A high-float rapid-setting emulsion comprised of asphalt, tall oil, tall oil derivatives or mixtures thereof, copolymer selected from the group consisting of a styrene-butadiene-styrene block and styrene-isoprene-styrene block, petroleum distillate, water, and strong base. In addition, methods of manufacturing a high-float, rapid-setting emulsion including a first method comprising mixing asphalt with tall oil, tall oil derivatives or mixtures thereof, and combining and mixing said mixture with treated water comprising tall oil, tall oil derivatives or mixtures thereof, strong base, and water. A second method comprises mixing asphalt with reacted tall oil, tall oil derivatives or mixtures thereof, said reacted tall oil, tall oil derivatives or mixtures thereof comprising tall oil, tall oil derivatives or mixtures thereof, reacted with a strong base, and mixing and combining the asphalt-reacted tall oil, tall oil derivatives or mixtures thereof mixture with treated water comprising tall oil, tall oil derivatives or mixtures thereof, strong base, and water. A third method comprises mixing asphalt with treated water comprising tall oil, tall oil derivatives or mixtures thereof, strong base, and water. A fourth method comprises mixing asphalt, copolymer selected from the group consisting of styrene-butadiene-styrene block and styrene-isoprene-styrene block, petroleum distillate, and mixing and combining the asphalt, copolymer, petroleum distillate mixture with treated water comprising tall oil, tall oil derivatives, or mixtures thereof, strong base, and water. A rapid-setting emulsion used primarily in surface treatments, such as chip seal coats, also possesses high-float properties normally found in medium-setting grades of emulsions. A method for preparation involves modifying the asphalt cement prior to emulsification, and then emulsifying with an emulsifier or agent normally used to manufacture rapid-setting emulsions such as ASTM D-977 RS-1 and RS-2 grades.

This invention relates generally to bituminous emulsions, and particularly 
to a seal coat grade material having both high-float properties and 
rapid-setting properties. Hereinafter, the inventive emulsions are 
frequently referred to as HFRS emulsions. 
Certain types of high-float, medium-setting emulsions have been developed 
in the past. One such is described in U.S. Pat. No. 2,855,319. Attention 
is also directed to the following U.S. Pat. Nos. 2,789,917; 3,036,015; 
3,979,323; 3,892,668; and 3,607,773, all cited in the above-identified 
patent application. 
"Float" is a term which refers to the resistance of a material to flow 
under given conditions. Typically, for bituminous high-float emulsions, 
float tests are conducted upon samples of emulsion residues. Tests are 
conducted at selected temperatures, e.g., 140.degree. F. on the residues. 
The "residues" of emulsion typically are considered to be what remains 
from an emulsion-containing emulsifier, water and asphalt cement, after 
the water is evaporated. The significance attached to the high-float 
property is that the residue from a high-float emulsion will not flow 
under the force of gravity at temperatures as high as 140.degree. F. This 
property, non-flow, allows a greater margin of safety in the applied 
quantity of emulsion without having a fat or flushed pavement, thus 
greatly enhancing the possibility of obtaining a satisfactory pavement. A 
significant coorelation has also been established between high-float 
characteristics and other properties of bituminous emulsions which are 
extremely desirable. 
One reason why the float test is used to determine the presence of other 
desirable characteristics is that the float test is relatively simple to 
perform. 
An emulsion is defined as "rapid-setting" if the emulsion has a 
demulsibility or "break" of 60 or more (ASTM D-977) or 30 or more (Indiana 
State Highway Standard Specifications) as defined by the ASTM D-244 
quick-break test. Rapid-setting emulsions are useful for seal coats, i.e., 
surface treatments of pavements. Such emulsions are also useful for 
penetration treatment of macadam, as sand seal coats and tack coats (to 
promote adhesion of overlayers), etc. 
In this regard, reference is made to ASTM D-977 and the State of Indiana 
902.04 Standard Specifications for emulsified asphalts. 
According to one embodiment of the invention, a black liquor soap skimming 
(a by-product of pine wood digestion by the sulfate process to make pulp) 
is added to an asphalt cement prior to being emulsified. The amount of 
skimming added may vary from about 1% to about 5% based on the weight of 
the blend, depending on the solids content of the skimming and the nature 
of the asphalt being used. This blend is then emulsified in accordance 
with accepted techniques to provide a rapid-setting emulsion. See, for 
example, U.S. Pat. No. 2,789,917. With the skimming in the asphalt, the 
blend has properties that are different from those of the asphalt itself. 
Further, by being in the asphalt, the addition of the black liquor soap 
skimming has litle effect on the soap or water phase of the emulsion, 
which controls the rate of break. If the skimming were to be added to the 
soap or water phase, it would modify the resulting residue, but also would 
become part of the soap or water phase and could undesirably alter the 
emulsions's rate of break. 
