Bitumen

Bitumen has been used in construction since ancient times, thanks to its key waterproofing properties. Unmodified bitumen is a highly viscous liquid, and its tendency to become brittle at low temperatures and soft at high temperatures has limited its use. For many decades, bitumen has been successfully used in asphalt concrete to pave roads. Despite continuous improvements to bitumen production processes, mix design and pavement design, there are limits to the extent that bitumen can surmount the challenge. Accelerating wear and tear caused by heavy traffic and harsh climates are taking a toll. In addition there are increasing demands for quieter and safer roads. Polymer modification of bitumen is helping to overcome the challenges. Today, millions of tons of polymer modified bitumen is used by the global roads industry Photo: Use of soft unmodified bitumen on a dyke to bind the stones and provide waterproofing. The flow patterns result from the non-elastic viscous characteristics of bitumen.

Composition
Bitumen is an complex mixture of hydrocarbons. It can be derived from a straight distillation of a single crude oil. However, it is usually a combination of the heavier products from different processes in a refinery, blended to obtain the right specification. Because of its complexity, the composition is expressed by determining the relative amounts of classes of molecules, asphaltenes and maltenes. Asphaltenes these are polar aromatics which associate in large structures to give solidity at ambient temperatures. Maltenes consist of:

Saturates segregated into paraffins and naphthenes. Regarded as carrier or solvent for the asphaltenes. Aromatics also regarded as carrier or solvent for the asphaltenes. Resins act as dispersion agents

Interaction
Modification
Kraton polymers can give bitumen the high-performance characteristics it needs for long term survival of even the toughest climates. The unique molecular structure of Kraton polymers interacts with the bitumen to add flexibility, elasticity and toughness over a wide temperature range. This will reduce bitumens sensitivity to extreme temperatures and significantly enhance its performance properties compared to unmodif ied bitumen.

Interaction
At lower temperatures, polystyrene and polybutadiene do not mix. Due to the composition of Kraton D polymers, the polystyrene blocks combine into a hard solid islands in a sea of polybutadiene chains. The rubbery polybutadiene connects the different polystyrene islands to form a network. Polybutadiene remains rubbery even at temperatures as low as 90C. Polystyrene remains solid up to the polystyrene glass transition temperature at around 100C. The resulting Kraton D polymer has rubbery properties over a large temperature range. This network structure is strong at temperatures up to 100C. Since the structure is based on the physical reversible bonds in the polystyrene domains, at higher temperatures the network breaks up into its individual SB and SBS molecules. Re-establishment of the network occurs on cooling. This reversible network is one of the main contributors to the versatility of Kraton polymers.

Absorption
Kraton D SBS polymer has almost the same solution parameters as the maltenes phase of the bitumen. It can absorb up to nine times its own weight of bituminous components, and the extended polymer can occupy a substantial volume fraction of the blend even at low concentrations. There is evidence that at a concentration of 3% in a highly compatible bitumen, the polymer rich phase may have achieved co-continuity with the other (asphaltene rich) phase. Bitumen composition is important with respect to the final properties of the blend and the level of compatibility. Certain carefully selected bitumens can have, for instance, a single phase structure at temperatures higher than 130C. The aromaticity and the average molecular weight of the maltenes phase determine the weakening of the styrene domains, and hence empirical properties like softening point.

Interaction
The compatibility of bitumen and polymer is key to the success of the ideally suited to be blended with bitumen because of their similar average to absorb bitumens oily components, while maintaining the network structure. This unique combination where a small amount of polymer creates a network absorbing its components and increasing its effective volume, has been polymer modified bitumen Bitumen is turned from a highly viscous material into a bituminous elastomer, behaviour over a larger temperature range. If necessary, by the right choice of polymer structure, the temperature range can be extended to cover virtually modification. Kraton polymers are solubility parameters and their ability

structure in the bitumen by integral to the success of Kraton D

with the key advantages of elastic bitumen, polymer concentration and any climate.

