Developments in bitumen emulsion mixtures for roads by D. Needham B.Sc. Thesis submitted to the University of Nottingham for the degree of Doctor of Philosophy. May 1996ABSTRACT Bitumen emulsion mixtures, or cold mix, offers certain advantages over hot bituminous road mixtures in terms of potential cost savings, environmental factors, energy savings and easing, of logistical difficulties inherent with hot mix. For these reasons, they are currently used in a number of regions including the United States of America, Continental Europe, Scandinavia, Southern Africa and Australia, However, cold mix has not been seriously evaluated or utilized in the UK until comparatively recently. This is due tothe slow rate at which it builds strength or cures and its susceptibility to rainfall, particularly during this curing period. The overall aim of this research was, therefore, to study the behaviour of cold mix in terms of mechanical properties and the mechanisms involved in emulsion breaking and mixture curing to gain an insight into how performance may be improved. ‘Mechanical properties were shown to be affected by a number of parameters, inctuding binder grade, void content, curing time and additives such as cement. Fatigue tests showed that without cement, the performance in-situ of cold mix would be very poor. Pavement design calculations revealed that, with cement, emulsion mixtures could be expected to perform similarly to equivalent hot mix. Field trials have indicated that cold mix can be manufactured using conventional hot mix plant and laid using similar techniques. However, problems are still to be overcome in terms of the control of mixture composition and laying in adverse weather conditions, Fundamental tests have shown that emulsion droplet coalescence (which is an essential part of the curing process) was affected by pressure, bitumen type, emulsifier level, cement and temperature and that cement can cause emulsion charges to become more positive (or less negative) but other parameters had no effect on charge. It was also proved that cement can cause bitumen emulsion to set completely and that the residual binder has an increased viscosity compared with unmodified binder. ‘This was shown to be due to the formation of a composite bitumen cement binder.ACKNOWLEDGEMENTS AND DECLARATION The author would like to thank all of the people who have provided help and advice throughout the course ofthese studies. In particular, he would like to express his gratitude to the following My excellent supervisor Prof. Stephen Brown, who was an endless source of knowledge and ideas, for the provision of the laboratory facilities at Nottingham University. Dr. Alan James, ‘my industrial supervisor (and boss), for his enthusiasm and pragmatism. Mr. Keith Cooper for sharing his vast experience and knowledge and for his assistance with the more practical aspects of this research. All ofthe members ofthe Pavement and Geotechnics Research Group - in particular John Read, Todd Scholz and Mike Gibb for advice in their respective areas of expertise. The technicians both at The University of Nottingham (Messrs. Dennis Lockyer, Sean Malkin and Eshan Sharegh) and Akzo Nobels laboratories in Lttleborough (Mrs. Deborah Leah, Mr. David Doyle and Miss Susan Furlong) for their assistance with the laboratory work. My employer, Akzo Nobel Chemicals Limited, for allowing me to carry out this PhD project and for their financial support and the use of materials, facilities and equipment. Camas Aggregates Ltd, (formerly ECC Quarries), Nynas UK AB and Northamptonshire County Council, for their generous help with field trials. Keith Dinsdsle, in the Departinent of Materials Engineering at the University of Nottingham, for kis help withthe eletron microscope studiés and Dr. Ian Richardson from the University of Leeds for his assistance in interpreting the electron micrographs. On a personal note, I would also like to thank my wife Kate for her love, support and encouragement throughout the course of this work and also my daughter Lucy who provided a ‘much needed diversion which ensured that I always had something else to think about. Thanks are also due to the rest of my family for their interest and support, ‘The work described in this thesis was carried out at the University of Nottingham and ‘Akzo Nobel Chemicals! Research Centre at Littleborough between October 1982 and October 1995. This thesis isthe result of my own work, except where specific reference has been made to the work of others. No part of this work has been or is currently being submitted for any other qualification.TABLE OF CONTENTS ABSTRACT ACKNOWLEDGEMENTS AND DECLARATION TABLE OF CONTENTS PART I - CURRENT TECHNOLOGY CHAPTER 1 INTRODUCTION 1.1 Roads, mixtures and cold mix 1.2 Historical review 1.3 Modern roads 13.1 Introduction to pavement mechanics 1.4 Hot mix 1.5 Bitumen emulsion mixtures 1.6 Current status of hot and cold mix 1.6.1 Benefits of bitumen emulsion mixtures 1.7. Objectives of research CHAPTER 2 MAKING, BREAKING AND USING BITUMEN EMULSIONS 2.1. Introduction 2.2. Bitumen and water 2.3. Emulsifiers 2.3.1 Types of emulsifiers 2.4 Emulsions 2.5 Manufacture of bitumen emulsions 2.6 Characterisation of bitumen emulsions 2.6.1 Bitumen content analysis 2.6.2 Particle size analysis 2.6.3 Break index 2.6.4 Viscosity 2.6.5 Sieve residue 2.6.6 Shake stability 2.7 Breaking of bitumen emulsions 2.7.1 Particle size and emulsion breaking 2.8 Emulsion inversion 2.9 Curing of bitumen emulsions -iii- ii iff 122.10. Applications of bitumen emulsions 2.10.1 Surface dressing 2.10.2 Tack coats 2.10.3 Fog seal 2.10.4 Prime coats 2.10.5 Slurry seal and microsurfacing 2.10.6 Bitumen emulsion mixtures - cold mix CHAPTER 3 BITUMEN EMULSION MIXTURES 35 - CURRENT PRACTICE 3.1 Introduction 3.2. Cold mix in general 3.3. European cold mix practices 3.3.1 Grave emulsion Mixture design Mixing laying and compaction Pavement design Performance of Grave in-situ 3.3.2 Cold mixes 3.3.3. Two stage mixing Mixture design ‘Mixing and laying 3.3.4 Double mixing process 3.3.5 Double treatment process 33.6 Spain 3.3.7 Germany 33.8 Italy 3.4 North American practice 3.5. Miscellaneous 3.5.1. Souther Africa 3.5.2. Australia and New Zealand 3.5.3 Developing countries 3.6 Foamed bitumen 3.7 Discussion CHAPTER 4 DEVELOPMENTS TO CURRENT PRACTICE 64 4.1 Introduction 4.2. Gap graded cold asphalt concrete 4.3. New UK specifications 4.4 Stone filled emulsion asphalt 45° Cold recycling in the UK 4.6 The addition of ordinary portland cement «iv.CHAPTER 5 5.1 5.2 53 54 55 CHAPTER 6 6.1 62 63 64 CHAPTER 7 1 12 MECHANICAL PROPERTIES OF BITUMINOUS 74 MIXTURES AND METHODS USED TO MEASURE THEM Introduction Manufacture of specimens used in laboratory tests, 5.2.1 Manufacture of mixtures 5.22. Compaction of mixtures The Marshall hammer method The Percentage Refusal Density apparatus The static load press The roller compactor The gyratory compactor Volumetric proportions 5.3.1 Measurement of volumetric proportions Mechanical properties 5.4.1 Stiffness modulus The Indirect Tensile Stiffness Modulus test 3.42 Fatigue Fatigue testing The Indirect Tensile Fatigue test The fatigue line 5.4.3 Resistance to permanent deformation The Repeated Load Axial test Summary PART I - EXPERIMENTAL PRODUCTION AND CHARACTERISATION OF 100 BITUMEN EMULSIONS Introduction Emulsion manufacture 6.2.1 Waterphase production 6.2.2. Emulsion mills 6.23 Emulsion production Emulsion formulations and results of characterisation tests Discussion FIELD TRIALS 108 Introduction Patching mixtures we73 14 15 CHAPTER 8 81 8.2 83 84 7.2.1. Laboratory tests 7.2.2 Plant mix Is 7.2.3. Laboratory tests on materials manufactured during plant trials 7.2.4 Conclusions Basecourse trials 73.1 Mixture design Aggregate gradation Binder content 7.3.2. Transportability tests Compaction in stockpile Shaking Run-off Control Results and discussion 73.3 Plant scale mixture production 73.4 Laying at the TRL site 73.5. Tests carried out by TRL Haunching basecourse trial Test of early life strength Mixture production Laying Conclusions THE EFFECT OF ORDINARY PORTLAND 129 (CEMENT ON MECHANICAL PROPERTIES OF BITUMEN EMULSION MIXTURES Introduction Cement Stiffness modulus 8.3.1 Materials 83.2 Mixture design 8.3.3. Specimen manufacture 8.3.4 ITSM and water loss tests 8.3.5 Discussion 8.3.6 Comparison of OPC with hydrated lime and calcium chloride Mixture design Discussion Resistance to permanent deformation 8.4.1 Specimen manufacture 8.4.2 Results from cold mix cores Discussion Strain rate85 8.6 87 CHAPTER 9 91 9.2 8.4.3 Hot mix Discussion 8.4.4 Confinement Resistance to fatigue cracking 8.5.1 Results Discussion 8.5.2. Effect of polymers on resistance to fatigue Results Discussion 8.5.3 Effect of stiffness on resistance to fatigue Durability Discussion Overall conclusions INDIRECT TENSILE STIFFNESS MODULUS —159 TESTS ON BITUMEN EMULSION MIXTURES Introduction Experimental 9.2.1 Materials 9.2.2 The effect of aggregate grading Mixture design Manufacture and testing of specimens Results Discussion 9.2.3 The effect of base binder penetration grade Mixture design Specimen manufacture Results Discussion : 9.24 The effect of emulsifier level Mixture design Specimen manufacture Results Discussion 9.2.5 The effect of compaction density Mixture design Specimen manufacture Results Discussion 9.2.6 The effect of polymer modified binders Polymer types Mixture design Specimen manufacture and testing Results ~vii-93 CHAPTER 10 10.1 10.2 10.3 10.4 CHAPTER 11 Mal 11.2 3 14 115 11.6 Discussion Overall conclusions STUDIES ON BREAKING OF BITUMEN 77 EMULSIONS IN MIXTURES Introduction Coalescence of bitumen emulsion onto aggregate in mixtures 10.2.1 Test procedure Aggregate preparation Mixture preparation and compaction Bitumen content analysis 10.2.2 Description of test parameters and results Base bitumen pen grade Emulsifier level Compaction load Number of blows of Marshall hammer Compaction load-time sequence Compaction frequency Ordinary Portland cement Rapid setting cements Polymer modification of emulsion Storage time of mixture and curing time Temperature Breaking agents Coalescence of bitumen emulsion in suspension 10.3.1 Tests and results Discussion ZETA POTENTIAL 204 Introducti Zeta potential 11.2.1 Zeta potential measurement 11.2.2 Variation of zeta potential with pH Experimental 11.3.1 Preparation of emulsion samples with additives 11.3.2 Zeta potential measurements 11.33 Limitations of the technique Results Discussion: Zeta potential measurements in run-off water 11.6.1 Results viiiDiscussion 11.7 Conclusions CHAPTER 12 PROPERTIES OF BITUMEN EMULSION 219 RESIDUES 12.1 Introduction 12.2 Bitumen and Ordinary Portland Cement mixtures 12.2.1 Breaking behaviour of emulsion and OPC mixtures 12.2.2 Penetration of cured binder and OPC masties 12.2.3 Rheological studies on mixtures of binder with OPC, hydrated lime and filler Basic rheological concepts Production of mixtures The dynamic shear rheometer Rheological measurements Results Discussion Temperature rise in emulsion and OPC mixtures Cement and water mixtures, Electron microscopy on mixtures of binder residues and OPC Core manufacture and curing ‘Specimen preparation Electron microscopy Results Discussion 12.3. Rheological measurements on polymer modified binder residues 12.3.1 Sample preparation 12.3.2 Rheological measurements Results Discussion 12.4 Overall conclusions PART III - PRACTICAL IMPLICATIONS AND CONCLUSIONS CHAPTER 13. PRACTICAL IMPLICATIONS OF RESEARCH — 252 13.1 Introduction “ix13.2 13.3 134 13.5 CHAPTER 14 14.1 14.2 Mechanical properties 13.2.1 Stiffness modulus 13.2.2. Resistance to permanent deformation 13.2.3. Resistance to fatigue cracking 13.2.4 Durability Implications of research in mixture and pavement design 13.3.1 Mixture design 13.3.2 The Analytical approach to pavement design Failure modes Pavement loading Conversion to load applications in laboratory tests to standard axles 13.3.3 Pavement design with hot mix 13.3.4 Pavement design with cold mix Design calculations based on data obtained in this research 13.4.1 Calculation of pavement thickness Cold mix Hot mix Comparing hot and cold mix Early life considerations OVERALL CONCLUSIONS AND FUTURE 270 WORK Overall conclusions Future work 14.2.1 Field trials 14.2.2 Development of laboratory tests 14.2.3 Performance criteria for-cold mix 14.2.4 New aggregate gradings 14.2.5 Development of new emulsifiers REFERENCES 276CHAPTER 1 INTRODUCTION 1.1 ROADS MIXTURES AND COLD MIX In recent years mankind has become increasingly dependant on road transport for both commercial and personal use. In the United Kingdom, the majority of Europe and the rest of the developed world, freight haulage has experienced a major shift from water and rail based transport to roads, and the use of the 'family car’ has become a way of life. Demand upon road networks in countries all around the world has risen far beyond the levels anticipated 20 years ago and axle loads have increased significantly. Inevitably, due to this increased burden, pavement structures are deteriorating as a result of structural failure and coupled with the need to build new roads to cary yet more traffic, the requirement for road construction is ever increasing. In the UK, traditional methods of road construction are employed in