If the skimming has a high solids content, the skimming added typically 
will be toward the lower end of its approximately 1% to approximately 5% 
range. If the skimming has a lower percentage solids, such as where 
considerable water is present in the skimming, it will be added more 
toward the higher end of its range. The amount of skimming also varies 
depending upon the asphalt. Variations in the asphalt which cause 
variation in the amount of skimming required include variations in the 
amount of petroleum-derived acids (PDA) in the particular asphalt being 
used. The higher the PDA, the less skimming will be needed. Another 
variable in determining the amount of skimming necessary is the solubility 
of the asphalt in a standard heptane-xylene mixture. A good technique for 
determining the necessary amount of skimming is simply to experiment with 
different amounts on a laboratory scale with a particular lot of asphalt 
and float test each trial to establish the optimum skimming-asphalt ratio. 
According to a second embodiment of the invention, a reacted tall oil, tall 
oil pitch, or tall oil derivatives, or combination thereof, is added to an 
asphalt cement prior to emulsification. The tall oil, pitch, derivatives, 
or combinations thereof are reacted with a strong base such as sodium 
hydroxide or potassium hydroxide in the range of about 3% to about 24% 
strong base, based on the weight of the tall oil, pitch, derivatives, or 
combinations. The range allows for the requirements of the different tall 
oil, pitch, derivatives, or combinations such as: tall oil pitch requires 
about 3% sodium hydroxide to form a suitable modifier; distilled tall oil 
requires about 16% sodium hydroxide or 24% potassium hydroxide to form a 
suitable modifier. This modifier is then added to the asphalt cement prior 
to emulsification in the range of about 0.4% to about 10% modifier, based 
on the weight of the blend, depending on the modifier and the nature of 
the asphalt being used. If the modifier were to be added to the soap or 
water phase of the emulsion, the rapid-setting characteristics would be 
lost. By making the addition to the asphalt phase, the modifier has little 
or no adverse effect on the rate of break of the emulsion. 
The exact amount of strong base depends upon the amount of rosin acids and 
fatty acids in the tall oil, pitch, derivatives, or mixtures. Distilled 
tall oil, for example, has much higher concentrations of rosin acids and 
fatty acids than tall oil pitch. Thus, distilled tall oil will require 
somewhat more strong base for addition to the asphalt. The acid number of 
the tall oil, pitch, derivatives, and mixtures thereof is one factor which 
controls the amount of strong base needed. 
The range of tall oil, pitch, derivatives, or combinations thereof, about 
0.4% to about 10%, based on the weight of the asphalt-tall oil, pitch, 
derivatives or combinations blend, is chosen to take into account 
variations in the asphalt. For example, in an asphalt with a higher PDA, 
less tall oil, pitch, derivatives or combinations will ordinarily be 
required. As another example, the greater the amount of soluble rosinous 
maltine fractions in the asphalt, the less tall oil, pitch, derivatives or 
combinations will ordinarily be required. A suitable technique for 
determining the optimum ratio of asphalt to tall oil, pitch and 
derivatives is to experiment with different ratios on a laboratory scale 
and float test each trail to establish the optimum tall oil, pitch, 
derivatives or mixtures-asphalt ratio. 
According to a third embodiment of the invention, a mixture of tall oil, 
tall oil pitch, and/or selected tall oil derivatives (illustratively, tall 
oil heads and tall oil rosins and fatty acids) is mixed with a water 
solution of a caustic composition, such as sodium hdyroxide or potassium 
hydroxide to form an emulsifier. Subsequently, this emulsifier is blended 
with the asphalt. The ratio in the blend will vary, dependent upon the 
asphalt used. For example, one asphalt may require a blend of 50 parts 
tall oil, 30 parts tall oil pitch, and 20 parts tall oil heads, while 
another asphalt from a different source may require a 45 parts tall oil, 
25 parts pitch, and 30 parts heads blend to produce an asphalt emulsion 
that is both high-float and rapid-setting. This method can be effective if 
the asphalt is not too variable. However, if there is substantial 
variability in the asphalt, as may be the case if asphalts from several 
different sources are used, the methods wherein the asphalt is treated 
prior to emulsification is preferred. 
This technique permits the user to adjust the amounts of various rosin 
acids and fatty acids in the blend through the use of various mixtures of 
various tall oil fractions. The lighter molecular weight fractions of tall 
oil (e.g., heads) typically have higher percentages of the lighter acids, 
such as fatty acids. The heavier constituents of tall oil, e.g., rosin 
acids, are typically found in higher concentrations in the heavier 
fractions, such as pitch or crude tall oil. 
