Hollow Glass Microspheres for Plastics, Elastomers, and Adhesives Compounds

Hollow Glass Microspheres for Plastics, Elastomers, and Adhesives Compounds
Edited by
Stephen E. Amos , Baris Yalcin
Table of contents

1. Introduction
   Early Application Examples
2. Characterization
   Density
   True Density Using Gas Pycnometer
   Bulk Isostatic Compression of HGMs
   Uniaxial Compression Testing of Individual HGMs
   Thermal Characterization
   Thermal Conductivity
   Electrical Properties and Dielectric Properties
   Microscopic Imaging of HGMs
3. Hollow Glass Microspheres in Thermoplastics
   Introduction
   Benefits of HGMs in Thermoplastics
   Productivity Benefits of HGMs Through Faster Cooling Rates from the Melt
   Dimensional Stability
   Processing of HGMs
   Pelletizing Effect on HGM Survival
   Effect of Polymer Melt Viscosity on HGM Survival
   Effect of Back Pressure on HGM Survival
   Effect of HGM Loading on HGM Survival
   HGMs in Polyolefins
   HGMs in GF Filled PP
   Case Study—Chemically Coupled GF Reinforced PP
   HGMs in Talc Filled PP
   HGMs in Unfilled Polyolefins
   HGMs in PA
   Comparative Review of other Thermoplastic Weight Reduction Methodologies and Combinations with HGMs
4. Hollow Glass Microspheres in Rubbers and Elastomers
   Benefits of HGM Use in Rubber
   Physical Property Changes
   Incorporation of HGMs in Rubber
   2-Roll Mills
   Internal Mixers
   Other Incorporation Methods
   Rubber Additive Formulations and HGM Considerations
   Application of HGM in Rubber; Example 1—Pneumatic Tires
   Application of HGM in Rubber; Example 2—Shoe Soles
   Application of HGM in Rubber; Example 3—Wire and Cable Compounds
5. Hollow Glass Microspheres in Sheet Molding Compounds
   Sheet Molding Compound Basics
   SMC Process
   Hollow Glass Microspheres in SMCs
6. Hollow Glass Microspheres in Thermosets—Epoxy Syntactic Foams
   Introduction
   Application of Epoxy Syntactic Foams
   Hollow Particle Properties
   Fabrication of Syntactic Foams
   Mechanical Properties
   Compressive Properties
   Tensile Properties
   Electrical Properties
   Thermal Properties
   Multifunctional Syntactic Foams
   Summary
   List of Symbols
7. Hollow Glass Microspheres in Polyurethanes
   Polyurethane Basics
   HGMs in Thermoplastic PUs
   HGMs in Thermoset PU
   Syntactic PU Foams
   Specialty PU Composites
   PU Foams
8. Hollow Glass Microspheres in Plastisols
   Background Information
   HGM Use and Benefits for Plastisols
   Plastisol Mixing and Preparation
9. Hollow Glass Microspheres in Repair Compounds
   Auto Repair Compounds
   Wall Repair (Spackle Compounds)
   Tape Joint Compound
10. Handling of Hollow Glass Microspheres
    Silos and Hoppers
    Transfer of HGMs
11. Mixing and Dispersion of Hollow Glass Microsphere Products
    Hollow Glass Microsphere Transport to Mixer
    Fundamentals of Dispersion
    Mixing and Dispersing Hollow Glass Microsphere Products
    Mixing Dynamics and Dispersion Blade Placement
    Mixer Design Options
    Difficulty in Mixing of Hollow Glass Microsphere-Filled Products
    The Science of Mixing and Dispersing
    Rheological Effects on Dispersion
    Index
    Note: Page numbers followed by “f ” and “t” indicate figures and tables respectively.
