NATIONAL BUREAU OF STANDARDS REPORT

4732

REPORT ON THE EVALUATION OF TWENTY- ONE

COATING-GRADE ROOFING ASPHALTS

by

Sidney H. Greenfeld

<NB^

U. S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS
IJ. S. DKPARTMENT OF COMMERCE

Sinclair Vi eeks, SecrrtarY

^ATI()^AL BUREAU OF STANDARDS

A. \. Aslin, Director THE NATIONAL BUREAU OF STANDARDS

The scope of activities of the National Bureau of Standards at its headquarters in Vi ashington,

D. C.. and its major fiehl laboratories in Boulder. Colorado, is suggested in the following listing of

the di\ isions and sections engaged in teehnieal work. In general, each section carries out specialized

research, development, and engineering in the field indicated h\ its title. A brief description of

the activities, anil of the resultant reports and publications, appears on the inside hack cover of

this re|»ort.

W ASHINGTON, 1). C.

F^lcctricity and Electronics. Resistance and Reactance. Electron Tubes. Electrical Instru- ments. Magnetic Measurements. Process Technology. Engineering Electronics. Electronic

Instrumentation. I.lectroehemistrv

.

Optics and Metrology. Photometry and Colorimetrv . Optical Instruments. Photographic

Technologv . Length, l .nginei'ring Metrologv.

Heat and Pow er, t emperature Nleasurements. t hermodv namics. Cryogenic Physics,

fmgines and I .uhrii'ation. lOigine Eiiels. Atomic and Radiation Physics. S|)ectroseopv . Radiometrv. Mass Spectrometrv . Solid

Slate Pin sics, fdcctron Bln sics. \tomic Phvsics. Nuclear Pln sies. Radioaetiv itv . X-ra\ s. Betatron. Nucleonic Instrumentation. Radiological I'.quipment. AliC Radiation Instruments.

('hcinislry. Organic (Joatings. .Surlace Clumiistrv . Organic Chemistrv . Anah tical Chemistry.

Inorganic (Jliemisti v . I Jccirodcposition. (ias Chemistrv. Phv sical Chemistrv . ThermochemisifN. Spcctrochemistrv . Pure Substances.

Mechanics. Sound. Mechanical Instruments. Fluid Mechanics. Engineering Mechanics.

Mass and Scali*. (iapacitv. Densitv. and Fluid Meters. Combustion Controls.

Organic aiul Fihrons Materials. Kubhiu-. textiles. Pa)u'r. Leather. Ti'Sting and Specifications. Pol\ mcr Structure, (irganic Plastics. Dental Research.

Metallurgy. Lhcrmal Mctallurgv. Chemical Mctallurgv. Mechanical Metallurgv. (Corrosion.

Mineral Products. Ceramic I'.ngincering. Porcelain and Potterv. (dass. Relractories.

I'.nameled Metals, (amcreting Materials. (Jonstitiition and Microstructure.

Building Teihnology. .Siriutural Engineering. I’irc Protection. Heating and Air Conditioning. I looi-. Rool. and Wall (!o\erings. ("odes and Specifications.

.Vp]>lie<l Mathematics. Numerical \nal\sis. (Computation. Statistical ICngineering. Mathematical PliNsiis. Data Proit'ssing Systi-ms. (Components and rechni<pi('s. Digital Circuilrv. Digital Systems.

\nalogue Svslcms. Applications I'.uginecring. • (ifliceol Basic Instrumentation • ( )fhce o( W eights and Measures IT BOl LDER. (COLORADO

(.ryogenii' I'Cngine«‘ring. ( Cr\ ogenic I ,(pii|Muen t. ( Cr\ ogimic Processes. Properties oi Materials.

(ia.-> Li<|u<‘laciion.

Railio Propagation Pliysics. I pjier Almo>phcre Research. Ionospheric Research. Regular

Propaga t ion ,'^er\ ices. Radio Propagal ion ICngimn'ring. Frcipicncv I tilization Research. Lroposplu'ric Propagation

RcM’arch.

Radio Slaiulards. High l•rc(plenc\ Standard> Branch: High l'rc(picnc\ l lectrical Standards.

Radio Broadcast .Service. High I'leiiucncv I mpcdance Standards. M icrow av c Standanls Branch:

I' xtreme High Ircipiencv and Noi.-c. Microwave |'|•c(plcncv and Spc<‘troscopv . Microwave

( Circuit .Standards.
NATIONAL BUREAU OF STANDARDS REPORT

NBS PROJECT NBS REPORT

1004-11-1017 July 1, 1956 4732

REPORT ON THE EVALUATION OF TWENTY-ONE

COATING- GRADE ROOFING ASPHALTS

prepared by

Sidney H., Greenfeld

Research Associate

Asphalt Roofing Industry Bureau

Floor, Roof and Wall Coverings Section

Building Technology Division

Staff

Lawrence R. Kleinschmidt

Shigeru Ishihara

Sidney H. Greenfeld

John P. Falzone

Jointly Sponsored by

Asphalt Roofing Industry Bureau

and

National Bureau of Standards

<NBS>

U. S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

The publication, re|

unless permission Is

25i D. C, Such pen

cally prepared if II

Approved for public release by the

t' 1 ^ • andards, Washington Director of the National Institute of port... has been specifi- Standards and Technology (NIST) , port for its own use, on October 9, 20 1 5. _______
I

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...1

-.J, ' • •l^t.

\
REPORT ON THE EVALUATION OF TWENTY- ONE

COATING-GRADE ROOFING ASPHALTS

prepared bySidney H. Greenfeld

Staff

Lawrence R. Kleinschmidt

Shigeru Ishihara

Sidney H. Greenfeld

John P. Falzone

ABSTRACT

The properties and weathering characteristics (accelerated durability machines) of 21 coating-grade roofing

asphalts were determined® Although the chemical and physical properties of these asphalts all fall within narrow

ranges, their weathering characteristics were very different

and their durabilities covered a six-fold range (51-9C

cycle)® Their weight losses at failure in the 51-9C cycle

or at periods of exposure of 200, 400, 600 and 900 hours to

the 22-1 cycle varied widely and were not related to any of

the measured characteristics of the asphalts. Degradation,

as determined by weight loss and change in components, is

more rapid in the 22-1 cycle than in the 51-9C cycle, even

though the lather results in a more rapid mechanical failure

of the asphalt' coatings.
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1« INTRODUCTION

Asphalt is not a single substance, but a complex mixture of

high-molecular-weight organic compounds* Both the nature of the

compounds and the proportions in which they are present determine

the physical characteristics by which asphalts are known* Thus,

by suitable processing of a single residuum, a large number of

different asphalt products can be obtained from the same asphalt

source. On the other hand, products of the same physical characteristics can be made from residua from different sources.

However, there are always some basic differences in the degradation characteristics of these products, differences that can

be related to the source.

Most of the early attempts to study the degradation of

asphalts were limited to the examination of physical changes.

Crack formation was by and large the most frequently used

criterion, but "rust" formation (1)*, weight loss (2), decrease

in solubility (3) and embrittlement (4) have also been used*

All of these are merely physical manifestations of chemical

changes that occur as degradation progresses. A number of

investigators, however, have made efforts to measure the

* The numbers in parentheses indicate references listed at the

end of this report.

