Determination of Refractive Index of Polymers
Determination of Refractive Index of Polymers
Determination of Refractive Index of Polymers
ANALYTICAL CHEMISTRY
cerned primarily with these methods. A few polymers are, however, markedly crystalline and are birefringent. Polyethylene,
polyvinylidene chloride, polyamides, cellulose and some of i t s
derivatives, and polytetrafluoroethylene are crystalline under
ordinary conditions. Rubber is crystalline under some conditions (SO, 31). Polyethylene has been observed t o be birefringent and the values of the two indexes as a function of temperature have been reported ('7, 12). The technique used in the
determination of the birefringence of polyethylene was not detailed. Rubber is birefringent when cooled or stretched and an
immersion technique for determining the values of the two refractive indexes has been carefully described (SO, 31).
I n determining the refractive index of amorphous polymers use
is usually made of critical angle instruments, immersion Oechniques, and measurement of apparent thickness. Spectrometers
( I f , 15), interferometers (20, S'i'), or specially designed refractometers (1, 5, 11, 15, 20, 25) have not been extensively used.
The use of an interferometer to measure the change in density of
V O L U M E 20, NO. 6, J U N E 1 9 4 8
rubber with change in temperature has been reported (45). A
spectrometric method using rubber prisms has been described
144) and Jelley (16) has successfully used the Leitz-Jelley microrefractometer by evaporating a toluene solution of polystyrene in
the bevel of the instrument. Both the spectrometer and interferometer have been used to determine the refractive index of
solids with a high degree of accuracy and can conceivably be
adapted to determination of the refractive index of polymers.
Such high precision methods are of limited usefulness with
polymers because extreme purity of sample is often difficult to
obtain.
METHODS USING CRITICAL A S G L E I h STRUMENTS
Transparent polymers are examined by means of the transmitted light or light a t grazing incidence. In either case the
principal problem in determining the refractive index of the polymer is in mounting the specimen. Several methods have been devised. The A.S.T.M. method ( 3 ) employs a specimen about
1 X 2 X 0.5 cm. Kith the 1 X 2 cm. surface polished flat and one
end surface polished perpendicular to the first. The edge of intersection must not be beveled. The large, flat surface is attached
t o the refracting prism with a contacting liquid inert to the
specimen and of higher refractive index than the specimen. The
illumination is then by grazing incidence The remainder of the
observation is made according to the usual procedures with
liquids. Temperature control is maintained and dispersion
noted.
For many polymers, suitable inert contact liquids are not available. The A.S.T.M. directions suggest the use of a-bromonaphthalene or other organic liquids. These often attack the polymers, as can be seen in a changing value for the refractive index
during the first few minutes. In such cases the use of potassium
mercuric iodide is suggested but it should be used carefully because experience has shown that this liquid readily attacks the
glass prisms (16). The use of cadmium borotungstate, n?$'
1.636 for a saturated solution, has been found not to attack the
glass uithin reasonable contact time and is less poisonous ( 1 6 ) .
Values reproducible to 1 3 in the fifth place have been obtained
by using polished moldings of polystyrene, poly-a-methylstyrene,
and poly-p-chlorostyrene ( 3 2 ) . A Bausch & Lomb horizontal
Abbe refractometer was used Tvith a potassium iodide-mercuric
iodide solution containing a little glycerol as contact liquid.
Various methods have been devised for mounting the specimen
to be viewed by transmitted light.
Kest (40) suggests pouring molten material onto the prism,
u i t h or without closing the back prism, and making readings after
521
solidification. Use of the prisni ill this rnariner t,ies up the iiist,rument and may damage the prism. To obviate these drawbacks
the polymer is mounted on a glass flat, having a refractive index
higher than the polymer under test'. Microscope slide glass is satisfactory for materials of refractive index below 1.51, and flint
glass with a value of 1.G3 is also used. The uncoated side of the
flat is then held to the upper prism with a contact liquid. Instead
of melting the specimen, a technique not often useful with polymers, the polymer may be dissolved in a volat'ile solvent and evaporated on the forms or on the prism (41). However, traces of solvent
in a solvent cast film can materially alber the refractive index, especially below the second-order transition temperature (4.9).
Care must be taken t o avoid scrakhing the prisms if films are
cast directly on them. Illumination of transparent samples by
polarized light using the tot,al reflection technique (35) has been
reported to give very good results (16).
Perhaps the most direct method of mount,ing a specimen for
the determination was used by McPherson (18, 19, 91). A thin
film of the polymer is clamped securely between the prisms and
the observation made with transmitt,ed light as with liquids. By
warming the prisms intimate contact is obtained and sharp fields
result. This method is useful with soft mat'erials such as well
milled rubber but must be used with caution because the stresses
put on the prisms by tight clamping may displace or loosen the
prisms and thereby impair the accuracy of the instrument or
measurement and because the finite thickness of the film introduces an error into the measurement. Compressing a thick film
sufficiently to alter its density will also introduce an error in the
measurement. Extreme caution must be exercised to avoid
scratching the very soft glass of the prism (16) and to avoid loosening the prism cement by excessive heating.