nearly all of the structural layers of road building projects. These involve the use of hot mixtures of aggregate and bitumen for which manufacturing and laying plant are well established and the technology has a proven record. However, over the last decade, there has been a realization that cold processes, which use bitumen emulsion in place of hot bitumen, have a part to play. A number of countries, such as the United States of America, France and those in Scandinavia, have made use of cold processes for many years as discussed in chapter 3 of this report, but current technology only allows them to be used for particular applications in certain situations. In the United Kingdom, bitumen emulsions are used only in surface overlay processes and bitumen emulsion based mixtures are in their infancy.1.2 HISTORICAL REVIEW Throughout history, as civilizations have developed and grown, road construction has been necessary to carry increasing levels of traffic to and from regions of dense population. The earliest examples of roads are known to have radiated from ancient Babylon and highways existed in Sth century B.C. Egypt for the transportation of stone used to build the pyramids and other such monuments (1). The Romans constructed approximately 80,000 km of road, consisting of 29 highways radiating from Rome and further networks in conquered territories, to link their various cities and encampments. These can still be seen in places today. Archaeological and historical investigations have revealed that the structure was 90 to 120 em in depth and consisted of a granular subbase and an aggregate basecourse, held together with mortar, and a cobbled wearing course. An important feature was the inclusion of side drainage channels which prevented waterlogging. Roman law stated that anybody could use their roads but that upkeep was the responsibility of the inhabitants of the land through which the road passed. Following the demise of the Roman empire these roads all but disintegrated due to the absence of a central authority. In the 17th century, the French government built about 24,000 km of roads using a system of enforced labour. Around the same time, the English Parliament instituted 2 franchise system inviting private companies to construct and maintain roads and allowing them to charge tolls for their use. More than 1,000 turnpike companies maintaining 32,000 km of road were in existence in England in the 1830's but the advent of the railways meant that toll roads became under used resulting in the collapse of the toll system. In the 19th century, two Scotsmen named Telford and Macadam, improved the methods of highway construction. They realized that the most 2important factor in a good road is an impermeable layer which evenly distributes the load over the subgrade. This describes the road as an engineering structure rather than one which has merely evolved through the ages. Both engineers devised structures with strong load bearing bases of crushed aggregate or cobbles, capped with fine aggregate. No binder was used in these designs. Up until the appearance of motor vehicles, these types of roads served society well. However, the extra weight of cars and trucks put unanticipated siress on the pavements which rapidly disintegrated due to rutting and potholing, particularly in wet weather. Conversely, during dry weather, dust was a problem from these fast moving vehicles. A method of sealing and firmly binding the aggregates was required. Initially a whole range of oils were tried but eventually it was discovered that Trinidad Lake Asphalt and then coal tar and finally bitumen were the best solutions. These binders were applied by hot spraying to existing surfaces. The process was fairly successful, at least as a stop gap solution. 13 MODERN ROADS Eventually, full depth restructuring of roads was necessary and methods which are still used today were developed. The general structure on which all roads are based is shown in Figure I-1 (1). The bottom three layers form the pavement foundation on which the more expensive and structurally more significant layers are built. The subgrade is the naturally occurring soil upon which the road is constructed. This layer is sometimes compacted to improve its bearing capacity. The overlying man-made layers serve to protect the subbase upon which the integrity of the entize structure depends. A capping layer may sometimes be placed on top of the subgrade and this is followed by the sub-base which consists of unbound aggregate. The layers above this form the main structural element of the pavement and are often comprised of graded aggregate and binder based on various recipes. The lower load bearing layer is termed the roadbase and this is followed by the basecourse layer or layers. The final layer Baeis the wearing course, which provides the surface texture and ride quality in terms of noise and spray levels. Pavement layers Catagories Wearing course ——— Surfacing | Road base Road base ‘Sub base Pavement foundation Capping Sub grade Figure 1-1: Generalised structure of modern roads 13.1 Introduction to pavement mechanies The purpose of a modern road is to facilitate the flow of traffic in a state of comfort and safety. In recent years the problems of traffic congestion have led to innovations which improve the flow of traffic but pavement reconstruction work itself can have disastrous effects on traffic movement. The objective of modem pavement design, therefore, is to build roads which have predictable lifespans which must be lengthy to minimize the frequency of repair. Road structures fail through two modes - namely cracking and rutting. The speed with which either of these phenomena occurs is dependent upon the ‘mechanical properties of the asphalt and underlying layers, the thickness of the bituminous layers and traffic volumes. The main purpose of the bituminous layers is to protect the natural underlying surface on which a pavement is built. In order to do this they must have a high stiffness modulus. Stiffness is discussed in detail in chapter 5 and can be likened to Young's modulus - being the ratio ofstress over strain. The higher the stiffness of the bituminous layers the greater the distribution of load over the underlying layers. In this context, therefore, mixtures with high stiffness are desirable as they offer more protection to the subgrade. Through analytical pavement design techniques, the engineer can design a pavement structure to provide a specified level of performance based on these factors. This topic is discussed in detail in chapters 5 and 13. 14 HOT MIX ‘The structural layers of modem roads consist of graded aggregate mixtures held together by a binder of some description. In the majority of cases in developed countries, the binder used today in the structural layers is bitumen. Some are constructed with concrete, utilizing cement as the binder, but these are outside the scope of this report. The material most often used to make bitumen bound layers is known as hot mix due to it being made and laid at elevated temperatures. Although bitumens are manufactured to have a range of viscosities, the grades used in the structural layers of roads are almost solid at ambient temperatures. In order to mix with the aggregate mixture, bitumen must first be liquified by heating. In the manufacturing process, hot bitumen is added to the hot aggregate mixture in a large blender and mixed until full coating of the aggregate is achieved. The bitumen and aggregate temperatures necessary for this are in the region of 110 to 180°C depending on the hardness grade of the bitumen being used. The hot material is then transported to the laying site in insulated lorries and must be laid and compacted while still hot. if the mixture is allowed to cool down too much, the bitumen viscosity becomes too high and the mixture begins to solidify. Below a certain temperature, depending on the grade of bitumen, a mixture will become unworkable, meaning that it can be neither placed nor compacted correctly. After laying, a hot mix pavement can be trafficked as soon as it has cooled to ambient temperature and the bitumen has hardened to regainedits original properties. 1.5 BITUMEN EMULSION MIXTURES, ‘An alternative method of liquifying bitumen is to emulsify it in water. In this case no heating of the binder nor aggregate mixture is necessary and mixing and laying are carried out at ambient temperature. This process has been in existence since the early part of the twentieth century and emulsions were actually used as binders for formerly unbound roads. 1.6 CURRENT STATUS OF HOT AND COLD MIX Bitumen emulsions are used today in a variety of road construction techniques, but mainly only for surface overlays. In most situations, the material used for the structural layers of roads in the UK is hot mix. Several countries use the emulsion based alternative, which has been generically termed "cold mix”, in a number of discreet applications but, even in these countries, the majority of paving is hot mix. In the United Kingdom, the road construction industry is only now starting to look to cold mix and lay materials, under pressure from environmentalists and new specifications for reinstatement materials (2). Cold mix is not utilized in the UK, for example, for a number of reasons. First and foremost, hot mix does an excellent job when manufactured and laid correctly. A great number of hot mix plants exist in developed countries and consequently materials are readily available. Hot mix technology is well developed even though this is based on empirical laboratory and field data rather than fundamental principles. Engineers and contractors have a great deal of experience with hot mix materials, enabling them to have confidence in the performance of a structure comprised of hot mix. Until recently the overall opinion in the industry was therefore one of "If the clock is not broken, don't it". Even advocates of cold mix would not claim that it is yet ready to beused in all situations in which hot mix is used and, without the use of modifiers, there is still a shortfall in performance in terms of mechanical properties. Cold mix has very litte stiffness during its early life and can, therefore, be damaged if trafficked. Emulsion based mixtures also have an inherent susceptibility to water damage, due to the fact that unset bitumen emulsions are partially water soluble and the binder can, therefore, be washed away by rainfall resulting in a very weak ‘material, There are, however, arguments for the use of cold mix and the debate is gaining momentum. Many of the arguments have an environmental basis. 1.6.1 Benefits of using bitumen emulsion mixtures ‘As aggregates do not have to be dried for use in emulsion mixtures, dust emissions are eliminated. Hot mix can also lead to gaseous emissions, which are potentially harmful to health (3) and the environment, if proper control measures are not employed. Some efforts are currently being made to contain emissions fiom both mix plant and paver. An example of the unacceptability of fumes from hot mix plants in the UK was recently reported (4). A major quarrying company planned to install a hot mix facility at one of their quarries in South Wales. Local residents collected scientific evidence on the possible impact and used it to oppose the plans. They succeeded in forcing the quarry company to withdraw their proposal. The quarry company did not accede to the residents! claims in relation to health concems but withdrew plans gn the grounds of the visual impact. Itis doubtful that the health concerns voiced by the locals were realistic but public perception proved powerful enough in forcing the issue. This kind of pressure is likely to increase in the future, and could prevent new hot mix plant from being commissioned and perhaps even threaten existing facilities close to populated areas, Production of emulsion based mixtures in place of hot mix could offer a solution te the problem. As well as very large organic molecules, bitumen contains many low molecular weight hydrocarbons and polycyclic aromatic compounds (PAC'S) which are vaporised at high temperatures such as those experienced during hotmix production, transport and laying. Hydrocarbons contribute to atmospheric pollution although this is small scale compared to other sources. Hydrogen sulphide is also released from hot bitumen, with some types being worse than others. In the open, this gas is not present at dangerous levels but in bulk storage tanks it can build up to levels at which it becomes hazardous to health. However, it is the PAC's which are of more concer as those with 3 to 7 fused rings are known or suspected carcinogens. In particular, benzo (a) pyrene and benz (a) anthracene are considered to be powerful carcinogens. However, the concentrations of these chemicals in bitumen are very low (5). A number of studies have been carried out to assess the potentially harmful effects of these compounds on road workers and the general public (6,7,8). Exposure can be in the form of fumes or contact with the skin; the latter applying only to workers. ‘Skin contact is not eliminated by the use of cold processes (cut-back (see pg 31) or emulsions) and in fact is more likely because a cold material is more