CA2102311A1 - Bitumen emulsions - Google Patents

Abstract

A bitumen emulsion comprising 40 to 80 wt. percent bitumen, 0.05 to 1.0 wt. percent emulsifier and 14 to 59.95 wt. percent water, the emulsion being substantially free of organic solvent, and containing emulsified bitumen droplets having a mean particle size of from 2 to 10 micrometres with a standard deviation of no more than 0.3. The emulsion is produced using a static mixing process.
The emulsion can be used, for example, in road repair applications and has the advantage that the emulsion can be prepared and stored before use ('delayed-set') without the need to include organic solvent in the emulsion mix.

Description

~1 21.~?.~11.

BITUMEN EM~I~SIONS

This invention relates to bitumen emulsions, mixes of bitumen emulsions with aggregate material, and their use in road-making and similar operations.
.
Many road surfaces are constructed, maintained and repaired using mixes of aggregate material with bitumen binder. In tne field of road repair this aggregate-bitumen mix is typically employed in one of the following forms:

(i) A hot mix of aggregate and heated bitumen.
This method has the advantage that it sets xapidly after application to the road surface, but the disadvantage is that it must be mixed, transported to the roadside and used immed~ately to prevent premature setting on cooling. In addition the hot bitumen is a hazard to road workers, potentially causing burns and scalds.

~ A mix of aggregate and cut-back asphalt, i.e. bitumen diluted with an organic solvent such as kerosene or creosote to provide wor~ability to the aggregate-bitumen mix. This has the advantage that it can be applied at ambient or near ambient temperatures and there can be some time delay, if desired, between preparing the mix and applying it to the surface.
However it h~s the disadvantage that the bitumen takes longer to hard~n after application to the road surface, as the rate of hardening is dependent upon evaporation of the solvent, and, even so, some solvent remains in the bitumen cl.~sing the road surface to be slightly soft Ql IR~C~TITI ITF !~::HFFT

WO92/1~ PCT/EP92~00935 2 1 ~
and therefore have a tendency to deform under the weight of passing traffic. Furthermore the evaporation of the solvent into the atmosphere during hardening of the bitumen is an environmental pollutant and therefore undesirable. -(iii) A mix of aggregate and bitumen-in-water emulsion. This method has the advantage that it can be applied to the road surface at ambient temperature but the disadvantage that it must be applied immediately as the action of mixing the aggregate with the emulsion causes the emulsion to break, i.e. the bitumen and water phases separate, and the bitumen starts to harden. To increase the stability of the emulsion, and hence storage capability of the mix, increased amounts of emulsifier can be included in the emulsio~, but this has the disadvantage that the emulsion c~n ta~e a considerable time to break after application to the road, which delays the hardening of the bitumen and increases the time that the road has to be closed to traffic. Alternatively the storage life of the mix can ^~
be improved by adding organic solvent to the emulsion, but this has the disadvantage of a soft road surface and pollution as described under (ii) above for the cut-back asphalt mixes.

There is therefore a need for an aggregate-bitumen mix which co~bines the advantages of delayed-set properties before application to a surface, for example a road surface, together with rapid setting properties after it has been applied to the surface.

The present invention pro~ides a bitumen emulsion comprising by weight based on the total weight of the emulsion:

C~l IQ~TITI ITC ~LI~T

Wo92/19683 PCT/EP92/~935 a) 40 to ~5 per cent bitumen:
b) 0.05 to 1.0 per cent emulsifier; ~
c) 14 to 59.95 per cent water, ;

the emulsion being substantially free of organic solvent, and containing emulsified bitumen droplets having a mean particle size of from 2 to 10 micrometres ;
(um) with a standard de~iation of no more than 0.3.
, .
We have found that by using bitumen droplets which have a particle size that is within a specific range and is substantially uniform, it is possible to form an emulsion which remains sufficiently stable when mixed with aggregate to act as a delayed-set emulsion without the need for an organic solvent and/or increased amounts of emulsifier, but which breaks suf~iciently quickly after it has been applied to the road so there is as short a time as possible before the road can ~e opened to traffic. ~he absence or substantial absence of solvent provides an ' n~ironmentally friendly' emulsion with little, if any, pollutants evaporating into th~ atmosphere when the emulsion breaks. The absence of solvent also has the advantage that, once the emulsion has broken, the road surface sets completely and is not subject to d~maging deformation.