    A
    Additives, 4e5, 54t, 175
    inorganic additives, 12
    low-profile additives, 127e128
    in plastisols, 201
    rubber additive formulations, 116, 117t
    Aluminum trihydrate, 35, 135t
    American Society for Testing and
    Materials (ASTM) Standard
    bulk isostatic compression, 14
    low-shrinkage phenolic molding
    compound, 143, 144t
    Aminosilane, 57, 182
    Ammonium nitrate and fuel oil (ANFO), 4
    Apparent density. See Bulk density
    Army Cardboard, 1
    Auger, 258e259
    helical, 211e212, 255, 258
    multishaft dispersers, 255
    side feeder auger system, 47e48
    Auto repair compounds, 215e219, 215f,
    217te219t
    ingredients of, 216
    metal patching compound, 216e217,
    217t
    performance with varying silica/talc
    filler admixture, 217e219, 218t
    silica/talc admixture and HGMs, 217,
    217t
    Axial pumper impeller, 246, 246f
    B
    Back pressure effect, on HGM survival,
    49e52, 50f
    Banbury
    mixer, 112, 114e115, 115f
    Binders, 220e221
    Bismaleimide, 148
    Box-angle blade, 256
    Bulk bag discharging, 235e237, 238f, 239f
    Bulk density, 7e9, 8f
    Bulk isostatic compression, 14, 15f
    Buoyancy, 121e122
    1,4-Butanediol (BDP), 176e177
    C
    Cable compounds, hollow glass
    microsphere use in, 121e122
    Cenospheres, 2e3
    Cis-polyisoprene, 107, 107f
    Coefficient of thermal expansion (CTE),
    4e6, 57
    of epoxy syntactic foams, 149
    Compression
    bulk isostatic, 14, 15f
    of epoxy syntactic foams, 153e156,
    154fe155f
    set, 110, 111f
    Compressive failure strain, 15
    Compressive properties, 148e149,
    153e156
    methods of measuring, 14
    strength and modulus, 154e156, 155f,
    195, 196t
    Compressive stresses, 49
    Contact angles, in mixing process, 264,
    264f
    Conveying lines, 234
    Cooling rate effect, 36e40, 38fe39f,
    39t, 40f
    Corporate Average Fuel Economy
    (CAFE´ ), 4
    Cothickeners, 221
    Cyanate ester, 148
    D
    DCPD (Dicyclopentadiene) resins, 126
    Deagglomeration, 243e244, 249,
    251e253, 268
    Density, 3e5, 5f, 7e9
    bulk, 7e9, 8f
    of cenospheres, 2e3
    measurement of, 9e13, 10f
    273Density (Continued)
    modification, 1e3, 108
    tap, 7
    true, 7e13, 8f
    Design options, mixer. See Mixer design
    options
    Dielectric constant
    defined, 21
    of HGMs, 22
    Dielectric properties, 19e25, 22t, 23f
    Differential thermal analysis (DTA), 16
    Diluents, 203
    Dimensional stability, 41e42, 42te43t,
    44f, 45t, 46f
    Direct injection molding method,
    29, 30f
    Dispersion
    blade placement, mixing dynamics and,
    252e254, 253fe254f
    fundamentals of, 242e248
    rheological effects on, 268e271,
    268fe269f
    Double diaphragm pneumatic pump
    transfer of HGMs, 231e232,
    232fe233f
    Dow Chemical Company, 4
    Dual-shaft dispersers, 244, 245f,
    255e260
    E
    Electrical properties
    of epoxy syntactic foams, 163e165,
    164t, 165f
    of hollow glass microspheres, 19e25,
    25f
    Elongation at break, 109e110, 110f
    Elution alkalinity, light weight
    unsaturated polyester compounds
    effects on, 134e137, 138t
    EP-diene rubber (EPDM), 54, 54t
    Epoxy syntactic foams, hollow glass
    microspheres in, 147e174
    application of, 148e149
    compressive properties, 153e156,
    154fe155f
    electrical properties, 163e165, 164t,
    165f
    fabrication, 152e153, 152f
    flexural properties, 160e162, 162f
    hollow particle properties, 149e152,
    151f, 151t
    mechanical properties, 153
    multifunctional syntactic foams,
