NATIONAL BUREAU OF STANDARDS REPORT

5935

RELATION OF RATE OF COMPONENT CHANGES IN

ASPHALTS TO ACCELERATED DURABILITY

by

John Po Falzone

U. S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

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NATIONAL BUREAU OF STANDARDS REPORTHBS PROJECT MBS REPORT

1004-11-1017 June 20, 1958 5935

RELATION OF RATE OF COMPONENT CHANGES IN

ASPHALTS TO ACCELERATED DURABILITY

by

John Po Falzone

Research AssociateAsphalt Roofing Industry Bureau

Floor, Roof and Wall Coverings SectionBuilding Technology Division

Jointly Sponsored by

Asphalt Roofing Industry Bureau

and

National Bureau of Standards

IMPORTANT NOTICE

NATIONAL BUREAU OF S

Intended for use within thi

tc additional evaluation anc

listing of this Report, elthe

the Office of the Director, I

however, by the Governmer

tc reproduce additional co(

Approved for public release by the

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on October 9, 201 5.

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lly prepared If that agency wishes

<NBS>

U. S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

RELATION OF RATE OF COMPONENT CHANGES IN

ASPHALTS TO ACCELERATED DURABILITY

by

John P. Faizone

ABSTRACT

Twenty asphalts from various sources of crude wereseparated chromatographically both before weatheringand at final failure in the 51-9C cycle of the AtlasWeather-O-Meter

o

By plotting the percent increase of the asphaltenesper day of exposure versus the durability of thegiven asphalt, a graphic relationship was obtained

o

Similar handling of rate changes of asphaltenes plusweight loss or rate changes in total oily constituentsversus accelerated durabilities gave rise to relatedcurve So Use of the asphaltene content was found tobe desirable because of its simplicity and precisenessfrom a laboratory point of viewo

The results indicate that a method for the rapid eval-uation of the relative accelerated durabilities of agroup of asphalts can be developed:,

Some important variables uncovered during the accumu-lation of the data are discussedo

^ ^ ^ ^ ^ ^ ^ ^ ^

1. INTRODUCTION

During the investigation of the filtration rate of the n-pehtanesolubles of a coating asphalt through its insolubles (asphaltenesit was necessary to recheck the accelerated durabilities of thetwenty-two asphalts being studied, since the latter had beenin storage for over two yearSo Analysis of weight loss datasubsequently acquired indicated a closer relationship to dura-bility than had been previously suspected „ This encouragingdevelopment logically indicated that a component rate of changestudy might prove more fruitful and reliable than one associatedwith the degradation products.

2

This report summarizes the manner by which this necessary in-formation was obtained, the recognized variables in the pro-cedures employed and the promising conclusions drawn from theanalysis of the results.

2.

ASPHALTS

Twenty asphalts representing east and west coast and niidcon-tinental sources of crude were used. Two additional asphaltswhose durability had been determined could not be consideredsince a sample of each prior to weathering was not available.These were C8l0 and 013^2 and were derived from west coastcrude s

,

3.

PROCEDURES

Accelerated durabilities and component separations were deter-mined for each asphalt. The latter was done by the method ofKleinschmidt (1)—^, The coatings for exposure in the 51-9Ccycle were prepared by the hydraulic press method (2)„ Sparkinspections were carried out twice weekly and in the mannerrecently reported (3).

4.

RESULTS AND DISCUSSION

The desired data obtained for the twenty asphalts is summarizedin Table 1.

If the rate of change per day for the asphaltene component is

plotted against the durability of that particular asphalt,a fairly smooth curve is obtained, as in Figure 1.

Figures 2 and 3 were obtained by similarly employing (a) theincrease per day of durability for the sum of asphaltenesand weight loss, and (b) the rate of decrease per day oftotal oils.