In this embodiment, both the ratios of the various tall oil constituents to 
each other and the ratio of the final tall oil constituent blend to the 
asphalt will be determined based upon variables in both the asphalt (e.g., 
PDA, and soluble rosinous maltine fractions to insoluble asphaltines in 
the asphalt) and the tall oil constituents (e.g., rosin acids to fatty 
acids ratios in the pitch, crude tall oil, heads, and whatever other 
"cuts" of the tall oil distillation process are used, and nature and 
physical properties--such as weights--of the various rosin acids and fatty 
acids in the various cuts used). 
According to a fourth embodiment of the invention, a rapid-setting emulsion 
that exhibits high-float characteristics is made by modifying an asphalt 
prior to emulsification with a sufficient amount of a copolymer rubber 
such as a styrene--butadine--styrene block (SBS) copolymer or a 
styrene--isoprene--styrene block (SIS) copolymer. This may be achieved by 
adding from about 1% to about 5% of the copolymer, depending on the 
copolymer rubber chosen and whether the copolymer rubber links radially or 
straight line. This blend is then emulsified as a rapid-setting emulsion 
as described in connection with the first or second embodiments discussed 
above. This method of manufacturing a high-float rapid-setting emulsion is 
somewhat more expensive than the embodiments discussed above. However, 
these "plasticized" asphalt compositions can be used in circumstances 
where they will outperform the previously discussed compositions. For 
example, where there are very high-volume traffic areas, and particularly 
where the traffic is predominantly heavy vehicles, such as semi-tractor 
trailers and the like, at relatively high speeds, the plasticized asphalt 
compositions provide durable high-float, rapid-setting seal coats. 
These finished emulsions exhibit high-float characteristics as well as 
other desirable characteristics indicated by high float. The emulsions are 
rapid-setting, making them seal coat- or tack coat-grade materials. 
One of the desirable properties of these asphalt emulsions residues, 
related to the high float characteristics, is a lower oxidation rate, as 
defined by penetration and the percent loss in penetration after the thin 
film test, or 
##EQU1## 
Penetration, simply defined, is a measure of relative hardness. ASTM 
Standard Test method D-5 describes a typical penetration test. The test is 
conducted to determine how far a standard configuration needle penetrates 
into a sample of, for example, an asphalt emulsion residue. 
To determine the relative hardness of a particular emulsion residue, the 
penetration of the emulsion residue is measured after the water has been 
evaporated from the emulsion, and before any substantial oxidation of the 
residue is permitted to take place. Typically, this is performed at 
77.degree. F., in accordance with ASTM D-5. Subsequently, a sample of the 
residue is prepared in accordance with ASTM D-1754 by oxidation in a thin 
film oven (TFO), and the thus-oxidized residue is measured for 
penetration, again at 77.degree. F. Then a comparison is made between the 
TFO penetration and the original penetration. This comparison may take two 
forms, both of which are helpful in evaluating emulsion residues. In the 
first form, a straight ratio is generated between TFO penetration and 
original penetration. In the second form, the percentage loss in 
penetration through oxidation is calculated. This percentage loss in 
penetration calculation is made by subtracting the TFO penetration from 
the original penetration, dividing the difference by the original 
penetration, and multiplying by 100%. The lower the percentage of loss can 
be interpreted that the residue will retain its life longer than those 
with higher percentage of loss. Therefore, the high-float residues should 
have a longer life expectancy than the asphalt cement and residues not 
processing the high-float characteristics. 
Another of these desirable properties related to the high-float 
characteristics is a significant increase in the kinematic and absolute 
viscosity. ASTM Standard Test Methods D-2170 and D-2171 describe these 
tests. The greater the viscosity, the greater the stiffness or strength as 
a binder at the elevated test temperatures. Also, with viscosities at two 
test temperatures (140.degree. F. and 275.degree. F.) and penetration at a 
third test temperature of 77.degree. F., a good prediction of the 
materials temperature susceptibility can be obtained. 
The following TABLE illustrates the test results for twenty-two EXAMPLES 
performed to determine the relative quality of the instant high-float 
rapid-setting emulsions and prior art emulsions. 
There are twelve column headings in the table. They are as follows: 
1. EX. NO.--EXAMPLE number; 
2. AC SOURCE--The supplier or source of the control asphalt; 
3. AC GRADE--The asphalt specification or grade of the source asphalt; 
4. EMUL. TYPE--The emulsion type, such as RS (rapid-setting) or HFRS 
(high-float rapid-setting); 
5. Q.B.--The quick break demulsibility, measured in accordance with ASTM 
D-977 and ASTM D-244, a measure of how rapidly the emulsion "breaks," or 
sets; 
6. PEN@77.degree. F.--The penetration of the asphalt cements and the 
emulsion residues at 77.degree. F. (ASTM D-5); 
7. FLOAT@140.degree. F.--The float test in seconds on the asphalt cements 
and the emulsion residues at 140.degree. F. (ASTM D-139); 
8. VIS.@140.degree. F.--The absolute viscosity in poise on the asphalt 
cements and the emulsion residues at 140.degree. F. (ASTM D-2171); 
9. VIS.@275.degree. F.--The kinematic viscosity in centistokes on the 
asphalt cements and the emulsion residues at 275.degree. F. (ASTM D-2170); 
10. TFO PEN@77.degree. F.--The penetration of thin film oven residues (ASTM 
D-1754 and D-5) of the asphalt cements and the emulsion residues--the 
penetration at 77.degree. F.; 
11. TFO PEN/PEN--The ratio of the thin film oven penetration and the 
original penetration; 
12. % PEN LOSS--The original penetration minus the thin film penetration, 
divided by the original penetration, then times 100%.

