAGENTS
An acid mixture of 150 ml. of phosphoric acid (sp. gr. 1.71),
200 ml. of nitric acid (sp. gr. 1.42), and 50 ml. of sulfuric acid
(sp. gr. 1.84).
Ammonium nitrate, c.p. Perchloric acid, 70%. Gelatin
solution, 1%. Sulfuric acid (1to 99). Sulfuric acid (1 to 1).
Hydrofluoric acid, 48%.
PROCEDURE
Dissolve 2 grams of the sample (1.5 to 4.5% silicon) or 1 gram
of the sample (4.5 to 10.0% silicon) in an 800-ml. beaker in 80 ml.
of acid mixture. For samples containing more than 10% silicon,
dissolve 0.5 gram of the sample in 60 ml. of acid mixture. After
the initial reaction has subsided and most of the alloy has dis-
solved, cover the beaker and warm until the sample is completely
in solution. Remove the cover glass and evaporate until the
solution clears. Immediately add a pinch of solid ammonium
nitrate to oxidize any sulfur, swirl, and remove the beaker from
the hot plate. Allow to cool slightly, add 60 ml. of perchloric
acid (70%), and evaporate to fumes of perchloric acid. Cover
the beaker and moderately boil the solution for 8 or 9 minutes.
Cool somewhat, cautiously add 300 ml. of hot distilled water and
40 ml. of gelatin solution (1%), and stir well. Filter immediately
on an 11-cm. No. 41 Whatman filter paper containing some paper

tl Present address, Franklin Institute, Laboratories of Research and pulp. Swab the beaker and wash the paper 12 times with hot
Development, Philadelphia 3, Pa. dilute sulfuric acid (1 to 99), followed by a few washes of hot dis-
252
VOLUME 19, NO. 4, APRIL 19 4 7 253

tilled water. Transfer the paper and precipitate to a platinum
crucible, char off the paper completely, and ignite the residue at
1100° C. to constant weight. Add 3 drops of dilute sulfuric acid
(1 to 1) and 5 ml. of hydrofluoric acid (48%), and evaporate care-
fully to dryness. Ignite at 1100° C. to constant weight. The
difference in the two weights represents the weight of silica which
contains 46.72% silicon.
not significant—i.e., all methods give substantially the same aver-
age. The proposed method values, on the other hand, are sig-
nificantly different from those obtained with the umpire method
in only one case (chemist 1, sample 32). In other words, the
Alcoa method and the proposed method gave substantially the
same results, while the modified A.S.T.M. procedure tended to

PRECISION AND ACCURACY
To test the reliability of the proposed method, six samples were
chosen as representative of the types of aluminum alloys usually
run for silicon in this laboratory ranging from 2.0 to 12.5% of
give low results on the high silicon-bearing samples.
In view of the demonstrated precision and accuracy, together
with the large saving in operational time effected, the proposed
method, in the opinion of the authors, constitutes an excellent
procedure for routine laboratory use.

Table I. Comparison of Methods for Determining Silicon in Aluminum Alloys

Chemist 1 Chemist 2
Standardc Standardc
Sample® Method^ % Silicon Av. deviation % Silicon Av. deviation
195A I 2. 17 2. 09 2. 03 2,.10 0. 07 2. 02 2. 00 2, 00 2, 01 0. 01
II 2. 01 1. 99 2, 04 2,.01 0. 02 2. 01 1, 99 2. 08 2. 03 0. 05
108 I 3 66 3 .59 3. 61 3 ,62 0. 04 3, 56 3. 56 3, 61 3,.58 0, 03
II 3 .64 3 .63 3,.47 3 .58 0. 10 3 ,65 3, 61 3. 67 3. 64 0, 03
355 I 5 .42 5 .37 5 .31 5 .37 0,.05 5 .18 5 .28 5 26 5 .24 0 .05
II 5. 40 5. 42 43 5. 42 0. 01 5. 30 5. 31 5. 26 5. 29 0. 03
43 I 5..48 5, 47 '. 43 5 .46 0. 03 5..38 5. 42 5, 42 5. 41 0. 02
II 5, 50 5..57 5. 52 5,.53 0. 04 5. 66 5. 60 5..54 5. 60 0. 06
III 5. 52 5 55, 5.,54 5 .54 .0. 02 5 45
. 5 .53 5 49 5 49 0. 04
356 I 6, 69 6 .82 6, 68 6 .73 0 08 6 .63 6 .63 6 .61 6 .62 0 .01
II 6, 76 6 75 6 82 6 .78 0 ,04 6 .78 6 .74 6 .88 6 .80 0 .07
III 6 86 6 .83 6..84 6 .84 0, 01 6 .79 6 .78 6 .81 6 .79 0 .01
32 I 11, 94 11 95 11. 98 11 .96 0. 02 11 .60 11 .90 11 .82 11 .77 0 .16
II 12 .36 12 .28 12 32 12 .32 0 04 12 .35 12 .29 12 .15 12 .26 0 .10
III 12 .14 12 .16 12 .26 12 .19 0 .06 12 .20 12 .06 12 .04 12 .10 0 .09
All samples I 0. 07 d 0 .07d
All samples II 0. 05¿ 0 ,06d
®
Sample 355, 0.5% magnesium. Sample 43, 0.13% titanium. Sample 356, 0.10% titanium and
0.3% magnesium. Sample 32, 1.0% magnesium.
>
I, modified A.S.T.M. method. II, acid attack method. Ill, Alcoa method.
c Calculated from Standard deviation -
\l—.
\n -
1’
where 2d2 = sum of squares of deviations of each
of 3 results from their average and = 3.
d Calculated from where 2s2 is the sum of squares of standard deviations and N is the number
V:
of standard deviations