Preferably the bitum~n droplets in the emul~ion according to the inYention have a mean particle size of from 3 to 9 ~m, more preferably from 5 to 8 ~m. The standard deviation of this mean is preferably no more than 0.2, for example in the range from 0.1 to 0.2.

The bitumen employed in the emulsion may be any commercially available natural or petroleum-based bitumen (also known as asphalt) suitable for use in road construction, maintenance and repair. It may be a C~l II~C!`TITI IT~ ~Ll~. -WO92/1~#~ PCT/EPg2/00935 straight-run b;tumen or a blown or oxidised grade. The penetration (IP 49) may vary from 20 to 500 at 25C, preferably 50 to 400, more preferably 100 to 250. Its Ring and Ball softening point (IP 58) is generally from 35 to 100C, preferably 35 to 60C. The amount of bitumen contained in the emulsion is from 40 to 85 weight percent, preferably 50 to 75 percent, more preferably 60 to 70 percent, based on the total weight of the emulsion.

The amount of emulsifier employed may range from O.OS to 1.0 weight percent, but usually an amount from 0.1 to 0.5 wt.%, more preferably 0.2 to 0.4 wt.% is employed, i.e. a typical amount of emulsifier for a bitumen emulsion. The emulsifier may be cationic, anionic or non-ionic, or a mixture of cationic and non-ioni~, or anionic and non-ionic emulsifiers, depending upon the chemical nature of the aggregate with which the emu~ion is to be mixed, and upon the desired electrochemical properties of the emulsion.

Suitable cationic emulsifiers include hydro-chlorides of fatty amines, fatty amido-amines, ethoxylated amines, imidoazalines, quartenary ammonium salts, and mixtures thereof. Preferably the cationic emulsifier is a diamine, for example tallow diamine hydrochloride, and more preferably is a mixture of a diamine with a quatenary ammonium salt. When a cationic emulsifier is employed, it is preferred to include an acid in the bitumen emulsion to counteract the alkalinity of the emulsifier. Generally acid is added to adjust the pH of the emulsion to approximately pH 3. Typically from 0.05 to 0.5, preferably from 0.1 to 0.3, weight percent acid based on the total weight of the emulsion is added. Suitable acids include inorganic acids, for example hydrochloric acid. `

~ TI ~S~ C~T

WO9~1 ~ 3 PCT/EP92/ ~ 35 Suitable anionic emulsifiers include long chain carboxylic and sulphonic acids, their salts and mixtures thereof.
~..
Suitable non-ionic emulsifiers include ethoxylated compounds, for example ethoxylates of sorbitan esters, alcohols and alkyl phenols, and mixtures thereof.

A salt, for example a mineral salt such as calcium chloride, may be included in the emulsion according to the invention to balance the salinity, and als/- to modify the emulsion viscosity. If a salt is employed, typically the amount is from 0.05 to 0.5, preferably from 0.1 to 0.3 weight percent based on the total weight of the emulsion.

If desired, the bitumen may be modified by tle incorporation into the bitumen o~ a polymeric additive, for example ethylene-vinyl acetate or styrene-butadiene poly-nrs, or mixtures thereof. These can be added in amounts up to about 25 weight percent based on the total weight of the emulsion. The polymers modify the bitumen to increase its resilience, which is benefi-cial, for example, when the bitumen is used for a road surface subject to heavy traffic.

The xemainder of the bitumen emulsion according to the invention comprises water. This remainder may be from 14 to just under 60 weight percent, but is preferably 20 to 50 percent, more preferably 30 to 40 percent, based on the total weight of the emulsion.
The emulsion is usually produced as a bitumen-in-water emulsion, i.e. the bitumen particles are surrounded by water molecules, although it may alternatively be produced as a water-in-bitumen emulsion.

~; QI IR~TITI ITC C~UC~T

W092/t9683 ~ PCT/EP92/00935 The bitumen emulsion may ~e prepared by a static mixing process as disclosed in published European Patent Application 283246A, the disclosure of which is incorporated herein by reference. The process preferably comprised the following steps:

a) feeding the bitumen into a first static mixer at a temperature above 50C;
b) introducing water under pressure into the first static mixer, the pressure being sufficient to preve~t substantial vapoJisa-tion of the water, the weight ratio of water to bitumen in the first static mixer being between 3:1 and 35:1;
c) introducing the em~lsifier into the first static mixer;
d) mixing the components in the first static mixer, and,then passing the resultant mixture from the first static mixer into at least one other mixer in which the temperature is below the boiling point of water;
e) introducing water into the other mixer(s) in an amount such that the total amount of water present in the resulting e~ulsion is from 14 to 60% by weight based on the total weight of the eml~lsion; and f) passing the mixture through the other mixer(s) and removing the resulting bitumen emulsion.