Compatibility
As indicated in the section on bitumen composition, bitumen consists of a mixture of larger and smaller molecules, some of which are oil-like. They are absorbed by the polymer. However, these oil-like components also act to dissolve the larger molecules ('Asphaltenes'). When the polymer absorbs too much of these oily 'solvents', a phase separation can occur, whereby an 'asphaltene' rich layer forms at the bottom and a polymer rich layer forms at the top of the mixture. The interaction of polymer and different components in the bitumen can also have other effects. A summary of these effects are shown in the compatibility chart on the right.

The S Curve
The S curve clearly shows the dramatic impact of a small amount of polymer on empirical properties such as Softening Point. Although the S-curve does not necessarily reflect the level of performance that can be achieved at the various polymer contents, it surely illustrates that securing complete dissolving and avoiding degeneration due to too severe processing conditions, are important to obtain a certain performance level.

Elastomeric
Addition of Kraton D polymer fundamentally changes the behaviour of bitumen from a highly viscous liquid to an elastomeric product at higher concentrations (+/-12%) These changes can be observed in the table:

Mechanical properties of blown bitumen compared to bitumen modified with high concentrations of Kraton D polymer Measurement Unit Blown bitumen Bitumen Bitumen 10% Kraton D 12% Kraton D Elongation % 140 1500 2000 Permanent set % >100 <10 <10 Breaking stress N 0.5 10 15 Cold Bend pass C -5 - 20 - 35

Findings:
Elongation shows that highly modified (+/-12%) test samples can be extended 20 times their original length before failure Permanent set shows that a less than 10% permanent deformation resulted from that extension The breaking stress had increased by a factor 20 to 30 Cold bend indicates its flexibility and non brittle behaviour at very low temperatures

Mixing
After choosing the polymer and bitumen, the two components need to be mixed to ensure homogeneous distribution and complete dissolution of the polymer. Generally high shear mixers are applied to secure a particle size reduction of the polymer and to obtain an intimate contact between bitumen and polymer. The set up of the system and the sequential process steps need to be chosen and controlled to ensure the best resulting product. When considering the use of Kraton D polymers please contact your local Kraton Polymers sales manager to ensure the application of the correct process conditions.

Morphologies
Kraton D polymer is supplied as porous pellets, which have excellent solids flow characteristics for handling and high bulk density for storage. This is a good combination for systems equipped with high shear mixers. Alternatively a powder versions are available which can be applied when low shear mixing equipment is used.

High Shear Mixers

High shear mixers grind the polymer while immersed in the bitumen. The polymer is mixed into the bitumen and passed through the high shear mixer, to cut the particles into small pieces. The size of the pieces is influenced by the gap width between the stator and the rotor. Decreasing size, increases the specific surface area, speeding up the absorption of the oily components in the bitumen. The absorption of oily components softens the polymer particles, and allows to tear and stretch these particles, further increasing the specific surface area. homogeneous dispersion of the polymer throughout the bitumen. shear forces in the high shear mixer Eventually this should result in a

Conditions
The high shear mixing process is typically carried out at 180C. A 10 ton batch of 12% polymer in 150 PEN bitumen has a batch cycle time of 1-2 hours. The energy input from the high shear mixer increases the temperature during the process. Further dilution then occurs to acheive the final desired Bitumen binder.

Typical Grades
The main grades used in bitumen applications are:

Kraton D 1184 polymer and KRATON D 1186 polymer are the industry benchmark polymers Kraton D 1101 polymer for exceptional low temperature performance Kraton G 1650 polymer for those applications that require outstanding heat and oxidation resistance such as hot mopping asphalt binders. Kraton D 1118 polymer for improved flow of self-adhesive products Kraton D polymer based on isoprene for increased tack in self-adhesive products, also at low temperatures.