- 3 -

chemical changes directly by oxygen absorption (5) and composition

of the degradation products (6), In all of these investigations

it was indicated that asphalts from the various sources degraded

differently.

As part of the study of the degradation of asphalts, samples

of coating-grade asphalts were obtained from the major sources

supplying asphalt in the United States. Nine asphalt producers

and five roofing manufacturers contributed 21 samples. Eight

samples were from west coast sources, seven were from the

central part of the country and six were imported. With two

exceptions, these asphalts were reported to be in commercial

production.

2, MATERIALS AND METHODS

The 21 asphalts studied are described in Table 1. The

physical data are those provided by the supplier, except where

indicated. The chemical and component ( 7 ) analyses were determined by methods described in the appendix. The components

are those described by Kleinschmidt ( 7 ) according to the method

by which they are separated, as follows;

Asphaltenes - That fraction of the asphalt insoluble in

n-pentane at room temperature.

White oils - That fraction of the n-pentane— soluble material in asphalt that is eluted from fuller's earth with

n-pentane

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Dark oils - That fraction of the n-pentane- soluble material

in asphalt that is eluted from fuller’s earth with methylene

chloride after the white oils have been removed with

n-pentane.

Asphaltic resins - That fraction of the n-pentane- soluble

material in asphalt that is eluted from fuller's earth with

methyl ethyl ketone after the dark oils have been removed

with methylene chloride, (The methyl ethyl ketone is saturated

with water.

)

Cleanup - The material that is removed from the fuller's

earth with chloroform after the fuller's earth has been

deactivated by the water in the methyl ethyl ketone.

The ethanol extract, as its name implies, contains the material extracted from the asphaltenes with 100 volumes/gram of hot

ethanol.

Each of the asphalts was melted in a l6-ounce, seamless

ointment can on a hot plate and maintained at about ^20®F until

all entrained air and moisture were eliminated. Then ten exposure specimens, 25 ^1 mil thick, were prepared by the hydraulicpress method (8). The following day, four were exposed in accelerated durability machines to the 22-1* cycle, four to the

*22-1 cycle - 22 hours per day of arc light followed by one

hour of soaking.
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51-9C* cycle and two outdoors on the roof of the Industrial

Building, National Bureau of Standards, facing due south at an

inclination of 45° » The accelerated durability machines have

been described previously (9).

Those specimens exposed outdoors were examined semi-annually

and those exposed to the 51-9C cycle weekly with a high-voltage

electric probe (8)o Specimens were considered "failed” when

failures occurred on a minimum of 50^ of the surface of the

coating, as determined through a 60- square grid on the spark

photograph. The 22-1 cycle was used primarily to follow changes

occurring in the components of the asphalts; hence, specimens

were removed at 200, 400, 600 and 900 hours for analysis. The

specimens exposed to the 51-90 cycle were analyzed at failure.

None of the roof exposures has failed and, consequently, none

has been analyzed.

3 . RESULTS

The component changes occurring in each asphalt during exposure to the 22-1 and 51-90 cycles are reported in Table 2.

For each asphalt the original analysis has been repeated for

reference

.

*51-90 cycle - 22 hours per day of a sequence of 51 minutes of

light followed by 9 minutes of cold (40‘^F) water spray.
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TABLE

1,

ASPHALT

CHARACTERISTICS

(a)

Central

United

States

Asphalts

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1

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ASPHALT

CHARACTERISTICS

(b)

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United

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Asphalts

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1

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ASPHALT

CHARACTERISTICS

(c)

Foreign

Asphalt

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TABLE 2„ CHANGE IN ASPHALTS DURING EXPOSURE

(Arranged in order of increasing durability.

)

C1175 - 25 Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Component s 0 200 400 600 900 540

Asphaltenes^, % 40.5 48.5 50.5 53.3 52.

50.3'^

Resins, $ 9.5 9.6 8.7 9.1 7.3 10.1

Dark Oils, % 20.0 13.5 11.8 8.7 7.1 10.6

White Oils, % 27.3 27.0 23.3 22.6 20.0 21.4

Cleanup, % 2.0 0.9 2.3 1.3 1.2 Trace

Loss, % 0.0 0.9 3.0 5.9 5.3

Ethanol Ext ,

,

1o 0.7 4.1 4.6 V.7 „b

Recovery 99.3 100.4 99.6 100.9 97.8 98,2

Middle East' - 18 Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 8328

Asphaltenes^, % 46.3 54.2 60.2 58.2 57.0 55.1

Resins, % 7 o 3 9 .

7.5 8.3 8.4 10.1

Dark Oils, % 25.5 16.3 l4.1 12.1 11.6 13.4

White Oils, % 18.8 17.2 16.1 14.2 13.8 l4.0

Cleanup, % 0.5 0.3 0.2 0.1 0.2 0.1

Loss, % 0.0 3.1 7.5 7.5

Ethanol Ext . , I0 0.6 ^b 2.8 _b 2.2 2.4

Recovery 98.4 98.9 101.2 98.0 98.5 99.5

Talco - 4^ Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 940

Asphaltenes $

1 43.6 48.2 51.3 51.9 53.7 53.2®

Resins, % 6,9 8.8 8.1 8.0 8.9 8.7

Dark Oils , % 25.3 20.4 17.9 17.7 13.4 l4.0

White Oils, % 20.2 19.1 19.3 18.5 16,3 15.0

Cleanup, % 1.1 0,

0.9 0.7 1.3 0.4

Loss, % 0.0 0.7 1.8 3.0 5.4 8.2

Ethanol Ext,, % 0.4 1.3 2.0 2.3 2.7 _b

Recovery v 97.1 97.8 99.3 99.9 99.4 99.5

^Includes Ethanol Extract. * ^One specimen with pre-

^Not determined. 3

mature failure excluded.

^Based on analysis of two specimens. Based on analysis of one

specimen.
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TABLE CHANGE IN ASPHALTS DURING EXPOSURE (CONTINUED-2)

C 21Q - Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 945

Asphaltenes i 4l.8 46.9 48.5 48.7 48.7 56 .

Resins, % 10.3 11.4 11.4 10.6 9.6 10.4

Dark Oils, % 18.2 13.6 11.3 10.0 8.9 10.3

White Oils, % 27.4 24.5 22.9 21.6 20.3 22.2

Cleanup, % -b -b -b -b _b 0.2

Loss, % 0.0 1.1 3ol 5.9 9.7 _b

Ethanol Ekt . , % 2.8 3.6 -b 4.9 -b -b

Recovery 97.7 97.5 97.2 100.9 97.2 99.6

Envoy - Days

Components, $

22-1 Cycle

Time, hours

- 5I- 9C Cycle

Final Failure

0 200 400 600 900 959

Asphaltenes % 44.1 47.0 48.2 52 . 6 52.4 50.2

Resins, % 8. 6 10.4 10,8 9.1 7.6 9.1

Dark Oils, % 19.8 17.3 14.5 11.9 9.7 10.3

White Oils, % 26 .24.6 23.4 21.8 22.1 22.1

Cleanup, % 0.6 Trace 0.2 0.03 Trace 0.2

Loss, % 0.0 0.5 2.3 4.3 8.0 7.7

Ethanol Ext ,

,

% -b -b 3o00 -b 4.81 -b

Recovery 99.7 99.8 99.4 99.7 - 99.8 99.6

Lasunillas - 47 Days

22-1 Cycle 5I- 9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 1030

Asphaltenes i 42.2 45.9 48.3 47.2 48.7 50.7

Resins, $ 9.1 10.5 10.3 11.1 12.3 12.1

Dark Oils, % 25.2 19.6 18.4 17.8 14.0 16.1

White Oils, % 20.0 19.3 18.4 18.5 17.8 17.3

Cleanup, % 1.3 0.9 1.3 0.9 1.9 0.3

Loss, % 0.0 1.3 2.8 3.7 4,6 4.4

Ethanol Ext .