The following EXAMPLES in TABLES I-III were formulated using the following 
asphalt cements: asphalt A-emulsion flux obtained from Ashland Oil 
Company, Inc., Refinery, Grand Island, Buffalo, New York; asphalt B-160 
penetration asphalt cement obtained from Laketon Asphalt Refining Company, 
Inc., Laketon, Indiana; asphalt C-emulsion flux obtained from Exxon 
Refinery, Bayonne, New Jersey; asphalt D-emulsion flux obtained from Arco 
Petroleum Products Company Refinery, Marcus Hook, Pennsylvania; and 
asphalt E-150/200 penetration asphalt cement from Amoco Oil Company 
Refinery, Whiting, Indiana. 
EXAMPLES I-1 and I-2 were high-float, rapid-setting (HFRS) emulsions made 
in accordance with the first embodiment of the present invention, and 
having properties as outlined in TABLE I. 
EXAMPLES I-3--I-5 were HFRS emulsions, made in accordance with the second 
embodiment of the invention, and had the properties outlined in TABLE I. 
EXAMPLES I-6--I-10 were HFRS emulsions, formulated according to the third 
embodiment of the invention. Five examples were performed to demonstrate 
that the mixture of tall oil, tall oil pitch, and/or selected tall oil 
derivatives can vary substantially, dependent upon the particular asphalt 
being emulsified, and the characteristics of that asphalt, which are not 
always readily identifiable. Variations in these characteristics account 
for a broad range for the various tall oil components. However, as 
discussed above, these ratios are considerably less variable if asphalt 
from a particular source can be obtained, and the physical and chemical 
characteristics of that asphalt are consistent. The properties of the 
emulsions of EXAMPLES I-6--I-10 are as outlined in TABLE I. 
EXAMPLES I-12 and I-13 were HFRS emulsions formulated according to the 
fourth embodiment described above. The emulsions of EXAMPLES I-12 and I-13 
exhibited the properties outlined in TABLE I. 
EXAMPLES II-1--II-5 were controls formulated in accordance with prior art 
rapid-setting (RS) emulsion techniques, with properties as outlined in 
TABLE II. 
The control emulsion of EXAMPLE II-1 was prepared as follows: 700 grams of 
asphalt A were mixed with 300 grams of treated water which contained 3.5 
grams tall oil, derivatives or combinations thereof, 0.525 grams of sodium 
hydroxide, and about 294 grams of water. The weight of the finished 
emulsion was about 1,000 grams. 
In EXAMPLE II-2, 700 grams of asphalt B were combined with 300 grams of 
treated water containing 3.5 grams of tall oil, derivatives or 
combinations thereof, 0.525 grams of sodium hydroxide and about 294 grams 
of water. The weight of the finished emulsion was about 1,000 grams. 
In EXAMPLE II-3, 700 grams of asphalt C were combined with 300 grams of 
treated water which contained 2.8 grams of tall oil, derivatives or 
combinations thereof, 0.42 grams of sodium hydroxide, and about 294 grams 
of water. The weight of the finished emulsion was about 1,000 grams. 
In EXAMPLE II-4, 700 grams of asphalt D were combined with 300 grams of 
treated water containing 3.5 grams of tall oil, derivatives or 
combinations thereof, 0.525 grams of sodium hydroxide, and about 294 grams 
of water. The weight of the finished emulsion was about 1,000 grams. 
In EXAMPLE II-5, 700 grams of asphalt E were combined with 300 grams of 
treated water, including 3.5 grams of tall oil derivatives or combinations 
thereof, 0.525 grams of sodium hydroxide, and about 294 grams of water. 
The weight of the finished emulsion was 1,000 grams. 
As will be appreciated, in each of these EXAMPLES, the weight of tall oil, 
derivatives or combinations thereof based on the weight of the total 
emulsion was about 0.35%. The tall oil was reacted with about 15%, by 
weight of the tall oil, derivatives or combinations, of sodium hydroxide. 
