Performance Comparison of Mineral Filled Olefins
Imerys Performance Additives, North America Maz Bolourchi Senior Manager, Polymer Applications OutlineTable of contents
IMERYS Talc
Minerals in Plastics/Automotive Talc, Mica & Wollastonite
Performances against Chopped Glass Fiber Mica Screening Approach & Objectives
Findings Trends/Relationships Wollastonite Case Studies
Performance Comparison
Conclusions
2 2017 Polyolefin Conference North America IMERYS – Leading Global Supplier of Performance Minerals for Plastics
2015 Sales €€€4,087€4,087 million
Energy Solutions & Filtration & High Resistance Ceramic Materials Specialties Performance Additives Minerals
Talc, Mica & Wollastonite 3 2017 Polyolefin Conference North America Imerys, North America
Leading supplier of mineral products Yellowstone, MT Argonaut, VT Penhorwood, ONT in North America: 3 Talc, 2 Wollastonite & 2 Mica mines 9 processing (milling, beneficiation, etc.) operations
Large portfolio of: Mica Mines, Boucherville QC Kings Mountain, NC ‒ Purity, Particle Size & Morphology Laboratory in San Jose, CA. ‒Processing ‒Testing
‒Analytical Wollastonite Mine, Oakhill, NY ‒Product Stewardship
4 2017 Polyolefin Conference North America Talc Properties & Structure
Hydrated magnesium silicate: Exterior Hydroxyl group Mg 3Si 4O10 (OH) 2 10 Å Naturally occurring Exterior SiO Layers Softest mineral; 1 on Mohs scale 2 Platy crystalline structure Hydrophobic exterior; relatively inert Delaminating Contains other minerals/impurities Macro-crystalline Micro-crystalline (Chlorite, Dolomite, Magnesite, etc.)
Talc Parameters: Purity Morphology Particle Size
5 2017 Polyolefin Conference North America Mica Properties & Structure
• Chemistry/Type • Phlogopite & Muscovite • Similar to Talc • Si substitution with Al • Interlayer ionic bond • Ionic interlayer interaction; more difficult to delaminate • Mohs hardness of 3 • Morphology - Platy • Delamination possible but more difficult than talc. • Surface modification possible
6 2017 Polyolefin Conference North America Wollastonite Properties & Structure
Chemistry
Calcium Silicate (CaSiO 3) Naturally occurring white mineral Morphology: Acicular Mohs hardness = 4.5 Surface modification possible Si – blue, O – red, Ca - yellow
7 2017 Polyolefin Conference North America Processing Optimization (Compounding)
Critical processing parameters include – Extruder type & L/D – Screw design & RPM – Throughput; SME – Feed location; side or upstream – Processing temperature Aggressive Mild – Resin & rheology – Screen Pack
Distributive Mixi ng Distributive & Dispersive Mixi ng Dispersive Mixing
Processing parameters critical in achieving optimal end performance
8 2017 Polyolefin Conference North America Processing Optimization: Various Minerals
Effect of Mineral & Process on Stiffness/Impact Balance Composition: 80% Hifax CA 387A (Reactor TPO), 20% Mineral by wt. 3500 Neat Resin
3000 CaCO3 - Supercoat 2500 Mica 150S
2000 Mica 325K
1500 HAR - H92 1000 FlexModulus, MPa Nyglos 4W 500 10992 Chopped Glass 0 Fiber 0.0 10.0 20.0 30.0 40.0 50.0 60.0 Notched Izod, kJ/m2
Melt compound on 25mm co-rotating/intermeshing TSE (46:1, L/D ) ISO test specimen prepared on Arburg 66T Injection molding
2017 Polyolefin Conference North America Processing Optimization: Various Minerals
Effect of Process on Morphology and Stiffness
1742 MPa 2790 MPa 2977 MPa
Chopped Glass Fiber
Neat 1400 MPa 2050 MPa
Nyglos 4W
1450 MPa 1800 MPa
Mica 150S
10 2017 Polyolefin Conference North America Results: Performance Comparison
4000
3000 2977 1989 1766 2000 1743 1621 1488 936
1000 788
0 Flex Modulus, Modulus, Flex MPa Base Resin HAR H92 HAR Coat GCC Mica,150S Nyglos 4W Nyglos Neat Resin Neat Glass Fiber Glass Jetfine 3CW Jetfine Mica, 325HK Mica, CaCO3, Super CaCO3, Mica 80 Talc 60 54 57 55.1 49 Wollastonite 45 Chopped GF 40 25 20 20 11
0 Notched Izod, kJ/m2 Izod, Notched HAR H92 Coat Mica,150S Nyglos 4W Neat Resin Glass Fiber Jetfine 3CW Mica, 325HK CaCO3,Super
Composition: 80% Hifax CA 387A (Reactor TPO), 20% Mineral by wt.