More or less opaque substances are studied by the total reflection method (22). The contrast is not so great as in the transmission or the grazing incidence methods, especially when the
more opaque specimens are being tested. According to West (@),
with thin films the film-air boundary gives reflections that may
weaken the contrast. The bright part of the field is due to
totally reflected light-light that enters the specimen a t the
crit,ical angle or greater. The darker portion of the field is due to
ordinarily reflected light; part of the light' passes through the
specimen and is lost as far as the field is concerned. The contrast
is sufficient for thick specimens, but not for thin films. JTrest
presents three methods for increasing contrast.
(1) The area of illuminat,ion and the angle a t which the light
strikes the refracting prism are varied. (2) The int.erna1reflection
a t the film-air boundary is suppressed by increasing the film
thickness or by adding a drop of inert liquid of higher refractive
index than the film and closing the illuminating prism, thus reducing stray light. Stray light increases the weak part of the
field, decreasing contrast. This method is not always possible or
convenient. (3) Polarized light is used to illuminate the sample.
ANALYTICAL CHEMISTRY
522
Table I.
Polymer
Condensation types
Phenol-formaldehydr
Urea-formaldehyde
Glyptals
Polyamides
Silicone (low mol. wt.)
Natural types
Proteins
Cellulose
Cellulose ethers
Rubber
Addition types
Polyethylene
Butadiene copolymer.
Polystyrene
Poly-wmethylstyrene
Poly-p-chlorostyrene
Polyisobutylene
Polyvinyl acetate and
chloroacetate
Polvvinvl chlorideacetate
Polytetrafluoroethylene
Method Used
Reference
Immersion
Liquid0
Immersion
Immersjon
Immersion
Film P
Liquidc
I n solution
Immersion
Film S, P
Immersion
Spectrometric
Film S , P
Reflection
0
26
9
9
7
43
39
IS
4s
30.Si
I
Third
Third
Third
Third
Third
Fourtli
Fourth
Fourth
Fourth
Third
Fourth
Fourth
Fourth
Third
Third
Fourth
Fourth
Fifth
Fifth
Fifth
Fourth
Fourth
I nimerqion
Film P
Film S , P
Solution cast
Polished block
Polished block
Polished block
Film P
Film S, P
Film P
Accuracyb
43
Fourth
Third
Third (1)
4;
Third
Seoprene
43
Fourth
Polyethy1 acrylate
43
F oii r t 11
S6
Styrene-maleic anhydride copolymer
u F solvent cast.
P , pressed.
b Results reported t o third place or fourth place as indicated. Accuracy
usually refers t o sharpness with which reading can be made: not to deviation
among samples except for rubber (81, 2 8 ) , polyyinyl acetate (48).and polyImiiiersion
rilm P
Film P
Film P
Polished block
styrene ( 3 2 ) .
c
Herinans et al. (15) have used an immersion method in determining the refractive indexes of viscose fibers. The fiber is inimersed in a mixture of butyl stearate and t,ricresyl phosphate of
suitable refractive index and observed with a polarizing microscope according to the Becke method. The determinatiori of the
two refractive indexes of birefringent rubber has been mentioned
(30, 31). Billmeyer ( 7 ) has recently described an immersion
method for polyethylene, nylon, and polytetrafluoroethylene.
Disadvantages of the immersion methods include the necessity
of having liquid standards available which are inert towards the
polymers being tested and whose refractive index does not change
on exposure to air over an appreciable period of time. Controlof
temperature is difficult unless special heating devices are affixed
to the microscope stage. The degree of accuracy obtained is
usually not, so great as t,hat obtainrd h y the use of critical angle
instruments.
11EA SUREM ENT 0 F APPARENT THICKNESS
;
imethod of determining the apparent thicknes; is dcscribed
by the ilnierican Society for Testing Materials 13).
-4 microscope with a magnifying poFT-er of a t least 200 diameters is used. The specimen, 0.25 inch thick with two parallel
surfaces, is placed with the bett,er polished surface nearer the
objective. The microscope is focused through the specimen on
the bottom surface and the longitudinal displacement of the lens
tube is recorded. Without moving the specimen, t,he microscope
is refocused on the top of the specimen and this displacement of
t,he lens tube is recorded. Both displacements are read to within
0.001 inch. The difference in the readings is the apparent, thickness of the specimen. The index of refraction is found by dividing
the actual thickness by the apparent thickness. It is often not
possible to make the readings wit,h t,he designated accuracy
(0.001 inch) because severe spherical aberration, requiring that
t,he cone of illumination be cut down, is encountered. Cndei
these eircumstancesthe accuracy may fall to *0.04. ( 1 6 ) .
