The Exudation Test for “Bleeding” in

Bituminous Roofing
G. L. OLIENSIS, The Barber Company, Inc., Madison, 111.

“Bleeding,” or “strike-through,” by There is evidence that when asphalts that are incompatible
which is meant the exudation of unsightly in the sense above indicated are placed in contact with one
another at room temperatures, there will develop at the inter-
black spots occasionally noted on the sur- face between the two a very thin layer of bitumen, of a softer
face of ready roofing, is due to a peculiar consistency than either, but that this film will remain per-
type of incompatibility, as yet unexplained, manently at the interface until it is encouraged to migrate
between the asphalt used as saturant and outward by capillarity, as when pinholes are present in the
that used as coating. During the last 7 coating layer, or when a layer of dusting has been applied at
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or adjacent to the interface or to the pores in the coating.

years the author has developed an “exuda- This outward migration results in the scattered black spots
tion test” for determining this lack of typical of bleeding in roofing.
compatibility bet ween the saturant and the These bleeding phenomena should not be confused with
coating, before their use in roofing manu- the normal exudation of very thin oily matter that occurs on
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facture. the surface of all blown asphalts on aging. For example, no

bleeding whatever will occur, even when a coating is of the
type that develops an extremely oily surface on aging, if
THE manufacture of ready roofing a felted sheet is that coating is used with a compatible saturant. On the
INsaturated with a hot, relatively soft bituminous saturant.
other hand, if the saturant is not compatible, marked bleed-
ing can occur even when the coating is of the type that does
The excess of saturant is removed and a substantial layer of
not readily develop an oily surface on aging.
relatively hard blown asphalt coating compound is applied in
a molten condition to both surfaces of the hot saturated sheet. Exudation Test
Intimate contact between the coating and saturant is thus
obtained. Granules may be applied to the upper surface of The exudation test, that has been developed by the author
the hot coated sheet to protect the coating from actinic light to detect this strike-through tendency as between any satu-
and to decorate the product. The finished sheet may then be rant and any coating, consists simply in applying a drop of the
cut into shingle shapes or shipped in rolls. In either event
the layers of the finished goods are tightly packed at a slightly
elevated temperature.
In case asphalts have been used that prove incompatible
in the sense just described, “bleeding,” or “strike-through,”
begins to develop in the warm package, and continues steadily,
not only after the product has cooled but also after ap-
plication and exposure to solar heat. It is first noted as
small, dull-black spots, that appear to have exuded through
the minute pores, or pinholes, that frequently occur in the
coating layer or at the edges of the roofing sheet. In time,
new spots appear, while the old ones grow steadily wider and
may eventually assume a glossy black color and a soft and
even oily consistency. Eventually some of the spots may
run together to form large black blotches all over the roofing
sheet and will even strike through the wrapping paper around
the package. The progressive development of bleeding is
shown in Figure 1 (a, b, and c).
Although in extreme cases the surface of the product and
the package may present a very unsightly appearance, the
exudation is not particularly apt to cause sticking in the pack-
age, as the spots appear to be less sticky than oily in char-
acter. Furthermore, after exposure for a few months during
hot summer weather, the slow accumulation of dust on the
roof and the effects of weathering gradually obscure these
black spots both on smooth and on granule-covered roofing,
until they are hardly discernible. This fading of the oily
spots on exposure is illustrated in Figure 1. d shows the
under side of a granule-surfaced shingle which displayed
marked bleeding after a period of exposure; e shows the
granule-covered surface of the same shingle. On e the bleed-
ing spots are visible on the upper portion which was pro-
tected by the superimposed shingle, but they have practically
Figure 1. Roofings Illustrating Progressive
disappeared on the lower portion which was exposed directly Development of Bleeding in Storage, and
to the weather. Effects of Exposure
199
 200 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 10, NO. 4

saturant to the talc-dusted surface of the coating, maintaining test will prevent the formation of the characteristic ring, even
the latter at a temperature of 43.33° C. (110° F.) for 72 hours, when a film of the exudate is knowrn to be present between the
and measuring the width of the black ring of discolored talc two asphalts involved.
that forms around the periphery of the spot. In an effort to The effect of time and temperature in curing the specimen
standardize the conditions of the test, the following technic has also been investigated. The completion of the reaction will
has been developed: require weeks at room temperature. At 43.33° C. (110° F.)
the reaction will be substantially complete in about 3 days.
The coating is warmed to a fluid condition. It may then be Twenty7-four hours at 60.0° C. (140° F.) and 5 hours at
poured into the lid of a 3-ounce (88.7-ml.) penetration tin 79.44° C. (175° F.) will give, very7 roughly7, the same results as
or other convenient receptacle in a layer 0.3 to 0.6 cm. (0.125 to
3 days at 110 F.; but the interfluxing of the coating, saturant,
0