In EXAMPLE I-1, 686 grams of asphalt A were combined with 14 grams of black 
liquor soap skimming to provide a total weight of 700 grams asphalt 
A/black liquor soap skimming. Thus, the weight of black liquor soap 
skimming based upon the total weight of asphalt A/black liquid soap 
skimming, was 2%. This was then combined with 300 grams treated water 
which contained 3.5 grams of tall oil, derivative or combinations thereof, 
0.525 grams of sodium hydroxide, and about 294 grams of water. Thus, the 
total weight of the finished emulsion was 1,000 grams. The emulsion 
included 68.6% asphalt A, 1.4% black liquor soap skimming, 0.35% tall oil, 
derivatives or combinations thereof, 0.0525% sodium hydroxide, and 29.4% 
water. 
In EXAMPLE I-2, 693 grams asphalt A were combined with 7 grams black liquor 
soap skimming. This mixture was then combined with 300 grams treated water 
containing 2.8 grams of tall oil, drivatives or combinations thereof, 0.42 
grams sodium hydroxide, and about 296.8 grams of water. The amount of 
black liquor soap skimmings in the blend was thus 1% of the combined 
asphalt A/black liquor soap skimming combination, or about 0.7% by weight 
of the finished emulsion. The asphalt A comprised about 69.3% of the 
weight of the finished emulsion, the tall oil, derivatives or combinations 
in the treated water comprised about 0.28% of the finished emulsion, the 
sodium hydroxide comprised about 0.042% of the finished emulsion, and the 
water comprised about 29.68% of the finished emulsion. 
In both of EXAMPLES I-1 and I-2, the black liquor soap skimming had a 
solids content of approximately 65%. Had the solids content of the black 
liquor soap skimming been lower (normally it is 50% or less), more of the 
black liquor soap skimming would have been required, and thus the black 
liquor soap skimming would have formed a somewhat larger percentage of the 
total weight of the finished emulsion. 
In EXAMPLE I-3, a HFRS emulsion formulated in accordance with the second 
embodiment, 697.2 grams asphalt B were combined with 2.8 grams of tall 
oil, derivatives or combinations thereof which had already been reacted 
with 12%, by weight of the tall oil, derivatives or combinations therof, 
of sodium hydroxide. Thus, approximately 0.336 grams of sodium hydroxide 
was reacted with approximately 2.464 grams tall oil, derivatives or 
combinations thereof. This mixture was then combined with 300 grams 
treated water containing 3.5 grams tall oil, derivatives or combinations 
thereof, 0.525 grams sodium hydroxide, and about 294 grams water. The 
weight of the finished emulsion was thus about 1,000 grams, with asphalt B 
comprising about 69.7% of the weight of the finished emulsion, water 
comprising about 29.4% of the weight of the finished emulsion, sodium 
hydroxide comprising about 0.861% of the weight of the finished emulsion 
and tall oil, derivatives or combinations thereof comprising about 0.5964% 
of the weight of the finished emulsion. 
In EXAMPLE I-4, 693 grams of asphalt B was first combined with 7.0 grams 
tall oil, derivatives or combinations thereof, which had been reacted with 
about 10% by weight (0.7 grams) sodium hydroxide. This mixture was then 
combined with 300 grams of treated water containing 2.1 grams of tall oil, 
derivatives or combinations thereof, 0.315 grams of sodium hydroxide, and 
about 297.6 grams water. The weight of the finished emulsion was 
approximately 1,000 grams. Asphalt B comprised about 69.3% of the weight 
of the finished emulsion. The water comprised about 29.76% of the weight 
of the finished emulsion. The tall oil, derivatives or combinations 
thereof comprised about 0.91% of the weight of the finished emulsion. The 
sodium hydroxide comprised about 0.1015% of the weight of the finished 
emulsion. 
In Example I-5, 665 grams of asphalt C were combined with 35 grams of tall 
oil derivatives or combinations thereof which had already been reacted 
with 3%, by weight of the tall oil, derivatives or combinations thereof, 
of sodium hydroxide. Thus approximately 1.05 grams of sodium hydroxide 
were reacted with the approximately 34 grams tall oil, derivatives or 
combinations thereof. This mixture was then combined with 300 grams of 
treated water containing 1.75 grams of tall oil, derivatives or 
combinations thereof, about 0.263 grams of sodium hydroxide, and about 298 
grams of water. The weight of the finished emulsion was approximately 
1,000 grams. Of that, 66.5% was asphalt C, 29.8% was water, 3.575% was 
tall oil, derivatives or combinations thereof, and 0.1313% by weight was 
sodium hydroxide. 
In the embodiments of EXAMPLES I-3 and I-4, the tall oil and tall oil 
derivatives blends had higher acid numbers and therefore required less of 
the modifier. In EXAMPLE I-5, the tall oil, derivatives or combinations 
thereof had a lower acid number and more modifier was required. 