,

% 0.4 1.3 1.3 1.4 1.7 -b

Recovery 97.8 97.5 99.5 99.2 99.3 100.9

^Includes Ethanol Extract. ^Not determined.

TABLE 2. CHANGE IN ASPHALTS DURING EXPOSURE (CONTINUED-3

)

East Venez-Qelan - h? Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 1033

Asphaltenes a

9 i 39.1 ^3.1 44.0 45.2 5-5.5 47.0

Resins, %

Dark Oils,

8,0 9.9 10.0 8.7 10.1 9.4

1o 22,8 17.7 16.0 14.9 12.9 14,9

White Oils, $ 28.3 24.8 24,5 23.5 23 o3 24.0

Cleanup, % 0.9 1.3 1,2 1.9 lo2 0,1

Loss, fo 0.0 1.5 3.6 4o9 6.0

Ethanol Ext o 9 Oo^ 1.5 1.8 1.7 1.7 _h

Recovery 99.1 98.3 99.3 100.1 99.0 100 o 5

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 00 600 900 1170 1 Asphaltenes 4l.8 46,8 48.7 52.4 54.0 53.5

Resins, % 8.

9.0 10.8 8.

7.7 7.6

Dark Oils, % 23.6 21,0 18.2 13.9 10,6 10,4

White Oils', % 26,8 22.5 20.3 21.5 20o2 17.1

Cleanup, % 0.05 0.2 0.2 0.03 0,02 0.1

Loss, % 0,0 0.2 1.3 3.2 6,8 10.8

Ethanol Ext., % _b _b 3.75 _b 5.72 5 . 5

Recovery 100.9 99.7 99.5 99.5 99.3 99.5

C135g - 5? Days

22-1 Cycle 5I- 9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 1257

Asphaltenes % 55.5 50.0 52 o 2 53.5 53.5 51.4c

Resins, % 9.6 11.4 11.3 10,1 8.9 9.7

Dark Oils , % 21,9 17.3 13.2 12.0 10,7 9.8

White Oils, ^ 21.1 l6o4 l6o4 16.8 16 ,

15.4

Cleanup, io 0.5 0.5 0.2 0,3 0.1 Trace

Loss, % 0.0 4.3 5o6 9.8 12.5

Ethanol Ext., 1o 0.9 _b 5.2 _b 5.3 _b

Recovery 980 6 96.5 97.6 98.2 99.5 98,8

^Includes Ethanol Extract. ^Based on analysis of one specimen.

t>Not determined.

TABLE 2o CHANGE IN ASPHALTS DUHING EXPOSURE (CONTINUED-^)

Catalytic - 68 Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 l‘+93

Asphaltenes % 42.1 46,0 46,9 48,3 47.0 47,1

Resins, % 10,8 12o0 12,1 10,9 11.1 7.6

Dark Oils,

White Oils, ^ 22.9 20.6 18.8 17.0 15« 8 12.9

22.7 20.6 19.8 19.0 19.5 22.4

Cleanup, % 0.4 0,3 0.2 0.4 0.3 0.2

Loss^ % 0,0 2,8 7.0

Ethanol Ext,, % 1.2 3.9 2.8 _b

Recovery 98.9 100,1 100,6 98.8 100.

99.9

Shallow Water - 72 Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 1589

Asphaltenes $ 37.2 40.8 42,6 44.6 44.6 42.6

PTesins, % 9.7 13.9- 13.6 11,4 10.7 8.4

Dark Oils, % 25.9 22.9 19.3 17.5 16.3 14.6

White Oils, % 24,8 22.0 20.3 19.6 19.3 21.6

Cleanup, % 0.

0.3 0,6 0,7 0.7 0.7

Loss, % 0.0 2,4 3^9 6.9 llo9

Ethanol Ext ,

,

% 0.8 _b 2,8 _b 2.7 _b

Recovery 98,2 99.9 98.7 97.6 98,4 99.7

M2QQ - 75 Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 1660

Asphaltenes 1o 39. 1 9-3.3 44,6 46.0 95.3 49.0

Resins, % 9. 9 10.9 10.7 10.6 10.0 10.3

Dark Oils, % 23. 3 18.3 16.9 15.7 14.4 15.9

White Oils, % 24, 4 23,6 23,0 23.0 21.3 29.3

Cleanup, %

-b _b -b _b _b 0,9

Loss, %

%

0. 0 0,7 2.2 3^l9 6.3 _b

Ethanol Ext,, 0, 7 _b 1.6 _b 2,0 _b

Recovery 96. 7 96,8 98.3 98.2 97.3 100.4

^Includes Ethanol Extract, ^Not determined
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TABLE 2o CHANGE IN ASPHALTS DURING EXPOSURE (CONTINUED-^)

C81Q - 8l Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, $ 0 200 400 600 900 1773

Aaphaltenes $ 46,5 50.6 52.9 52.5 53.8 52,1

Resins, % 13 »

15.9 15.2 16.8 16,2 16.8

Dark Oils, $ 23.5 20.3 18.8 17o4 15.6 l5o8

White Oils, % 12,4 llo9 llo8 11.2 10.9 11,0

Cleanup, % 1.0 0.2 0.3 0.2 0,2 0,1

Loss, % 0,0 1.3 2,4 4,0

Ethanol Ext , , % 1,2 _b 3.5 _b 5.5 _b

Recovery 97.0 99.6 100.3 99.8 99.1 99.8

Louisiana - 84 Days

22-1 Cycle 51-9C Cycle

Time, Hours Final Failure

Components, % 0 200 400 600 900 1844

Asphaltenes,^ % 38.5 42,1 42.6 53.7 55.3 43.1

Resins, % 10.0 13 o 0 12o4 10.5 11.0 9.5

Dark Oils, % 27.0 22,3 20.7 19.7 16.9 18.1

White Oils, % 22.4 20.3 20.3 20.5 20.2 19.5

Cleanup, $ 0.7 0.8 0,3 0.4 0.3 0,6

Loss, % 0.0 2.4 5.7 8.