0.25 inch) thick. To remove air bubbles the surface of the

and exudate that occurs at temperatures higher than 110° F.
coating may be momentarily heated. The surface area and
total weight of the specimen are determined and the surface is is objectionable and mars the distinctness of the reaction.
then given a preliminary dusting with fine roofer’s talc, evenly Hence, 110° F. for 3 days w7as finally decided on.
distributed over the surface, neither the surface nor the talc
being handled by the fingers during this operation. The excess
of nonadherent powder is removed by inverting the specimen
and allowing the container to drop 2.5 cm. (1 inch) onto the table
top. A second application of fine talc is then made by gently-
shaking or tapping a 300-mesh sieve held 7.5 cm. (3 inches)
above the surface of the specimen, so that a fine mist rather than
agglomerated particles of the powder may7 accumulate on the
specimen. This operation is continued with occasional weighings
until a uniform film of talc weighing 0.025 gram per square inch
(6.45 sq. cm.) has been obtained. LTniformity in the thickness
of the talc film is of great importance in obtaining reproducible
results, for the thicker the layer of talc (up to a certain limit), the
wider will be the ring formed.
A drop of the saturant about 0.16 cm. (0.0625 inch) in diameter
is placed upon the talc-dusted surface of the coating. This may
be done most conveniently by plunging the end of a heated spatula
or paring knife into the cold saturant and, after the excess has
drained off, allowing a drop of suitable size to fall on the dusted
surface from a height of about 1.25 cm. (0.5 inch). Several drops
of the same or different saturants may be applied to a single
specimen of dusted coating.

The specimen is then placed in an oven maintained at a

temperature of 43.33° =*= 2.8° C., (110° =*= 5° F.) for a period
of 72 hours. With some asphalts that are entirely free from
strike-through tendencies towards each other, no reaction
whatever will occur in this test, except for the very slow
flattening of the spherical drop and the gradual yellowing
of the dusting. With other asphalts that do have strike-
through tendencies, the drop will flatten more rapidly; and
relatively early in the test a thin ring of a darker color than
the surrounding area will form on the dusted surface right
around the periphery of the drop, and will grow wider
blacker, and glossier, till it reaches a maximum width and
gloss characteristic of that combination of asphalts, and of
that type and quantity of dusting, after winch it spreads and
darkens no further.
The average width of the dark-brown or black ring of dis-
colored talc that has formed at the end of 72 hours around
the periphery of the spot is determined to the closest 0.1 mm.
by means of a scale of suitable dimensions and a good mag-
Figure 2. Progressive Stages of Exudation
nifying glass. This dark ring is usually sharply defined, and Test
the vague penumbra that sometimes develops beyond the
area of marked discoloration should be disregarded. A
roughly quantitative estimate of the degree of bleeding to
be anticipated in roofing in which any two asphalts are to be The progressive development of the exudation reaction at
used, may be based on the width of ring of discolored talc 110° F. is demonstrated in Figure 2 by means of two square
that they develop in the exudation test. If no ring whatever panels of coating showm in the successive stages of the test.
is formed in that test not the least traces of bleeding will The coating used on panel a differed as to source from that
occur in the roofing made with the twro asphalts. used on panel b, but both coatings w7ere of approximately
Although the technic described above has been found to 20 penetration and 98.89° C. (210° F.) melting point (ring and
be most reliable and convenient for routine work, many varia- ball). The two panels were coated and prepared in the
tions may7 be made in the method of test. For example, standard manner described above. Three varieties of hard
fine and coarse dustings of limestone, silica, mica, lamp- saturant (HI, H2, and H3) were applied one below the other
black, slate, wood flour, asbestos, and other fibrous and non- in that sequence on the left-hand side of each panel, and three
fibrous products have been used with some degree of success, soft saturants (SI, S2, and S3) were applied similarly on the
though some will form a wider and some a narrower ring right-hand side. The source and method of processing were
than an equally thick layer of talc. On the other hand, different for each of the saturants, except that H3 and S2 were
the total absence of dusting on the surface of the coating in the both produced by vacuum distillation from the same crude.
APRIL 15, 1938 ANALYTICAL EDITION 201