PREFERRED METHODS FOR DETERMINING REFRACTIVE
INDEXES OF SPECIFIC POLYMERS
305 (1940).
(2) Alexander, A. E., I d . EWJ. Chem., S e w s Ed., 13, 330 (1935).
(3) Am. SOC. Testing Materials, Philadelphia, Standards, Part 111,
p. 397,1942.
(4) ..irmstrong, S.H., Budka, M.J. E., Morrison, K . C., and Hasson, M . , J . Bm. Chem. SOC.,69, 1747 (194i).
( 5 ) Rauer, N. M., and Fajans, K., in Keissberger, A , Physical
,Methods of Organic Chemistry, Vol. 1, p. 653, Ken. Yolk.
Interscience Publishers, 1945.
(ti) Bausch & Lonib Optical Co., New York, Bausch & I m n h
Refractometers, Catalog D202 (1945).
(7) Billmeyer, F. V., J . Applied Phys., 18, 431 (1947).
(8) Boyer, R. F., and Spencer, R . S., Advances in Colloid Cheiiiist r y , Vol. 11,p. 1, K e w York, Interscience Publishers, 1046.
(9) Bradley, T. F., ISD.ESG. CHEM.,i l x ; a ~ED.,
.
3, 304 (1931).
(10) Ellis, C., Chemistry of Synthetic Resins, Vol. I, p . 1258. X e w
York, Reinhold Publishing Corp., 1935.
(11) Frediani, H. A , IKD.ENG.CHEM.,AXAL.ED., 14, 439 (1942).
(12) Hahn, F. C., Macht, 51. L., and Fletcher, D. A, Ind. Eng.
Chem., 37, 526 (1945).
(13) Hermans, P. H., Herman-, J. J., and Vermaas, D., .I. Polwmw
Sci., 1, 156 (1946).
(14) Horner, L., J.makromol. Chem., 1, 234 (1943).
(15) Jelley, E. E., J . R o y . Microscop. Soc., 54, 234 (1934).
(16) Jelley, E. E., personal communication.
(17) Jelley, E. E., in Weissberger, A, Physical Method- of Oigniiic
Chemistry, Vol. I, p. 489, New York, Interarience Pithlisheis, 1945.
(18) Jones, H. C., Ind. Eng. Chem., 32, 331 (1940).
(19) Kirchhof, F., Rubber Chem Technol., 6,92 (1933).
(20) Lowe, F., Optische Messungen, 4th ed., p. 146, D ~ e - d e n .
Theodor Steirikopff. 1943.
(21) RlcPherson, A. T., J . Research S a t l Bur. Standards, 8 , i 5 6
(1932).
( 2 2 ) McPheraon, 9.
T., and Cummings, A , D., Zbid., 14, 553 (18353.
(23) Moore. H.. Chemistry R. I n d u s t r y , 58, 1027 (1939).
(24) Morrell, R. S.,ed., Synthetic Resins and Allied Plastiras, 2nd
ed,, p. 505, Oxford I 7 n i v r ~ e i t yPress, 1943.
V O L U M E 2 0 , N O . 6, J U N E 1 9 4 8
(25)
(26)
(27)
(28)
(29)
(30)
(1933).
( 3 2 ) Spencer, R. S., personal communication.
523
(36) Vieweg, K., Kunststoffe, 27, 213 (1937).
(37) Wagner, A. F.. Experimental Optics, New York, John miley
and Sons, 1929.
(38) Wahlstrom, E. E., Optical Crystallography, p. 37, New York,
John Wile>-and Sons, 1943.
(39) Warrick, E. L., J . Am. Chem. sot., 68, 2455 (1946).
(40) West,, C. D., IND.EXG.CHEM.,,4r;a~.ED., 10,627 (1938).
(41) Wile>-,R. H., I n d . En!=?.Chem., 38, 959 (1946).
(42) WileY, R. H., -7.
Polymer sei., 2, 10 (1947).
(43) V p y , R . H., and co-workers, unpublished observations.
(44) Wood, L. A., J . Oplical Physics, 12, 119 (1941); Rubber Chem.
Technol., 15,23 (1942).
(45) Wood, L. A., Bekkedahl, N.,and Peters, C. G., J.
N u t l . B u r . Sfandards, 23, 571 (1939).
RECEIVED
September 5 , 1947.
2%.
I-.
from the others. The present authors development, while basically the same as the others.
differs substantially in many essential details.
~~
ADHERENCE TESTER
__
1
Deceased.
.G.)
t f
I
T
Figure 1.
idherence Tester
a2bc
2(ahc
- dlef
+ def)
(1)