Roads
Polymer modification of bitumen with Kraton polymers is an effective and widely used method of improving road performance and road life expectancy. Kraton Polymers is the worlds leading producer of styrenic block copolymers for the roads industry with its range of Kraton D polymers successfully applied in many road, runway and race track projects around the world. Damaged roads are a safety hazard and an inconvenience. Larger volumes of heavier traffic are speeding up the wearing process, while demands from the general public for safer, faster and more comfortable travel are on the increase. A tough challenge for the roads industry to meet. Kraton polymers give key advantages to bitumen-based roads that can significantly reduce climate and traffic-induced damage, leading to fewer disruptions for maintenance, and improved ride safety and comfort. Use the links to find out why, how and where Kraton D polymers are making a real difference to road development around the world.

Uses
Polymer-modified bitumen is widely used, not only in traditional and modern hot asphalt mixes, but also in slurry-based systems and tack coats. Traditionally, polymer modification has focused on the pavement wearing course, binder course and on specialist applications such as bridge decks. More recently the application of polymers in the base course has enabled durability improvement and cost savings when combined with an overall thinner road structure.

The use of bitumen modified with Kraton D polymer in the asphalt mix helps to: 1. 2. 3. 4. Lower permanent deformation Increase crack resistance Reduce effects from aging Increase binder toughness to resist stone losses

Typical asphalt mixes for pavement are from about 4 to 12% bitumen. Porous asphalt mixes consist of a porous wearing layer on top of an impervious base layer.

Stone Mastic Asphalt

A stone mastic asphalt is essentially a stone, skeleton like, porous asphalt with the voids filled with mortar. The traffic loads are carried by the stone skeleton. Slight variations in bitumen content can lead to an incompletelyformed skeleton and hence permanent deformation. The relatively low amount of binder also makes this mix sensitive to cracking despite its somewhat softer base bitumen.

Slurry / Emulsion
Emulsions are widely used for:

Tack coats Chip seal surface dressings Slurry seals Emulsions are small bitumen droplets suspended in water using surfactants. These surfactants prevent the droplets from coagulating. Upon contact with the aggregate, the droplets coalesce and the water separates causing the bitumen to form a layer on the stones surface.

Sealants
Quick repairs using crack sealants ensure the water tightness of the road until major maintenance work can be carried out. The crack sealant fills the crack, but does not reconstitute the mechanical link between the sections. Any movements either through shrinkage or loading will be absorbed by the crack filler. The filler therefore needs to be soft and elastic over the full temperature range. In addition, the crack filler needs to have adhesive properties. Special formulations of selected Kraton polymer grades and specific bitumen give a very good overall performance which can ensure the structure is watertight and elastic over the full temperature range.

Cement Concrete Overlays

Cement concrete used to be widely used during the construction of main roads. Maintenance budgets often do not allow the full replacement of these roads with asphalt roads. If the cement concrete foundation is still in a good condition it can provide a rigid base layer for an asphalt concrete road. Road authorities find that asphalt refurbishment on a cement concrete road enables restoration with the added advantages of the asphalt such as

comfort and safety. The resulting elasticity, toughness and tack can achieve a durable layer, which will resist cracking under deformation and can arrests cracks coming from the cracked cement concrete layers, preventing failure of the water tightness of the asphalt. As a result, the restored structure can retain its watertight nature.

Stress Absorbing Membrane Interlayer (SAMI)

The SAMI is used to reduce reflective cracking when overlaying existing roads. It should not only secure the adhesion between the two layers, but should also have the potential to absorb the movement in the existing pavement without acting as a slip layer. The SAMI must have:

Tackiness Toughness A high cohesive strength A high viscosity at service temperature All these characteristics can be achieved by modifying the bitumen using Kraton polymers. The use of a SAMI can also be applied in newly constructed roads with rigid, lean cement-concrete base layers.

