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 REPORT

HBS 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 Associate

Asphalt Roofing Industry Bureau

Floor, Roof and Wall Coverings Section

Building 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

Director of the National Institute of

Standards and Technology (NIST)

on October 9, 201 5.

r progress accounting documents

formally published It is subjected

ng, reproduction, or open-literature

nisslon is obtained in writing from

). Such permission is not needed,

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 were

separated chromatographically both before weathering

and at final failure in the 51-9C cycle of the Atlas

Weather-O-Meter

By plotting the percent increase of the asphaltenes

per day of exposure versus the durability of the

given asphalt, a graphic relationship was obtained

Similar handling of rate changes of asphaltenes plus

weight loss or rate changes in total oily constituents

versus accelerated durabilities gave rise to related

curve So Use of the asphaltene content was found to

be desirable because of its simplicity and preciseness

from a laboratory point of viewo

The results indicate that a method for the rapid evaluation of the relative accelerated durabilities of a

group of asphalts can be developed:,

Some important variables uncovered during the accumulation of the data are discussedo

^ ^ ^ ^ ^ ^ ^ ^ ^

1. INTRODUCTION

During the investigation of the filtration rate of the n-pehtane

solubles of a coating asphalt through its insolubles (asphaltenes

it was necessary to recheck the accelerated durabilities of the

twenty-two asphalts being studied, since the latter had been

in storage for over two yearSo Analysis of weight loss data

subsequently acquired indicated a closer relationship to durability than had been previously suspected „ This encouraging

development logically indicated that a component rate of change

study might prove more fruitful and reliable than one associated

with the degradation products.

2

This report summarizes the manner by which this necessary information was obtained, the recognized variables in the procedures employed and the promising conclusions drawn from the

analysis of the results.

2.

ASPHALTS

Twenty asphalts representing east and west coast and niidcontinental sources of crude were used. Two additional asphalts

whose durability had been determined could not be considered

since a sample of each prior to weathering was not available.

These were C8l0 and 013^2 and were derived from west coast

crude s

,

3.

PROCEDURES

Accelerated durabilities and component separations were determined for each asphalt. The latter was done by the method of

Kleinschmidt (1)—^, The coatings for exposure in the 51-9C

cycle were prepared by the hydraulic press method (2)„ Spark

inspections were carried out twice weekly and in the manner

recently reported (3).

4.

RESULTS AND DISCUSSION

The desired data obtained for the twenty asphalts is summarized

in 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) the

increase per day of durability for the sum of asphaltenes

and weight loss, and (b) the rate of decrease per day of

total oils.

1 /Figure s end of

in parentheses

this report.

indicate literature references at the
•V 'U-lrrJ^'W ^ 3v;
TABLE 1

Asphalt

and

Components

Final

Failure

Before

Weathering

Durability

(51-9C)

% % Days

C 1175 ( 1 ) 48,0

23

Asphaltene s 39.8

White Oils 21.5 26,

8

Dark Oils 12,6 22,5

Be sins 10,3 10,6

Cleanup 0,0 0,0

Weight Loss 7.5 — Recovery 99o9 99.7

Middle East (3) 42

Asphaltene s 52,7 46,4

White Oils 12,9 16.8

Dark Oils 15.3 25.4

Re sins 9.1 10,1

Cleanup 0.2 0,3

Weight Loss 9o3 — Recovery 99.5 99.0

Talco (4) 34

Asphaltene s 48,7 4l,6

White Oils 12.8 19.0

Dark Oils 19o4 32,2

Re sins 9o5 7o2

Cleanup 0,1

Recovery

Weight Loss 9o0 — 99 A 100,1

C-210 (4) 37

Asphaltene s 44,6 39ol

White Oils 19.7 26,8

Dark Oils 11.3 21,6

Re sins 10,3 12,7

Cleanup 0.0 0.2

Weight Loss 13.3 — Recovery 99.2 100,4

Envoy (2)

48.0

30

Asphaltene s 4o , 6

White Oils 19.4 26,4

Dark Oils 13.1 23cO

Re sins 11.7 10,2

Cleanup 0.1 0,0

Recovery

Weight Loss 8.8 — 100.1 100.2

(Continued on next page)

Total

Change

in

Fraction

%

8o2

5o3

9o9

0.3

OoO

7o5

6o3

3o9

lOol

loO

Ool

9o3

7ol

6.

