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Adhesive and Coating Formulation with Polymer Modified Asphalt - 2 Day Course

Course Number: AP6847
Date: 07/15/2020 - 07/16/2020
Time: 8:00 AM - 4:00 PM
Location: Akron Polymer Training Center, Akron, OH 44325-5404, U.S.A.
Cost: $1,000 USD
Online Registration
CEU's: 1.6
Instructor: David Ploense

Course Overview

  • Outline
  • Introduction
  • Asphalt Chemistry
  • Polymer Modification
  • Types of Polymers
  • Compatibility of Polymers
  • Chemistry of Modifiers and Asphalt
  • Chemistry of PMA
  • Chemistry/Macrostructure of Modified Asphalt
  • Application Areas
  • Roofing
  • Asphalt Paving
  • Polymer Modification

Instructor Biography:

David is a highly skilled and experienced innovative formulator, developing over his career a number of pioneering new products, and improving many other existing products. His expertise includes the use of polymer modification of asphalt to produce sealants, pressure sensitive and hot melt adhesives, mastics, coatings, emulsions, and both solvent and water-based materials.

David has held an ASQ Certified Six Sigma Black Belt (CSSBB) with extensive, successful quality, product, and process improvement projects, reducing costs and increasing efficiency for improved profitability. He has created and presented professional training programs on technical topics for hundreds of people at all levels of industry. He has also had his own consulting business for several years.

He has been an editor of the Residential Roofing Manual for the American Roofing Manufacturers Association, ARMA. David is a member of the Adhesives and Sealants Council, ASC, the Association of Modified Asphalt Producers, AMAP, and the Asphalt Institute, AI. He holds five US patents with 9 more pending.

David studied chemistry and mathematics at Illinois State University in Normal, IL and completed his degree at the University of St. Francis in Joliet, IL. He was raised in the Chicago area but has lived all over the United States, now residing once again in the Chicago suburbs.

Introduction to polymer modification of asphalt

  1. Polymer modified asphalts are used across a wide range of businesses
    1. Roofing
    2.  Sealants and Adhesives (MLA, MSA)
    3. Coating –
      1. Residential Roofing
      2. Commercial roll roofing
    4. Self-Adhering Underlayment’s
    5. Industrial Specialty Business
      1. Paving Asphalt
      2. asphalt emulsion
      3. Automotive Applications
      4. Other Specialty
  2. Polymer Modified History
    1. Oxidized Coating has been the primary material used in shingles for the last 70+ years.
    2. Catalytic modified coatings were the next generation
      1. Lewis acids
      2. Ferric Chloride (1930’s)
      3. Polyphosphoric Acid (2000’s)
    3. Polymer modified asphalt for paving (1960’s)
    4. Polymer modified sealants (1970’s)
    5. Polymer modified asphalt shingle (1980’s)
    6. Self-adhering Peel-n-Stick underlayment’s (1990’s)
  3. Why Polymer Modification
    1. Polymers are added to asphalt to impact many properties:
      1. Reduce temperature susceptibility
      2. Increase high temperature stiffness
      3. Increase tensile strength
      4. Increase elasticity
      5. Improve low temperature fracture properties
      6. Improve adhesion (aggregate, granule)
      7. Improved creep properties