Ethanol Ext., % 0.3 _b 1.2 _b 0,9 0c8

Recovery 98,6 99.5 98.3 98.5 99 . ‘t 99.5-

Columbia - 86 Days

22-1 Cycle 51-9C Cycle

Time, Hours Final Failure

Components, % 0 200 400 600 900 1903

Asphaltenes % 36.6 41.4 41.2 44.5 53.5 42.8

Resins, $ 11.0 12.1 12.8 10.3 llo4 9.4

bark Oils, % 21.7 17.3 16.4 14.0 12.3 12.5

White Oils, % 27.0 27.5 24.6 23.9 25.8 23.2

Cleanup, % 1,8 0.4 0.5 0o3 0.1 0,1

Loss, % 0.0 1.1 3.5 5.4 6.1 12.2

Ethanol Ext ,

,

i 0.5 _b 1.5 _b 2.0 3o9

Recovery 98.1 99.8 99.0 98.4 99.2 100.2

^Includes Ethanol Extract o ^Not determined.
-ivi-
TABLE 2. CHANGE IN ASPHALTS DURING EXPOSURE (CONTINUED*6)

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 1912^

Asphaltenes,^ % 37.8 44.0 46.7 45.4 49.0 47 c 1

Resins, % llo9 12,8 lie? 12.1 11.4 11.0

Dark Oils, % 28.0 21.7 19.6 18.6 16.9 16.8

White Oils, % 19.5 18.9 17 A 16.3 15.0 I5c4

Cleanup, % lo3 0.

0.2 0.5 0.3 0.6

Loss, % 0.0 0.6 2.4 6.5 8.9

Ethanol Ext, , % 0.3 _b 1.2 „b 1.5 1.8

Recovery [98.5 98 .98.0 97.6 99ol 99.5

Kansas 2-88 Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 1933

Asphaltenes,^ 37.0 43.2 46,2 46.3 47.0 44o 5

Resins^ 9.4 12.2 11.0 12.0 11.2 9.7

Dark Oils, % 27.5 22.4 19.8 17.9 16.1 I6c5

White Oils, % 22.5 19.9 18.1 18.0 17.3 16.4

Cleanup, % 1.3 0.7 0,4 0,1 0.3 0.7

Loss, % 0.0 2.7 4.2 7*3 llo3

Ethanol Ext.

,

% 0.3 _b _b _b 1.7 1.8

Recovery 97.7 99ol 98,2 98,5 99c 2 99.1

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 1966

Asphaltenes % 43.7 47.3 48.1 51.8 51.6 52.0

Resins* % 8.9 10.0 10.6 9.7 9.1 8.4

Dark Oils, $ 21.8 19^2 17.8 12.9 12.0 9.7

White Oils, $ 24.4 22.2 21.2 20.9 19.8 15.3

Cleanup, % 0.05 0.

0.04 0.1 0.03 0.1

Loss, % 0.0 0.06 1.7 4.1 7.1 13.8

Ethanol Ext<^, %

_b _b 2.97 _b 3.53 _b

Recovery 98.9 99.4 99.4 99.5 99.6 99.3

^Includes Ethanol Extract „ ^One specimen with premature failure

^Not determined. excluded.

TABLE 2. CHANGE IN ASPHALTS DURING EXPOSURE (CONTINUED-?)

Mexico #12 - 95 Days

22-1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, ^ 0 200 400 600 900 2186^

Asphaltenes,®- % 42.9 W.5 50.4 52.2 53.2 54c 6

Resins, % 9.0 lOoO 10.3 9.9 10.0 7.9

Dark Oils, % 25.2 21.9 19.1 17.1 l4.6 12.5

White Oils, % 21.6 17.5 16.7 15.3 l4.8 13 o 8

Cleanup, % 0.6 0o8 0.4 0.7 0.0 0c2

Loss, % 0.0 0.6 2.1 8.0 10.3

Ethanol Ext., % 0. 6 _D 1.8 _b 2.5 1,8

Recovery 99.3 99o3 100.0 99.1 100.6 99.3

Shell - 101 Days

22- 1 Cycle 51-9C Cycle

Time, hours Final Failure

Components, % 0 200 400 600 900 2218

Asphaltenes,^ % 42.9 47.4 49.6 5-9.7 51.2

Resins, % 8.4 9.5 10.2 9.9 9.0 7.5

Dark Oils, % 22.8 20.3 17.3 13.7 12.1 9.5

White Oils, % 25.2 23.2 22.2 ‘21.3 21.2 15.3

Cleanup, % Trace 0.3 0.3 0.4 0.03 Trace

Loss, % 0.0 0.04 2.2 4.3 7.3 16. 6

Ethanol Ext . , % _b _b 3.11 _b 3.40 4.2

Recovery 99o3 98.8 99.6 99.2 99.3 100,1

Oklahoma - Illinois - 150 Davs

22-1 Cycle 51-9C Cycle

Time, hours Final Pa±lur-e

Components, % 0 200 400 600 900 3305

Asphaltenes,® % 37.5 53.5 42,5 55.5 46.0 53.5

Resins, % 12.8 12.4 12.4 12.1 11.2 9.3

Dark Oils, $ 24.6 19.7 19.6 16.7 15.6 13.1

White Oils, % 21.0 22.5 19.7 18.9 19o2 16.3

Cleanup, % 2.5 0.5 0.8 0.9 0.7 loO

Loss, % 0.0 0.3 2.5 4.3 6.8 15.4

Ethanol Ext . , % 0.5 _b 1.4 _b 1.8 0.9

Recovery 98.3 98.7 97.5 98,4 99.5 98.5

^One specimen with premature

failure excluded.

^Includes Ethanol Extract.

^Not determined.
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4. DISCUSSION OF RESULTS

Variations in Properties and Composition

Of the 21 asphalts evaluated, only one (C8l0) was represented

by its supplier as being other than a typical coating-grade roofing asphalt. However, C8l0 was included in the program because

it was an asphalt low in white oils, but normal in dark oils.

Its resins and asphaltenes, consequently, were higher than average.

The Mexico #12 ^sphalt had a low softening point and a high

penetration index.

Despite the fact that these 20 asphalts (excluding C8l0)

came from over half the surface of the earth, their properties

are not too dissimilar. The softening points, penetrations,

specific gravities and ductilities fell within narrow ranges.

The west coast asphalts had relatively low flash points and

high losses-on-heating-at-325°F.

The sulfur contents of the Talco, Mexico #12, Middle East and

west coast asphalts tended to be higher than the others and the

nitrogen content of the west coast asphalts was high, as well;

but the remainder of the elements were within rather narrow

ranges. For example, the carbon-hydrogen ratios for all of the

asphalts ranged from 0.66 to 0.74, but Kansas 1 and Kansas 2,

asphalts from the same group of fields, were 0.74 and 0,69 respectively. Hence, the variations in carbon-hydrogen ratio
' •-

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- 7

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among all of the asphalts are not much wider than the variation in a single source. If the properties of all of the

asphalts, except C8l0 and Mexico #12, are averaged, the results

might be considered a typical asphalt, as shovm in Table 3.

