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Measurement of Distensibilitv of J

Organic Finishes
A. E. SCHUH AND H. C. THEUERER, Bell Telephone Laboratories, New York, N. Y.

0 NE of the most important physical characteristics


determining the serviceability of an organic finish is
distensibility. This property perhaps more than any other
improved mandrel test, in which a number of mandrels of
different diameters are used, and the other employs a direct-
extension test in which a standard A. s. T, M. tensile specimen
furnishes an excellent means of following the ravages of age for sheet metals is coated with the finish and is stretched to
on a finish. By comparing their rates of change of distensi- the first sign of film rupture. At this point the per cent
bility with time, otherwise seemingly similar finishes can elongation is determined directly. I n either method the test
often be readily differentiated. I n the case of oleoresinous is performed under conditions of known temperature and
varnishes and enamels, differences in oil length are clearly humidity, and the age and thickness of the specimen are
reflected in the degree of distensibility, and progressive em- known.
brittlement with age is readily followed. I n the case of cellu-
lose-ester finishes the effects of varying the amount and kind Mandrel Test
of plasticizer are revealed by distensibility measurements. The mandrel test, as developed in this laboratory, employs
I n this paper the several variables that affect the flexibility an apparatus (Figure 1) in which six test strips, 3 inches by
of a finish will be briefly discussed. Two test devices for
measuring the distensibility of organic finishes will be de-
scribed in detail and the results obtained with them compared.
TABLEI. EFFECTOF COMPOSITION
ON DISTENSIBILITY
OF ESTER
The variables that determine the distensibility of an organic GUMVARNISH
finish are: (1) composition of the film-forming material, (2) Oil Length Elongation
thickness of the organic finish, (3) age and exposure history Ual. %
of the finish, (4)temperature and humidity a t time of test, 10 3.2
and ( 5 ) the rate of stress application. 25
40
36.5
43.8
These constitute the major variables that any distensibility Thickness of coatings, 0.0005 inch. Aged 1 month indoors plus 1.5 montha
method must take into eonsideration. Some idea of the outdoors.
relative importance of several of these factors can be had
by examining the illustrative experimental values shown in
Tables I, 11,111,and VII. The per cent elongation shown in TABLE11. EFFECTOF TBMPERATUREAND HUMIDITY
ON
DISTENSIBILITY
these tables was determined by stretching finish specimens to -Per Cent Elongation-
point of rupture, by a method described a t a later point in Temperature, Relative Humidity,
this paper. 77' F. 50 Per Cent
Material 26%. 50%" 90%" 55'F. 77O F. 95O F.
Methods of Test 10-gallon ester gum varnish 1 . 5 4 . 2 49.9 0 . 6 4 . 2 54.0
Synthetio enamel (air dry) 15.0 15.1 54.9 2 . 4 15.1 53.2
There are two general methods of measuring the distensi- Lacquer enamel (highly plaati-
cized) 2 2 . 5 24.6 31.2 12.8 24.6 31.6
bility of organic finishes. One is the free-film method, and the Synthetic enamel (baked) 43.0 42.3 46.6 12.5 42.3 48.9
second is by bending or stretching a metal specimen coated Relative humidity.
In all cases coatings are 2 weeks old. All films are approximately 0,001
with an organic finish. I n the first method, a suitably shaped inch thick.
and detached film of the h i s h is stretched between two
clamps, and the tensile strength and per cent elongation up
to the point of rupture are directly determined. The value of TABLE111. EFFECTOF THICKNESS
AND AaE ON DISTENSIBILITY
this test was clearly shown by Nelson (I, 34) and his co- Per Cent Elongation
Material Thickness '1 IIb 1110
workers a number of years ago. More recently Hunt and 0.001 inch
Lansing (2) have published an interesting and important IO-gallon ester gum varnish 0.5 8.5 2.4 2.9
paper in which the same method was used to determine the 1.0 8.2 2.1 2.1
3.0 4.7 ... 3.2
significance of the change of the humidity and temperature 6.0 4.2 ... 7.1
coefficients of distensibility with age. 25-gallon ester gum varnish 0.5 >60 25.5 49.7
1.0 59 48.3 64.4
I n this laboratory the authors have for several reasons 3.0 >60 >60 >60
6.0 58.6 >60 >60
preferred to measure distensibility of actual finish specimens, Lacquer A 0.5 19.4 2.9 13.7
even though this is attended by a limitation of the test to 1.0 19.6 6.0 9.8
2.5 9.4 1.7 2.4
flexible base materials. The distensibility of a paint film 4.0 11.2 2.7 3.0
attached to its basis material is affected by both cohesional Lacquer B 0.5 36.1 2.7 22.4
1.0 30.9 5.6 21.1
and adhesional factors. The relation between these factors 3.0 23.0 8.7 19.5
is not as yet quantitatively known. However, the user of 6.0 24.0 12.5 20.2
Baked synthetic varnish
paint materials is interested in the degree to which a given enamel A 0.5 42.2 10.3 9.6
finish may actually be bent or stretched. I n the case of those 1.0 43.7 2.0 7.6
3.0 38.5 2.3 3.8
finishes in which the adherence of the organic coating is of 6.0 28.9 1.6 2.3
a very low order, distension tests using a finish specimen
yield distensibility values approximating those obtained by
the free-.film method a t equivalent rates of distension.
Two methods of measuring the effective distensibility of Test specimens aged one month a t 77O F. and 50 per cent relative hu-
organic finishes have been investigated. I n each case, sample midity.
b Same as in 5 plus 13 months outdoors.
specimens of the actual finish-that is, organic coating applied c Test specimens aged 16 months as in a.
to its base material-are used. One method employs an
9
10 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 9. NO. 1