11 2017 Polyolefin Conference North America Results: Performance Comparison
Melt Flow, 230C/2.16kg 18.0 17.7 Base Resin 20.0 15.4 13.3 12.9 11.8 12.7 GCC 10.0 5.3 Mica g/10min Talc 0.0 Wollastonite Chopped GF HAR H92 Coat Mica,150S Nyglos 4W Nyglos Neat Neat Resin Glass Fiber Glass Jetfine Jetfine 3CW Mica, 325HK CaCO3, CaCO3, Super Composition: 80% Hifax CA 387A (Reactor TPO), 20% Mineral by wt. Findings Superior attributes with Chopped GF in Modulus (Strength, HDT and Shrinkage) but inferior in other properties: Impact retention (both Notched Izod & Multiaxial Impact) Flow Anisotropic Warpage Surface finish/aesthetic Equipment wear Balance of Properties often Critical
12 2017 Polyolefin Conference North America Screening Objectives/Approach
Objectives
Evaluate commercial Talc, Mica & Wollastonite grades in PP Copolymer at 20% by wt. loading Identify performance space, trends/relationships Approach
Melt compound via 25mm co-rotating/intermeshing TSE (46:1, L/D)
Screw Design
Profile at 15kg/hr & 200/450 screw RPM, Atmospheric Vent Materials Resin: Braskem PP Copolymer # T16200Q4 Minerals: Talc (15 grades), Mica (10 grades) and Wollastonite (4 grades - neat & surface treated)
13 2017 Polyolefin Conference North America Test Results - Talc
Macro-Crystalline Talc Micro-Crystalline Talc 2400 2191 2119 1984 1957 1931 1884 1938 1927 2000 1797 1774 1721 1628 1590 1642 1581 1600 2 2 µm 2 2 µm 2 2 µm 2.2 µm 1.1 µm 2.5 2.5 µm 12 µm 8.5 8.5 µm 1.9 1.9 µm 0.8 0.8 µm 4.5 µm 3.3 µm 3.9 3.9 µm 4.8 4.8 µm 1200 1.5 µm Flex Modulus, Modulus, Flex MPa 002 HAR T84 HAR H92 Silverline N 674-DT2 JetFil JetFil T590 JetFil T290 JetFil JetFil 700C JetFil 625C Nicron Nicron 403 Jetfine Jetfine 3CC Nicron Nicron 554 JetWhite 7C JetWhite 6C JetWhite 5C Jetfine 3CW
49.9 2 50 39.4 38.2 39.1 33.0 31.7 32.4 28.1 27.2 24.6 25 21.0 19.9 16.6 17.0 11.6 2 2 µm 2 2 µm 2.2 2.2 µm 1.1 µm 2 2 µm 2.5 2.5 µm 12 µm 1.9 1.9 µm 0.8 0.8 µm 3.3 3.3 µm 3.9 3.9 µm 4.8 4.8 µm 1.5 1.5 µm 4.5 4.5 µm 0 8.5 µm Notched Izod, kJ/m Izod, Notched HAR T84 HAR H92 N 674-DT2 JetFil JetFil T590 JetFil T290 JetFil JetFil 700C JetFil 625C Nicron Nicron 403 Jetfine Jetfine 3CC Nicron Nicron 554 JetWhite 7C JetWhite 6C JetWhite 5C Jetfine 3CW Silverline 002 Silverline
Composition: Braskem PP Copolymer & 20% Mineral by wt. Baseline Braskem PP Copolymer Fex modulus: 850 Mpa, Notched Izod – No Break 14 2017 Polyolefin Conference North America Test Results - Talc
Multiaxial Impact at 0 ºC, 4.4 m/s (ISO 6603)