TABLE PROPERTIES OF A TYPICAL ASPHALT

Softening Point, °F 220

Penetration at 32°F 12

at 77^’F 19

at 115''F 33

Specific Gravity 1.01

Ductility, cm. 2.8

Loss at 325°?, % 0o2

Flash Point (C.OoC.), °F 530

Chemical Analysis:

Oxygen, % 1.34

Sulfur, % 3o21

Nitrogen, % 0.97

Carbon 84.00

Hydrogen, % lOolO

Total, % 99.62

Carbon/Hydrogen Ratio 0,69

Component Analyses: , Asphaltenes, % 40.9^^

Ethanol Extract, % 1.6

Resins, % 9.9

Dark Oils, % 23.1

White Oils, % . 23.5

Cleanup, % 1.3

Recovery, % 100o3 ~ Includes Ethanol Extract.

Variations in Behavior

When an asphalt is exposed to light, heat and water, marked

changes take place (8), The light induces the absorption of

and reaction with oxygen, resulting in the formation of more
.3 ^.
8

polar molecules. Some of these products are water soluble and

result in weight losses when the asphalt is washed. Some are

volatile and escape into the atmosphere as the reaction progresses.

Others become pentane-insoluble and remain with the asphaltenes

when the asphalt is separated into its components. Some of

these can be extracted from the asphaltenes with hot ethanol.

The rates of the reactions are increased as the temperature is

elevated 5 as is that of a polymerization of some of the lighter

components to form asphaltenes. The loss of the pentane- soluble

components as water-solubles and volatiles and through polymerization tends to harden and embrittle the asphalt to the point

where even small temperature changes will make it crack.

The changes taking place during exposure were followed

very closely in asphalts C210 and M200 and will be reported in

detail in two other reports. The changes taking place during

the first 900 hours of exposure to the 22-1 cycle of all 21

asphalts are reported here. Again, as in the physical and

chemical characteristics of the asphalts, there were differences among the 21 asphalts, but the trends were all nearly the

same. The asphaltenes increased rather rapidly during the first

200 to ^00 hours and then remained almost constant. The

ethanol extract increased progressively and tended to level

off or start decreasing by 900 hours. The dark oils decreased

to about one-half to two-thirds of their original value in
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900 hours, while the white oils decreased less rapidly. The

resins increased during the first 200 to 400 hours and then remained constant or decreased slightly. Water-solubles formed

slowly during the first 200 hours, but more rapidly afterward.

It seems that in all instances, the asphaltenes, ethanol extract

and water-solubles increased at the expense of the oils. Because the determinations at each exposure interval were made

on individual specimens, irregularities in the results of as

much as must be Ignored.

Specimens of these 21 asphalts were also exposed to the

51-90 cycle until crack failures occurred. The time to failure

and composition and weight loss at failure are recorded with

each asphalt in Table 2. The time to failure and loss at

failure are again tabulated in Table h along with the weight

losses at the various intervals of exposure in the 22-1 cycle.

A number of interesting comparisons can be made among the

data in Tables 2 and 4, These are best considered when the

conditions of exposure are kept in mind. In the 22-1 cycle, the

specimens are exposed to the arc light for 22 hours daily,

about 21.5 of which are at l40 *5°F. Then the specimens are

removed from the machines and soaked for 45 minutes in one

water bath at room temperature. A mild thermal shock results

during the immersion. The specimens are transferred to another
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TABLE 4. COMPARISON OF THE DURABILITY AND WEIGHT LOSS

AT FAILURE IN THE 51-9C CYCLE WITH WEIGHT

LOSS IN THE 22-1 CYCLE.

Asphalt

Final

51 - Failure—^

-90 Cycle Weight Loss in 22-1 Cycle

Days Wt, Loss, % 10 Days

%

20 Days

%

4o Days

I0 C1175 25 5.8 0.9 3.0 9.6

Middle East 38 6.8 1.3 3ci 7.5

Talco 43 8.2./ 0.7 1.8 5.4

C210 43 1.1 3.1 9.7

Envoy 44 7.7 0.5 2.3 8.0

E. Yen. 47 5 = 1 1.5 3.6 6.0

Lagunillas 47 4.4 1.3 2.8 4 „ 6

Ambit 53 10.8 0.2 1.3 6.8

CI342 57 12.5 0.9 4.3 9c8

Catalytic 68 9.7 0.5 2.8 7.0

Shallow Water 72 11.9 , 0.5 2.4 6.9

M200 75 0.7 2.2 6.3

C 8IO 81 4.0 0.7 1.3 2.4

Louisiana 84 8.6 0.9 2.4 5o7

Columbia 86 12.2 1.1 3.5 6.1

Kansas - 1 87 9o3 O 06 2.4 6.

Kansas - 2 88 11.3 0.7 2.7 7.3

Union 90 13 c 8 0.

1.7 7.1

Mexico - 12 95 10.3 0.6 2.2 7.3

Shell 101 160 6 0.4 2,2 7.3

Oklahoma 150 15.4 0.3 2.5 6.8

a/ U/

50^ Failure c Not Determined.

10

water bath for 15 minutes and then replaced in the accelerated

durability machines, where the arc is turned on after about an

hour. This cycle may be characterized as one having a long

period of exposure at elevated temperature and one thorough

washing period » In the 51-9^ cycle, the specimens are exposed

for 22 hours to a sequence of 51 minutes of dry light followed

by nine minutes of light and cold (40°F ) water spray. The

specimens are at l40 ^5°F for only about 20 minutes each hour.

The nine minutes of cold-water spray each hour do not provide

sufficiently thorough washing to remove all of the water-soluble

degradation products formed. This cycle may be characterized as

one providing frequent thermal shocks and incomplete removal of

the degradation products. The average operating temperature is

lower than in the 22-1 cycle.

With these characteristics in mind, an examination of Table

2 yields some interesting facts: 1) In general, the increase

in asphaltenes is less rapid in the 51-9C cycle at failure than

would have been predicted from the changes observed in the 22-1

cycle. Since this increase is generally considered to be a bulk, thermal reaction, i.e,, polymerization, the higher average

temperature of the 22-1 cycle would be expected to yield a more

rapid increase in asphaltenes. 2) The weight losses at failure

in the 51-9C cycle are generally less than would have been predicted from the losses in the 22-1 cycle. The cold-water spray
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is insufficient to remove all of the water-soluble products that

form during the 5l minutes of dry light exposure. Those that

are not removed tend to screen the asphalt and protect it from

the light. The lower average temperature of the specimens also

tends to slow the reactions, 3) The resins, dark and white

oils in the specimens at failure in the 51-9C cycle tend to be

higher than would be predicted from the 22-1 cycle data. This

condition, of course, follows from the previous two, for these

three components are the sources for the increase in asphaltenes

and the formation of the water-soluble degradation products.

While the above discussion applies qualitatively to the

data, no quantitative correlation seems to exist between the

time to failure in the 51-9C cycle and the weight losses in

either the 51-9C or the 22-1 cycles. If such a correlation

existed at one period of exposure, it would not necessarily

exist at others, for the weight-loss vs, exposure curves for

the various asphalts had different slopes.

The 21 asphalts varied widely in durability in the 51-9C

cycle, there being exactly a sixfold difference between the

most and least durable. However, if the most durable and two

least durable asphalts are not considered, the other l8 differ

by little more than a factor of two. There is a gradual change

in durability from a minimum of 25 days to a maximum of 150
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days, with the only sharp break occurring between the two most

durable asphalts. Those asphalts produced from crudes in the

Mid-Continent basin are consistently among the more durable.