likely to be handled than one at over 100 °C. The current consensus is that there is little risk from the carcinogenic compounds in bitumen, but the fact that these materials are present at all is still cause for concem. This seems to be supported by the fact that manufacturers of mix production and laying plant are still attempting to develop systems to prevent the release of fumes. These emissions can be eliminated completely by the use of bitumen emulsion mixtures, as bitumen is only heated during the emulsification process and here it is very easy to contain harmful gases. Energy and, therefore, cost savings can also be realized through the use of cold mixtures. Hot mix production requires that the binder is heated to temperatures in excess of 140°C (9). Aggregate mixtures must also be dried and heated to similar temperatures. In the case of cold mix, the emulsification process requires energy to heat the bitumen and drive the emulsion mill, but once made, the emulsion can be used cold and no drying nor heating of the aggregate mixture is necessary. As hot mix plants are more complicated than cold mix versions,they are not normally considered to be portable. This means that transport costs are generally higher for hot mix as both raw materials and finished product have to be carried over longer distances. A number of reports have shown that cold mix uses about half the energy of hot mix on a tonne for tonne basis (10, 11,12). Additionally, investment in cold mix plant is far lower than in the more complicated hot mix plant which, although it is not an important factor in countries with an established network of hot mix facilities, is particularly advantageous in developing countries. ‘An emerging problem in certain countries is being solved by the use of emulsion mixtures. Old tar containing roads are releasing harmful polycyclic aromatic compounds into the environment due to water leaching (13). Coupled with the fact that these roads are in need of repair, there is a need to carry out reconstruction work using methods which do not allow the pollutants to enter the environment. This subject is dealt with in detail in chapter 3 Emulsion mixtures also offer potential improvements in performance. Hardening of binder through oxidation and other processes, which can occur during the heating process (14) and can lead to embritlement and cracking, is avoided. Polymers in latex form can be easily incorporated which is not possible with hot mix, but the effect of these materials on cold mix has not yet been tested. Finally, cold mix has logistical advantages over hot mix, in that it can be stockpiled or transported over longer distances and it is not necessary to use insulated trucks for shorter journeys. It is, therefore, very useful for small scale reinstatement work or for projects in remote areas. 1.7 OBJECTIVES OF THE RESEARCH As has already been discussed, cold mix has been utilized in various forms in various regions for a number of years. It is, however, still applicable only forspecific environments and types of roads. It is still not possible to use it in all situations due the low structural competence of the material in early life and its lack of resistance to water damage compared with hot mix (15,16). The ultimate objective of the research was, therefore, to develop improved cold mix which could be used in place of hot mix in any situation. The approach taken was to look at the effects of various parameters on mechanical properties of emulsions and mixtures in terms of stiffness modulus, resistance to permanent deformation and resistance to fatigue. Mechanisms for these effects were investigated through studies on the coalescence of emulsion, electrochemical measurements and evaluation of emulsified binders, Mixture designs were limited to dense aggregate gradings and high binder contents (in accordance with BS4987 (9)) and solventless binders. Only one emulsifier was investigated as it was the best available option for dense aggregate gradings. These restrictions meant that some areas of cold mix, such as those which use open graded aggregate mixtures and different emulsifier types or different binder contents, were not covered, but time did not allow every avenue to be investigated. The work was carried out partly at the University of ‘Nottingham and partly at Akzo Nobel's laboratories near Manchester. This thesis first describes emulsion technology and the principle of the process of emulsion breaking which returns emulsified bitumen to its original form. The current level of technology and developments to these systems is then discussed. Several field trials are described which helped to define the current level of performance of the mixture type employed in this research. The experimental work consisted of comprehensive testing on the effects of various parameters on the mechanical properties of mixtures. Fundamental tests were then developed and carried out in which the breaking behaviour of emulsion in contact with aggregate, the electrochemical properties of the emulsion and the properties of the -10-binder residue were studied. The penultimate chapter uses the results obtained to discuss the practical implications of the use of bitumen emulsion mixtures in major road construction in terms of mixture and pavement design. Finally, overall conclusions are drawn regarding the performance of cold mix and possible mechanisms through which various parameters affect performance. The approach taken in this research is summarised in the flow chart in Figure 1-2. Voomcan ; [ete Coalesoonce | electrochemical] | mui | eee wore Field Trias | | varabies on | Tes || we || mies | | Fundemenia’ | woeure | | Pavement ‘Behaviour Design | | Design Figure 1-2 : Flow chart to illustrate approach of studies “lleCHAPTER 2 MAKING, BREAKING AND USING BITUMEN EMULSIONS 2.1 INTRODUCTION An emulsion is a dispersion of fine droplets of one liquid in another liquid, In contrast to solutions, the two liquids are coexistent rather than mutually mixed, In the case of a bitumen emulsion, these are bitumen, which is a liquid with a very high viscosity, and water, Normally, in good quality bitumen emulsions, the droplets are in the order of 1 to 30 pm in diameter with the majority <1 wm and the largest volume or mass between 5 and 10 ym. The bitumen content is normally in the region of 60 to 70 % but can be as low as 40 % or as high as 80%. The globules of bitumen are termed the disperse phase, as they are discreet droplets, and the water is the continuous phase in which the droplets are suspended. 22 BITUMEN AND WATER Under normal citeumstances, an oil, such as bitumen, and water, are totally immiscible. This is due to the chemistry of the two materials. Bitumen is composed of two groups of organic molecules called asphaltenes and maltenes (17). The system can be regarded as colloidal, with the asphaltenes being dispersed in the maltenes. Asphaltenes are molecules of very high molecular weight, ranging from 1,000 to 100,000, composed of mainly carbon and hydrogen with some nitrogen, sulphur and oxygen. They are amorphous solids wiich are fairly polar due to the unsaturate (C=C double bond), nitrogen, sulphur and oxygen content. These are dispersed in the maltenes which can be further broken down into three types of molecules; saturates, aromatics and resins, The saturates are non-polar straight chaim and branched aliphatic hydrocarbons which make up between 5 and 20 % of the bitumen. The aromatic portion consists of non-polar Fi24aliphatic chains and unsaturated rings with molecular weights of 300 to 2,000. This portion constitutes 40 to 60 % of a bitumen and is the medium in which the peptized asphaltenes reside. Resins have a similar chemical composition to the asphaltenes and act as dispersing agents or peptizers for the asphaltenes. The ratio of resins to asphaltenes dictates the physical nature of a bitumen. Bitumen is a very complex material which is, overall, non-polar, even though it does contain some polar components, The term “non-polar” means that, generally, the electron distributions in the constituent molecules are evenly spread all over the structures and there are, therefore, no areas of charge concentration or deficiency, Conversely, water is a very polar medium consisting of various ionic species, such as H,0*, OH: and H’, and the polar water molecule itself. The HO molecule is polar as it contains oxygen, which is a very electronegative atom, and hydrogen which is very electropositive. This has the overall effect of concentrating the electrons in the molecule around the oxygen atoms, leaving the . Thus the molecule hydrogen atoms short of electrons as depicted in Figure 2- gains a small negative charge around the oxygen atom and positive charges around the hydrogen atoms. It is then said to be polar. Figure 2-1 : Electron distribution in a water molecule Under normal circumstances, if an attempt is made to mix polar and non polar compounds, the two substances will separate as the molecules in the polar -13-medium prefer to be in contact with each other in order to cancel out positive and negative regions of charge. 23 EMULSIFIERS In order to produce a stable homogeneous mix of these two immiscible materials a surface active agent or surfactant is required. These molecules are so called because they concentrate and are active at the surface befween two immiscible substances in contact (18, 19). This could be a solid and a liquid, a gas and liquid or, as in the case of emulsions, a liquid and another liquid. Surface activity arises due to these molecules consisting of two portions with different properties. One section is composed of a hydrocarbon tail, which is hydrophobic (water fearing) or lipophilic (oil loving), and the other either carries a charge or is polar, making it hydrophilic (water loving) or oleophobic (oil fearing). There are three classes of surfactant - anionic, cationic and nonionic. 2.3.1. Types of emulsifiers Anionic bitumen emulsifiers are normally fatty acids or alkyl sulphates orsulphonates. These types of molecules were first used as emulsifiers during the late 1920's. In order to become active, these molecules must be deprotonated by a base, such as sodium hydroxide, to give rise to a negative charge on the head group as depicted in Figure 2-2, Nat + NeoH ——> _~_-CH-S—0 + 1,0] ° Negative charge Figure 2-2 : Activation of an alkyl sulphonate emulsifier -14-The cationic set of emulsifiers is comprised of a range of fatty amines and cationic emulsions have their derivatives. After first appearing in the 1950's, become the favoured type in most road applications. Cationic emulsifiers range from simple primary, secondary or tertiary amines to quaternary amine salts, ethoxylated amines, amides and imidazolines which are shown in Figure 2-3. In order to activate these molecules, the head groups must be protonated by an acid (with the exception of quaternary amines which inherently carry a positive charge) thus gaining a positive charge as shown in Figure 2-4. Figure 2-3 : General structure of some amines and derivatives used as cationic emulsifiers ereR z i i OO en eee | | [Secondary arine Positive charge Figure 2-4 : Activation of cationic emulsifier ‘Nonionic emulsifiers are different from anionic and cationics in that they do not have to be deprotonated or protonated in order to be active. The head groups in these types of molecules are typically but not exclusively chains of ethoxylate groups - C,H,0. The situation here is similar to that in H,O, in that the molecule is polarized as the electrons again become concentrated around the oxygen atoms thus making them into sites of negative charge, leaving the carbon atoms electron deficient and, therefore, positive. An example of a nonionic emulsifier would be ethoxylated nonyl phenol as shown in Figure 2-5, | CL Ap WON” | | | | Figure 2-5 : Nonyl phenol ethoxylate 2.4 EMULSIONS The principle of emulsification is quite simple but the science itself is highly complex. In basic terms, an emulsion consists of globules of one liquid phase dispersed in a second continuous liquid phase. There are two types of aqueous emulsion, namely oil in water (o/w), in which the oil is the disperse phase and water the continuous phase, and water in oil (w/o), where water is the disperse phase and oil is the continuous phase. A bitumen emulsion is an example of an oil in water emulsion, under normal circumstances, but it is postulated that they can invert to water in oil emulsions during the setting process, Setting of bitumen emulsions involves reversion from a dispersion of -16-bitumen in water to pure bitumen and this process is discussed in detail below. The arrangement in a bitumen emulsion, employing a cationic emulsifier, is as shown in Figure 2-6 but obviously the relative size of the emulsifier molecules has been grossly exaggerated for diagrammatic purposes (as they are actually only a few Angstroms in size compared to micron sized bitumen droplets) and they would be much more numerous. The bitumen droplets are suspended in a continuous water phase with the emulsifier residing at the bitumen/water interface, thus stabilizing the system by imparting a charged or polar nature to the droplet surfaces thus making them water miscible. Surfactants also