1 /Figure s

end ofin parentheses

this report.indicate literature references at the

•V 'U-lrrJ^'W

^ 3v;

TABLE 1

Asphaltand

ComponentsFinal

FailureBefore

WeatheringDurability(51-9C)

% % Days

C 1175 ( 1 )

48,023

Asphaltene s 39.8White Oils 21.5 26,

8

Dark Oils 12,6 22,5Be sins 10,3 10,6Cleanup 0,0 0,0Weight Loss 7.5 —Recovery 99o9 99.7

Middle East (3) 42Asphaltene s 52,7 46,4White Oils 12,9 16.8Dark Oils 15.3 25.4Re sins 9.1 10,1Cleanup 0.2 0,3Weight Loss 9o3 —Recovery 99.5 99.0

Talco (4) 34Asphaltene s 48,7 4l,6White Oils 12.8 19.0Dark Oils 19o4 32,2Re sins 9o5 7o2Cleanup 0,1Weight Loss 9o0 —Recovery 99A 100,1

C-210 (4) 37Asphaltene s 44,6 39olWhite Oils 19.7 26,8Dark Oils 11.3 21,6Re sins 10,3 12,7Cleanup 0.0 0.2Weight Loss 13.3 —Recovery 99.2 100,4

Envoy (2)48.0

30Asphaltene s 4o , 6White Oils 19.4 26,4Dark Oils 13.1 23cORe sins 11.7 10,2Cleanup 0.1 0,0Weight Loss 8.8 —Recovery 100.1 100.2

(Continued on next page)

TotalChangein

Fraction

%

8o25o39o90.3OoO7o5

6o33o9lOolloOOol9o3

7ol6.

2

12o82o3

9o0

5c57ol

10„32,4

13o3

7o47c09o9lo5

8~8

Changein

Fraction

^/Day

0,3760,2300,430

0,326

0,1500,0930,24l

0,221

0,2080,1820,376

0,265

0,1490,1920,279

0,359

0,2470,2330,330

0,293

XL-'iiqZh^

TABLE lo (Continued) - 2

Asphaltand

Compone nt

s

Lag. (4)AsphaltenesWhite OilsDark OilsRe sinsCleanupWeight LossRecovery

East Ven. (3)Asphaltene s

White OilsDark OilsRe sinsCleanupWeight LossRecovery

Ambit (^-)

Asphaltene s

White OilsDark OilsResinsCleanupWeight LossRecovery

V-200 (2)Asphaltene s

White OilsDark OilsRe sinsCleanupWeight LossRecovery

Cat. (2)AsphaltenesWhite OilsDark OilsRe sinsCleanupWeight LossRecovery

FinalFailure

BeforeWeathering

Durability(51-90)

% % Days

6148.1 40.514.9 19.118.4 30.012.1 10.30.1 0.26.9

100.5 100.1

50*+3.7 37c221.5 25o417o3 29.09.8 9o4— 0,28.0 —

100.3 101.2

3450.3 38,314,4 21.214.0 29,69.5 10.00.1 0.2

12.0 —100.3 99o3

6444.9 38.315o2 20.717.5 30.7llo3 10.10.3 0.5

10.6 —99.8 99o3

8846,0 38.1l5o6 22.1l5o8 3I0610,5 8,2— 0.312.5 —

100.4 100.3

(Continued -on next page)

TotalChangein

Fraction

7 o 64.2llo6lo 8Ool6 o 9

6 . 53.9

llo 70 e 4

8.0

12 o 06.8

i 5 o 6

0.5Ool

12„0

6 o 6

5 o 513.2lo 20o2

10,6

6 o 5i 5 o 82 o 3

12 o 5

Changein

Fraction

^/Day

O0I25O0O690.190

O0II3

O0I3OO0O780.234

0.160

0.3530.2000.459

Oo353

0.103O0O890.206

0. 166

0.0900.0740.180

0.142

j

nr ^

liffB-

<3 .iii;9?!Misc

awi.'3'^

'»'*!*.' j

TABLE lo (Continued) - 3

TotalAsphalt

andComponents

FinalFailure

BeforeWeathering

Durability(51-9C)