silicon. The series of six samples was analyzed for silicon by two ACKNOWLEDGMENT

operators, using the proposed method and the modified A.S.T.M. The authors wish to express their gratitude to M. Kaplan for
procedure, both operators running each series three separate the statistical analysis of the data, to G. Norwitz for assistance
times. The results obtained are shown in Table I. in the experimental work, and to K. L. Proctor for his continued
In studying precision, a distinction should be made between interest in the investigation.
the ability of a chemist to reproduce his own results with a given
method and the ability of different chemists, perhaps in different LITERATURE CITED
laboratories, to check each other. Since only two chemists were
used in this study, both from one laboratory, only the first can be (1) Aluminum Co. of America, “Chemical Analysis of Aluminum",
2nd ed., pp. 28-30, 1941.
estimated with any validity. In this sense, the results show the
(2) Am. Soc. Testing Materials, “Methods of Chemical Analysis of
two methods to be substantially the same, with an average stand- Metals", p. 131, 1943.
ard deviation of about 0.06% silicon. Using this figure, the pre- (3) Callender, L. H., Analyst, 58, 81 (1933).
cision may be expressed as follows: In the long run, a single de- (4) Churchill, . V., Bridges, R. W., and Lee, M. F., Ind. Eso.
termination on a given sample by a given chemist by either Chem., Anal. Ed., 9, 201, (1937).
(5) Ibid, 9, 533-4 (1937).
method would not be expected to differ from the average of a (6) Fuchshuber, ., Z. anal. Chem., 116, 421 (1939),
large number of determinations under the same conditions, by (7) Hadley, B. W., Analyst, 66, 486 (1941).
more than 0.12% silicon, 95% of the time. (8) Ibid., 67, 5 (1942).
Examination of the averages in Table I shows that in the case (9) Ibid., 70, 43 (1945).
(10) Nikolaev, N. S., Zavodskaya Lab., 10, 536-8 (1941).
of the high silicon-bearing alloys, the modified A.S.T.M. method (11) Osborn, G. H., and Clark, J., Metallurgia, 31, No. 185, 230
tends to give lower results than the proposed method (note es- (1945).
pecially sample 32 and chemist 2 results on samples 43 and 356). (12) Rider, P. R„ “Modern Statistical Methods”, New York, John
The testing of these differences by the t test {12) indicates that Wiley & Sons, 1939.
(13) Salzer, Erhard, and Theissig, F., Chem.-Ztg., 64, 468 (1940).
they are statistically significant on the 95% level. (14) Shishkin, B. M., Zavodskaya Lab. 7, 96 (1938).
To determine whether the higher or lower results are the more (15) Shkotova, S. N.,/bid., 8, 213 (1939).
reliable, three of the samples (43, 356, and 32) were reanalyzed by (16) Stross, W., Analyst, 69, 44 (1944).
the Alcoa method which, because of the additional peroxide evapo- (17) Term, A., and Moravia, G., Atti Xo congr. intern, chim., 3, 470
(1939).
rations and the double dehydration employed, may be consid- (18) Urech, P., Z, anorg. allgem. Chem., 214, 111 (1933).
ered as an umpire method. The values obtained by the latter (19) Vasil’ev, K. A., and Vegrin, M. L., Zavodskaya Lab,, 7, 263
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A.S.T.M. method, as can be seen from Table I. In all cases ex-
The opinions expressed are those of the authors and are not to be construed
cept one, these differences are statistically significant on the 95% as reflecting the official views of the Navy Department, through whose
level; in the one case, chemist 1 on sample 356, the difference is permission this article is published.