EXAMPLES I-6--I-10 and III-1--III-5 were all prepared using the third 
embodiment of the invention, with the same quantity of asphalt (700 grams) 
and the same quantity of treated water (300 grams). However, in the 
treated water, different mixtures of tall oil, derivatives or combinations 
thereof were used. Specifically, in EXAMPLES I-6, III-5, and I-8, the 300 
grams treated water contained 2.1 grams tall oil heads (25 parts), 2.1 
grams tall oil pitch (25 parts), and 4.2 grams crude tall oil (50 parts), 
as well as 1.1 grams sodium hydroxide and 290.5 grams water. Of these, 
EXAMPLES I-6 and I-8 formed acceptable HFRS emulsions, with the emulsion 
of EXAMPLE III-5 being less than acceptable as a HFRS emulsion. 
EXAMPLES I-7 and I-10 both were formulated utilizing 2.4 grams tall oil 
heads (29.1 parts), 2.5 grams tall oil pitch (29.7 parts), and 3.5 grams 
crude tall oil (41.2 parts), as well as 1.2 grams sodium hydroxide and 
290.4 grams water. EXAMPLES I-7 formed an acceptable HFRS emulsion, even 
though it employed the same asphalt as EXAMPLE III-5 which did not form an 
acceptable HFRS emulsion. EXAMPLE I-10 formed a borderline HFRS emulsion, 
although it used the same asphalt as EXAMPLE I-8 which formed a much more 
acceptable HFRS emulsion. 
The emulsion of EXAMPLE III-1 was formulated using 4.2 grams tall oil heads 
(50 parts) and 4.2 grams crude tall oil (50 parts), as well as 1.2 grams 
sodium hydroxide and 290.4 grams water. The asphalt emulsion of EXAMPLE 
III-1 was somewhat less than acceptable as an HFRS emulsion, although it 
employed the same asphalt as EXAMPLE I-7 which did provide an acceptable 
HFRS emulsion. 
EXAMPLE III-2 employed 4.9 grams (100 parts) distilled tall oil, as well as 
0.8 grams sodium hydroxide and 294.3 grams water. EXAMPLE III-2 provided a 
less than suitable HFRS emulsion. However, it used the same asphalt as did 
EXAMPLE I-7 which provided an acceptable HFRS emulsion. 
EXAMPLE III-3 included 7 grams tall oil pitch (50 parts) and 7 grams tall 
oil (50 parts) in addition to 2 grams sodium hydroxide and 284 grams 
water. Although it employed asphalt C, which had formed a suitable HFRS 
emulsion in EXAMPLE I-7, the emulsion of EXAMPLE III-3 was a less than 
satisfactory HFRS emulsion. 
EXAMPLE III-4 employed 4.2 grams tall oil pitch (50 parts), 4.2 grams tall 
oil (50 parts), 1.2 grams sodium hydroxide, and 290.4 grams water. Again, 
although asphalt C, which had formed a suitable HFRS emulsion in EXAMPLE 
I-7, was used, the emulsion of EXAMPLE III-4 was not a suitable HFRS 
emulsion. 
EXAMPLE I-9 was formulated to include 3.6 grams tall oil heads (42.7 
parts), 2.3 grams tall oil pitch (27.4 parts), 2.5 grams crude tall oil 
(29.9 parts), as well as 1.3 grams sodium hydroxide and 290.3 grams water. 
Although this formulation used asphalt D, which had been used in the 
preparation of a suitable HFRS emulsion in EXAMPLE I-8, the EXAMPLE I-9 
emulsion was less than satisfactory as a HFRS emulsion. 
The specific percentages of the various constituents in EXAMPLES I-6--I-10 
and III-1--III-5. 
EXAMPLE I-6 70% by weight, asphalt A; 29.05% water: 0.21% by weight tall 
oil heads; 0.21% by weight tall oil pitch; 0.42% by weight crude tall oil; 
and 0.11% by weight sodium hydroxide. 
EXAMPLE I-7, 70% by weight; asphalt C; 29.04% water; 0.24% tall oil heads; 
0.25% tall oil pitch; 0.35% crude tall oil; and 0.12% sodium hydroxide. 
EXAMPLE III-1 was formulated using 70% asphalt C; 29.04% water; 0.42% tall 
oil heads; 0.42% crude tall oil; and 0.12% sodium hydroxide. 
The EXAMPLE III-2 formulation included 70% asphalt C; 29.43% water; 0.49% 
distilled tall oil; and 0.08% sodium hydroxide. 
EXAMPLE III-3 included 70% asphalt C; 28.4% water; 0.7% tall oil pitch; 
0.7% tall oil; and 0.2% sodium hydroxide. 
EXAMPLE III-4 employed 70% asphalt C; 29.04% water; 0.42% tall oil pitch; 
0.42% tall oil; and 0.12% sodium hydroxide. 