Changein

Fraction

Changein

Fraction

% % Days % fo/'Day

Shallow H2O (4) 63Asphaltene s 42.1 35.8 6.3 0.098White Oils 16.3 20.0 3o7 0.058Dark Oils 1808 33.5 14.7 0.230Resins 9o5 8.4 0.7Cleanup 0.4 0.4Weight Loss 12.9 — 12.9 0.205Recovery 100 oO 98.1

Midconto 200 (4) 87Asphaltene s 45„0 39.6 5c4 0.062White Oils 16.8 22.8 6.0 0.068Dark Oils 15.7 26.5 10.8 0.124Re sins 8o9 10.0 lolCleanup 0o5 0.7 0.2Weight Loss 12.8 — 12.8 0.147Recovery 99o7 99.6

Louisiana (3) 64Asphaltene s 42.5 36.9 6.

6

0.103White Oils 16.6 21.5 4.9 0.077Dark Oils 2O 0 O 31.5 11.5 0.180Re sins 10.9 9o7 1.2Cleanup 0,4 0.8 0.4Weight Loss 9ol — 9 = 1 0.142Recovery 99.5 100.4

Columbia (1) 70Asphaltene s 41.9 36.7 5.2 0.074White Oils 2O 08 28.8 8,0 0.114Dark Oils 14.6 25.6 11.0 0.157Re sins 8.9 8.7 0.2Cleanup 0o4 0.3 0.1Weight Loss 13o4 — 13 = 4 0.192Recovery 100.0 100.1

Kansas-I (1) 79Asphaltenes 44.3 39.6 4.7 0.060White Oils 15.5 22.5 7.0 0.089Dark Oils 17.5 27»9 10.4 0.132Re sins 8.

5

8.2 0.3Cleanup lo4 0.5 0.9Weight Loss 11.7 — 11.7 0.148Recovery 98,9 98.7

(Continued . on next page)

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- uu.i^XXs4^^^ n'j£i.iO'’^4-N

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TABLE lo (Continued) - 4

TotalAsphalt Change

and Final Before Durability inComponents Failure Weathering ( 51 - 9C) Fraction

fo

Kansas-II ( 3 )

Asphaltene s 43o9White Oils 13ADark Oils 13.5Re sins 13 0 2Cleanup 1.2Weight Loss 13o9Recovery 99 ol

Union ( 3 )

Asphaltene s 48.7White Oils l5o 6Dark Oils 13.0Resins 10.4Cleanup 0.0Weight Loss 13.2Recovery 100.9

Mexican ( 2 )

Asphaltene s 55.7White Oils 11.1Dark Oils 14.2Re sins 6.3Cleanup 2.0Weight Loss 9 o 6Recovery 98.9

Oklahoma ( 4 )

Asphaltene s 42.5White Oils 13

»

7Dark Oils l5o2Re sins 11.3Cleanup 1.0Weight Loss 16.1Recovery 99.8

Shell ( 4 )

Asphaltenes ‘+7.3White Oils 13.8Dark Oils 12.3Re sins 10.2Cleanup 0.1Weight Loss 16.8

Recovery 100.5

Days

8635.3 8.

6

24.1 10.726.2 12.711.9 lo30.5 0.7

98.0

43

13.9

‘+3.3 7o424.1 8.

5

23.6 10.69ol lo30.1 0.1

!CM

10

1

01

01

—1

76

13o2

42.5 13 0 216.2 5ol33o2 19o07ol 0.80.5 1=5

99.5

115

9o 6

36.0 6.

5

20.9 7o230.9 15.710.5 0.81.2 0.2— 16.1

99.5

67

~

40.8 6.

5

26.0 12.222.9 10068.7 lo51.8 lo7

100.216.8

Changein

Fraction

^/Day

0.1000ol240ol48

0.162

0.1260.1980.247

0.307

0.1740.0670.250

0.126

0.0560.0630.136

0.l40

0.0970.1820.158

0.251

I.

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3

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ssamd^moO

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- 3 -

Several important variables which are discussed in the nextsection restrict more exact quantitative interpretation of theresults. Nonetheless, the following information may be validlyderived from a study of the graphs?