Asphalt and asphalt chemistry

  1. Asphaltic Crudes
    1. Most critical aspect of any flux is the crude source.
    2. There are over 1,500 different crudes used in today refining industry.
    3. Less than 20% make acceptable asphalts
    4. New sources are still being discovered and developed all over the world
  2. Asphalt Composition
  3. PDA, 0 pen, or hard asphalt
    1. Propane Distilled Asphalt
    2. Prepared by dissolving VTB in a low boiling solvent like liquid propane or butane.
    3. Solvent with dissolved fractions is drawn off and “hard” asphalt remains. Primarily “asphaltenes”, the most complex asphalt components
    4. Solvent is flashed off and residue is returned to the refinery for processing into more valuable products
    5. Hard asphalt is used for blending with softer grades to produce asphalt with desired specifications
  4. PG Asphalt
    1. Paving Grade or Performance Grade
    2. Designed to meet specifications and long-term performance requirements for road paving needs
    3. Blended by the refinery to meet PG requirements from hard and soft stocks
    4. Similar to “AC” designations used in the past. For example, AC 20 is similar to PG64-22
  5. Asphalt Chemistry -part 1
    1. Asphalt is a Complex Material
    2. A function of the crude slate and refinery process
    3. Asphalt contains the largest most complex molecules in crude oil
    4. A simple “single molecule” does not exist
    5. Composed of many different molecular groups (C30-C60+)
    6. Most asphalt groups cannot be successfully isolated
  6. Asphalt Chemistry -part 2
    1. Some molecules are beneficial for asphalt and some are not
    2. Different crudes have different proportions of “good” versus “bad” molecular types
    3. Asphalt species from different crudes may or may not be compatible
    4. Rheology of asphalt govern by molecular interaction of the various chemical groups
  7. Asphalt Chemistry-part 3
    1. Asphalt can be separated into fractions based on chemical and physical properties:
    2. Saturates, Naphthene Aromatics, Polar Aromatics and Asphaltenes
    3. Acids, bases, amphoterics and neutrals
    4. Over 125 different molecular groups found in the aromatic fraction only
  8. SARA Analysis
    1. Oils (two types)
    2. Saturated components are white non-polar viscous oils and waxes. 
      1. Effect on low temperature properties and weathering depends on wax content. More wax is bad.
      2. Generally do not react during oxidation and amount does not change in making Oxidized Base Asphalt.
      3. Aromatic oils are dark brown viscous oils.
        1. Important for dispersion of Asphaltenes.
        2. Important for low temperature and weathering properties.
        3. Tend to react during oxidation with loss of hydrogen and addition of oxygen.
        4. Because of these reactions the amount of this component decreases during oxidation.
    3. Resins/Asphaltenes
    4. Resins are dark brown solids or semi-solids
      1. Very polar and therefore good adhesive properties.
      2. Act to Peptize/Solubilize/Dissolve asphaltenes.
      3. Tend to react during oxidation.
      4. Amount either decreases as asphaltenes are formed or stays the same because of aromatic oils advancing to resins.
    5. Asphaltenes are black or brown solids
      1. Defined as not soluble in n-Heptane.
      2. Contain sulfur, oxygen, nitrogen and heteroatoms in addition to carbon and hydrogen.
      3. Provide softening point, body, and hardness.
      4. Increase in concentration as asphalt is oxidized.
  9. Asphaltene Structure
  10. Asphalt Model
  11. Representation of peptized asphaltene molecules
  12. Effect of Asphalt Composition on Properties
  13. Effect of Aromaticity and Asphaltene Content
  14. Summary -Asphalt Chemistry
    1. Chemistry determines structure
    2. Structure determines rheology (viscosity)
    3. Rheology determines product performance

Polymer Modified Asphalt

  1. Introduction to Polymers
  2. Types of Structures (Monomers)
  4. SBS Structure
  5. Block Structure
  6. SBS Manufacturing Process
  7. SBS Block Copolymers
  8. SBS and Polyolefins
  9. Impact of SBS Properties on Formula Properties
  10. Polyphosphoric Acid (PPA)
    1. Improves the high temperature grade of the binder.
    2. 0.25-0.75 wt.% of the asphalt binder.
    3. Has synergies with SBS modified systems
    4. Used in roofing to improve the blown coating properties
    5. Lower Penetration at equal Softening Point
  11. Cross linking with Sulfur
    1. Cross linking –structural change
    2. Crosslinks tie all the polymer molecules together.
    3. Because they're tied together, when the rubber is heated, they can't flow past each other.
    4. Since all the polymer molecules are connected, the material does not melt.
  12. Low Shear Mixer Process
  13. High Shear Mixing Process
  14. Mixing Process
  15. Types of Systems
  16. Effect of Modification on Pen/SP
  17. Compatibility
  18. Polymer Dispersion
  19. Polymer Dispersion (Cont.)
  20. UV Microscopy as a tool for processing and product development
  21. Polymer Separation During Storage
  22. Temperature Susceptibility
  23. Handling PMA at the Plant
  24. Vertical or Horizontal tanks?
    1. PMA requires agitation to prevent separation
    2. Vertical tanks provide more efficient agitation
  25. Check and maintain proper temperatures
  26. Hot oil heated versus fire tube
  27. Effect of Time and Temperature
  28. Effect of Time and Temperature
  29. PMA for Residential Roofing
    1. Shingle Adhesives and Sealants
    2. Modified laminating adhesive market growing with growth in laminated shingles
    3. Modified shingle adhesive should grow with changes in building codes requiring shingle wind performance. 
    4. Use of PMA’s in Self-Adhered Roofing Underlayment
      1. PMA’s are used:
        1. Provide tear, scuff, and crack resistance, low temp flexibility
        2. Provides adhesion – 40F to 120F – for wood decks
        3. Designed to meet D1970
        4. Must maintain shelf-life
  30. Alternative polymers and Additives
  31. Alternative polymers and Additives
  32. Polymer Modified Asphalt Performance
  33. Polymer Modified Shingle Coating
  34. Patent History
  35. 1983, Hansen (Shell)
    1. Impregnated glass mat with SBS modified asphalt
      1. 6 -30 wt.% SBS, asphaltene content < 20%
    2. Then coated with air-blown filled coating
    3. Claimed improved Cold Mandrel Bend and Tear Strength
  36. 1994, Trumbore (OC)
    1. Oxidized SBS/SIS with Ferric Chloride
      1. 1-15 wt.% SBS/SIS target a polystyrene content of 14-40 wt.%
      2. 0. to 0.5% Ferric Chloride
    2. Forms a chemically grafted polymer system
    3. Potential to use in adhesive applications
  37. Patent History (cont.)
  38. Patent History (Continued)
  39. Impact of PIB modified coatings
  40. Impact of SEBS Modified Coatings
  41. Applied to a paving grade asphalt
  42.  Same approach starting with a harder asphalt
    1. Hard asphalt 210/9.3 SP/Pen
    2. Requires more than 6% SEBS to hit target properties
  43. US Polyco - SCIR