approximately 0.5 inch, are bent either singly or simultane- faces of the specimen was next measured and the new extended
ously around six mandrels of diameters 0.126, 0.25, 0.375, length between gage marks calculated. Using this method,
0.8, 0.75, and 1 inch, respectively. Each test strip is securely values for all but the 0.125-inch mandrel were determined.
locked in place a t the lower end and is then bent by a drawbar The values for the 0.125-inch mandrel were obtained by ex-
in a manner that assures close contact of the specimen trapolation (values plotted on double logarithmic paper)
against the mandrel surface during the entire bend of almost from the values for the other mandrels. The values obtained
180’. Smooth motion of bending is assured by the use of a for the per cent elongation of l/&nch sheet stock of hard and
worm-gear mechanism between the crank handle and the annealed brass and of cold-rolled mild steel are shown in
drawbar. Table V.
It is of interest to note that the annealed
metal which has the least elastic range shows
the greatest deviation from the values-given in
Table._
~
IV.~

The values recorded in Table V are consid-


erably higher than those computed from
Equation 1 (see Table IV), particularly for
the smaller mandrel sizes. However, since a
high degree of accuracy is not necessary for
most finish investigations, the computed values
of Table IV may be used where the true values
are unavailable.
1. APPARATUS FOR MANDREL
FIGURE TEST
TABLF,V. ACTUALPERCENTELONGATION
AT VARIOUS
I n this test, it is important to ascertain the degree to which MANDRELSIZES
the surface of the test specimen is actually stretched during ---Mandrel Diameter in Inches -7