    166e169, 168f
    tensile properties, 156e162, 157f,
    159f, 161f
    thermal properties, 166, 167f
    Ethyleneebutadiene (EB), 54, 54t
    Ethyleneeoctene (EO), 54, 54t
    Ethylene propylene rubber (EPR), 54
    -diene rubber. See EP-diene rubber
    (EPDM)
    Extrusion, 49e50, 115e116
    reactive extrusion, 178e179, 180t
    F
    Feet per minute (FPM), 247, 249
    Fiber-reinforced flame retardant
    polyurethane compositions, 193t
    Fiber reinforcement, 123, 142e143
    Fillers
    inorganic, 222e225
    synthetic inorganic, 221
    Flame retardant polyurethane
    compositions, 193t
    fiber-reinforced, 193t
    Flexural modulus, as function of density,
    101, 103f
    Flexural properties, of epoxy syntactic
    foams, 160e162, 162f
    Flow aids, 234, 235f
    Fluoroelastomer, 109e110, 109fe111f,
    115
    Fly ash, 2e3
    Foaming technology, 92
    epoxy syntactic foams. See Epoxy
    syntactic foams, hollow glass
    microspheres in
    MuCell
    injection molding technology,
    87, 91f, 92e93, 93fe94f
    multifunctional syntactic foams, hollow
    glass microspheres in, 166e169,
    168f
    syntactic PU foams, hollow glass
    microspheres in, 190e191
    Focal plane merging, 31e32
    274 INDEXG
    Gas pycnometer, true density
    measurement using, 9e13, 10f
    Gate blade, 258
    Glass fiber (GF)
    filled polypropylene, hollow glass
    microspheres in, 57e63, 58f,
    59te60t
    mechanical properties, 61e63, 62t,
    64t
    molded part formulas, 61, 61t
    reinforced heat stabilized PA6, HGMSCF benefits in, 95e100, 95t, 96f,
    96te97t, 98f, 99te100t
    in sheet moulding compounds,
    126e129, 132, 142e143
    Glycerin, 14
    Ground calcium carbonate (GCC), 202
    H
    Heat distortion temperature (HDT),
    54, 63
    Heat stabilizers, 203
    Helical auger, 258. See also Auger
    Helical sweep blade, 256
    High density polyethylene (HDPE).
    See also Polyethylene (PE)
    wood composites, HGM two-step
    compounding process in,
    100e101, 101fe102f, 102t,
    103f
    High-shear dispersion blades, 251e252,
    251f
    Hollow glass microspheres (HGMs),
    1e6, 5f
    bulk isostatic compression of,
    14, 15f
    density of, 7e13
    dielectric properties of, 19e25,
    22t, 23f
    electrical properties of, 19e25, 25f
    in epoxy syntactic systems. See Epoxy
    syntactic systems, hollow glass
    microspheres in
    flow issues with, 230f
    handling of, 229e240
    microscopic imaging of, 26e33,
    26fe33f
    in plastisols. See Plastisols
    in polyurethanes, 183e188. See also
    Thermoplastic polyurethanes
    (TPUs)
    reaction injection molding, 183e188,
    187te189t
    products, mixing and dispersion of,
    241e272
    in repair compound. See Repair
    compound, hollow glass
    microsphere in
    in rubbers and elastomers, 107e122
    in sheet moulding compounds. See
    Sheet moulding compounds
    (SMC)
    thermal characterization, 16
    thermal conductivity of, 16e19, 18f,
    18t, 20t, 21f
    in thermoplastics. See Thermoplastics,
    hollow glass microspheres in
    transfer of. See Transfer of HGMs
    transport to mixer, 241e242
    uniaxial compression testing of,
    15e16
    Hoppers, 229e231
    asymmetric design, 231f
    day and weigh combinations, 230f
    Hoses, 234
    I
    In situ polymerization, 178e179
    Ideal gas law, 9e10
    Injection molding
    direct injection molding method,
    29, 30f
    MuCell
    injection molding technology,
    87, 91f, 92e93, 93fe94f
    reaction injection molding, 183e188,
    187te189t
    Inorganic fillers, 222e225