24.0 Impact Rating Total Energy 20.2 18.2 18.0 15.8 16.4 14.5 15.2 14.9 14.1 13.3 13.7 12.6 11.8 12.0 10.4 9.9 7.3 6.0 2.8 2.8 2.7 2.0 2.0 1.7 1.6 1.6 1.5 1.5 1.3 1.3 1.2 1.2 0.6 0.0 Impact Rating & Total Energy (J) (J) Energy Total & Rating Impact HAR T84 HAR HAR H92 HAR N674DT2 Jetfil 625C Jetfil JetFil T590 JetFil T290 JetFil JetFil 700C JetFil Nicron 403 Nicron Jetfine 3CC Jetfine Nicron 554 Nicron JetWhite 7C JetWhite 6C JetWhite 5C JetWhite JetFine 3CW JetFine Silverline 002 Silverline Impact Rating 3 – Extended Ductile 2 – Ductile Finer d50 psd = Superior Impact Retension 1 – Semi - Ductile 0 – Brittle
Composition: Braskem PP Copolymer & 20% Mineral by wt. 15 2017 Polyolefin Conference North America Test Results - Talc
Heat Deflection Temperature at 0.45 psi
130
124 124
121 120 118 120 118 116 114 113 113 113 112 112 112 110 107 Temeprature (C) Temeprature 100
90 002 HAR T84 HAR HAR H92 HAR Silverline N 674-DT2 N JetFil T590 JetFil T290 JetFil JetFil 700C JetFil 625C JetFil Nicron 403 Nicron Jetfine 3CC Jetfine Nicron 554 Nicron JetWhite 7C JetWhite 6C JetWhite 5C JetWhite Jetfine 3CW Jetfine
Composition: Braskem PP Copolymer & 20% Mineral by wt.
16 2017 Polyolefin Conference North America Test Results - Talc
Brightness 100 79.2 76.6 74.9 76.3 74.3 80 67.8 63.6 65.1 67.0 66.6 65.2 66.5 66.4 61.4 58.0 60
CIE, L* CIE, 40 20 HAR T84 HAR H92 N 674-DT2 JetFil JetFil T590 JetFil T290 JetFil JetFil 700C JetFil 625C Nicron Nicron 403 Jetfine Jetfine 3CC Nicron Nicron 554 JetWhite 7C JetWhite 6C JetWhite 5C Jetfine 3CW Silverline 002 Silverline Composition: Braskem PP Copolymer & 20% Mineral High Brightness Grades Talc Findings HAR – Best reinforcing talc Particle size: ↓ Particle size results in ↑ Modulus & ↑ Impact retention; finer particles are generally better Purity influences Brightness (↑ Purity ↑ Brightness) Macro-crystalline generally superior in mechanicals vs. Micro-crystalline
17 2017 Polyolefin Conference North America Test Results - Mica
Muscovite High Brightness Muscovite Phlogopite 2400 2176 1991 2000 1882 1935 1807 1855 1777 1748 1665 1711 1600 48 48 µm 45 45 µm 55 µm 26 26 µm 32 µm 150 150 µm 25 25 µm 25 25 µm 35 µm 45 µm 1200 Flex Modulus, Modulus, Flex MPa 4K 250-L 325-G 80-SF 200-S 150-S 500-C C-3000 325- HK 325- WG 325
50.0
25.0 12.8 12.5 10.4 9.8 9.8 10.4 11.5 10.1 11.5 12.0 48 48 µm 45 µm 55 µm 26 26 µm 32 µm 150 150 µm 25 25 µm 35 µm 45 µm 25 µm 0.0 4K 250-L 325-G 80-SF 200-S 150-S 500-C Notched Izod, kJ/m2 Izod, Notched C-3000 325- HK WG325
Composition: Braskem PP Copolymer & 20% Mineral Baseline Braskem PP Copolymer Fex modulus: 850 Mpa, Notched Izod – No Break
18 2017 Polyolefin Conference North America Test Results - Mica
Multiaxial Impact at 0 ºC , 4.4 m/s (ISO 6603)
8.0
7.0 Impact Rating Total Energy 6.3 6.0 5.7 5.3 4.8 5.0 4.7 4.2 4.2 4.0 3.5 3.1 3.0 2.2 2.3 2.0
1.0 0.7 0.3 0.0 0.0 0.0 0.0 0.0 0.1 0.2 0.2 0.2