2

12o8

2o3

9o0

5c5

7ol

10„3

2,4

13o3

7o4

7c0

9o9

lo5

8~8

Change

in

Fraction

^/Day

0,376

0,230

0,430

0,326

0,150

0,093

0,24l

0,221

0,208

0,182

0,376

0,265

0,149

0,192

0,279

0,359

0,247

0,233

0,330

0,293
XL-'iiqZh^
TABLE lo (Continued) - 2

Asphalt

and

Compone nt

s

Lag. (4)

Asphaltenes

White Oils

Dark Oils

Re sins

Cleanup

Weight Loss

Recovery

East Ven. (3)

Asphaltene s White Oils

Dark Oils

Re sins

Cleanup

Weight Loss

Recovery

Ambit (^-)

Asphaltene s White Oils

Dark Oils

Resins

Cleanup

Weight Loss

Recovery

V-200 (2)

Asphaltene s White Oils

Dark Oils

Re sins

Cleanup

Weight Loss

Recovery

Cat. (2)

Asphaltenes

White Oils

Dark Oils

Re sins

Cleanup

Weight Loss

Recovery

Final

Failure

Before

Weathering

Durability

(51-90)

% % Days

61

48.1 40.5

14.9 19.1

18.4 30.0

12.1 10.3

0.1 0.2

6.9

100.5 100.1

50

*+3.7 37c2

21.5 25o4

17o3 29.0 —9.8 9o4

0,2

8.0 — 100.3 101.2

34

50.3 38,3

14,4 21.2

14.0 29,6

9.5 10.0

0.1 0.2

12.0 — 100.3 99o3

64

44.9 38.3

15o2 20.7

17.5 30.7

llo3 10.1

0.3 0.5

10.6 — 99.8 99o3

88

46,0 38.1

l5o6 22.1

l5o8 3I06

10,5 — 8,2

0.3

12.5 — 100.4 100.3

(Continued -on next page)

Total

Change

in

Fraction

7 o 6

4.2

llo6

lo 8

Ool

6 o 9

6 . 5

3.9

llo 7

0 e 4

8.0

12 o 0

6.8

i 5 o 6

0.5

Ool

12„0

6 o 6

5 o 5

13.2

lo 2

0o2

10,6

6 o 5

i 5 o 8

2 o 3

12 o 5

Change

in

Fraction

^/Day

O0I25

O0O69

0.190

O0II3

O0I3O

O0O78

0.234

0.160

0.353

0.200

0.459

Oo353

0.103

O0O89

0.206

0. 166

0.090

0.074

0.180

0.142
j nr ^

liffB-

<3 .iii;9?!Misc

awi.'3'^

'»'*!*.' j
TABLE lo (Continued) - 3

Total

Asphalt

and

Components

Final

Failure

Before

Weathering

Durability

(51-9C)

Change

in

Fraction

Change

in

Fraction

% % Days % fo/'Day

Shallow H2O (4) 63

Asphaltene s 42.1 35.8 6.3 0.098

White Oils 16.3 20.0 3o7 0.058

Dark Oils 1808 33.5 14.7 0.230

Resins 9o5 8.4 0.7

Cleanup 0.4 0.4

Weight Loss 12.9 — 12.9 0.205

Recovery 100 oO 98.1

Midconto 200 (4) 87

Asphaltene s 45„0 39.6 5c4 0.062

White Oils 16.8 22.8 6.0 0.068

Dark Oils 15.7 26.5 10.8 0.124

Re sins 8o9 10.0 lol

Cleanup 0o5 0.7 0.2

Weight Loss 12.8 — 12.8 0.147

Recovery 99o7 99.6

Louisiana (3) 64

Asphaltene s 42.5 36.9 6.