    Interference fringe analysis, 33
    Interferometry-based technique, 31e32,
    33f
    Intermediate speed blades, 257e258
    Isophthalic resins, 126
    J
    JELL-O
    , 112
    INDEX 275K
    Kanamite, 3
    Kanium Corporation, 3
    Kneading devices, 115e116
    L
    Lacquers, 244
    Laser confocal method, 33
    Limiting oxygen index (LOI), 192, 193t
    Loading effect, on HGM survival,
    51e53, 51f
    Low-profile blade, 255e256
    M
    Melt flow index (MFI), 48fe49f, 49, 51f,
    52, 65e72, 75
    Melt flow rate (MFR), 50e51, 63,
    92, 92f
    4,40-Methylenediphenyl diisocyanate
    (MDI), 175e179
    Microcellular foam (MuCell
    ) injection
    molding technology, 87, 91f,
    92e93, 93fe94f
    Microscopic imaging, of hollow glass
    microspheres, 26e33, 26fe33f
    Mixer design options, 254e260
    dual-shaft dispersers, 255e260
    single shaft dispersers, 255
    tri-shaft dispersers, 255e260
    Mixers
    and dispersers. See Mixer design options
    internal mixers, 114e115
    multishaft mixers, 211
    recommended mixers, 131
    rotary mixers, 186
    static mixers, 186
    Mixing of hollow glass microspherefilled products, 241e272
    design options. See Mixer design options
    difficulties in, 260e262
    additions, location of, 262, 263f
    particle size and shape effect, on
    dispersibility, 261e262
    Multifunctional syntactic foams, hollow
    glass microspheres in, 166e169,
    168f
    Multishaft mixer, blade configuration
    of, 257f
    N
    National Oceanic and Atmospheric
    Administration (NOAA),
    148e149
    Nylon. See Polyamide (PA)
    O
    Optical microscopy, 29e32,
    29fe32f
    Organosol, 201, 203
    Orthophthalic resins, 126
    P
    Pelletizing effect, on HGM survival,
    48e49, 48f
    Perlite, 3, 3f
    Phenol, 148
    Philadelphia Quartz (PQ) Corporation, 2
    Physical property changes, 109e111,
    109fe111f
    Pitched-angle blade, 256
    Plasterboard, heavyweight versus
    lightweight spackle in, 220,
    220f
    Plastic, 1. See also Thermoplastics,
    hollow glass microspheres in
    HGM versus CaCO3-filled laminated
    plastic, 137, 142t
    polyurethanes, 183e188. See also
    Thermoplastic polyurethanes
    (TPUs)
    reasons to use HGMs in, 5e6
    optical microscopy, 29
    Plasticizers, 175, 201e202, 212,
    225
    Plastisols, 201e214
    background information,
    201e204
    blocked polyisocyanurate-containing,
    208f
    HGM use and benefits for, 204e211,
    207t, 208f, 208te211t
    high- and low-density compositions,
    207t
    lightweight abrasion-resistant
    composition, 211t
    manufacturing of, 205f
    mixing and preparation, 211e212
    276 INDEXPMMA (para-Methoxymethamphetamine),
    202e203
    Pneumatic tires, hollow glass
    microsphere use in, 117e119,
    118f
    Polyamide (PA)
    cycle time analysis for, 42t
    hollow glass microspheres in, 75e87,
    82te84t, 86t, 88te89t, 90fe91f
    Polyamide 6 (PA6)
    composites, 38e39
    GF reinforced heat stabilized, HGMSCF benefits in, 95e100, 95t, 96f,
    96te97t, 98f, 99te100t
    Polyaminoamides (PAA), 203
    Polyethylene (PE)
    high density. See High density
    polyethylene (HDPE)
    hollow glass microspheres in, 53
    Polymeric isocyanate, 191
    Polymer melt viscosity effect, on HGM
    survival, 49, 49f
    Polymer wood composites (PWC), 40,
    100e101
    drawback of, 101e103
    Polyolefins, hollow glass microspheres
    in, 53e57
    unfilled, 65e75, 69te71t, 72f, 73t, 74f,
    76te80t
    Polypropylene (PP), 30f, 32f
    glass fiber filled, hollow glass
    microspheres in, 57e63, 58f,
    59te60t