stabilize the system by keeping droplets apart due to charge repulsion or steric effects. Figure 2-6 : Schematic diagram of a bitumen emulsion 2.5 MANUFACTURE OF BITUMEN EMULSIONS Bitumen emulsions are manufactured by the intensive mixing together of bitumen and water, dividing up and dispersing the bitumen in the waterphase. ‘The waterphase normally carries the emulsifier in solution in an activated form, ie. acidified or basified. Intensive mixing is achieved by means of a high shear mixer known as a colloid mill which is necessary to finely divide the bitumen. Mill heads come in several forms. The simplest consists of two closely spaced plates, similar to a normal grinding mill, between which the bitumen and Figs‘waterphase are passed. Another common type consists of two intermeshing sets of cirenlarly placed teeth, one of which rotates with respect to the other. The fixed teeth are termed the stator and the rotating teeth the rotor. A third type of, mill, called the SMEP (20), has recently been developed by Esso and does not use rotating high shear mixing head at all. Instead, the bitumen is dispersed due to intense turbulence created by high pressure injection of bitumen and waterphase into a mixing zone. It is claimed that this method produces an emulsion with an extremely narrow droplet size distribution. In order for the bitumen and water to mix in the mill, the emulsifier must be added to the system in some manner. It is usually added via the waterphase. There are two methods of doing this. The first technique is to make up batches of waterphase prior to use, by dissolving the emulsifier in water, at the correct calculated dosage, along with acid or base depending upon the type of emulsifier being used. The second technique is to dose the emulsifier and acid/base to the water en-route to the mill. This is known as in-line mixing and requires that the emulsifier dissolves very rapidly in water, as the residence time is very short, The first method is used in laboratory scale applications and smalll industrial plants, whereas the second is used in larger and generally more up-to-date plants only. ‘The manufacturing process is batch or continuous. Bitumen must be in a liquid state in order to be pumpable and able to pass through the mill head. This means that it needs to be heated to lower its viscosity sufficiently to allow it to flow; the temperature being dependant upon the penetration grade of the bitumen in question. Penetration is a method of specifying the viscosity of bitumens in simple and easily measurable terms. The test involves measuring the depth to which a standard shaped needle of a specific weight penetrates into a sample of bitumen in a specific period of time (21, 22). The depth of penetration in 1/10 ths mm is the grade of the binder. Obviously, the stiffer the binder the less the needle will penetrate consequently the harder the binder the lower the penetration grade. As an example of the temperature necessary for -18-emulsification, 100 pen bitumen must be heated to approximately 140 to 160 °C. More specifically, the bitumen must be heated to a temperature at which its viscosity is approximately 200 eps. As a rule of thumb, this is about 100 °C above the softening point (temperature at which binder viscosity drops below a certain value) of the binder in question, The waterphase and mill head are also warmed to prevent too much cooling of the bitumen during emulsification which would cause the bitumen to solidify. According to Marchal and Boussad (23), the thermal shock which occurs when hot bitumen meets cooler water, is a cause of the formation of coarse bitumen droplets in an emulsion. Water phase and bitumen are pumped towards the mill head at calculated rates which are controlled to produce an emulsion of the desired bitumen content. Bitumen and waterphase come together just before entering the mill. They then pass through the colloid mill, where the bitumen is finely divided into droplets of predominantly | to 5 um in size, and dispersed in the water. During the mixing process, the surfactant molecules orientate themselves at the bitumen-water interface, thus stabilizing the system as described above. The emulsion then passes out of the mill and is collected. The temperature of the emulsion must be below ~95°C as it leaves the mill in order to prevent boiling off of the water which would push up the bitumen content. If the temperature of the ingredients is too high for this to be possible (eg in the case of polymer modified or oxidised bitumen where the temperature of the binder may have to be in excess of 180 or 200 °C), the mill is pressurised to prevent boiling of the water during emulsification and a heat exchanger is placed on the outlet in order to cool the emulsion before reducing the pressure. Emulsions manufactured on an industrial scale are stored either in tanks (which may be heated in some cases, with agitation provided to prevent settlement of the bitumen droplets) or in transportable vessels such as drums. The diagram in Figure 2-7 is a representation of the emulsification process. The mill head depicted is similar to that found in the Hurrell mill used to manufacture emulsions used in this research. Note that in this mill the rotor is merely a smooth steel wheel and the stator a smooth steel casing around the rotor. The bitumen is dispersed by the turbulence effect created -19-in the waterphase by the rapidly rotating surface of the rotor. iagram of emulsification process ‘igure 2-7: 2.6 CHARACTERISATION OF BITUMEN EMULSIONS After manufacture, the quality, and in the case of a novel emulsion, the characteristics, of the emulsion must be checked. A number of standard tests have been developed in order to do this. 2.6.1. Bitumen content analysis A simple test is normally used to determine the bitumen content of an emulsion (24, 25). The test involves gravimetric measurements to find the percentage weight loss from a sample of emulsion subjected to water evaporation in an oven at ~120°C. Bitumen emulsions are designed to have a range of binder contents necessary to the application for which they are intended and this is covered in detail below. The maximum binder content possible for normal emulsions with spherical or near spherical droplets is ~75 %. Above this level droplet sizes become larger and shape distortion occurs to allow for the high -20-internal phase ratio. 2.6.2 Particle size analysis ‘The particie size distribution of the bitumen droplets in an emulsion has an effect on the performance of emulsions as it dictates : + the surface area of the emulsified bitumen + the amount of free emulsifier in the water phase + the packing arrangement of the droplets, The first two from the above list will be discussed in detail later in this chapter. Packing arrangement partly determines the physical properties of an emulsion in terms of the maximum achievable binder content, viscosity and storage stability. As indicated above the particle size distribution in a normal, ‘good quality emuision ranges from sub-micron to a maximum of 30 jm with the majority lying below 1 ym and the largest volume between 5 and 10 pm. The simplest method of determining particle size is visually by use of a microscope. This method is laborious and probably not as accurate as instrumental methods due to the small number of particles which are sized. There are two main types of instrument for the measurement of particle size which can be applied to bitumen emulsions. ‘These use the electrozone method, developed by Coulter (25), and laser light scattering. The electrozone method is based on monitoring the flow of current between two electrodes placed in an electrolyte which contains a sample of the particles under assessment. As a particle passes through an orifice positioned between the electrodes, the electrolyte is displaced causing an increase in resistance in the circuit. The size of this increase is proportional to the volume of the particle and thus the dimensions can be calculated. The laser method looks at the diffraction pattem of laser light emerging from a particle dispersion. Through a complicated 21.calculation method, which utilizes the optical properties of the particles under study, the particle size distribution can be found. 2.63 Break index ‘The application of a bitumen emulsion is dependent to a large extent upon its breaking behaviour. Break is the term used to describe the reversion of emulsified bitumen droplets to continuous bitumen. ‘The break index test is used to determine the comparative breaking behaviour of emulsions (26). It involves mixing 2 100 g portion of emulsion with a fine aggregate which is normally a quartz sand. Several standard sands or fillers are prescribed in standard test methods, The filler is added to the emulsion in small increments, with stirring for a few seconds after each addition, until the emulsion is seen to break. The mass ‘of aggregate required to break the emulsion is the break index. With rapid setting emulsions, this testis fairly definitive but with slower setting systems the point of emulsion break can be difficult to define accurately. The test does, however, allow emulsions to be ranked as rapid, medium or slow setting quite easily. As a general guide, emulsions with break indices below 80 g are rapid setting and above 120 g are slow setting. 2.6.4 Viscosity Viscosity or rheology is the flow of a liquid under the action of a force. Viscosity of bitumen emulsions is an important parameter in evaiuating bitumen emulsions as it dictates how a material will behave physically in an application. In surface dressing, for example, an emulsion must be viscous enough to remain on the road surface after spraying and not run off. For mixing purposes, emulsions must be of low viscosity to allow them to easily spread over the aggregate during the mixing process. Measurement of emulsion viscosity is performed on two levels. Most national standards use a flow cup. Flow cups are more or less described by their ‘own name and there are several different versions of the test which differ merely 22-in dimensions and architecture (24). A sample of emulsion is placed in a vessel which has a hole of a specific size in its base. The time required for a certain volume to flow out of the cup is determined and this figure is used to specify viscosity. Several versions of this test exist, each with its own parameters of temperature, hole diameter and collected volume. These tests do not give values with any fundamental basis and merely give comparisons. Rheometers are used to give more information. These instruments will be discussed in detail in Chapter 12. 2.6.5 Sieve residue ‘The majority of the bitumen droplets in an emulsion are in the order of a few microns in diameter but a small percentage are much coarser. This can arise due to poor dispersion of the bitumen in the mill head or flocculation and coalescence of droplets after manufacture of the emulsion. The sieve residue test is designed to measure the percentage of bitumen above a certain sieve size - normally 150 or 300 pm (24). An emulsion is poured through a sieve and the weight of retained particles determined. The percentage oversize is then calculated. The figures should lie below 0.5 % for a good quality emulsion. High sieve residues can be an indication that an emulsion is unstable. If particle size analysis is available, which can provide results over a wide size range (ie. <1 um to 600 jum) then the use of a sieve residue test is redundant, 2.6.6 Shake Stability After manufacture, emulsions must be transported to their place of use. ‘Transportation involves a certain amount of agitation of the emulsion and the shake stability test is designed to check a product's transportability. Unstable emulsions can begin to coalesce due to agitation which would have consequences in the field. Tests have been devised in various forms which involve firstly determining the sieve residue of the emulsion. A sample is shaken and then allowed to settle for 2 hours. A sieve residue is then performed. The difference between the sieve residues before and after shaking gives an indication -23-of the emulsion's stability to transport. 