But west coast asphalts varied widely in durability. The four

South American asphalts were in the middle-durability range,

with Venezuelan at the lower end and Columbian near the upper.

The addition of the datalyst to the Lagunillas stock

before blowing increased somewhat the durability of that asphalt.

The four replicate specimens of only eight of the asphalts

failed simultaneously, but for seven of the asphalts the failure was spread over an interval of 200 hours. For the others,

failures occurred over a 100-hour interval. The uniformity

of failure seems to be a characteristic of the asphalt, the

cycle, and the arbitrary failure point, and is related to the

nature of the strains and the relative ability of the asphalts

to relieve the stresses set up during weathering.

5. SUMMARY AM) CONCLUSIONS

Twenty-one coating-grade roofing asphalts from the United

States, Mexico, South America, and the Middle East were exposed

in accelerated durability machines to the 22-1 and 51 - 9C cycles,

and the changes in components occurring during exposure determined. The compositions of the asphalts varied within narrow

limits, and the changes in components on exposure differed only
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in degree. The weight losses varied widely and the durability

in the 51 - 9C cycle varied over a six-fold range, from 25 to 150

days. There was no correlation between durability and any of the

properties of the asphalts that were measured.
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5. APPENDIX

Methods of Analysis

(1 ) Oxygen

The physical changes that occur during weathering have been

observed for many years and the physical breaking of the coating

has been used as a criterion of failure. However, little work

has been done on the chemical changes that are simultaneously

occurring. A number of publications have appeared on the absorption of oxygen by asphalt during weathering (10, 11, 12) with

sufficiently interesting results to indicate that oxidation is

one of the processes Involved in the degradation of asphalt.

Accordingly, a method for the direct determination of oxygen was

developed, based on the Aluise (13) modification of the Unterzaucher (l4) method. The apparatus was modified by the addition

of a low-temperature trap ( 15 ) to remove the non- acidic sulfur

compounds that were formed during the combustion. Because

pyrolytic hydrogen, as well as carbon monoxide, liberated iodine

from the iodine pentoxide the results were invariably high.

Therefore, a modification of the method published by Dundy and

Stehr (l6) was adopted. The iodine was absorbed in a tube of

sodium thiosulfate followed by anhydrone and ^2^5 carbon

dioxide was absorbed in an ascarite filled tube and weighed.

Thus, the final apparatus consisted of a cylinder of Linde High

Purely nitrogen followed by a purefication system, bubble
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counter, drying tube, combustion tube and reaction furnace as

published by Aluise (13 ), a low-temperature trap and ascarlte

tube as in Hinkel’s (15) apparatus, an iodine pentoxide furnace

as in Aluise 's (13) apparatus and a sodium thiosulfate tube

and ascarlte tube as proposed by Dundy (l6). The particular

type of ascarlte tube used was developed by Corwin (17). It

consisted of a stainless steel tube with teflon valves on each

end, thus reducing the opportunity for ambient gases to diffuse

through the tube while it was being weighed

Because the details of the apparatus and procedure must

be given rather meticulously in order to have any significance,

they will not be reported here. The interested reader is referred to the references for this information. However, in

order to permit evaluation of the data, results on pure compounds are reported in Table A-I and reproducibility figures

are presented in Table A-II.

TABLE A-I. ACCURACY OF OXYGEN DETERMINATIONS

Compound

Percent

Found

Oxygen

Theory

Benzoic Acid 26.2 26.2

Sucrose 51.0 51.4

Cystine 26.87 26.62

Acetanilide 11.78 11.83

16 -

TABLE A-II. REPRODUCIBILITY OF RESULTS

Oxygen Control

Percent

Material 1 2 Ave,

Middle East Asphalt 1.16 1,13 l.l4

C-3500 - Asphaltenes 5.36 5.34 5.35

C -3500 - Resins 5.97 5.93 5.95

C-3500 - Dark Oils 2.42 2.42 2,42

C -3500 - White Oils 0.11 0.09 0.10

C -3500 - Water Soluble 33.08 33.02 33.05

( 2 ) Carbon and Hydrogen

The principal element in all of the compounds in asphalt is

carbon. In combination with hydrogen it represents more than

90^ of the asphalt. The ratio of carbon to hydrogen has proved

to be a satisfactory means of characterizing the various homologous series of compounds in petroleum; and carries its significance into the heavy asphalt fractions. For example, the

f'ollowing ratios represent the important classes of petroleum

compound s,

TABLE A-III, CARBON-HYDROGEN RATIOS

Ratio Compounds

0.5 paraffins

0.5 naphthenes, olefins

0.6 - 0.6 polyolefins

0.8 - 0.9 porphyrins

1.0 monocyclic aromatics

1.0 polycyclic aromatics

1.6 condensed aromatics
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The determination of carbon and hydrogen was essential to

following the changes that take place during weathering. As in

the oxygen determination, a micro-method was sought, but unlike

the former, little difficulty was encountered. The method has

been in use for a relatively long time and is reported in great

detail by Niederl and Niederl (l 8 ) and Steyermark ( 19 ). The

compound is burned in an atmosphere of oxygen and the combustion products are passed over hot platinum and copper oxide to

insure complete conversion of the carbon and hydrogen to CO2

and H2O, respectively. Contaminating elements are removed by

means of hot silver ribbon (sulfur) and lead peroxide (nitrogen).

The water is absorbed in a tube filled with magnesium perchlorate

and the carbon dioxide is absorbed in an ascarite tube, as

described above. Results on standard materials are reported in

Table A-IV and the reproducibility on unknown samples is shown

in Table A-V.

TABLE A-IV. CARBON AND HYDROGEN ANALYSES

Compound

Carbon Hydrogen

F ound Theory Found Theory

Acetanilid 70.93 71.1 6.77 6.70

Benzoic Acid* 68.92 68.84 5.05 4.95

Benzoic Acid 68.89 68.84 4.96 4.95

Benzoid Acid 68.78 68.84 4.98 4.95

*Benzoic acid is used as a standard and every time

a new combustion or absorption tube filling is

used, a sample is analyzed before any determination on unknowns are made.
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TABLE A-V. REPRODUCIBILITY OF CARBON AND

HYDROGEN DETERMINATIONS

Material

Analyses

Carbon Hydrogen

1 2 Ave

1 2 Ave

Mid East Asphalt 82.25 82.17 82.21 9.91 9.89 9.00

C 2500 Asphaltenes 81.53 81.07 81.30 8.18 8.38 8.28

C 2500 Resins 79.71 79.11 79 o 31 10.53 10.53 10.53

C 2500 Dark Oils 84.25 83.73 83.99 11.05 10.98 11.02

C 2500 White Oils 85.79 85.63 85.71 13.1^ 12.75 12.95

(3 ) Sulfur

There are numerous methods for determining sulfur in

organic materials, differing primarily in the method by which

the sulfur is converted to the sulfate. The Parr Bomb was

selected arbitrarily because of its rapid, simple and efficient

operation. The reliability of the method is attested by its

acceptance in standard procedures of the A.S.T.M. ( 20 ), A.S.A.

( 21 ), and A.P.I. ( 22 ).