EXAMPLE III-5 was formulated using 70% asphalt C; 29.05% water; 0.21% tall 
oil heads; 0.21% tall oil pitch; 0.42% crude tall oil; and 0.11% sodium 
hydroxide. 
Example I-8 formulation included 70% asphalt D; 29.05% water; 0.21% tall 
oil heads; 0.21% tall oil pitch; 0.42% crude tall oil; and 0.11% sodium 
hydroxide. 
The EXAMPLE I-9 formulation was blended using 70% asphalt D; 29.03% water; 
0.36% tall oil heads; 0.23% tall oil pitch; 0.25% crude tall oil; and 1.3% 
sodium hydroxide. 
EXAMPLE I-10 was formulated employing 70% asphalt D; 29.04% water; 0.24% 
tall oil heads; 0.25% tall oil pitch; 0.35% crude tall oil; and 0.12% 
sodium hydroxide. 
EXAMPLE I-11 was formulated employing 70% asphalt C; 28.9% water; 0.49% 
tall oil pitch; 0.49% tall oil; and 0.14% sodium hydroxide. 
EXAMPLES I-12 and I-13 were formulated using the fourth embodiment of the 
present invention. Specifically, styrene-isoprene-styrene block copolymer 
was added to an asphalt prior to emulsification. In the embodiment of 
EXAMPLE I-12, the SIS copolymer was added to a percentage by weight of an 
asphalt/fuel oil/copolymer blend of about 1%. In EXAMPLE I-13, the SIS 
copolymer was added to a percentage by weight of about 3% of an 
asphalt/fuel oil/copolymer blend. 
Specifically, in EXAMPLE I-12, 665 grams of asphalt E was blended with 7 
grams SIS copolymer and 28 grams No. 2 fuel oil. This blend was then 
emulsified with treated water including 3.5 grams tall oil, derivatives or 
combinations thereof; 0.525 grams sodium hydroxide and about 294 grams of 
water for a finished emulsion having a weight of 1,000 grams. Thus, the 
relative weights of the constitutents in the finished emulsion included 
66.5% asphalt E; 0.7% by weight SIS copolymer; 2.8% by weight No. 2 fuel 
oil; 29.4% by weight water; 0.35% by weight tall oil, derivatives or 
combinations thereof; and 0.0525% by weight sodium hydroxide. This blend 
formed a suitable HFRS emulsion. However, SIS copolymer is a 
radial-linking copolymer. A greater percentage by weight of the copolymer 
may be necessary in a particular blend if a linear linking copolymer (such 
as SBS) is used. 
In EXAMPLE I-13, a blend of 651 grams asphalt E, 21 grams SIS copolymer, 
and 28 grams of No. 2 fuel oil was prepared. In this blend, the SIS 
copolymer formed about 3% by weight of the asphalt/No. 2 fuel 
oil/copolymer blend. This was then combined with treated water including 
3.5 grams tall oil, derivatives or combinations thereof, 0.525 grams 
sodium hydroxide, and about 294 grams of water. Thus, the relative 
percentages by weight of the various constitutents in this emulsion were 
65.1% asphalt E; 2.1% SIS copolymer; 2.8% No. 2 fuel oil; 29.4% water; 
0.35% tall oil, derivatives or combinations thereof; and 0.0525% sodium 
hydroxide. Again, this emulsion was a suitable HFRS emulsion. 
Finally, it should be noted that the precise chemical identity of the tall 
oil, derivatives or combinations mix is dependent in large part upon the 
source of the mix. Tall oil generally is a by-product of the process of 
manufacturing kraft paper. In the process, a particular wood, 
illustratively pine, is digested with sodium hydroxide and sodium sulfide 
in water solution. When the waste liquid from digestion is concentrated by 
evaporation, certain sodium soaps of rosin acids and fatty acids coagulate 
into a superficial layer which is skimmed from the liquid and acidified 
with sulfuric acid to produce crude tall oil. As may be appreciated, 
different tall oils may require different amounts of the caustic compound 
to form the water soluble emulsifier. The amount of the caustic compound 
required is attributable to the different saponification numbers of the 
various compounds of crude tall oil. The identities of these components 
and the determination of the relative concentrations and saponification 
numbers depend, in part, on the type of wood digested and the particular 
process for manufacturing the crude tall oil. It may be appreciated, for 
example, that the crude tall oil itself may contain a small percentage of 
sodium hydroxide already in it, owing to the method of manufacture of 
crude tall oil. 
It further should be appreciated that, while sodium hydroxide was the 
caustic compound used in the examples because of its relatively low cost, 
potassium hydroxide could also be used. The amount of potassium hydroxide 
necessary to obtain a water soluble emulsifier may vary from the typically 
10% to 15%, by weight, of caustic compound to tall oil illustrated in the 
examples. However, such variations can be readily determined without undue 
experimentation. 