2.7 BREAKING OF BITUMEN EMULSIONS For an emulsion to revert from discreet particles back to continuous bitumen, the droplets must join together or coalesce. The speed of the coalescence process is often termed the breaking or setting rate of an emulsion, ‘The rate at which breaking occurs determines the performance behaviour of an emulsion and, therefore, the application for which it is best suited (27). Applications such as surface dressing, involving the placement of chippings on an emulsion sprayed onto the road surface, require very rapid setting emulsions because the contact area between aggregate and emulsion is very low. Conversely, mixtures of dense graded aggregate and emulsion necessitate the use of slow setting emulsions as the contact area is very large. Applications of bitumen emulsions are discussed in detail below. Mechanisms for the breaking processes of both anionic and cationic emulsions involve an interaction between aggregate and emulsion.” According to Gaestel, there are two breaking mechanisms in the case of anionic emulsions (28). In mixtures with calcareous aggregates, such as limestone which is positively charged, the emulsifier forms a salt with the calcium ions contained in the aggregate thus removing it from the bitumen water interface and causing the emulsion to break. With negative, siliceous aggregates itis the inorganic cation which is adsorbed onto the aggregate surface, Since the emulsifier is deactivated through the loss of the counterion, the emulsion is destabilized and will break. The rate of emulsion break by this mechanism is, therefore, proportional to the concentration of the inorganic cation. The emulsion can be over stabilized by the use of excess base. According to Wates and James (29), there are three methods by which cationic emulsions are thought to break onto negatively charged, siliceous 24.aggregates. The first is known as emulsifier abstraction. In this case, the emulsifier is withdrawn from the bitumen/water interface by the aggregate surface. The loss of emulsifier causes the emulsion to become unstable leading to coalescence of the droplets (Figure 2-7a). A second process involves deprotonation of the acidified emulsifier, as protons are adsorbed onto basic sites on the aggregate surface, deactivating the emulsifier and thus causing the emulsion to break (Figure 2-7b). The last, and most important process, is termed droplet migration. Here the bitumen droplets are attracted towards the aggregate due to the positively charged emulsifiers on their surfaces. The droplets then spread over the aggregate surface, aided by the surfactant. The final situation is very beneficial as the bitumen is bound to the surface by the surfactant molecules which subsequently act as adhesion or antistripping agents (Figure 2-7c). This is the main reason why cationic emulsifiers have become more widely used than anionics in road construction applications. Probably all of the above processes occur during the breaking of a bitumen emulsion to a greater or lesser extent, depending upon the conditions present in the system. sla, she Kix, Kh, ean S6 IESE the LF ND ch SDs) Figure 2-7a : Breaking mechanisms of bitumen emulsion - Emulsifier abstraction -25-3. Derbi innen pls ep solee Figure 2-7b : Bitumen emulsion breaking mechanisms - emulsifier deprotonation xt, wa meee KISS ae se Se ~ FN a pt Coe _—— 2. Buen dopes move tds rept mi |. Baler es wah eee \Tasl- LETS. Figure 2-7e : Bitumen emulsion breaking mechanisms - droplet migration -26-Plotnikova considered the mechanism of breaking to be slightly different (30). Itis proposed that firstly the free emulsifier is adsorbed onto the aggregate surface, Next, emulsifier is abstracted from the bitumen droplets and adsorbed onto the aggregate. The bitumen is then attracted to the hydrophobically modified aggregate surface, being hydrophobic itself due to the desorption of, emulsifier. This process is illustrated in Figure 2-8. According to this process, the rate of emulsion break would be dependent on the rate of adsorption of the emulsifier onto the aggregate, which is governed by the surface area and chemical nature of the aggregate and emulsified bitumen. ita, Kl xh, xt eo eS ala, AIA, sree CSE \ SD emis i ) Re ALD ADL 5. Bianco opie agree varie Figure 2-8 : Bitumen emulsion breaking mechanisms - emulsifier adsorption ‘The mechanism by which emulsifier is adsorbed onto the aggregate is thought to be partly chemical and partly physical. Chemi-sorption involves ion exchange between the aggregate and emulsifier. In the case of siliceous aggregates and a cationic emulsion employing a primary amine hydrochloride as -27-the emulsifier, the ion exchange reaction would be : SiOH + RNH,CI SiORNH, + HCl @) Tonic exchange can also occur between cationic emulsions and calcareous aggregates and in fact the ion exchange capacity of these aggregates is ten times larger than that of siliceous materials. The reaction in this case would be : CaCO, + 2RNH,CI > (RNH,),CO; + CaCl @2) Plotnikova states that there are insufficient sites available on an aggregate for all of the emulsifier to adsorb chemically and, therefore, physical adsorption must account for the additional adsorption. Physical adsorption arises from the attraction between positively charged cationic emulsifiers and negative sites on the aggregate surface. Studies were conducted on the adsorption rates of anionic and cationic emulsifiers onto wet and dry aggregate surfaces. Anionics were found to adsorb more slowly onto wet aggregates whereas cationics adsorbed more quickly. Wetting of an aggregate surface was therefore seen as a method of controlling the break of anionic mixtures but was not applicable for cationics. Plotnikova found that doping of the aggregate with quatemary amine prior to the addition of emulsion, slowed down the break of a cationic emulsion. The effect was more pronounced on acidic (negative) aggregates but also occurred on calcareous aggregates which are normally considered to be positively charged. The amine dope can be applied either in solution with pre-wet water or directly during milling of the fine aggregate. The latter was found to be more effective in the laboratory but is not so practical on full scale. Itis more difficult to theorise a mechanism for the breaking of nonionic emulsions as there is no possibility for electrochemical interaction. Breaking of these emulsions, therefore, probably has more to do with the water absorbency of -28-the aggregate or evaporation of water. As discussed above, it is the water medium which keeps the bitumen droplets apart. Thus, if the dispersing phase is removed the bitumen droplets are forced to coalesce. In emulsion mixtures it is, therefore, usually necessary to pre-wet the aggregate before the emulsion is added to prevent rapid absorption of emulsion water which would lead to instant break. Water absorption also plays a part in breaking of ionic emulsions. 2.7.1. Particle size and emulsion breaking The particle size distribution of an emulsion has an effect on breaking behaviour (31). The finer the emulsion, the larger the surface area at the bitumen water interface. This affects the emulsion behaviour in two ways. Firstly, as with any chemical reaction, an increase in surface area will increase the number of available reaction sites thus speeding up the breaking process. Secondly, the larger the surface area, the greater the capacity for emulsifier adsorption at the bitumen water interface and, conversely, the larger the particle size distribution, the more free emulsifier in the water phase. Logically, if there is more free emulsifier available this will use up the active sites on an aggregate thus slowing down the breaking process according to the mechanism shown above. These behavioural differences have implications in the adhesion of residual bitumen to aggregate. It can be inferred, and has been proven to some extent (32), that if there is a large amount of free surfactant in an emulsion, this will rapidly attach to the aggregate surface and prevent the binder from breaking onto the aggregate. Instead, the bitumen droplets coalesce away from the aggregate, leading to poor binding of the total mixture. This can result in poor adhesion, resistance to fatigue and ravelling. If, on the other hand, the level of free emulsifier is low, the bitumen droplets will break onto the aggregate thus ensuring that a good binding matrix is formed. ‘The effect of particle size on emulsion stability should also be taken into account as it works in the opposite direction. In this case the larger the particle 29.size distribution, the less stable the emulsion. Additionally, as suggested by Stoke's equation (2-3), larger particles are more prone to settlement which can Jead to a further increase in particle size while the emulsion is in storage. 2er(d,-d,) oF 23) Where; v= _ velocity of settlement (ms") g = acceleration of gravity (ms?) 1 = radius of bitumen droplet (m) 4,= specific gravity of the dispersed phase (bitumen) d,= specific gravity of the dispersing phase (water) n= viscosity of the dispersing phase (water) (mPa.s) 2.8 | EMULSION INVERSION During the breaking process of bitumen emulsions, it is generally thought that at some stage emulsion inversion must occur. The term means that the system inverts from being bitumen dispersed in water to water dispersed in bitumen, As water is lost from an oil in water emulsion, at some point there will be insufficient water to separate the bitumen droplets. Beyond this point, the water will be dispersed in a continuous bitumen phase which constitutes emulsion inversion, It can be appreciated that in this situation it is difficult for water to get out of the mixture as it is sealed in, It seems reasonable to assume that this would have the effect of softening the binder causing a reduction in strength of a mixture containing it. 2.9 CURING OF BITUMEN EMULSIONS After a bitumen emulsion has coalesced or broken it must fully cure or set for the binder to recover its original physical properties and water resistance. The -30-process seems to be mainly dependent on the evaporation of water but it is not fully understood. Curing is to a large extent dependent upon climatic conditions in the field. Wet and cold conditions have an adverse effect on curing whereas hot, dry conditions have a beneficial effect. Additional rolling can assist in the expulsion of water but only up until a density at which the minimum achievable void content of the mixture has been reached. At this point the excess water merely fills the available air voids and no pressure can be exerted on the water to squeeze it out. 2.10 APPLICATIONS OF BITUMEN EMULSIONS The range of surfactants available, impart different characteristics to the emulsions they produce, Emulsions with different setting characteristics are necessary for different applications. 2.10.1 Surface dressing Surface dressing, or chip sealing as it is known in some countries, is 4 cost effective process used for improving the texture of and sealing smai! cracks in deteriorating pavement surfaces (33). It also corrects minor irregularities in profile but does not give any structural improvements. A rapid setting cationic emulsion is used for this application (coded K170 ia the UK, where K = cationic, rapid setting, 70 = 70 % bitumen) as the binder must cure quickly to allow early trafficking and sweeping to remove excess chips. The technique involves applying warm (60 °C) bitumen emulsion to the road surface by spraying and then immediately placing single sized aggregate chippings onto the unbroken emulsion. A number of variations on the basic theme have been developed which can involve several layers of emulsion and aggregate. Another process, known as Cape seal due to its place of origin, consists of a surface dressing followed by aslury seal. A slurry seal is a mixture of fine graded aggregate and emulsion and is discussed in detail below. Whatever the makeup, the dressing is rolled after laying to align the chippings into a good interlocking matrix. As the contact learea between emulsion and aggregate is very low in surface dressing procedures in general, the breaking processes described above are minimal. For this reason, the emulsion has to be very easy to break. ‘Thus, very highly charged emulsifiers such as diamines are used as discussed above. 2.10.2 Tack coats A tack coat is a very light spray of diluted bitumen emulsion used to provide a bond between an old surface and a newly applied layer. It is considered to be good practice to use a tack coat whenever an old surface is overlaid as weathered bitumen can lose its adhesive properties (34). Anionic and cationic slow setting emulsions are used, after dilution with warm water, at an application rate of 0.25 to 0.7 Vim?, A tack coat emulsion must be able to penetrate any surface cracks or unbound material before breaking, but it must set quickly to allow the new layer to be applied. Tack coats are also used in patching operations, After all loose material has been removed from an excavation, the emulsion is applied to the base and sides. This helps to keep the patch in place and provides a watertight seal between the patch and the surrounding pavement. 2.10.3 Fog seal A fog seal is similar to a tack coat in composition but it is used as a surface treatment itself rather than an aid to another, resurfacing process (34). Fog seals are used on surfaces which have become deficient in binder and are therefore susceptible to loss of chippings or ravelling, or to seal minor cracks. If applied conscientiously and in good time, fog seals can extend the life of a pavement considerably. 2.10.4 Prime coat A prime coat is an application of bitumen to a granular base in preparation for a bituminous overlay (34). Cut-back bitumen (bitumen diluted with solvent to lower its viscosity) and bitumen emulsion are both used. A prime coat serves several purposes : 32.- coats and bonds loose particles = hardens or toughens the surface - waterproofs the surface - plugs voids in the aggregate surface - provides adhesion between the base and overlying course In order for the prime coat to satisfy these criteria, it must be able to penetrate into the base material. Therefore, slow setting anionic or cationic emulsions are utilized. Until recently, prime coats were considered to be an essential part of good pavement construction, but latterly, they have only been deemed necessary when a granular base is to remain exposed during prolonged periods of adverse weather conditions. 