After approximately 0.2 grams of material has been combusted with about 0,3 grams of sucrose (to increase the thermal

output and prevent the heat capacity of the bomb from quenching

the combustion) the bomb is cooled and its contents washed into

a 50 ml volumetric flask and diluted to 50 ml. An aliquot of

10 ml is removed to a 250 ml ehrlenmeyer flask, diluted with

10 ml of 95^ ethanol (to lower the solubility of the BaSOb) and
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titrated with O.OIN barium chloride solution to the pink

endpoint of the monopotassium rhodizonate indicator ( 23 )® The

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the gravimetric procedure, once the operator has been trained

to recognize the endpoint. Table A-VI contains some data on

the reproducibility of the method.

TABLE A-VI. REPRODUCIBILITY OF SULFUR DETERMINATIONS

Percent Sulfur

Material 1 2 Ave

,

C -2500 Asphaltenes 2.91 2 o 89 2.90

C-2500 Resins 2.69 2.73 2.71

C-2500 Dark Oils 1.43 1.42 1.42

C-2500 White Oils 0.197 0.201 0.199

C-2500 Water Solubles 3.72 3.78 3.75

( 4 ) Nitrogen

Because of the extremely inert nature of some of the components of asphalt, the conventional methods for determining

nitrogen did not yield accurate results. The Kjeldahl procedures do not completely decompose the nitrogen compounds and,

thus, produce low results. Considerable time and effort were

expended on the micro Dumas procedure (l8) as modified by

Hershberg and Wellwood ( 24 ), and others ( 19 ), but the results

were always high on materials similar to asphalts.
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A new method was sought and the idea of converting all of

the nitrogen to the nitrate form by combustion under oxygen

pressure in a Parr Bomb was investigated. Once in the nitrate

form, a colorimetric procedure based on the reaction of

aqueous nitrates with 2,^ - phenoldisulf onic acid can be

usedo This procedure has been standard practice in the testing for nitrates in drinking water for many years (25). However, the nitrogen was not converted entirely to nitrate,

even with a subsequent oxidation with bromine. While the

ratio between the nitrogen found and the nitrogen present was

fairly constant for any particular material, it was very different for different materials, and therefore, the method could

not be used.

Finally, communication with W. C. Alford, of the National

Institutes of Health, resulted in making about a dozen analyses

on his apparatus, which has been modified somewhat from that

reported in the literature (26). The results were entirely

satisfactory and an apparatus was built similar to his, but

incorporating some of Alford's suggestions for improvement.

The apparatus yielded its first satisfactory results at the

close of 195^. Table A-VII contains data on the reproducibility

of this method. The accuracy of this procedure has been covered

rather thoroughly by Alford with many more products than are

available to this apparatus.
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TABLE A-VII. REPRODUCIBILITY OF NITROGEN DETERMINATIONS

Percent Nitrogen

Material 1 2 0 Ave. Theory

Cystine

Acetanilid

Shale Oil

11.65

10.49

3.94

11.71

10.55

3.87

10.36

11 068

10.47

3.90

11.66

10.36 (Kjeldahl)

4.00 (Alford)

( 5 ) Unsaturation

There is considerable unsaturation in asphalts and it has

long been believed that the unsaturation may play an important

part in the way it weathers* Numerous procedures have been

developed for determining unsaturation, including direct

addition of bromine and iodine, selective oxidation and ozonation and reduction with hydrogen. The type of double bonds

measured and the nature of conflicting reactions vary with the

types of compounds being evaluated. After investigating many

methods, theoretically and a few experimentally, it was found

that an iodine number technique proved satisfactory. It is

based on the Federal Specification TT-P-l4lb, Method ^06-l,

varying primarily in quantities of reagents used. Because

the method was originally developed for relatively low molecular

weight materials, the quantity of Wijs solution was reduced

from 25 to 5 ml and the quantity of solvent increased from

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molecules, i.e., styrene (vinyl benzene) has one double bond

per molecule by this method. Results on reproducibility appear

in Table A-VIII.

TABLE A-VIII, REPRODUCIBILITY OF IODINE HUMBER

Material

Unsaturation, Double Bonds/gram

1 2 Ave.

C210 - 2500 Asphaltenes 1o94 1.97 1.96

C210 - 2500 Resins 1.45 1,40 1.42

C210 - 2500 Dark Oils 1.28 1.24 1,26

0210 - 2500 White Oils 0.363 0o358 0.360

( 6) Molecular Weight

The molecular weight is extremely important in the ultimate identification of compounds and much effort has been expended in developing numerous methods for its determination.

For materials of molecular weight below 1000, such methods as

vapor density, boiling point elevation and freezing point

depression and viscosity change have proved successful, while

in the range above 30,000, viscosities in drlute solution,

osmotic pressure effects, isothermal distillation, light

scattering and sedimentation analyses have worked, but between

1000 and 30,000 is a region in which no method is very reliable,

even on pure compounds. Since asphalts are complex mixtures of

molecules ranging from about kOO to 4,000 in molecular weight,

interpretation of a determination by any method would involve
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considerable speculation. When measuring non-uniform materials

some average molecular weight is obtained and because the average is different for each type of measurement, results are

not directly comparable. It is extremely desirable to make

measurements on a material that is as uniform as possible.

The asphalts were separated into five groups of components

and their degradation products into two types of materials

(section 7)« While these each had many molecular species,

their molecular weight ranges were relatively small and readily

lent themselves to analysis. It was desirable to use one procedure for the molecular weight determination on all of the

components, if possible, in order that the figures might be

readily comparable. Since all of the materials were not volatile, vapor density measurements were excluded and since there

is a strong tendency toward aggregation of some of the components as the temperature is lowered, the' cryoscopic method

cannot be used. Eckert and Weetman (27) have reported difficulties in attempting to measure the molecular weight of the

asphaltenes by the viscosity method. Thus, the ebullioscopic

method, offering the most promise, was extended by means of

sensitive instruments to cover the range of 100 to 5000° Because the ebullioscopic constant varies with molecular weight

it was decided to use an empirical method, with the ebullio0 meter calibrated directly with materials of known molecular

weight
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The ebulliometer used was that described by Matteson (28),

but by careful evacuation of the vapor pressure thermometer

and by using benzene instead of chloroform, an apparatus capable

of measurement to molecular weights of 5000 was obtained. A

second ebulliometer, using methyl ethyl ketone as solvent and

working on 5? instead of 10, ml of solution was also constructed. (The degradation products are soluble in methyl

ethyl ketone, but not in benzene,) The manisci in both

instruments are read by a traveling telescope, which reads to

0.001 mm.

The instrument was calibrated with the following materials

of known molecular weight:

TABLE A_IX„ MOLECULAR WEIGHT STANDARDS

Benzene Naphthalene 128

1, 2, 4, 5-Tetrachlorobenzene

1, 2, 4, 5-Tetrabromobenzene

216

Tristearin 891

Tritrityl Pentacetyl Sucrose 1280

Methyl Styrene 2200

Methyl Styrene 3750

o<'" Methyl Styrene 5400

Inulin Acetate 11000

Methyl ethyl ketone Indole 117

Sebacic acid 202

Phenolphthalein 318

Triiodophenol 472
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While in the conventional ebullioscopic method the results

are extrapolated to zero concentration to determine the ebullioscopic constant, in this procedure the deflection of the maniscus in the vapor pressure thermometer at some finite concentration is plotted against the molecular weight on semilogarithmic paper; the molecular weight of the unknown is read

directly from this graph.