the bending. This is dependent primarily on the radius of Material 0.125 0.25 0.375 0.5 0.75 1
curvature of the mandrel and the thickness of the test strip. % % % % % %
hard brass 29.1 14.2 9.6 6.9 4.6 3.4
A first approximation to the actual per cent elongation of the 3/4
Annealed brass 33.5 15.9 10.3 7.5 4.9 3.6
finish as a result of bending can be computed on the assump- Cold-rolled ateel 28.0 13.8 9.0 6.7 4.4 3.3
tion that the neutral surface lies halfway between the outer
surfaces of the strip. This is the condition that would pre- In the authors’ studies of the physical characteristics of
vail if the stresses were within the elastic limit of the metal finishes it was of interest to ascertain the effect of change
base. With this assumption it ca-n be readily shown that the of thickness of the organic coating on distensibility. Since
elongation is the organic coatings increase the effective mandrel diameter,
it is necessary to apply a correction factor to the previously
e=--
2r + t - 100 2r_+_t per cent (1) determined values to get the true surface elongation of the fin-
ish. This correction becomes more important as the thickness
where r is the radius of the mandrel
t is the thickness of the strip of the coating increases. On the assumption that the paint
coatings are comparatively weak in tensile properties and
Table IV, which is based on Equation 1, gives the values of therefore exert a negligible effect on the bending resistance
per cent elongation for three panel thicknesses and the six of the specimen, a correction formula for coating thickness
mandrel sizes. was developed. It can be shown that the elongation, e‘, of
TABLEIV. VARIATION
IN DISTENSIBILITY
WITH PANEL
the outer surface of the finish is given by
THICKNESS
(Per cent elongation)
e’ = e + ‘M,
r+t
where t’ is the thickness of coating (2)
Panel
Thlck- I Mandrel Diameter in Inches
ness 0.125 0.25 0.375 0.5 0.75 1 Table V I lists the corrections, as computed from Equation
Inch % % % % % % 2, in per cent elongation per 0.001 inch of coating to be added
l/84 11.1 5.9 4.0 3.0 2.0 1.5
1/6s 20.0 11.1 7.7 5.9 4.0 3.0 to the elongation values of Table V. Equation 2 may also
t/18 33.3 20.0 14.3 11.1 7.7 5.9 be used to correct the values of Table IV for coating thickness.
Since the corrections to be added are small in comparison to
Actually the elastic limit is definitely exceeded in most of
the bending operations, the neutral surface shifts toward the
compressed side of the specimen, and the elongation of the
stretched surface therefore increases. This increase in elonga-
tion cannot be calculated directly, but must be determined
experimentally. The authors have performed such an ex-
periment for 1/S2-inch panel stock and for three commonly
used metals in order to determine the magnitude of this in-
crease in elongation.
To do this a special jig shown in Figure 2 was devised in
which metal strips were securely bent around * mandrels of
several sizes. Each strip prior to bending was marked with
two finely scratched lines. The distance between lines was
determined with a comparator to an accuracy of 0.00008
inch (0.0002 cm.). With the strip in position on the mandrel,
the angle subtended at the center by the distance between the
hair lines was determined to within * 5 seconds of arc. The
total distance between the center of the mandrel and the sur- 2. SPECIALJIG
FIGURE
JANUARY 15, 1937 ANALYTICAL EDITION 11

the normal values of elongation, they may be


neglected for coating thickness up to 0.001 inch.
However, as the coating thickness is increased
the corrections become increasingly important,
particularly for the smaller mandrel sizes, and
therefore cannot be neglected.