Preferably the said other mixer is also a static mixer .

5UBSTITUTE SHEET ~

W092/l9~3 PCT/EP92/00935 2~11 .
To facilitate the introduction of the emulsifying agent into the first static mixer, the emulsifier, in part or in total, may be mixed with the water to be added to the first mixer to form an aqueous solution or "soap". If desired, the bitumen may be premixed with the water and/or the emulsifying agent prior to introduction into the first mixer.

The bitumen is preferably introduced into the first static mixer at a temperature of 100 to 200C, more preferably 120 to 190C, and at a pressure of 2 to 80 bars, more preferably 10 to 30 bars. The water or soap is preferably introduced into the same mixer at a temperature of 20 to 70C, more preferably 30 to 50C, and also at a pressure of 2 to 80 bars, more preferably 10 to 30 bars. The temperature in the first mixer is usually 70 to 250C, more preferably 100 to 150C. A
high temperature facilitates the emulsification of the bitumen and water, and the relatively high pressure prevents the water from evaporating.

It is preferred to pass the resultant mixture from the first static mixer directly into the other mixer, which is also preferably a static mixer. The remainder of the water is introduced into this other mixer, preferably cold, for example 50 to 20C, ~o that it cools the emulsion enabling the resultant emulsion to exit the other mixer below the boiling point of water.
It is al50 advantageous to operate this other mixer at a reduced pressure relative to the first mixer so that the emulsion emerges from the other mixture at atmospheric pressure.

If other additives are to be included in the emulsion, they may be added at any stage during the process, although are preferably added to the first SUBSTITUTE SHEET

W092/1g683 2 i ~3 ~ 3 1 1 pcr/Ep92/oog3s static mixer to ensure thorough mixing, and conveniently are added at the same time as the emulsifier. If they are water soluble, as in an inorganic acid and/or a metal salt, they may be added to the water-emulsifier soap.

The process is preferably a two-mixer process, but more than two mixers may be used. These additional mixers may be static mixers or other types of mixers, such as a colloid mill. Examples of suitable static mixers are those known as Sulzer or Kenics mixers, which are well known to those skilled in the art of static mixing.

The bitumen emulsion may be used in the construc-tion, maintenance and repair of road surfaces and in other applications where bitumen is required. However, the bitumen emulsion is especially beneficial fôr mixing with aggregate to be used for road repair, for example the filling in of cracks and pot-holes caused for example by the passage of heavy and/or frequent vehicles or frost damage, and trenches dug to bury pipelines or cable, for example, under the road. Road repair often requires the use of relatively small amounts of aggregate mix and the delayed-set property of the aggregate-em~lsion mix of the invention enables one larger amount of mix to be prepared and stored, with small quantiti2s being taken from the stored mix as and when needed.

In use the bitumen emulsion is mixed with aggregate, which may be of any type of aggregate suitable for the required application, provided the bitumen contains an emulsifier appropriate for the type Sl lBSTITUTE SHEET :

WO92/1~3 PCT/EP92/~s35 ?, ~ Q '~ 3 1 1 of aggregate selected, and is usually either siliceous or calcareous. The aggregate is mixed with the emulsion using conventional mixing techniques, typical proportions of aggregate to emulsion being from 6:1 to 30~

The emulsion-aggregate mix can be app~ied to the road using con~entional techniques. It may be applied hot or cold, although for ease of handling it is applied at ambient temperatures, for example from 10 to 25C. Once the emulsion-aggregate mix has been applied to the road the emulsion breaks and the bitumen hardens relatively rapidly and the road surface is ready for use. The actual time taken for the bitumen to harden depends upon a number of factors in addition to the characteristics of the bitumen emulsion including the speed and pressure of compaction of the bitumen-aggregate layer, for example by rolling; the porosity of the surface to w~ich the emulsion-aggregate mix is being applied; the chemical and physical influence of the aggregate; and the weather conditions. Neverthe-less the uniformity of the bitumen droplet size in the emulsion and the absence of organic solvent and excessive amounts of emulsifier significantly assist the breaking of the emulsion so that the hardening of the bitumen is generally fast~r than would be expected for conventional delayed-set mixes. The bitumen hardening time for a surface prepared from an emulsion-aggregate mix according to the invention may vary, for example, from about 10 minutes to a number of days, for example 5 days or more, but usually the surface can be used by traffic as soon as the mix has been compacted, especially in the case of road repair.