As used in this specification and in the claims appended hereto, the term 
"emulsifier" shall have the same meaning as the term "soap concentrate" as 
that term is used in the field. It is the mixture which reacts in the 
reactor tank or kettle. As used in this specification and in the claims 
appended hereto, the term "cut-back emulsifier" shall have the same 
meaning as the terms "run water" and "soap water" as those terms are used 
in the field. 
TABLE I 
__________________________________________________________________________ 
HFRS EMULSIONS 
TFO TFO 
EX AC AC EMUL 
DEMUL 
PEN FLOAT VIS VIS PEN PEN % PEN 
NO. 
SOURCE GRADE TYPE 
QB @77.degree. F. 
@140.degree. F. 
@140.degree. F. 
@275.degree. F. 
@77.degree. F. 
PEN LOSS 
__________________________________________________________________________ 
I-1 
ASHLAND 
EMUL.FLUX 
HFRS 
63.1 93 1200+ 3303 17,562 
76 .817 18.3 
I-2 
ASHLAND 
EMUL.FLUX 
HFRS 
82.1 71 1200+ 
I-3 
LAKETON 
160 PEN HFRS 
66.9 135 1200+ 
I-4 
LAKETON 
160 PEN HFRS 
90.4 130 1200+ 4120 MATERIAL WOULD NOT 
FLOW UNDER 
TEST CONDITIONS 
I-5 
EXXON EMUL.FLUX 
HFRS 
77.9 160 1200+ 
I-6 
ASHLAND 
EMUL.FLUX 
HFRS 
97.5 127 1200+ 1033 1079 
108 .850 15.0 
I-7 
EXXON EMUL.FLUX 
HFRS 
98.5 131 1200+ 1514 
I-8 
ARCO EMUL.FLUX 
HFRS 
95.5 15.7 1200+ 
I-9 
ARCO EMUL.FLUX 
HFRS 
31.0 150 1200+ BORDERLINE DEMULSIBILITY 
I-10 
ARCO EMUL.FLUX 
HFRS 
32.8 155 1200+ BORDERLINE DEMULSIBILITY 
I-11 
EXXON EMUL.FLUX 
HFRS 
81.4 122 1200+ 
I-12 
AMOCO 150/200 PEN 
HFRS 
86.4 105 1200+ 
I-13 
AMOCO 150/200 PEN 
HFRS 
98.4 140 1200+ 
__________________________________________________________________________ 
TABLE II 
__________________________________________________________________________ 
PRIOR ART RS EMULSIONS WITH 
ASPHALTS OF EXAMPLES I-1 - I-13 
TFO 
EX AC AC EMUL 
DEMUL 
PEN FLOAT 
VIS VIS PEN TFO 
% PEN 
NO. 
SOURCE GRADE TYPE 
QB @77.degree. F. 
@140.degree. F. 
@140.degree. F. 
@275.degree. F. 
@77.degree. F. 
PEN LOSS 
__________________________________________________________________________ 
II-1 
ASHLAND 
EMUL.FLUX 
RS 94.6 114 660 915 498 86 .754 24.6 
II-2 
LAKETON 
160 PEN RS 84.7 103 682 
II-3 
EXXON EMUL.FLUX 
RS 72.9 127 256 
II-4 
ARCO EMUL.FLUX 
RS 92.6 147 500 
II-5 
AMOCO 150/200 PEN 
RS 99.3 137 379 
__________________________________________________________________________ 
TABLE III 
__________________________________________________________________________ 
EXAMPLES OF EMBODIMENT 3 WHICH DEMONSTRATE 
THE ASPHALT SENSITIVITY OF THIS EMBODIMENT 
EX AC AC EMUL 
DEMUL 
PEN FLOAT 
VIS VIS TFO PEN 
TFO 
% PEN 
NO. 
SOURCE 
GRADE TYPE 
QB @77.degree. F. 
@140.degree. F. 
@140.degree. F. 
@275.degree. F. 
@77.degree. F. 
PEN LOSS 
__________________________________________________________________________ 
III-1 
EXXON EMUL.FLUX 
HFRS 
22.1 128 1074 DID NOT PASS FLOAT OR DEMULSIBILITY 
III-2 
EXXON EMUL.FLUX 
HFRS 
34.6 125 412 DID NOT PASS FLOAT OR DEMULSIBILITY 
III-3 
EXXON EMUL.FLUX 
HFRS 
23.3 145 1200+ 
DID NOT PASS DEMULSIBILITY 
III-4 
EXXON EMUL.FLUX 
HFRS 
93.4 119 766 DID NOT PASS FLOAT 
III-5 
EXXON EMUL.FLUX 
HFRS 
48.6 129 744 DID NOT PASS FLOAT OR 
__________________________________________________________________________ 
DEMULSIBILITY