Direct-Extension Method
The mandrel test has the inherent draw-
back of being a discontinuous process-that is,
with a convenient number of mandrel sizes, in
order to cover a moderate range of values, the
elongations are measurable only a t fairly wide
intervals. One way of overcoming this is by
increasing the number of mandrels. Another
way is to use a means of extension in which
any degree of elongation can be directly meas-
ured. This has been accomplished with the
apparatus shown in Figure 3. The finish to
be tested is applied to a standard A. 8. T. M.
tensile specimen for sheet metal which is then
fastened between two jaws, one of which is
pulled a t a slow even rate by means of a screw
driven through reduction gears by a motor. FIGURE 3. APPARATUSFOR DIRECT-EXTENSION METHOD
During stretching, the surface of the finish
is observed with a low-power microscope, and the elongation was disconcerting but illuminating. Although the same ma-
is measured at the point of film rupture. This is done by terials over a common base metal at equivalent thicknesses of
measuring the change in length of 1-inch gage marks which coating and a t the same age were measured under identical
had been scratched on the surface of the specimen with the conditions of temperature and relative humidity, it was
aid of the marking instrument also shown in Figure 3. The found that about half of the values for distension as deter-
measurements are made with the aid of an extensometer, mined by the mandrel test were considerably below those
which consists of a vernier caliper, to the measuring head of obtained by direct extension. Correction for coating thick-
which is attached a small microscope with a cross-hair eye- ness and using the values for actual surface extension as
piece. The cross hair is focused on each of the gage marks recorded in Tables V and VI reduced the disagreement be-
and the corresponding vernier readings are noted, from which tween the two methods only moderately.
the elongation can be directly determined. Regarding the The discrepancy was consistently larger for coatings com-
precision of the direct extension method, it was found that bining high tensile strength and high distensibility. This
the average deviation from the mean elongation values was suggested that the rate of stretching, being quite different in
* 8 per cent on the basis of several hundred determinations. the two tests, might account for the disagreements. I n the
I n this test, as in the mandrel test, a qualitative measure mandrel test a 180" bend is completed in about 15 seconds,
of the adherence of the distended film to the base metal is whereas in the case of the direct-extension test the rate of
provided. The distensibility of the coating determines the stretching was about 0.6 inch per minute. Furthermore,
point of failure, and the adherence, the character of the failure. there is a fundamental difference in the rate of stretch in the
With good adherence the initial rupture is in the form of two methods. I n the mandrel test, only a small fraction of
many fine cracks, whereas with poor adherence the coating the test specimen is under tension at any one moment, but
may tear off conipletely and loosen over long distances behind at that moment this fraction receives the complete bending
the point of rupture. stress as it enters the bending zone. I n the second test,
however, the entire surface of the specimen is subjected to an
TABLEVI. CORRECTIOX IN PERCENTELONGATION FOR MAN- even, but steadily increasing stress. It became of interest
DREL DISTBWSIBILITY VALUESPER 0.001 INCH OF COATING therefore to see what effect varying the rate of stretch would
-Mandrel Diameter in Inches-- have on the distensibility values obtained by each of these
Material 0.125 0.25 0.375 0.5 0.75 1 methods. The mandrel test was performed at rates ranging
% % % % % % from 15 seconds to 55 minutes to complete a full bend of 180' C.
YCold-rolled
4 hard brass
nnealed brass
steel
1.38
1.43
1.37
0.73
0.74
0.73
0.50
0.50
0.50
0.38
0.38
0.38
0.26
0.26
0.26
0.21
0.21
0.21
The rate of the direct extension test was varied from 3.3
inches to 0.2 inch per minute. The effect of varying the rate
of stretch is shown in Table VI1 for four different finishes,
compared at equivalent film thickness.
I n both these methods of measuring finish distensibility,
granulation of the metal occurs increasingly with degree of
extension. This granulation is dependent on the metal or TABLEVII. EFFECTOF RATEOF STRETCH ON DISTENSIBILITY
alloy used and serves to increase the actual surface extension OF FINISHES
of the paint-metal interface. I n the values for distensibility Per Cent Elongation
Extension Test
reported in this paper this secondary effect due to granulation Mandrel Test 0.2!n./ 0.6,1n./ 3.3in./
Material 15 sec. 55 min. min. min. min.
has not been determined quantitatively.
I n one study in which several hundred determinations of A 10.3-15.9 15.9-33.5 25 25 21
B C3.6 3.6- 4.9 5.9 5.9 8.9
distensibility of the same finishes were made by both methods C C3.6 7.5-10.3 . 9.5 9.0 8.5
D 10.3-15.9 >33 26.0 21.0 18.0
of distension, an opportunity wafi offered for a comparison All films are approximately 0.001 inch thick. The thickness variation
of the results obtained by the two methods. The result between specimens of the same material was within 0,0001inoh.
12 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 9, NO. 1

I n ea,ch method the effect of slowing down the rate of stretch elongation value or determining actual elongation of mandrel
was to increase the value for distensibility, as is the case for specimens are described. A correction for thickness of finish
metals and other materials. This indicates that, as more time is given.
is allowed for stretching, an opportunity for internal flow A direct-extension method for coated specimens is described
within the finish coating is provided, by means of which the which has the advantage of permitting any degree of disten-
finish can partially accommodate itself to the applied stress. sibility up t o rupture of the supporting base material to be
This effect was particularly noticeable in the case of finishes measured.
that have aged not more than about one month. The effect The factors that affect the distensibility of an organic
diminished rapidly with age with thin-finish coatings, and finish are discussed and the relative importance of these
slowly as the coating thickness was increased. The fact that factors is illustrated by experimental values.
the distensibility values are influenced by rate of stretch means
that with either test a constant rate of extension should be Literature Cited
used. The authors have found the rate of 15 seconds for the (1) Gardner,H. A., Am. Paint Varnish Mfrs. Assoc., Circ.240 (1925).
complete bend in the mandrel test and 0.6 inch per minute (2) Hunt, J. K., and Lansing, W. P., IND. E m . CHEM.,27, 26 (1935).
for the extension test satisfactory. (3) Nelson, H. A . , Proc. Am. SOC.Testang Materials, 21, 1111 (1921).
(4) Ibid., 23, Part I, 290-9 (1923).
(5) Nelson, H. A,, and Rundle, G. W., Ibid., 23, Part 2, 356-68
Summary (1923).
(6) Rundle, G. W., and Norris, W. C., Ibid., 26, Part 2, 546-55
Two methods of measuring distensibility of organic finishes (1926).
are described. R I D C ~ I VSeptember
~D 14, 1936. Presented before the Division of Paint and
I n order to be able to express results in per cent elongation, Varnish Chemistry a t the 92nd Meeting of the Amerioan Chemical Society,
methods for either calculating an approximate per cent Pittsburgh, Pa., September 7 to 11, 1936.

