INDUSTRIAL
ENGINEERING CHEMISTRY
AND
A N A L Y T I C A L E DITI 0N PUBLISHED
BY
T H E AMERICAN
CHEMICAL
SOCIETY
0
WALTER
J.
MURPHY,
EDITOR
The Viscositv of Pitches W. F. FAIR, JR., Mellon Institute,
AND
J E. W. VOLKMANN, Koppers Company, Pittsburgh, Penna.
The viscosities of the less fluid bituminous materials are usually determined at elevated temperatures, under which conditions the consistencies may be convenient for estimation with empirical or capillarytype viscometers. To determine the viscosity of such materials at lower temperatures a simplified falling coaxial cylinder viscometer was devised, following therecommendations of Trader and co-workers. Results obtained for a group of pitches indicate that these pitches' exhibit viscous flow
at 25.0' C., and have better temperature susceptibilities below their softening points than at higher temperatures. Viscosities calculated from the Saal viscosity-penetration relation do not agree with the results obtained with the falling cylinder viscometer. Similar studies on a special pitch distillate demonstrate that this material changes upon standing with progressive increase in apparent viscosity and probable development of yield values.
T
Two instruments were made, one of brass, B, and one of aluminum, A; each set of cylinders rested upon a base equipped with detachable rods, upon which additional weights might be suspended, so that a wide range of weights could be used, and the material under examination thus subjected to widely differing stresses. The apparatus had the following dimensions: the height, L, of both inner and outer cylinders, was 2.54 em., the inner radius, R, of the outer cylinder was 1.905 em., and the radius, r , of the inner cylinder was 1.270 cm., as recommended by Trader and Schweyer. The low-weight aluminum cylinder was used when the effects of relatively lower shearing stresses were being studied. To make a determination, the space between the two concentric cylinders was filled with the molten pitch, which was allowed to cool to room temperature, then the excess material was trimmed off with a hot spatula, and the instrument was suspended in a constant-temperature bath. The viscometer assembly was placed upon a stand which supported the outside cylinder only, thus allowing the inner cylinder to fall at a slow rate, depending upon the nature of the material in the annular space, and the total weight of the inner cylinder, stem, and base, plus any suspended additional weights. The drop of this inner cylinder was observed by following a mark near the top of the upright stem attached through the inner cylinder t o the base, by means of a micrometer microscope.
HE absolute viscosities of tars and pitches may be readily determined a t different temperatures by means of capillary rise viscometers as shown by Volkmann, Rhodes, and Work (6), and the change in viscosity with temperature thereby studied. However, the practical use of this method is restricted to temperature ranges in which the bituminous material under investigation is fluid enough to exhibit a measurable rise in a reasonable period of time, corresponding roughly to temperatures above the ring and ball softening point of the material. As a linear relation between log log viscosity and log absolute temperature has been found to hold for tars and pitches in this temperature interval by Rhodes, Volkmann, and Barker (S), confirming the earlier work of C'bbelohde and associates ( 5 ) , it has been thought that viscosities at lower temperatures might be estimated by extrapolation of curves based on results obtained at the higher temperatures. The slope of this linear curve furnishes a convenient numerical reference for temperature susceptibility. Because the normal use of many tars and pitches depends upon their properties at much lower temperatures than the ones at which the capillary rise method can be applied, it n-as determined to try to investigate the viscosities of these materials at lower temperatures by some other method, if possible, to determine whether or not the extrapolated viscosity values were of the correct order of magnitude. After some time spent on studying the various methods which might give reliable results, it mas decided to employ a simplified falling coaxial cylinder viscometer, such as has been described by Trader and Schweyer ( 4 ) .
In Figure 1 are shown the filled B set of cylinders, three weights, two rods, the -4set of cylinders, and the stem. I n Figure 2 the viscometer is illustrated fully assembled but supported by a wire attached to the top of the stem to prevent any movement while the sample is coming to temperature. I n Figure 3 the viscometer is presented as it appears while a determination is being made, with the inner cylinder and attached base and stem free to fall. After observing the distance, h, in centimeters, through 235
236
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 15, No. 4
TABLEI. SOFTENING POINTS
-
softening Point (Ring and BdIl
Sample
c.