Environmental Impact
Use of polymer modification can improve the environmental impact of a road by:

Enabling designs that require less raw materials Sustaining a smooth and safe road surface over a longer part of the roads lifetime, and thereby reducing the environmental impact over the roads lifetime Extending the lifetime of a road, and thus reducing maintenance and impact on the environment. Using Kraton polymers therefore makes not only economic sense but also environmental sense

Roofing
The primary function of a roof is to present a waterproof barrier of lasting effectiveness. Flat or slightly inclined roofs have proven to be highly space economical and have therefore been applied in commercial buildings over many years. Flat roofs have now also gained acceptance in the housing market, although perception is influenced by the bad performance of early flat roofs. The modification of roofing material with Kraton D polymers has been a major factor in improving the quality and performance of roofing materials for flat roofs to become reputable and inspire public confidence for waterproofing of flat or slightly inclined roofs. While these modified roofing materials have become the standard in Europe and North America in regions with hot and cold climates, the use of modification has not developed throughout the world. This section of Kraton Polymers' website aims to inform anyone on the merits of polymermodification of roofing materials, and also focuses on recent developments related to bituminous roofing materials.

Coatings and Gels

Kraton D and G polymers offer a broad range of performance characteristics that make them ideally suited for the production of coatings and gels. These firm-forming polymers are UV, ozone and oxidation resistant, strippable, protective, high friction, waterproof, sound deadening and shatter retentive. Kraton polymers are suitable for solution or melt processing, and can be formulated with other polymers, resins, filters, pigments, oils, thickeners, waxes and stabilizers to obtain a desired balance of properties. Kraton G polymers are particularly well-suited for use as oil thickeners in oil gel compounds for filling communication cables. Properties include high tensile strength, elongation, resilience, flexibility and rebound.

Coatings
The unique properties and wide grade range of Kraton polymers provide the customer options for various applications.

Features and Benefits

The unique properties and wide grade range of Kraton polymers provide the customer different options for the coating markets.

Chip resistant Flexible at low temperatures Elongation and elasticity Adhesion to a wide variety of substrates Formulate for removable or permanent adhesion Kraton G polymers offer good durability in exterior applications. Kraton FG polymers yield better adhesion to polar substrates and crosslinkable

Products
Elastomeric Roof Coatings: Roof coatings can be solvent or hot melt sprayed. They need less resurfacing since they do not wash off readily. They can be formulated to provide low volatile organic compounds (VOC). Kraton G MD6932 polymer is a low viscosity polymer and offers a wider VOC exempt formulation ability. They can be applied in high humidity and colder environments. Kraton RP6924, G1652 polymers and blends with G1726 polymers are

also good candidates for this type of coating. Can Coatings: Kraton FG1901 has maleic anhydride grafted onto the rubber block thus improves adhesion to polar substrates and is crosslinkable. As a result, it is attractive for solvent resistant, chip resistant, good adhesion to metal, and corrosion protection applications. Temporary coatings: Kraton G polymers such as G1652, RP6924, and RP6932 can formulated with oil and sprayed on surfaces that when peeled leave no residue. They provide protection to metal substrates during chemical milling (etching) and can be removed later with no residue.

Medical Applications
We have applied our 40+ years of expertise in polymer chemistry to provide solutions to many medical applications. We serve customer applications in IV bag films, surgical draping, compression devices, diagnostic equipment (flexible and rigid), gloves, medical films, tubing, and other applications. We offer a range of extremely tough, transparent, flexible and rigid polymers that are compatible with a variety of polymers. All of our polymers are non-PVC, DEHP free and provide, high performance, proven alternatives to PVC. Kraton G polymers are for applications that require high strength, UV resistance and heat stability. Kraton FG polymers are functionalized Kraton G polymers that provide compatibility and adhesion to polar polymers and substrates. Kraton D polymers are cost effective solutions for various soft touch applications, with less stringent requirements. Kraton IR polymers are synthetic polyisoprene rubbers and can be formulated to replace many natural rubber applications. Kraton IR Latex is an ideal substitute for natural rubber latex, particularly in applications with high purity requirements such as medical, healthcare, personal care and food contact.