A Photoelectric Method for the Determination


of Phosphorus’
C. W. EDDY AND FLOYD DEEDS
Bureau of Chemistry and Soils, U. S. Department of Agriculture, at the Department o f Pharmacology, Stanford
University School of Medicine, San Francisco, Calif.

W I T H existing quantitative methods for detecting phos-


phorus it is not possible to determine with a high degree
of accuracy quantities as small as 0.001 mg. The device
vanometer scale, since by its use compensation for battery
depletion is regulated.
A number of precautions in the use of this photoelectric color-
herein described was constructed to give a sensitive, simple imeter are essential, when great accuracy is desired. Cleanliness
and rapid, yet accurate, method for phosphorus determina- of Nessler tubes, light bulb, photoelectric cell, and the apparatus
tions when applied to the methods of Fiske and Subbarow in general is necessary. The effect of finger marks is appreciable
( I ) , Kuttner and Cohen (6),or Kuttner and Lichtenstein (6). and, unless the Nessler tube is kept clean, is reflected in deflec-
tion of the galvanometer to the extent of 1 to 2 mm. It is cus-
The apparatus has been entirely satisfactory when applied tomary, prior to making a determination, to clean the tube with
t o the determination of blood sugar by Folin’s method (a),the chromic acid solution, followed by washing with distilled water.
study of phosphatase activity by Jenner and Kay’s (4) modi- Before each reading is made, the outside of the tube is wiped dry
fication of the Kuttner and Cohen procedure, and the deter- and free from finger marks.
The resistance RI must be capable of carrying 10 amperes;
mination of yeast population by turbidity measurements. otherwise tem erature changes of the resistance will cause fluctua-
The use of the photoelectric cell for colorimetric and tur- tions in the gafhnorneter, producing erroneous results.
bidity estimations is not new, It has been applied by Osborn It is essential to use the same Nessler tube for all determina-
(7), Greene (a), and Samuel and Shockey (8). tions, since the authors have not found two tubes characterized
by the same calibration curve. This will be seen by comparing
The apparatus described makes use of the circuit outlined Tables I, 11, and 111with Figure 2, three different Nessler tubes
by Samuel and Shockey (8) modified to permit the use of a having been used.
sensitive galvanometer, and a smaller light source.
The modified circuit of the apparatus is given in Figure 1. TABLEI. REPRODUCIBILITY
OF CALIBRATION
CURVE
A single light source of low intensity directed vertically up- 0,00093 0.001868 0.00467 0.00934
Phosphorus Blank mg. mg. mg. mg.
ward through a 50-ml. flat-bottomed Nessler tube containing Readingso 42.2 37.6 30.6 19.6 10.4
the solution to be tested, and impinging on the photronic cell, 43.2 37.6 31.6 20.2 10.6
42.0 36.4 31.4 19.9 10.0
causes a deflection of the galvanometer, the amount of the 43.2 36.2 30.4 19.6 10.2
deflection being a function of the quantity of light allowed to 43.6 37.0 30.8 ... 10.8
Mean 42.84 36.86 30.98 19.78 10.62
pass through the solution. Photronio cell No. 9. Nessler tube No. 3.
The circuit used in the apparatus described has two de-
cided advantages over previously described photocolorimeters : Photronic cells vary appreciabl in the current output relative
The use of a light source of small intensity eliminates tempera- to a given change in depth of c o h . Therefore, each photronic
cell must have its own calibration curve.
ture effects, the solutions can remain in the apparatus for ex- Because of the sensitivity of the e uipment to minute changes
tended periods without being influenced by temperature. in depth of color, it is always essenti3 to follow the identical pro-
The use of a variable resistor (Ea) instead of a fixed resistor cedure in developing the color in a series of determinations that
was employed in establishing the calibration curve. The same
makes it possible to maintain a constant spread on the gal- precaution applies to turbidity measurements.
a Since presentation of this method a similar photoelectric colorimeter has The characteristics of the photronic cell are such that colorimet-
been described (9). ric methods involving transmitted light of yellow or orange color

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