2.10.5 Slurry seal and microsurfacing Slurry sealing and microsurfacing are two very similar techniques which are used as surface treatments to improve surface texture and correct minor irregularities (34). ‘The only difference between the two is that microsurfacing uses langer aggregate sizes and is used in thicker layers. Unlike surface dressing, these processes can be used on high speed roads as they give a surface with a very even profile with good skid resistance and a secure finish. The level of technology is very highly developed as systems are designed very specifically for certain road conditions, aggregates and climate. Slurry seal and microsurfacing mixtures comprise finely graded aggregate mixtures, water, cement and bitumen emulsion, There are three different aggregate mixture designs which are used for different applications. The coarsest, type ITI is used for surface corrections and to impart skid resistance. The second, type Il, is slightly finer and is used to correct severe ravelling and loss of binder. ‘The finest mixture, type I, is used for crack filling and pretreatment for hot mix or surface dressing overlays. A slurry seal mixture is produced by first pre- wetting the aggregate mixture with water. This ensures that when the emulsion -33-is added it does not immediately break onto the aggregate due to absorption of the emulsion water into the aggregate. Additive or dope solution may then be added which controls the rate of break of the mixture to a high degree of accuracy when used correctly. This consists of a weak solution of emulsifier which neutralizes the negative sites on the aggregate to some extent thus slowing down the reaction with the emulsion itself, Ordinary portland cement is often added to control the breaking process and improve the setting behaviour and final properties of the seal, The addition levels of dope solution and OPC must be carefully pre- determined and controlled to obtain the desired mixing, breaking and setting rate of the mixture. Finally, the emulsion is added and mixed for a short time. Emulsions used in slurry sealing were traditionally slow to medium setting but in recent years the need for quick set slurries has led to the use of rapid setting emulsions. Slurry seal can be applied either by hand or a specialized paving machine. ‘The hand method is used on smail scale jobs and involves dumping a mixture onto the pavement and spreading it out using squeegees. Slurry seal machines are very sophisticated mix pavers, The mixture components are stored within the machine, mixed together and laid in a continuous process. On today's roads, slurry seals must set within a 1 hour to be acceptable. No rolling is carried out and the seal is merely allowed to cure due to chemical breaking and evaporation of the water. 2.10.6 Bitumen emulsion mixtures - Cold mix Potentially the largest application area for bitumen emulsions and the subject of the studies reported here, is in place of asphalt mixtures or hot mix. Cold mix technology is discussed in detail in the following chapter. 34.CHAPTER 3 BITUMEN EMULSION MIXTURES -CURRENT PRACTICE 3.1. INTRODUCTION Bituminous mixtures consist of graded aggregate bonded together with bitumen which produces a flexible concrete, The material is ideal for pavement structures as it offers a degree of flexibility (which gives excellent riding properties), is cheap and produces tough roads which are resistant to the elements and the action of traffic. Hot mix is currently the principal material used in each of the structural and surfacing {ayers of roads in the UK and most other countries, from roadbase through basecourse to wearing course. Many different types of asphalt mixtures are used throughout the world and in 1990 it was reported that there were over 350 recipe based mixture designs currently in use in the UK alone (35). These mixtures have been developed or evolved to accomplish certain requirements in terms of load bearing capacity, durability, surface texture, permeability ete. In recent years, there have been moves to rationalise the approach to mix design on a performance basis. This means that the mechanical properties of the material be fully known and utilized to design a pavement which will withstand predicted traffic levels for the desired period of time. Research has shown that improvements to current practice can enhance mixture performance but implementation of the findings is in its early stages (36, 37) Bitumen emulsion mixtures have been developed in a number of countries with quite varied designs suited to the situations in which they are used. The driving forces behind their integration into the road builders’ palette have been -35-covered in the introduction. The emphasis on these factors varies from case to case. For example, in densely populated areas environmental benefits are very important whereas in remote regions logistics would be the main attraction. The following section aims to introduce the general concept of cold mix and then describe specific types of emulsion mixture technology as they exist and are used today. 3.2. COLD MIX IN GENERAL Cold mix is currently used in a number of European countries, Scandinavia, the United States of America, Australia and New Zealand, Southern Africa and an increasing number of developing countries. The specific mixtures used in these areas will be covered below but the general principles of ‘manufacture and laying are similar in all cases. {As indicated above, cold mix is manufactured at ambient temperatures, although some processes can use the emulsion warmed to around 60 °C. The aggregate can be used without drying although the water content must be controlled as it has a great effect on the nature of the mixture. The aggregate mixture is fed to a mixing device such as a pug mill, or a rolling drum mixer. Typical layouts for batch and continuous cold mix plants are shown in Figures 3-1 and 3-2 respectively. The main difference between hot and cold mix plants is the absence of heating and drying facilities in the latter, the benefits of which have been discussed above. Pre-wet water is added to surface wet the aggregate to prevent premature break of the emulsion. Bitumen emulsion is then added and mixed until maximum coating is obtained. Care must be taken not to over mix as the input of mechanical energy will cause the emulsion to break further which can lead to a stripped or unworkable mixture. -36-erstociple oe ——“ tar Wateriank | ee Meter ® Pregrad segs oT sory bar YY ¥ i Figure 3-2 : Continuous cold mix plant 37.Cold mix can be manufactured to cater for a range of different applicational regimes. Small scale use of cold mix requires that a mixture be manufactured in batch sizes in the order of 20 tonnes and then stockpiled for a number of days or even weeks to reduce costs. Unfortunately this necessitates the production of very slow setting mixtures which are very slow to build up strength after laying. For large scale applications, such as major construction or reconstruction, stockpile life is not as important and, therefore, quicker setting mixtures can be produced. Bitumen emulsion mixtures are used mainly for basecourse and sometimes for roadbase or wearing course. They are applied through a number of methods ranging from hand application, through graders, finishers or pavers to self contained mixing and laying plants. Compaction regimes for cold mix are quite varied at present as different companies advocate and utilize different techniques. However, the preferred method seems to be steel rolling followed by very heavy pneumatic tyred roller (PTR) and finally finishing with steel. As with mixing, operators must exercise a degree of caution as over rolling can lead to excessive emulsion break, which can seal the surface preventing curing, and cracking. 3.3. EUROPEAN COLD MIX PRACTICES A number of processes have been developed and are in use in Europe. These are Grave emulsion, the Two Stage Mixing process, the Double Mixing process and the Double Treatment process. Each of these processes will be described in the following section. 3.3.1 Grave emulsion The process known as Grave emulsion (emulsion stabilized aggregate) has been in use in southern France for approximately 40 years (38). It is used extensively as basecourse and for reprofiling, overlaying and strengthening old -38-pavements and construction and reconstruction of lightly trafficked roads. It can also be used for overlaying cement bound basecourse to prevent crack propagation. Being the oldest form of emulsion mixture, at least in Europe, many of the other techniques which will be covered below have some similarities with it, particularly in terms of mixture production and laying methods. Several other countries, notably Spain (39) and Eire (40, 41), have adopted the Grave emulsion technique with little or no alteration. Grave emulsion was not specified in France until 1974 with the publication of "Instruction for the manufacture of grave-emulsion pavement courses" edited by L.CP.C. and S.E.T.R.A (42). Grave is not used by all regional authorities in France and it is probably fair to say that it is mainly used in the warmer and drier southem regions due to the water sensitivity of emulsion based mixtures. However, since 1988, quite a large tonnage of Grave emulsion has been laid in the much wetter climate of Eire (40), and such contracts have met with a high degree of success, Mixture design ‘The aggregate mixture used in Grave emulsion is densely graded as shown in Figure 3-1. The optimum design has a high sand content to give high internal friction in the aggregate mixture during curing and good surface texture. The latter is often an interim requirement as Grave emulsion layers are nearly always overlaid with a surface dressing to seal the surface. A low filler content is also preferred to minimize the susceptibility to rutting which can occur if the voids are overfilled with a bituminous/filler mastic (43). A maximum void content of 15 % is specified which is very high compared with other densely graded mixtures but is a relic of the presence of water in the mixture initially. Nominal grading sizes are 10mm, 14mm, 20mm and 31.5mm. Most regions are now using the 14mm grade. The aggregate may be either a crushed rock or gravel. Sand is sometimes incorporated to aid compaction. Aggregates must comply with French -39-specifications on durability, angularity and cleanliness. >——— Percentage passing Size (mm) Figure 3-3 : Grave emulsion aggregate mixture design ‘The most notable feature of Grave emulsion mixtures is the partial coating of the aggregate. The classic binder content is only 3 to 3.5% on the mixture. This gives a Grave mixture a very lean appearance and leaves it potentially susceptible to the ingress of water which is the reason for the normal practice of surface dressing. Low binder contents were used originally in order to promote a high level of aggregate contact to maximise intemal friction which resists rutting. In recent years, there has been a move towards higher binder contents of 4% or more, which are not outside the scope of the original French specifications. The specifications have recently been revised to allow even higher residual binder contents to be used. Emulsions used in Grave mixtures are designed to have a medium setting rate. This only enables the emulsified bitumen to coat the fine aggregate before partial coalescence takes place. The fine coated mastic then acts as a -40-discontinuous cement to bind the larger aggregate matrix together. It is claimed that this property prevents underlying cracks from propagating up through a layer of grave. After mixing, the binder is in a partially coalesced state (38). This means that the binder is hydrophobic and, therefore, ensures that it cannot be rinsed off the aggregate by rainfall. However, the mixture remains workable for several days. With the inclusion of a small amount of flux oil, this can be extended to several weeks but these mixtures can only be used for patching and is inhibits the setting process for reprofiling. It is preferred not to use solvent, as many months. The standard method of mixture design for grave emulsion is the Duriez test (44), which was developed by L.C.P.C. approximately 30 years ago. ‘The test is used to determine the best aggregate/emulsion proportions to satisfy the specification. Samples of the test mixture are fabricated in 80mm moulds using a compaction load of 12 t applied for S minutes. Half of the specimens are then cured at room temperature for 14 days. The other half are cured at room temperature for 7 days and then 7 days under water. The compression strengths of all samples are measured using a hydraulic ram which applies a load at a deformation rate of Imm/s. The maximum load required to achieve this rate of compression is taken as the compression strength of the mixture. The ratio of wet to dry compression strength is then calculated and taken as the final Duriez test result. To pass the test a material must have a wet to dry strength ratio greater than 0.55 and a minimum compressive