Features and Benefits

Kraton polymers offer the following:

USP class VI Toxicology requirements FDA clearance Easy processability Superior toughness Clarity (pure and in blends) No plasticizers Non-allergenic EO, EB and gamma sterilization are possible with neat Kraton G polymers. Steam sterilization is possible when the polymers are used in combination with other polymers, or in co- extrusions. Grades are offered with high resilience, low compression set, good puncture and reseal properties and with no plasticizers needed. Kraton polymers also offer enhanced oxidation, higher service temperatures, and increased processing stability. They provide formulation flexibility, ease of processing in commonly used thermoplastic technology, clarity in polyolefin blends, and offer such performance benefits as soft-touch, improved grip, and increase toughness. The medical industry continues to demand higher quality, fit for purpose materials. Kraton Polymers is the solution provider that gives innovators their edge. Our extensive knowledge in designing polymers and our dedication to customer relationships make us the ideal partner to support your product and service needs

Packaging and Films

Packaging is an essential component of almost every product which is marketed and sold. From its early origins in materials such as shells and leaves, packaging has served the purpose of containing a product, protecting it from spoilage and damage during the distribution process and throughout its shelf life. Today packaging provides a medium for conveying product information to the consumer as well as providing shelf appeal, safety, security and convenience features. Package designers are continuously looking for materials that provide the right combination of these features and in most cases no one polymer is suited for the job. Many flexible and rigid packages contain multiple materials in compounds, blends and coextrusions to meet the demands of the consumer. As packaging becomes increasingly sophisticated, so do the requirements for advanced materials that meet a range of performance expectations. Whether you design or manufacture flexible or rigid packaging Kraton polymers are well suited to meet the needs of your package design. Kraton polymers bring toughness and flexibility to packaging and can be blended or coextruded with many plastics to modify and maximize their performance. Processing capabilities include blown and cast film, injection molding, extrusion, thermoforming and blow molding applications. At Kraton Polymers we value the relationships we have with our customers and know that through teamwork we can help solve your package design problems. You can count on our integrity and resilence in working with you to provide the results you desire. Contact your Kraton Sales Representative today and you will see that when it comes to packaging, Kraton Polymers is Giving Innovators Their Edge.

Personal Care
Kraton Polymers has decades of experience in developing polymer and compound solutions to meet the end use requirements of our customers. The unique structure of our polymers impart flexibility and elasticity to a wide range of personal care applications including disposable diapers, adult incontinence products, wipes, and many other industrial film and nonwoven products. Kraton polymers are compatible with an array of materials from polyolefins to more polar materials. Kraton polymers can also be used to modify many types of oils for use in personal care applications such as cosmetics for skin, hair, and nail care.

Cosmetics, Skin Care and Oil Gels

Kraton polymers offer customers the ability to modify the viscosity of mineral oils and natural oils to produce a wide range of viscosities suitable for hand creams and other skin care products. Oil gels are primarily blends of oil and gelling agents. The oil comprises the majority of the blend and can be a naphthenic or paraffinic processing oil, a mineral oil, a synthetic product such as a polybutene or a silicone. Natural oils can also utilize our technology. Our products offer the formulator low temperature performance and compounds with excellent oil retention. Formulations can vary from strong elastomers to weak gels and greases. They are used for sealants, corrosion protection, binders and in the cosmetic industry.

Polymer Modification
Kraton polymers can be blended with many plastics; such as styrenics, polyolefins, and engineering thermoplastics to improve their performance, particularly their impact performance. Kraton polymers can toughen such plastics both at room and low temperatures and can be clear or opaque depending upon the application. Kraton polymers can help compatibilize dissimilar plastics and bring out the best in each material. They can also revive the impact of scrap or regrind materials.