Polymer Modified Paving Asphalt

  1. Polymer modified asphalt makes up 20% of all paving asphalt used in roads the United States.
  2. Polymer modified asphalt is used to address a variety of pavement distresses:
  3. Permanent Deformation – Rutting
    1. Low Temperature Handling
    2. Reduced Moisture Sensitivity
    3. Improved Fatigue Properties
    4. PG Plus Testing Requirements
    5. Elastic Recovery
  4. Crumb Rubber Technologies
  5. Crumb rubber
      1. Scrap tire rubber (landfills)
      2. Industrial pre-consumer waste
      3. Two Types:
        1. Wet process
          1. Incorporated into the asphalt cement
          2. Technologies have advanced to make highly compatible modified asphalts
        2. Dry process
          1. Incorporated into the mixture (AC/Aggregate) in paving applications

Compounding PMA adhesives

  1. SBS Structure
  2. Polymer considerations
      1. Styrene percent
      2. Molecular structure-Linear vs. radial
      3. Butadiene vs. isoprene
      4. Coupling efficiency
      5. Molecular weight
      6. Molecular weight distribution
      7. Philips vs. Kraton patent
      8. High vinyl
      9. Hydrogenated
      10. Physical form-crumb, pellet, ground, oiled
  3. Polymer options
  4. Technical data sheet example
  5. Technical data sheet example.
  6. Molecular weight distribution
  7. Molecular weight distribution –con’t
  8. SBS Block Copolymers
  9. SBS Copolymers
  10. Cross linking with Sulfur
    1. Cross linking –structural change
    2. These crosslinks tie all the polymer molecules together. Because they're tied together, when the rubber gets hot, they can't flow past each other, nor around each other. Therefore, it doesn't melt. Also, because all the polymer molecules are tied
    3. Cross linkers
  11. Tackifiers and adhesion promoters
  12. Tackifiers and adhesion promoters
  13. plasticizers
  14. Process oils
  15. stiffening agents
    1. polymers
    2. hydrated lime
  16. Fillers
    1. Limestone
    2. Talc
    3. Kaolin clay
    4. Bentonite-Bentone
    5. Wollastonite
    6. Silica
    7. Carbon black
    8. Calcium silicate
    9. Cellulose
  17. Viscosity modifiers
    1. Surfactants
    2. Waxes
    3. TSP -hydrated phosphates
  18. Antioxidants
  19. Raw materials and properties example


  3. Rheology
  9. Rheology
  10. Study of the flow/deformation of materials
  11. Viscoelastic (VE)
  12. Materials that exhibit the material properties of both a liquid (viscous) and solid (elastic)
  13. Water? Not VE and Newtonian
  14. Asphalt flux? VE and (mostly) Newtonian
  15. Filled asphalt? VE and non-Newtonian
  16. Polymers? VE and non-Newtonian
  17. Filled asphalt + polymers? VE and non-Newtonian