strength of 30 bar using 80/120 pen bitumen. A compactivity test is also carried out and a material must have a value above 87 % to be acceptable. Mixing, laying and compaction Grave emulsion is mixed in a simple plant similar to that represented in the schematic diagram in Figure 3-2. As Grave is often used in fairly remote regions, the plant is often of the mobile variety which can be located in 2 quarry near to the -4l-road construction site. Laying of Grave emulsion is normally carried out by use of a grader. Pavers are also used. Both techniques have their merits and drawbacks, Whilst pavers allow very even layers to be laid rapidly, they can lead to segregation of the mixture. Graders, on the other hand, do not cause segregation, but the processes of working and reworking the mixture is slow and can [ead to less even profiles. Compaction of grave emulsion is a very important and well developed factor in the success of the technique. It serves two purposes, namely placing of the material and redistribution of the binder from separate globules to continuous films, Effective densification prevents future settlement or rutting and increases internal friction and cohesion. Compaction can become difficult to carry out effectively due to one or more of the following factors: . the water content is too low due to mixture design or drying out of the mixture coalescence of the emulsion is too far advanced : the base binder pen is too low - the ambient temperature is too low . the bitumen globules are poorly dispersed : the aggregate is being crushed or the aggregate surface texture is granular Heavy pneumatic tyred rollers (PTR) are often advised for compaction because their kneading action is very effective in achieving the objectives of densification and redistribution of the bitumen. Vibrating steel wheeled rollers are preferred to dead weight rollers. Care must be taken to achieve an adequate level of compaction without over compacting, as this can lead to surface cracking. As the binder approaches a state of full break, it becomes somewhat dry and crumbly. -42-This is often referred to as the "cheesy" state. At this point the binder is lacking in cohesion and application of a heavy load can cause the material to break apart rather than stick together. The final layer in a grave construction is nearly always overlaid with a surface dressing to prevent ravelling by increasing the surface cohesion and thereby resist shearing stresses. As grave mixtures also have a certain amount of porosity, surface treatments are also necessary to prevent the penetration of water. Grave emulsion can be trafficked immediately after compaction and in fact in some instances, it may even be trafficked during and after grading. This is due to the high intemal friction and cohesion which exists in early life of the system. ‘The full strength potential is achieved as a result of water evaporation which is a slow process and is dependent on climactic conditions and partly assisted by the action of traffic. Provided that compaction has been carried out effectively, no deformation should occur during the curing period. Pavement design Design of pavement with grave emulsion is carried out in much the same way as with any other material. The design parameters are type and amount of traffic, type and nature of the underlying layer and properties of the new course or courses. Three methods are used: : experimental, involving deflection or CBR measurements on site 0 consult the instruction handbook : use computerized model Performance of Grave in-situ In 1993, Lafon et al. (45) carried out a survey of emulsion based pavement -43-in France which yielded information on the in-situ performance of Grave emulsion. It was found that the aggregate gradings were always dense, having 6 - 10% <80 pm, but air void contents were high at a level of 10 - 15%, The binder contents of mixtures were surprisingly high in the range 4 - 4.5 % and the penetration grade of recovered binders was between 50 and 120. Stifiiness moduli ranged from 4,200 to 5,200 MPa tested at 20°C with a load rise time of 120 ms. 33.2 Cold mixes Cold mixes are utilized in a number of European countries (38, 46). There are two classifications based on the storage requirement of the mixtures. Storable mixtures are made with cut-back or fluxed bitumen emulsions. The presence of solvent keeps the binder soft and thus keeps the mix workable. Immediate use or non-storable cold mixes contain non-fluxed emulsions. These mixtures therefore give rise to stiffer mixtures as soon as the water is expelled. Three types of cold mix, based on aggregate grading are used for repair and maintenance. These are open, semi-dense and dense graded. Open graded mixtures are storable and can be laid with low technology but they are highly porous and easily deformable. Semi dense mixtures have greater cohesion and are less permeable, however when fluxed they are slower to cure. Dense mixtures contain no solvent therefore cure much faster. They have bigh cohesion and good resistance to deformation due to aggregate interlock. Permeability is also far lower. Cold mixes are also used for wearing course. They are layable in thicknesses varying from 3 to 22 cm and are designed to have high surface rugosity and allow drainage which can alleviate aquaplaning. If used as a drainage layer, a suitable drainage pipe system must be provided in the basecourse and the road base must be fully sealed. Cold mix wearing course can be used on all but the most highly trafficked roads. AdMixtures can be produced in specialized mixing plant, motor pavers or simple concrete mixers in which case the mixture can be produced on site. For small jobs, laying is carried out by hand and compacted using a small vibrating roller. Reshaping work usually employs a grader but pavers are also used. As the grading used in these mixtures is typically open, layers normally require the application of a sealing coat. 3.3.3. Two-stage mixing The two-stage mixing process was developed in Sweden and is used on fairly remote roads carrying less than 1500 vehicles per day. It is covered by a specification in the Swedish road manual (47). Both virgin and recycled material can be used with adjustment to the mix design. The basis of the procedure is that coating of the coarse and fine aggregate fractions is carried out in two stages to prevent preferential break of the emulsion onto the fines. The aggregate mixture design for a 16 mm mix is shown in Figure 3-4. The division between coarse and fine aggregate is made at a size of 3 mm. Figure 3-4: Aggregate grading curve for two-stage mixing -45-Mixture design Two stage mixing uses emulsions with very soft binders to avoid low temperature cracking during extremely cold periods, as very heavy logging trucks tend to use these roads. The binder type is expressed in terms of viscosity at 60 °C rather than penetration. Grades range from 2,000 to 10,000 centistokes. For comparison, 100 pen bitumen has a viscosity of 100,000 centistokes at 60 °C which illustrates how soft the binders really are. The soft binders are produced by adding heavy flux oil to normal penetration grade bitumens, and they are often doped with fatty amine based adhesion agents to improve durability. Emulsions are formulated with different levels of emulsifier to give different setting rates. ‘A rapid setting emulsion is used on the coarse fraction and a medium setting version is added with the fines. The reasoning behind this lies in the surface area of the aggregate fractions in that a slower setting emulsion is required to coat the fine aggregate. Mixing and laying ‘The mixing procedure itself is continuous and is represented in Figure 3-5. Firstly the 6-12 and 12-16 mm aggregate fractions are charged to the mixer, with pre-wer water being added en-route at a level of <1%. ‘The rapid setting emulsion with the harder bitumen is then added via a spray bar during the mixing process ‘After ~20 seconds mixing, the pre-wetted fine aggregate fraction is added, shortly followed by the second medium setting emulsion containing the softer binder. Final mixing continues for ~20 seconds after which the completed mixture flows out of the mixer to be collected. -46-a __ Rapid setting Hl Siow setting emulsion emulsion 6/12 & 12/16 mm ene te Fine aggregate Figure 3-5 : Schematic diagram of two stage mixer Two stage mixing plants are often mobile and can, therefore, be located near to the area of application. One such example is shown in Figure 3-6. Mixtures are laid using graders or pavers as shown in Figure 3-7. -47-3.3.4 Double mixing process ‘The double mixing process was patented by Maheas (48). The method was later adopted and exploited by the French company SCREG and goes under the trade name of COMPOMAC*. It is similar to the two stage mixing process, in that itis designed to avoid preferential coating of the fine aggregate fraction, but it is carried out the opposite way around (49, 50). ‘A Grave emulsion type aggregate mixture is used with the fine and coarse division being made at the 2 mm size. Figure 3-8 shows the procedure for the double mixing process. Firstly, the fine aggregate fraction is mixed with part of the bitumen emulsion. Alternatively, hot bitumen can also be used at this stage. The mixture is then stockpiled for later use, The second stage involves mixing the stone fraction with the second portion of emulsion and then adding the coated fines. The total residual binder content lies between 5 and 5.8 % which makes this a much richer mixture than normal Grave. It is claimed that the mixture is very uniformly coated which gives rise to benefits in handling and performance characteristics. a —— | | / Zz Coated fines stockpile Figure 3-8 : Double mixing process -48-3.3.5 Double treatment process The double treatment process of cold mix is utilized in France and Germany and recently in the Benelux countries for basecourse, Over the years it has displaced recycling of bituminous roads using solely cementitious binders. ‘Two French examples of the process are Flexocim® from Beugnet and Stabicol® from Colas. The double treatment process is so called because it uses two binders, namely bitumen and cement (51, 52). The two binders can be added in various orders to both virgin and recycled materials. Due to the nature of the binders, the cured mixture is both hard and flexible. This combination gives rise to great resistance to cracking and also rutting at high temperatures. The increased stiffness means that thinner layers are required in a pavement structure. Interest from Benelux in this type of mixture has arisen from its ability to seal in old binder when recycled planings from old tar containing roads are used. In the Netherlands and Belgium there are a great number of tar containing roads which are wearing out and will, therefore, have to be repaired. Additionally, it has been found that the harmful polycyclic aromatic components are leaching out, due to rainfall, and entering watercourses. It is not easy to dispose of the planings as leaching would merely continue in landfill. It has now been found that by recycling these pavements, with a combination of bitumen and cement as binders, the old tar binder can be sealed in, It was not possible to hot recycle as the heating process would very quickly release harmful gases into the atmosphere. Thus, the cold bitumen emulsion based double treatment process offers an ideal solution to the problem. The aggregate grading used in the double treatment process is often based on a Grave design, but other dense gradings are also used. Sand is often added when recycled planings are used to increase the fines content which assists the emulsion breaking process. Slow setting emulsions are used. These are mostly cationic, and bitumen penetration grades of 40/50 or 180/220 are used. The -49-bitumen emulsion is added at a level of 2.2 to 4 % (dependent on whether virgin or recycled material is used) and the hydraulic binder is used at a level between 2 and 2.6 %. The ratio between the two binders affects the nature and performance of the mix in that more bitumen leads to a more flexible pavement which is more susceptible to rutting, whereas more cement gives rise to greater resistance to rutting but also a brittle layer which can be susceptible to cracking and shrinkage. By careful mix design, an optimum mixture can be obtained. 