~'~l IR~:TITUTE SHEET

WO 92/19683 PCr/EP92/00935 21~311 ' '` ", The invention shall now be illustrated by the following examples:

Exam~le I

A bitumen emulsion having the following composition and properties was prepared. The percentages of components are weight percents based on the total weight of the emulsion unless otherwise specified:

Bitumen: Amount 64%
Penetration 25C/10 mm/5 sec 200 Ring and Ball softening point 39C

Emulsifier (N-tallow diamine hydrochloride) 0.6~ ~
Hydrochloric acid 0.2%. ~-Calcium chloride 0.2%
Water 35%
, .
The emulsion was prepared using a two-stage static mixing process as disclosed in published European patent application 0283246A2. The two static mixers employed were both Kenics mixers of the type described in Chemineers brochure 80~E published by Chemineers Ltd~, 1984. The bitumen and a soap solution comprising the emulsifier, hydrochloric acid, calcium chloride and one-third of the total amount of the water were in~ected into the first static mixer. The bitumen was injected under a pressure o* 2400 kPa and was at a temperature of 150C. The soap solution and water were both injected under a pressure of 2400 kPa and at a temperature of 50C. The flowspeed into the first static mixer was about 14m/sec and the flowrate about 15m3/hr. The shear produced by the first static mixer was calculated, based on the Darcy equation and taking C~l IQC!TITI ITC C~LICCT

W092/1~3 PCT/EP92/~35 flowspeed, ~lowrate and size of pipes into account, to be about 35,000 sec~~

After passing through the first static mixer, the mixture was fed directly into the second static mixer into which the remainder of the water was in~ected at a pressure of 400 kPa and a temperature of about 18C.
The shear rate in the second static mixer was calculated to be about 5,000 sec~l and the flowrate was about 2Om3 per hour. After passing through the second mixer the resulting emulsion exited at atmospheric pressure and a temperature of about 85C. The total amount of water present in the mixture was 35% by weight of the total weight of the final product.

Using a Coulter particle size analyser the emulsion was found to contain bitumen droplets having a median particle diameter of 5.5~um and a standard deviation of 0.18.

An aggregate/bitumen emulsion mix was prepared by combining 93.8 wt.% limestone aggregate and 6.2 wt.% of the above bitumen emulsion. The size gradings of the aggregate conformed to British Standard 4987 (Table S) for a 20 mm dense graded base coarse macadam and were as follows:

0-2 mm 30%
2-6 mm 15%
6-10 mm 10%
10-14 mm 15~
14-20 mm 30%

The aggregate and emulsion were mixed together at ambient temperature using a conventional mixer and mixing was continued until the emulsion had coated the aggregate particles.

~1 IQC!TITI IT~ C~U~T

WO92~ 3 pcT/Epg2~oD93s ~1~
The2~e~ mix was laid into damaged areas and pot-holes in a macadam simulated road surface. The mix was spread and approximately levelled by a hand-held leveller in the usual manner. It was then compacted into place by a small vibrating hard-steel roller machine, the mix becoming hard on compaction.

The road, which had been closed to traffic during repair, was re-opened immediately after the mix had been compacted. During the following 4-6 hours after compaction the water separated and flowed from the emulsion and the repaired patches began to harden. The macadam reached its normal strength of ~0 mm pen within about 4 days.

To test the ability of the aggregate/bitumen emulsion mix during storage a sample of the mix was placed in an open container and stored for one month at ambient temperature. After this time there was no sign of cohesion between aggregate particles and no apparent ;
loss of workability of the mix.

Example II

An emulsion was prepared using a two-stage-static mixing process ~imilar to that used in Example I. The emulsion had the following composition, with the individual components expressed as weight percentages of the total weight of the emulsion:-6S% bitumen: straight run lO0 penetration at 25C(IP49) 0.8% emulsifier: N-tallow polyamine, manufactured and sold by the French company CECA under the Trade Mark Polyram S.
0.74% hydrochloric acid 33.46% water.

~UBStlTUTE SHEET -WO92/1~3 PCT/EP92/~935 2~.9~3~.1.