    mechanical properties, 61e63, 62t,
    64t
    molded part formulas, 61, 61t
    GF reinforced heat stabilized, HGMSCF benefits in, 98e100, 99te100t
    peroxide visbreaking in, 92
    talc filled, hollow glass microspheres in,
    63e65, 66te68t
    Polyurethanes (PUs)
    flame retardant compositions, 193t
    fiber-reinforced, 193t
    foams, 194e195, 196te198t
    hollow glass microspheres in,
    175e200
    specialty composites, 191e192
    syntactic PU foams. See Syntactic PU
    foams; hollow glass
    microspheres in
    thermoplastic. See Thermoplastic
    polyurethanes (TPUs)
    thermoset. See Thermoset
    polyurethanes; hollow glass
    microspheres in
    two-step reaction, 176f
    Polyvinyl acetate (PVAc), 220e221,
    226e227
    Polyvinyl alcohol (PVA), 220,
    222e224
    Poly(vinyl chloride) (PVC) plastisol,
    201e202, 205f, 212
    Precipitated calcium carbonate (PCC),
    202
    Q
    Quantification, 16
    R
    Radial pumper (super pumper),
    249e251, 249f
    Ram presses discharge high-viscosity
    products, 212, 213f
    Reaction injection molding (RIM),
    183e188, 185f
    Repair compound, hollow glass
    microsphere in, 215e228
    auto repair compound, 215e219, 215f,
    217te219t. See also Auto repair
    compounds
    tape joint compound, 225e227, 226t
    wall repair (spackle compounds),
    220e225
    binders, 220e221
    cothickeners, 221
    inorganic fillers, 222e225,
    223te225t
    synthetic inorganic fillers, 221
    thickeners, 221
    water, 222
    Revolutions per minute (RPM), 247e248
    Roll mills
    2-roll mills, 112e114, 113f, 114t
    three-roll mills, 242
    Rotor blade selection, 115, 115f
    INDEX 277Rubber, hollow glass microsphere use in,
    107e122
    additive formulations, 116, 117t
    applications of, 117e122, 118f,
    120t
    benefits of, 108e109
    incorporation of, 111e112, 115e116
    internal mixers, 114e115, 115f
    physical property changes, 109e111,
    109fe111f
    2-roll mills. See Roll mills
    S
    Sandability, 217e219
    Scanning electron microscopy (SEM)
    broken spheres, wall thickness planes of,
    26e28, 27f
    compositional mode of, 26, 26f
    level of binding, 28f, 29
    topography mode of, 26, 27f
    Scotch
    tape, 29
    Screw feeder, nonuniform and uniform
    discharge using, 237f
    Separation inhibitors, 203
    Shear rate
    dependent viscosity data, 49, 49f
    effect on channel depth and screw speed,
    44, 47f
    viscosity behavior, 204
    Sheet moulding compounds (SMC),
    123e146
    basics of, 123e128
    categories of, 125e128, 128f
    hollow glass microspheres in, 129e143,
    132te135t, 137f, 138t, 140t, 141f,
    142t, 144t
    ingredients, 124t
    low density-low profile, 132e133,
    135t
    low-density flame retardant, 132e133,
    135t
    sheet moulding compound process,
    128e129, 129f
    Shoe soles, hollow glass microsphere
    use in, 119e121, 120t
    Sight tubes, 235
    Sight windows, 235
    Silos, 229e231
    Single shaft dispersers, 255
    Spackling, 220
    STRUKTOL
    TPW 104, 100e101
    Styrene, 127f
    Styreneeethyleneebutadieneestyrene
    (SEBS), 54
    Supercritical fluid (SCF) molding,
    92e95
    hollow glass microspheres with,
    95e100
    Surface tension, 263e264
    Syntactic PU foams, hollow glass
    microspheres in, 190e191
    Synthetic inorganic fillers, 221
    T
    Talc filled polypropylene, hollow
    glass microspheres in, 63e65,
    66te68t
    Tap density, 7
    Tape joint compound, 225e227
    low-shrinkage, 225e227, 226t
    Tensile properties, of epoxy syntactic