1
53.4
2 3 20
52.2
4
56.0 57.0
55.1 56.8
5
which the inner cylinder dropped in t seconds, under the influence of total weight, W , in grams, theviscosityis calculated by substituting in the following equation:
For the specified dimensions of the instrument described above, this expression reduces to Ti = (0.4055) (61.466)
v)
(
= 25.0
( W X t7 )
From this formula the apparent viscosity for any given weight may he calculated. If the material being examined exhibits truly viscous flow, the viscosity will he constant, independent of the weight used; hut if the material is nonviscons, the apparent viscosity will increase with decreasing weights. For this reason it is of value to know the shearing stress and the rate of shear, for a graph showing these fnnctions indicates the apparent viscosity and the yield value. If the material exhibits viscous flow, the curve will he a straight line directed toward the origin. These values may he calculated according to the following equations: Shearing stress, F
A(*-2rL =
dv Average rate of shear, dr
=
R h ~
1
-
A)
r
(Zi! - r)
= 16.1 X
W
= (0.635)
h (-) f
vlscOSlty at 25" ti. (within an expenmental error of about 5 per cent) over a wide range of applied stresses. In Figure 4, the respective shearing stresses, E", are plotted against the corresponding rates of shear
(3
- ; inspection of these
curves clearly indicates that these pitches exhibit truly viscous flow a t 25" C. The linear curves obtained hy plotting stress against rate of shear in all cases may he extrapolated to the origin, thus emphasizing the purely viscous nature of these materials. To obtain a rough evaluation of the temperature susceptihility of these pitches a t low temperatures it was decided to
TABLE11. VISCOSITY, SEEAEING STRESS,AND RATEOF SEEB war Sample
W
Drop
Time
Visoositv
F
X 105
4
87.0 169.3 216.8 300.3 435.1
1.64 2.49 3.06 3.95 3.06
3635 2842 2622 2565 1319
4.82 X 10' 4.83 4.65 4.84
1400 2730 3500 4830 7000
2.90 5.66 7.55
FLGURE 1. CYLINDERS, WEIGHTS,RODS,AND STEM A".
Five different coal-tar pitches were obtained for measnrement of viscosity in this apparatus and a sixth pitch, No. 20, was prepared hy distilling heavy water-gas tar in the lahoratory. Their softening points (ring and hall) are given in Table I I n Table I1 are set forth the experimental observations and calculated results for the viscosity, shearing stress, and the rate of shear, as determined a t 25" C. for these pitches. Inspection of this tabulation shows that reproducible results have been obtained, and that these pitches have constant
2
AT. 1
AT. 3
AV.
4.68
4.77
87.0 170.5 217.5 300.6 435.3
3.76 4.69 3.98 5.34 5.91
3643 2269 1466 1431 1104
87.0 170.5 217.5 300.6 435.3
3 72 4.36 4.15 5.48 6.39
2751
87.0 217.5
1.19 2.60
1553 1284
1656
1188 1158 909
x
10, 2.11 X 10, 2.13 2.01 2.01 2.07 2.07 x 10, 1.61 X 10' 1.63 1.57 1.59 1.55 1.59 x 10' 2.84 X 10' 2.69 2.77 x 10'
10.0
14.9
1400 2740
6.64 12.9
3510 4830 7000
24.0 17.5 33.8
1400 2740 3510 4830
8.70 16.8
roo0
22.3 30.4 45.1
1400 3510
4.93 13.1
April 15, 1943
ANALYTICAL EDITION ru
T4BlE 111. Sample
softening Point
* c. 5 20 3 4
2 1
57.0
56.8 52.2 56.0 55.1 53.4
11
TEMPERATURE SUSCEPTIBILIlT
viscosity at Soitening Point Cmlislokes 1 x 10' 1 106 1 108 1 108 1 101
x x x x 1 x 101
viscosity at 25' c. ccn1iatoncs 4.68 X 10'
2.33 X 2.25 X 4.00 X 1.67 X 1.30 x
109 101
10' 10' 10s
a1
S
231 I 1 FIG.4 SHEARING STRESS-RATE OF SHEAR.
-
1.04
0.98 1.12 1.05 0.99 1.02
convert the above viscosities to kinematic viscosity a t 25' C. and use the approximate relation of a viscosity of 1 X IO8 centistokes a t the temperature of the ring and hall softening point. The values. for the temperature susceptibility thus obtained are given in Table 111. These values are the slopes of the straight lines obtained by plotting log log viscosity against log absolute temperature in each case.