The consistencies of the six saturants were as follows:

Table I. Width of Ring
Saturant Penetration Saturant Penetration On Coating A On Coating B
HI 30 Si 150-175 After After After After After After
H2 65 S2 150-175 Saturant 1 day 3 days 6 days 1day 3days 6days
H3 40 S3 150-175 Mm. Mm. Mm. Mm. Mm. Mm.
Hard HI 0.0 0.0 0.0 0.0 0,0 0.0
The pictures at the top of Figure 2 show the two panels H2 0.0 0.0 0.0 0.25 0.35 0.65
H3 0.15 0.25 0.3 1 .2 2,0 2.2
before they were placed in the oven. The second set, im- Soft SI 0.0 0.0 0.0 0.75 1.0 1,0
S2 0.25 0.7 0.9 1.8 2.9 3.4
mediately below, shows their condition after exposure for S3 0.9 1 .5 1 7 2.0 4.7 5.0
one day at 110° F.; the third and fourth sets, after 3 and 6
days' exposure, respectively. It will be observed that no
discolored ring was formed on either coating around saturant Several years of practical experience with the exudation
HI. However, saturants H3, S2, and S3 developed rings test have led to the conclusion that while it is safest practice
on both coatings, while saturants H2 and SI developed rings
to use only saturants and coatings that show no ring whatever
on coating B but not on coating A. The rings widen with in that test, no visible bleeding will occur in roofings made
time to a definite maximum, and when the test is conducted with a saturant and coating that in the standard exudation
at 110° F. they are of substantially maximum width at the test at 110° F. develop a ring not wider than 0.5 mm.
end of 3 days. The average width of ring for each of the
twelve combinations illustrated in Figure 2 is given in Table I. Received January 12. 1938.

Internal Electrolysis without Diaphragms

Determination of Small Amounts of Nickel, Cobalt, and Copper in Ores
Poor in These Metals
J. J. LURIE and L. B. GINSBURG
Institute of Nonferrous Metals, Moscow 17, U. S. S. R.

authors (7) have shown the advantages of internal 0.44 volt) would indicate that nickel and cobalt would be
THE
electrolysis over external electrolysis in the determination deposited on the platinum cathode, if the anode were an iron
of small amounts of metals, and have pointed out that a very plate. The potential difference, 0.19 volt, is sufficient for
simple apparatus without diaphragm may be substituted for such a deposition. However, because of the very small over-
the complicated apparatus, proposed by a number of authors voltage of hydrogen on nickel and cobalt, these metals cannot
(1, 2, 4, 5, 11, 12), without impairing the accuracy of the be deposited by elec tro h’sis in an acid medium, while in am-
analysis {6, 9, 10). moniacal solutions they form complex ions, as a result of which
In addition (1) having selected a suitable anode, we obtain their potentials are shifted and become more negative than in
a definite potential difference not exceeded at any moment an acid medium.
during the course of the electrolysis but very slowly and
gradually diminishing by 0.1 to 0.2 volt. Therefore by
internal electrolysis it is possible to make separations which
by external electrolysis require a constant control of the
cathode potential and a suitable apparatus. (2) The chief
oxidizing process occurring at the anode is the dissolution of
the anode with the formation of the corresponding ions of this
metal in the solution. This eliminates many difficulties of
electrolysis due to the oxidation at the anode of a number of
ions to their higher valency states.
We are therefore justified in hoping that small amounts of
nickel and cobalt may be separated from large quantities of
iron and from chromium by this method. This was the
chief purpose of the present work.

Apparatus
The apparatus for internal hydrolysis used by the authors is
shown in Figure 1 (and in Figure 1 of an earlier article, 7). The
cathode is a Fischer’s platinum gauze; the anode is a metallic
plate of iron, zinc, or aluminum, depending on the metal to be
precipitated and on the conditions of precipitation. To secure a
full contact, the electrodes are firmly held together by a copper
or aluminum clamp, which replaces the copper wire formerly used
(7) and somewhat simplifies manipulations. The places of con-
tact must always be well cleaned with emery paper before pro-
ceeding to work.
Determination of Nickel and Cobalt
The normal potentials (E0) of nickel, cobalt, and iron
(Exi, Sit. 0.25 volt; Eco.-co4·-, 0.255 volt; EFe/ Fo-+,