    foams, 156e162, 157f, 159f, 161f
    Tensile strength, 110e111, 111f
    Thermal characterization, 16
    Thermal conductivity, 16e19, 18f, 18t,
    20t, 21f, 104f
    Thermal properties, of epoxy syntactic
    foams, 166, 167f
    Thermoplastic elastomers (TPEs),
    107e108, 121e122
    Thermoplastic olefin (TPO), 35e36,
    53e58, 63
    components and functions of, 54t
    Thermoplastic polyurethanes (TPUs),
    176
    hollow glass microspheres in, 178e182,
    180te181t, 182f
    changes in swelling ratios,
    185f
    mechanical properties, 182, 183t
    surface treatment options, 184f
    tensile strength, 184f
    twin screw compounding
    configuration, 179e182, 182f
    volume loss percent due to HGM
    breakage, 181t
    278 INDEXThermoplastics, hollow glass
    microspheres in, 35e106
    back pressure effect, on HGM survival,
    49e51, 50f
    benefits of, 36
    dimensional stability, 41e42,
    42te43t, 44f, 45t, 46f
    productivity benefits through faster
    cooling rates from melt, 36e40,
    38fe39f, 39t, 40f
    GF filled polypropylene, 57e63, 58f,
    59te60t
    mechanical properties, 61e63, 62t,
    64t
    molded part formulas, 61, 61t
    HGM loading effect on HGM survival,
    51e53, 51f
    pelletizing effect on HGM survival,
    48e49, 48f
    polyamide. See Polyamide (PA)
    polymer melt viscosity effect on HGM
    survival, 49, 49f
    polyolefins. See Polyolefins; hollow
    glass microspheres in
    processing of, 42e48, 46fe47f
    talc filled polypropylene, 63e65,
    66te68t
    weight reduction technologies,
    comparative review, 87e103,
    91fe92f
    Thermoset polyurethanes, hollow glass
    microspheres in, 183e188
    reaction injection molding, 183e188,
    187te189t
    Thermosetting resin, 123, 142e143
    3M Company, 1e2, 2f, 4, 38, 115, 121
    Thickeners, 221
    Tilt table, 235
    Tolylenediisocyanate (TDI), 175e177
    Transfer of HGMs, 231e239
    bulk bag discharging, 235e237, 238f,
    239f
    conveying lines, 234
    double diaphragm pneumatic pump
    transfer, 231e232, 232fe233f
    flow aids, 234, 235f
    hoses, 234
    tilt table, 235
    vacuum transfer, 235e237, 236f
    vacuum wand pickup, 233
    Transportation, hollow glass microsphere
    use in, 107e108, 121
    Tri-shaft dispersers, 255e260
    Tri-shaft mixer, 211e212, 212f, 259
    True density, 7e9, 8f
    measurement of, using gas pycnometer,
    9e13, 10f
    Turbine blades, 258
    Twin screw extruder (TSE), 42e44, 47f,
    100e101
    U
    Unfilled polyolefins, hollow glass
    microspheres in, 65e75, 69te71t,
    72f, 73t, 74f, 76te80t
    Uniaxial compression testing,
    15e16
    Union Carbide Corporation, 2
    Unsaturated polyester (UP), 123
    Unsaturated polyester resin (UPR), 123,
    126e128
    raw materials for, 123e126, 125t
    Urethane polymers. See Polyurethanes
    (PUs)
    USS Zumwalt, 148
    V
    Vacuum wand pickup, 233, 234f
    van der Waals forces, 244
    Vinyl ester (VE), 123, 148
    Vinyl urethane, modified, 123
    Viscosity, estimating effects on,
    263e264, 267f
    W
    Wall repair (spackle compounds),
    220e225
    binders, 220e221
    cothickeners, 221
    inorganic fillers, 222e225,
    223te225t
    synthetic inorganic fillers, 221
    thickeners, 221
    water, 222
    Water, 222
    Wear resistance, 110
    Wetting phenomena, 264
    INDEX 279Wiper blades, 256e257
    Wire compounds, hollow glass
    microsphere use in, 121e122
    X
    Xylene, 192
    Y
    Yield stress, 267
    YoungeDupre equation, 263
    Z
    Z-stacking, 31e32

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