6

0.103

White Oils 16.6 21.5 4.9 0.077

Dark Oils 2O 0 O 31.5 11.5 0.180

Re sins 10.9 9o7 1.2

Cleanup 0,4 0.8 0.4

Weight Loss 9ol — 9 = 1 0.142

Recovery 99.5 100.4

Columbia (1) 70

Asphaltene s 41.9 36.7 5.2 0.074

White Oils 2 O 08 28.8 8,0 0.114

Dark Oils 14.6 25.6 11.0 0.157

Re sins 8.9 8.7 0.2

Cleanup 0o4 0.3 0.1

Weight Loss 13o4 — 13 = 4 0.192

Recovery 100.0 100.1

Kansas-I (1) 79

Asphaltenes 44.3 39.6 4.7 0.060

White Oils 15.5 22.5 7.0 0.089

Dark Oils 17.5 27»9 10.4 0.132

Re sins 8.

5

8.2 0.3

Cleanup lo4 0.5 0.9

Weight Loss 11.7 — 11.7 0.148

Recovery 98,9 98.7

(Continued . on next page)
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V-:

- uu.i^XXs4^^

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£i.iO'’^4-N

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TABLE lo (Continued) - 4

Total

Asphalt Change

and Final Before Durability in

Components Failure Weathering ( 51 - 9C) Fraction

fo Kansas-II ( 3 ) Asphaltene s 43o9

White Oils 13A

Dark Oils 13.5

Re sins 13 0 2

Cleanup 1.2

Weight Loss 13o9

Recovery 99 ol

Union ( 3 ) Asphaltene s 48.7

White Oils l5o 6

Dark Oils 13.0

Resins 10.4

Cleanup 0.0

Weight Loss 13.2

Recovery 100.9

Mexican ( 2 ) Asphaltene s 55.7

White Oils 11.1

Dark Oils 14.2

Re sins 6.3

Cleanup 2.0

Weight Loss 9 o 6

Recovery 98.9

Oklahoma ( 4 ) Asphaltene s 42.5

White Oils 13

»

7

Dark Oils l5o2

Re sins 11.3

Cleanup 1.0

Weight Loss 16.1

Recovery 99.8

Shell ( 4 ) Asphaltenes ‘+7.3

White Oils 13.8

Dark Oils 12.3

Re sins 10.2

Cleanup 0.1

Weight Loss 16.8

Recovery 100.5

Days

86

35.3 8.

6

24.1 10.7

26.2 12.7

11.9 lo3

0.5 0.7

98.0

43

13.9

‘+3.3 7o4

24.1 8.

5

23.6 10.6

9ol lo3

0.1 0.1

!

CM 1

0 1

0

1

0

11—

76

13o2

42.5 13 0 2

16.2 5ol

33o2 19o0

7ol 0.8

0.5 1=5

99.5

115

9o 6

36.0 6.

5

20.9 7o2

30.9 15.7

10.5 0.8 —1.2 0.2

16.1

99.5

67

~

40.8 6.

5

26.0 12.2

22.9 1006

8.7 lo5

1.8 lo7

100.2

16.8

Change

in

Fraction

^/Day

0.100

0ol24

0ol48

0.162

0.126

0.198

0.247

0.307

0.174

0.067

0.250

0.126

0.056

0.063

0.136

0.l40

0.097

0.182

0.158

0.251
I.

^ .

m

i

-: A I 3

\

DEM :': ssamd^moO

.ua

s to ^ a^t|;;i

' A'l^5!#i
- 3

-

Several important variables which are discussed in the next

section restrict more exact quantitative interpretation of the

results. Nonetheless, the following information may be validly

derived from a study of the graphs?