(1) Irrespective of the source of crude, a fairly goodcorrelation exists between the rate of formationof asphaltenes and accelerated durability. Alter-natively, the rate of decrease of total oils or therate of increase of asphaltenes plus weight lossversus accelerated durability may be used, the latteryielding similar relationships which align theasphalts, generally, in the same relative positionsobtained by employing the former,

(2) The rate of increase of asphaltenes plus weightloss is approximately equal to the rate of decreaseof total oils. Consequently, Figures 2 and 3 arevirtually the same,

(3) The slope of the curves in all three figures issteepest in the region where the poorest weatherersare found. Consequently, sharper end-points andgood reproducibility can be expected for coatingsthat fail in roughly 50 days or less. Conversely,the gradual change in the slope of the curves inthe region representing the better weatheringasphalts shows that the durabilities are extremelysensitive to small differences in rates of change.Much poorer precision and reproducibility can beexpected then for those asphalts having durabilitiesof approximately sixty days or more. In general,this observation is in agreement with actual prac-tice, This effect can be minimized to some extentby re-emphasizing temperature control during ex-posure and rigid adherence to a standardized in-spection procedure.

^• iio;

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- '1' > 4'>

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- 4 -

5o VARIABLES PRESENT

During the normal development of this approach^ it became evi-dent that two important factors were contributing heavily to

the uncertainty and scatter that was present in the datao

The first of these was concerned with the fact that thespark inspection procedure was not sufficiently standardizedto yield comparable and reasonably reproducible failurepointSo Although the proper steps have now been taken tocorrect this condition, about half of the durabilities inthis report were obtained without the benefit of the revisedprocedure o

A second and far more significant variable was one concerningsamplingo The approach being studied intrinsically dependsupon an accurate knowledge of the component composition ofa particular asphalt both at the time of initial exposureto the accelerated cycle and at final failure o The evolu-tionary nature of this study made it necessary to determinecomponent analysis of the asphalts, before weathering, onsamples obtained from the five-gallon pails in which they hadbeen stored for three years* These samples were not necessar-ily representative of those taken for durability studies* Itwas subsequently shown that the component composition of thesurface of these aged asphalts was significantly differentthan that of the body of the material which was naturallyprotected from atmospheric influences* In addition, it wasshown that the depth to which the various asphalts wereaffected was not the same* Table 2 illustrates the differencein component composition between the surface and body of fiveof the asphalts studied*

TABLE 2*

Asphalt% Asphaltenes

Surface% Asphaltenes

Body

Ambit 46*3 38*4Envoy 44*8 40*6East Venezuelan 40*6 37o2Laguinillas 42*9 40*5Louisiana 43 ol 36* 5

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Since the actual initial composition of the material thatwas weathered lies somewhere between these two extremes,the scatter of points obtained both above and below therepresentative curve was expected o In future work, thiseffect will easily be minimized by making the necessaryanalysis on a sample poured from the same batch beingused to make coatings for accelerated exposureso

6o CONCLUSIONS

For the twenty asphalts employed and within the limitsof the variables previously cited, a good correlationappears to exist between the rate of formation ofasphaltenes and the accelerated durability of an asphalto

The rate of change of total oils may similarly and per-haps more rigorously be employed to obtain a similarrelationshipo However, the former may be used tobetter advantage since it requires less time to deter-mine and is very reproducible

»

7. REFERENCES

(1) Kleinschmidt5

Lo Ro,"Chromatographic Method for

the Fractionation of Asphalts Into DistinctiveGroups of Components", Jo ReSo NBS 163-166,1955o

(2) Greenfeld, S„ Ho, "A Method of Preparing UniformFilms of Bituminous Materials, ASTM Bulletin 193 o

50-53, October 1953

o

(3) Monthly Progress Report NOo 108, Asphalt RoofingIndustry Bureau, May 8, 1958o

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U. S. DKrAHTMKNT OF COMMERCESinrluir W«H‘ks. Svcretiiry

NATIONAF- nUHEAlI OF STANDARDSA. V. Aslin, Director

THE NATIONAL BUREAU OF STANDARDS

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