Results with this instrument agreed well with the coaxial viscometer referred to. The temperature suscept!bility of these pitches a t low temperatures thus appears to he better (lower) than has been previously suspected. If log log viscosity is plotted against log absolute temperature over the intervals discussed, it appears (Figures 5 and 6) that for two typical pitches the temperature susceptibility below the softening point is lower than it is above that temperature. Included for comparison (Figure 7) is a curve based on Pochettino's results roughly converted to centistokes (taken from #). which also seems to indicate a break in the cinve near t h i softening point region, hut in the opposite direction than was found for the two pitches discussed ahove; in other words,this pitoh sbowedapoorer susceptibility a t low temperatures than a t high temperatures, which is just the reverse of the results found for the pitches here described. It is believed that the results described trnly represent changes in Susceptibility occurring in the general region of the softening point a,qd are not due to instrumental differences, since the results of Table IV indicate 'that viscosity measurements ~
With the exception of pitches 3 and 20, these values are somewhat lower than has previously heen generally found for similar tars, where the calculation of the temperature susceptibility was based upon viscosity determinations made a t higher temperatures. Assuming the softening point relation to be sufficiently accurate for these considerations, it is obvious that either the viscosity as above measured is incorrect, or the temperature susceptibility of these pitches a t low temperatures is better than has been generally believed. In continuing this investigation it was decided to determine the viscosity coefficients for TABLE IV. Viscosiry some of these pitches a t different temperatures Temlle*BTemperaby the more reliable falling cylinder and capilt"re Method Viscoaitv ture c. Centidokea C. lary rise methods. Typical results, converted 5 25 Cylinder 4.68 X 1Oe 35 to centistokes, are summarized in Table IV. 45 Cylinder 1.55 X 10' 45.1 From these findings it appears by indirect com55 Small 55 parison that the falling cylinder viscometer 08 illsrY 1.43 x 10' 70 amat;. 85 gives values comparable to results obtained by capillary 6.84 x 10' 20 25 Cylinder 2.33 X IC* 35 the small capillary rise instrument. Some time 45 Cylinder 1.40 X 10' 35 after thesedeterminations had beencompletedan 70 Small 85 open-end rotating cylinder viscometer as deospillary 1.23 x 10% vised by Ford and Arabian ( 1 ) was available.
-
Method
Cylinder Large oapillsry Large oapillary Smsll ospillary Cylinder Large capillary Small oa~illsry
~
~~~
~
Visooaity Ccntialoka 2.0 x 108
1.46 X IC' 1.51
x loa
x 10' 1.50 X 108
1.81
1.63 x IP x 10'
1.55
238
INDUSTRIAL AND ENGINEERING CHEMISTRY
made by the capillary and falling cylinder viscometers are in agreement. Penetration measurements were made for these pitches and viscosity results were then calculated by the Saal relation. The results were much lower than were reported above, but the ratio of the viscosity determined by the falling cylinder to that calculated by the Saal formula seemed to decrease with increasing penetrations, as shown in Table V.
Vol. 15, No. 4
TABLE V. VISCOSITY Viscosity by Cylinder,
Penetration
Sample 1
27.3 26.2 22.9 22.7 18.4
2 3 20
4 5
16.1
250
c.
Poises 1.59 x 107 2.07 2.77 2.89 4.77 2.95
Ratio of Viscosities 1.78 2.00 2.25 2.28 2.47 2.44
To learn whether or not the ratio of these viscosities might approach unity for softer pitches, as seems to be indicated, several pitches of lower softening points were prepared and investigated. The results obtained will be given in a subsequent paper. As these results agreed well with earlier reports concerning the viscous flow of pitches, it was decided to investigate, as a possible interesting contrast, the flow properties of a highboiling pitch distillate, which is in the state of a soft paste a t room temperature. Previously empirical investigations had indicated the probability of anomalous flow for this material. Viscosity determinations were therefore made a t 25 O C., using the falling coaxial cylinder viscometer described previously. At first the results for pitch distillate, with a softening point (ring and ball) of approximately 43.0' C., were rather scattered, but later, when standard test procedures were arbitrarily adopted, and strictly adhered to, better agreement was obtained. A summary of the preparations, test procedures, and the experimental data is given in Table VI, and the stressrate of shear curves is presented in Figure 8. Comments on these flow properties have been included with each set of determinations. From these results it is obvious that the flow properties of pitch distillate will depend upon its previous treatment, and
.97
s
Q
.I? .15
73 .?I
1
FfG.7
1
LOG 'LOG VISCOSITY-LO6 TPMPLRATURk 1
April 15, 1943
upon the stresses to which it is-subjected, as well as upon intermediate fluctuations in temperature, in all of which factors this distillate differs from residual straight-distilled tars and pitches.