33.6 Spain Emulsion mixtures have been used in Spain since the late 1950's. Gravel and open graded mixtures, which are now widely used, appeared in the 1970's (53). High viscosity, medium setting, cationic or anionic emulsions are used in open graded mixtures which ensure thick bitumen coatings on the aggregate. Cold mix is used on all but the highest volume roads without modified binders but, with modified binders, even these roads can be constructed using cold mix. In addition to the environmental and logistical benefits, open graded emulsion mixtures, with more than 20 % voids, are claimed to have other important properties. These mixtures are resistant to fatigue cracking which can be a problem in thin surfaces like those used in Spain. They also have good skid resistance due to drainage and surface friction. Thick binder films used in open mixtures are resistant to ageing. Ithas been found that open graded mixtures are more storage stable and yet cure more rapidly once layed. Due to mobilization of the interlocking large aggregate skeleton, they are also said to be more resistant to deformation. Polymer modification of the binder has been employed in these mixtures to further enhance properties (54), 33.7 Germany Rode and Weinert (35) stated in 1993, that "Cold placing methods have not yet been sufficiently proven in road -50-construction practice in Germany and it is not yet clear on which grades of roads this mix is to be used” At that time, more than 90 % of roads were constructed using hot methods but it was predicted that ecological considerations may obstruct the use of hot processes in the future. Due to claims that fumes from bitumen are carcinogenic, hot mix plant was becoming more sophisticated and consequently more expensive. This is a very effective driving force for companies concemed with road construction to look for ways around the problem. Two methods of cold laying have been identified as mix in plant and mix in place - the latter being particularly useful for recycling. A substantial amount of material has been laid in Germany using milled road material or demolition waste with emulsion and cement as binders. Roads of this nature have been of very high quality. Laboratory tests have been devised to asses the properties which can be expected from cold layed materials and these are based on density specifications, Marshall tests on samples before and after water soaking and splitting tests. Cold mix placing is known to require different techniques from hot mix. Due to the altered flow properties of the material, the angle of the placing beam in the paver is changed to give the correct layer thickness. Compaction begins immediately after laying using a twin steel drum roller. The use of very heavy equipment is common and pneumatic tyred rollers are recommended. Minimal vibration is necessary apart from small amount of "deep" vibration, Lower roller speeds compared with hot mix are said to be most effective. Inan environmentally considerate country such as Germany, mix in place cold road recycling is a very appreciated method of road construction, Before any ‘work commences the nature of the road to be recycled must be well known, Old 51Spavement is often milled to a depth of 30 cm. Millings are reduced in size and then combined with a slurry of cement and water and bitumen emulsion. The mixture is then relayed and compacted using the techniques outlined above. Pavement thus constructed has been found to make excellent foundation or sub- base. It is predicted that due to the excellent performance thus far and the likelihood of improvements in the future, cold laid pavement will become more widely used in Germany in the future. 33.8 Italy In recent years, cold worked bituminous mixtures have come into widespread use in Italy for both the reinforcement of existing roads and the construction of new roads (56). Asa consequence, the national research council in Italy has drawn up a set of regulations to control mixtures and construction techniques. The normal cold mix types, design methods and laying techniques are employed and the Italian climate favours the use of emulsion mixtures. 34 NORTH AMERICAN PRACTICE Cold mix has been used in the United States of America since the 1960's. Due to the remoteness of some areas of the country, cold mix is an essential part ble of the road construction industry. Information on US practice is easily av. in manuals compiled by various organizations (57, 58, 59) to advise on all aspects, of production and laying of cold mix as well as cold recycling. ‘Two classifications of cold mix are identified according to mixing method. These are plant-mixed and mix-in-place (road mix). The environmental, economic and versatility benefits are recognized as are the limitations such as sensitivity to wet weather and slow build up of strength. “52.jueyd xm afies om, : 9-¢ amin,ssapoad xr ofeys oa Suysn paamyaeymaeut aamyxtU yA Supsed + /-¢ 2aNB 1‘Two types of bituminous binder are prescribed for cold mix, namely cut- back and emulsified asphalt. Due to environmental concems, the former is becoming restricted in many areas. Thirteen grades of bitumen emulsion are used with a range of setting rates and binder types. It should be stressed that American emulsions alnost always contain solvent. The anionic grades are labelled MS or SS, for medium or slow setting, followed by a number to indicate the relative viscosity of the emulsion - the higher the number the greater the viscosity - eg. MS-2and SS-1. Cationic emulsions are denoted by placing a C in front ie. CMS- 2. Additionally the letters HF may be placed in front or h at the end of the code. HF, which stands for high float, indicates that certain chemicals have been added to give thicker films of bitumen on aggregate particles. An "h placed at the end means that a harder base bitumen has been used. Different grades of cut-back are also used. This cold applied binder is produced by diluting bitumen with solvent to liquify the binder at low temperature. Medium curing (MC) cutbacks use kerosene as solvent, which is relatively volatile, whereas slow curing (SC) cutbacks use heavy flux oils or are made by distilling the crude directly to the desired grade. The setting rate is dependent upon the rate of evaporation of the solvent. A table, reproduced here as Table 3-1, assists the engineer in the selection of a suitable emulsion or cutback for a particular type of job. The use of a binder with the highest viscosity possible is advocated as a general rule. It is interesting to note that the use of emulsions for storage stable patching mixtures is not recommended and only fluxed materials can be used. Conversely, fluxed binders cannot be used in open graded mixtures. Consideration is given to atmospheric conditions in the use of cold mix. As setting is dependent upon the evaporation of water, damp and cold conditions will inhibit curing whereas dry and warm conditions will speed it up. Both extremes have consequences in handling and performance after laying. Cationic emulsions are to be used if possible due to their built in breaking mechanism and adhesion properties. Some emulsions used in the US contain a small amount of -53-solvent to aid mixing and workability. When used, time for evaporation of the solvent, in addition to water, must be given before any overlaying takes place. Table 3-1 : Guide for uses of asphalt in cold mix Emulsified asphalt Cut-back asphalts Anionic Cationic | Medium | slow curing | curing Type ofconstruction TTT ye {ele tu lu ls [s fos fo fo ls fo [e $ afals [om a ° CCold-laid plant mix pavement base and surfaces Open-graded agaregate x [x x |x Well-graded aggregate x [x[x x[x] [x[x|[x]x[x[x Patching, immediate use x |x x[x]| [x[x x Patching, Stockpile x] [x|x Mixed in place(Road mix) Pavement base and surfaces Open-graded aggregate | X | X x} x x|x] |x}x Well graded aggregate x|x|x x]x| |x{x] |x|x Sand x|xX|X x|x]x]x|x Sandy soil x} x|x x{x| | x|x Patching, immediate use x} x|X x}|x| | x]x x old mix recycling All mixtures X|X/|X{|X}|X|X{|X}]X}]xX A whole range of aggregate types from soil-aggregate combinations to silty sands and well graded aggregate mixtures are successfully cold mixed. High quality aggregates will give rise to optimum mixtures but in areas where these are 54.scarce, inferior substitutes are accommodated. For this reason, no strict gradings are given and mix designs are left to the engineer. ‘There is no universally accepted bitumen emulsion mixture design method. However, either the Marshall (60) or Hveem (61) methods, or modified versions, are nearly always used. Examples are the Illinois method which is based on the Marshall procedure, and the Asphalt Institute's method which contains elements of the Hveem method plus resilient modulus tests. Resilient modulus or, as it is termed in the UK, stiffness modulus is discussed in detail in chapter 8. If laboratory tests are not possible, empirical formulae for addition ievels of emulsified or cut-back asphalt to densely graded aggregate mixtures are provided as a substitute, The formula for the former binder is as shown below. P=(0.05A + 0.1B + 0.5C) x (0.7) @-1) Where : P= Percent by weight of asphalt emulsion, based on weight of graded mineral aggregate A= Percent of mineral aggregate > 2.36 mm B = Percent of mineral aggregate < 2.36 mm and > 75 wm C= Percent of mineral aggregate < 75 um Two types of mixing plant are used, namely in-place and central plant mixing equipment. Mixers for in-place production comprise of rotary mixers which are essentially mobile mixing chambers used for adding binder to formerly anbound roads, motor graders which mix on the roadbed and travel plants which are used for placing mixtures of new material. The last two alternatives can also be fed with planings in a cold recycling process. Spreading equipment includes motor graders and pavers. Compaction is carried out using a combination of pneumatic tyred rollers, for initial compaction, and steel rollers with and without vibration for finishing. Central plant mixers are essentially the same as hot mix -55-plants, except that there are no drying and heating facilities, and can be either batch type or continuous. In addition to cold mix with new materials, a great deal of cold mix recycling has been carried out in North America since the 1970's (62, 63, 64, 65). This option is growing in popularity due to potential cost savings and logistical benefits as availability of good quality aggregates becomes limited in some regions due to depletion of deposits. The asphalt contained in the old layers is also being seen as a valuable resource which should not be squandered. Additionally, dumping restrictions make it preferable to reuse material rather than to attempt to dispose of it. In the American Asphalt Recycling Manual (written in 1983) it was stated that there are more than a million miles of roads in the United States, which are either already in need of repair or soon will be, that are recyclable (66). Before a recycling project can be carried out, an assessment of the existing pavement structure, including the subgrade, and the materials used must be carried out (67, 68). Binder content of the mixture is determined and then a sieve analysis is performed on the aggregate mixture. The aggregate should also have either an acceptable plasticity index if it isa soil type material (69) or sand equivalent value (70) to ensure that it does not contain excessive amounts of clay or other fine aggregate. The aggregate's resistance to binder stripping is also sometimes evaluated. If new aggregate is required, this should also be of an acceptable quality. Medium or slow setting emulsions are used and mix tests are carried out to determine whether a cationic or anionic emulsion is best suited to the recycled material. MS emulsions are utilized if the gradation is coarse and SS for finer gradings. Mix design is based upon laboratory tests, empirical formulae or past experience as no universally accepted method exists. Firstly, the aggregate mixture design is formulated. This will be based on the recovered aggregate 56-grading plus any new material that is required. Both open and dense graded mixtures are used. The binder requirement of the mixture is determined and then the amount of new asphalt required is found from the difference between the residual binder content of the coated material and the total bitumen requirement of the uncoated aggregate. In the case of open graded mixtures, the objective is to use as much bitumen as possible without excessive run-off. Adjustments to the pre-determined design are made on site. Pavement design is treated in exactly the same way as cold mix with virgin materials with the three factors of traffic volume, subgrade modulus and mixture properties being utilized along with design charts (71, 72). Pavement design is described in more detail in chapter 13. ‘The favoured and most economical method of pavement recycling involves all steps being carried out in-situ. This is known as in-place recycling. Firstly, drainage must be established as failure to provide a competent system will lead to failure of an emulsified asphalt pavement. The old pavement is then ripped up and size reduction of the material carried out. Alternatively, a process of cold milling is used which directly grinds up the old road on the road bed. Motor graders, rotary mixers or travel plant, which have been discussed above, are used to ‘manufacture the mixture. The final product is often placed on the road surface in a windrow and may be allowed to dry out to some extent to optimize the water content for compaction. This is then spread using a grader. Compaction is carried out with a combination of pneumatic tyred and stee! rollers. Central plant recycling is also used for projects that require high rates of production or close control of mixture desiga. The old road can either be ripped up and then transported away to be crushed and screened or size reduced in situ for later transport to the mixing plant. Stationary mixing plant consists merely of a batch drum or continuous type mixer and auxiliary equipment and can therefore “ST