The particle size was measured to have a median diameter of 5.2 pm and standard deviation of 0.18. The emulsion was used to coat a granite type material at a rate that resulted in 4% by weight residual bitumen on the aggregate~. The composition of the material (as percentages are weight percentages of the total weight of the material) was:

40% - dust 12% - 6 mm 10% - 10 mm 10% - 14 mm 18% - ~0 mm 10% - 28 mm `

One batch of coated material was prepared and samples of compacted mix were m~nufactured right away according to the so-called DURIEZ procedure. In this procedure moulds of mix are compacted under static compaction. Once the samples have been prepared they are allowed to cure. Half (three) of the æamples are cured for 14 days at 18C and 50% humidity. The other half are first cured for seven days at 18C and S0%
h~idity and then immersed into water at 18C for another seven days. After the curing time is completed, the static resistance of the samples i5 measured and recorded, where "static resi~tance" refers to the pressure applied between two plates, between which a sample is positioned, which pressure is just sufficient to cause the sample to be crushed. The average value is determined for the samples cured dry, and for the samples cured in water. Additionally determined is the ratio of the static resistance of the wet samples to that of the dry samples. The given ratio indicates the behaviour of the mix in the presence of water and thus its water-stripping resistance.

~ ~ U C ~T

3 ? rJ ~ 3 ` ~ 4 The obtained results were as follows:-dry resistance : 49.5 bar~
wet resistance : 42.2 bars wet/dry ratio : O.85 ~

Another batch of uncompacted mix was prepared and :
stored in closed plastic bags for one month. Plastic bags were used in order to avoid too much evaporation ;~:
of water. After this time of storage, moulds were ~.
prepared exactly according to the same procedure as in :
the preceding paragraph. The results were as follows:-dry resistance : 48.0 bars --wet resistance : 40.3 bars .:~
wet/dry ratio : O.83 ;

As these results compare very well with the preceding data, the coated materi~l described above can ~e stored for a period of at least one month, and its performance is not impaired by the storage providing it remains humid enough.

The same moulds were prepared, according to the same procedure as above, with an emulsion containing 7~
solvent in place of part of the bitumen : the emulsion had the following composition (percentages again being expressed as weight percentages of the total weiight of the emulsion):-58% bitumen: straight run lO0 penetration at 25C(IP49) 7% solvent: kerosene 0.8% emu~sifier: N-tallow polyamine, manufactured and sold by the French company CECA under the Trade Mark Polyram S.

~1 IQrlTI ITE SHEET

W092/~ PCT/EP92/~35 0.74% hydrochloric acid 33.46% water.

Some difficulties were experienced getting the samples out from the moulds after compaction. Indeed, they were very soft and did not show any cohesion. The static resistance of the mix after 21 days curing at 18C and 50% humid~ty was very low, normally 13.2 bars.

This example demonstrates that solventless, deferred set, cold mix emulsion prepared as de~;cribed above can be stored for at least two weeks and then applied, after which the applied emulsion exhibits good ~tatic resistance after 14 days. However, a cold mix emulsion, identical except that a quantity of solvent (kerosene) was substituted for part of the bitumien, showed inferior static resistance after a longer period of curing.

_. .~__._. .__ ~. .___

Claims (10)

1. A composition comprising a mixture of bitumen emulsion and aggregate material, the bitumen emulsion comprising by weight based on the total weight of the emulsion:

(a) 40 to 85 per cent bitumen;
(b) 0.05 to 1.0 per cent emulsifier; and (c) 14 to 59.95 per cent water, the composition being substantially free of organic solvent and containing emulsified bitumen droplets having a mean particle size of from 2 to 10 micrometres with a standard deviation of no more than 0.3.

2. A composition according to claim 1 wherein the emulsified bitumen droplets have a mean particle size of from 3 to 9 micrometres.

3. A composition according to claim 1 or 2 wherein the standard deviation in the mean particle size of the emulsified bitumen droplets is no more than 0.2.

4. A composition according to any preceding claim wherein the emulsifier is a cationic emulsifier.

5. A composition according to any preceding claim which also comprises 0.05 to 0.5 weight percent acid.

6. A composition according to claim 5 wherein the acid is an inorganic acid.

7. A composition according to any preceding claim which also comprises 0.05 to 0.5 weight percent of a salt.

8. A composition according to claim 7 wherein the salt is calcium chloride.

9. Use of a bitumen emulsion comprising by weight based on the weight of the emulsion:

(a) 40 to 85 per cent bitumen;
(b) 0.05 to 1.0 per cent emulsifier; and (c) 14 to 59.95 per cent water in the preparation of a delayed-set bitumen emulsion-aggregate mix.

10. Use of a composition according to any one of claims 1 to 8 in the repair of a road or pavement surface.