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ebulliometer and boilded until equilibrium conditions are obtained, Then small increments of solute are added one at a time through the condenser and the deflection produced by each

is recorded. The deflection where the straight portion of

the curve of deflection vs. weight added intersects the

particular reference weight chosen is the point at which the

molecular weight is obtained from the calibration curve. Table

A-X shows the reproducibility of this method.

TABLE A-X, REPRODUCIBILITY OF MOLECULAR WEIGHTS.

Material

Determination

1 2 Ave

Cal. Flux Dark Oils 670 670 670

Cal. Flux Resin 990 1020 1005

C25OO Asphaltenes 2250 2250 2250

M25OO Resins 1160 1210 1185

C210-3MO-D. 0. 575 630 603

26 -

(7) Separations

As emphasized previously, it is extremely difficult to

make many of the necessary determinations on materials as complex as asphalt. It was also desired to see if there were

internal changes taking place in the asphalts during weathering

that were not apparent from studying the degradation products.

Methods for separating asphalts into a number of component

groups were investigated, primarily by N.B.S, staff members.

Because there are many methods of fractionating asphalts

available (29), all depending on either selective solvents or

adsorbents, or both, and each method having its particular

applications, only the final method selected will be discussed. This method was developed by Kleinschmidt (7) and

has been reported to the Asphalt Roofing Industry Bureau

Research Committee.

Essentially the method comprises the following steps;

(1) Solution of the maltenes in n-pentane - asphaltenes

are removed by filtrationo

(2) Adsorption of the resins and dark oils on Fuller's

earth - white oils are washed from the column with

an excess of pentane.

(3) Elution of the dark oils with methylene chloride.

(4) Elution of the resins with methyl ethyl ketone

(saturated with water).

(5) Cleaning up the column with chloroform.
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REFERENCES

(1) Photosensitivity Test, Johns-Manville Research Center,

Manville, New Jersey.

(2) Fair, W. F, , Beck, H. R. and McKee, B. K. , A.S.T.M.

Spec. Tech. No. 9^? 109-21, 19^9.

(3) Walther, H, , Mitt. Dachpappen Ind., 135-52, 1938.

(4) Nisikawa, E. , Rept. Res., Office Pub. Works, Dept. Home

Affairs, Japan 29-86, 1937.

(5) Thurston, R, R. , and Knowles, E. C., Ind. & Engr, Chem. , 28 , 88 , 1936 . Walther, H. , Asphalt Teer Strassenbautech, 3^, 1001-4,

1936.

(6) Strieter, 0. G. , & Snoke, H. R. , J. Res. NBS, l6, 481-5,

1936.

(7) Kleinschmidt , L, R. , J. Res. NBS, 163-66, 1955,

(RP2577).

(8) Greenfeld, S. H. , A.S.T.M. Bulletin 193, 50-53, Oct. 1953.

(9) Greenfeld, S. H. , Ibid., 46-50.

(10)

Walther, H. , "The Action of Light Upon Bituminous Coatings",

Asphalt, Teer Strassenbautech, 3^, 1001-4, 1936. "Influence

of Weathering on Bitumen", Mitt. Dachpappen Ind., 135-52,

1938.

28 -

REFERENCES (Continued) - 2.

(11) Thurston, R. R. , and Knowles, E. C., "Oxidation at Service

Temperatures", Ind. Eng. Chem. , 320-4, 1941,

(12) Ebberts, , "Oxid,ation of Asphalt in Thin Films", Ind.

Eng. Chem., ^4, 1048-51, 1942.

(13) Aluise, V. A. et al, "Oxygen in Organic Components",

Anal. Chem., !£, 347-51, 194?.

(14) Uterzaucher, J. , Ber, 73B . 391-4o4, 1950*

(15) Hinkel, R. D, , and Raymond, R. , Direct Semimicrodetermination of Oxygen in Organic Substances", Anal. Chem.

25, h 70-h 9 , 1953.

(16) Dundy, M. , and Stehr, E. , "Determinations of Oxygen In

Organic Materials by Modified Schut ze-Unter zaucher

Method", Anal. Chem. l408-l4l3, 1951.'

(17) Corwin, A. H, , Johns-Hdpkins University; Private Communication.

(18) Niederl, J. B, , and Niederl, V., "Micromethods of Quantitative Organic Analysis", John Wiley and Sons, Inc.,

New York, 1952.

(19) Steyermark, A., "Quantitative Organic Microanalysis",

The Blakiston Co., N. Y.

,

1951.

(20) ASTM, D271-46, D129-44, D894-46T.

(21) ASA, K18. 1-1947, 211.13-1944.
. I

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29 -

REFERENCES (Continued) - 3.

(22) API, 516-44.

(23) Sundberg, 0, E. and Royce, G, L, , "Microdetermination of

Halogen and Sulfur", Anal. Chem. ]^, 719-24, 1946.

(24) Hershberg, E. B. and Wellwood, G. W. , Ind. Eng. Chem.

Anal,, Ed. 303, 1937.

(25) Scott, A. W. , "Methods of Chemical Analysis", D. Van

Nostrand & Co.

,

1430.

(26) Alford, W. C. , "Microdetermination of Nitrogen in Organic

Compounds", Anal, Chem. 881-84, 1952.

(27) Eckert, G. W. and Weetman, B. , "Mean Molecular Weights of

Asphalts and Their Constituents", Ind. Eng. Chem. 39 . 1512-16, 1947.

(28) Matteson, R. , "Modified Molecular Weight Apparatus", Anal.

Chem. 172-175, 1950.

(29) Several of these ares

(1) Hoiberg, A. J. and Garies, W<> E. , "Analytical Fractionation of Asphalts", Ind. Eng. Chem. 294-302,

1944.

(2) Hubbard, R. L. and Stanfield, K. E. , "Determination

of Asphaltenes, Oils and Resins in Asphalt", Anal.

Chem. 460-5, 1948.

(3) Mariani, E. , "Constitution of Natural Bitumen", Bull.

Aci. Faculta Chim. Ind. 8, 70-6, 1950.

- 30 -

REFERENCES (Continued) - 4o

(4) O'Donnell, G, , "Separating Asphalt Into Its Chemical

Constituents", Analo Chem* £3.? 89^4-8, 1951.

(5) Rostler, F« S. , and Sternberg, Ho W. , "Compounding

Rubber with Petroleum Products", Indo Eng, Chem. 4l , 598-608, 1949 .

(6) Traxler, R. N. , and Schweyer, H. E., "Separating

Asphalt Materials", Oil and Gas Journal, 1953.
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THE NATIONAL BUREAU OF STANDARDS

Functions and Activities

The functions of the National Bureau of Standards are set forth in the Act of Congress, March

3, 1901, as amended by Congress in Public Law 619, 1950. These include the development and

maintenance of the national standards of measurement and the provision of means and methods

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