Conclusions
ANALYTICAL EDITION
TABLE VI.
SUMMARY OF
W
Sample 363-B (dehydrated pitch distillate, poured a t 100’ C,., in air 20 minutes, in b a t h 15 minutes)
Av. 363-C (363-B, poured a t 100’ C., in air 16 hours, in bath 15 minutes)
239
Drop
DATA
Grams
,vm.
Time Sec.
59.9 87.0 121.9 217.5
3.95 4.39 4.74 4.52
739 545 423 228
217.5 87 0 59.9 121.9 Increased apparent viscosity, nonviscous
4.10 229.3 4.02 670 3.64 1030 4.57 49 1 flow, yield value about
du/dr x 103
Viscosity Poises
F
0 . 2 ~ 0x 107 0.271 0.272 0.275 0.276 X 10’
963 1400 1960 3510
34.3 51.9 72.0 128.0
0.304 X 10’ 3510 0.364 1400 0.424 963 0.318 1960 350 dynes per sq. cm.
114.0 38.6
22.7 In consequence of this in61.7 vestigation it is felt that the 363-D falling cylinder viscometer (363-B, poured a t 100°,C.! cooled, 3 217.5 4.58 230.2 0.273 X l o 7 3510 127.0 falls and recoveries in air. in b a t h 15 87.0 4.66 632 0.294 1400 will prove to be a valuable 47.6 minutes) 121.9 4.86 431 0.269 1960 73.0 tool for the determination 59.9 4.27 834 0.292 963 33.0 AV. 0.282 x 107 and comparison of the rheoSlightly increased apparent viscosity, small yield value of about 100 dynes per sq. om. logical properties of tar 363-F (363-B, in air 16 hours, then 1 hour 217.5 0.0 3000 (high) 3510 0 products. Some typical a t 60’ C. in oven) 443.4 0.62 1591 2.84 X 108 7120 2.51 pitches exhibit viscous flow 573.5 1.37 1553 1.63 9240 5.65 Greatly increased apparent viscosity, nonviscous flow, yield value of about 6000 dynes and have better tempera363-H-1 (363-B in air 47 hours) 217.5 3.32 933 1.53 X 10’ 3510 ture susceptibilities below 22.9 87.0 1.56 1302 1.82 1400 7.70 their softening Doints than 762-U-I -”(363-H-1 recovered, and redeter121.9 3.24 1222 1.14 1960 17.2 has been previously thought mined) 59.9 1.76 1866 1.59 963 6.05 to be the case from conIncreased apparent viscosity with time, decreased b y ”working”, yield value unchanged, remaining about 350 dynes per sq. cm. (compare with 363-C) siderations based upon ex363-1 trapolations from viscosity (363-B, poufed at 100’ C., cooled, 87.0 1.77 507 0.626 X 10’ 1400 22.4 20 minutes in oven a t 60’ C., t h e n 217.5 4.29 242 0.308 3510 114.0 measurements a t higher determined) 59.9 2.79 846 0.456 963 21.1 temeeratures. 121.9 5.08 532 0.319 196C 61.5 These tentative conclusions may be modified after future research. It is beLiterature Cited lieved that continued experimentation along these lines will add materially to our present knowledge of the flow (1) Ford and -4rabian, Proc. Bm. SOC.Testing MMateriaZs, 40, 1174 (1940). properties of tars and pitches.
__
(2) Hatschek, E., “Viscosity of Liquids”, London, G. Bell & Son, 1928. (3) Rhodes, Volkmann, and Barker, Am. SOC.Testing Materials, Sym-
Acknowledgment The authors wish t o express their appreciation to H. R. Beck and E. J. Maloney for assistance in laboratory determinations and in the preparation of the graphs.
posium on Consistencu, 1937,30-46 (1938). (4) T r a d e r and Schweyer, Proc. Am. SOC.Testing 31 aterials, 36,P a r t 11, 518 (1936). (5) Ubbelohde et al., Oel Kohle, 11, No. 36, 684 (1935). (6) Volkmann, Rhodes, and Work, IND. ENG.CHEM.,28, 721 (1936). PRESEPFTED before the Society of Rheology, October, 1941.