(1) Irrespective of the source of crude, a fairly good

correlation exists between the rate of formation

of asphaltenes and accelerated durability. Alternatively, the rate of decrease of total oils or the

rate of increase of asphaltenes plus weight loss

versus accelerated durability may be used, the latter

yielding similar relationships which align the

asphalts, generally, in the same relative positions

obtained by employing the former,

(2) The rate of increase of asphaltenes plus weight

loss is approximately equal to the rate of decrease

of total oils. Consequently, Figures 2 and 3 are

virtually the same,

(3) The slope of the curves in all three figures is

steepest in the region where the poorest weatherers

are found. Consequently, sharper end-points and

good reproducibility can be expected for coatings

that fail in roughly 50 days or less. Conversely,

the gradual change in the slope of the curves in

the region representing the better weathering

asphalts shows that the durabilities are extremely

sensitive to small differences in rates of change.

Much poorer precision and reproducibility can be

expected then for those asphalts having durabilities

of approximately sixty days or more. In general,

this observation is in agreement with actual practice, This effect can be minimized to some extent

by re-emphasizing temperature control during exposure and rigid adherence to a standardized inspection procedure.
^ • iio; f - '1' > 4 '> J i Ji^Ji 4 'i ^ -

•' Cl)
- 4 -

5o VARIABLES PRESENT

During the normal development of this approach^ it became evident 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 the

spark inspection procedure was not sufficiently standardized

to yield comparable and reasonably reproducible failure

pointSo Although the proper steps have now been taken to

correct this condition, about half of the durabilities in

this report were obtained without the benefit of the revised

procedure o A second and far more significant variable was one concerning

samplingo The approach being studied intrinsically depends

upon an accurate knowledge of the component composition of

a particular asphalt both at the time of initial exposure

to the accelerated cycle and at final failure o The evolutionary nature of this study made it necessary to determine

component analysis of the asphalts, before weathering, on

samples obtained from the five-gallon pails in which they had

been stored for three years* These samples were not necessarily representative of those taken for durability studies* It

was subsequently shown that the component composition of the

surface of these aged asphalts was significantly different

than that of the body of the material which was naturally

protected from atmospheric influences* In addition, it was

shown that the depth to which the various asphalts were

affected was not the same* Table 2 illustrates the difference

in component composition between the surface and body of five

of the asphalts studied*

TABLE 2*

Asphalt

% Asphaltenes

Surface

% Asphaltenes

Body

Ambit 46*3 38*4

Envoy 44*8 40*6

East Venezuelan 40*6 37o2

Laguinillas 42*9 40*5

Louisiana 43 ol 36* 5
r ;r-.i /s'-f-v :;#i

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- -;a CS< ' ' ^ ‘

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- 5

-

Since the actual initial composition of the material that

was weathered lies somewhere between these two extremes,

the scatter of points obtained both above and below the

representative curve was expected o In future work, this

effect will easily be minimized by making the necessary

analysis on a sample poured from the same batch being

used to make coatings for accelerated exposureso

6o CONCLUSIONS

For the twenty asphalts employed and within the limits

of the variables previously cited, a good correlation

appears to exist between the rate of formation of

asphaltenes and the accelerated durability of an asphalto

The rate of change of total oils may similarly and perhaps more rigorously be employed to obtain a similar

relationshipo However, the former may be used to

better advantage since it requires less time to determine and is very reproducible

»

7. REFERENCES

(1) Kleinschmidt 5 Lo Ro , "Chromatographic Method for

the Fractionation of Asphalts Into Distinctive

Groups of Components", Jo ReSo NBS 163-166,

1955o

(2) Greenfeld, S„ Ho, "A Method of Preparing Uniform

Films of Bituminous Materials, ASTM Bulletin 193 o 50-53, October 1953

o

(3) Monthly Progress Report NOo 108, Asphalt Roofing

Industry Bureau, May 8, 1958o

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U. S. DKrAHTMKNT OF COMMERCE

Sinrluir W«H‘ks. Svcretiiry

NATIONAF- nUHEAlI OF STANDARDS

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