Impact Rating & Total Energy (J) Energy & Total Rating Impact 0.0 4K 250-L 500-C 325-G C-3000 WG 325 WG Impact Rating Suzorite 150-S Suzorite Suzorite 80-SF Suzorite 80-SF Suzorite 3 – Extended Ductile 200-S Suzorite 2 – Ductile HK 325- Suzorite 1 – Semi - Ductile 0 – Brittle All Mica grades exhibit Brittle Failure
Composition: Braskem PP Copolymer & 20% Mineral
19 2017 Polyolefin Conference North America Test Results - Mica
Heat Deflection Temperature at 0.45 psi
130 124 120 120 115 114 110 109 110 108 106 105 105 Temeprature (C) Temeprature 100
90 4K 250-L 325-G 80-SF 200-S 150-S 500-C C-3000 325- HK 325- WG 325 WG
Coarser Mica Grades yield Superior HDT
Composition: Braskem PP Copolymer & 20% Mineral
20 2017 Polyolefin Conference North America Test Results - Mica
Brightness 100.0 Higher Brightness Grades 80.0 62.0 61.0 61.1 60.0 52.5 53.6 52.5 CIE, CIE, L* 40.0 35.2 35.2 33.2 31.7
20.0 4K 250-L 325-G 80-SF 200-S 150-S 500-C C-3000 325- HK WG325 Composition: Braskem PP Copolymer & 20% Mineral
Mica Findings Coarse grade, Mica 150-S best reinforcing (similar to HAR talc); both at 2200 MPa Effect of Particle size (opposite to talc): ↑ Particle size provides↑ Modulus. Impact retention generally poor (killer variable) Purity influences Brightness (↑ Purity ↑ Brightness) Overall lower L* value than talc
21 2017 Polyolefin Conference North America Test Results - Wollastonite
Neat Surface Treated 2446 2358 2400 2283 2149 2,097 2,063 1,911 2000 1,809 Length: 63 µm Length: 156 µm Length: 234 µm 1600 Length: 300 µm Diameter: 7 µm Diameter: 12 µm Diameter: 18 µm Diameter: 30 µm
Flex Mod, Mod, MPa Flex Aspect Ratio: 9 Aspect Ratio: 13 Aspect Ratio: 13 Aspect Ratio: 10 1200 Nyglos 8 Nyglos Nyglos 12 Nyglos 20 Nyglos Nyglos 4W Nyglos 50 Neat Surface Treated
26.4 25 17.8 18.9 15.9 15.7 17.5 15.6 17.0
0 Notched Izod, kJ/m2 Izod, Notched Nyglos 8 Nyglos Nyglos 20 Nyglos Nyglos 12 Nyglos Nyglos 4W Nyglos
Composition: Braskem PP Copolymer & 20% Mineral Baseline Braskem PP Copolymer Fex modulus: 850 Mpa, Notched Izod – No Break
22 2017 Polyolefin Conference North America Test Results - Wollastonite
Multiaxial Impact at 0 ºC, 4.4 m/s (ISO 6603)
24
Impact Rating Total Energy 18 13.8 12 6.7 6.5 6 4.1 0.6 0.0 0.1 0.1 0 Impact Rating & Total Energy (J) Energy & Total Rating Impact
Impact Rating 8 10992 Nyglos Nyglos20 10992 Nyglos20 Nyglos12-10992
3 – Extended Ductile 4W 10992 Nyglos 2 – Ductile 1 – Semi - Ductile Brittle Failure; slightly better than Mica but inferior to Talc 0 – Brittle
Composition: Braskem PP Copolymer & 20% Mineral
23 2017 Polyolefin Conference North America Test Results - Wollastonite
Heat Deflection Temperature at 0.45 psi
130
120 116
112 112
110 108
Temeprature (C) Temeprature 100
90 (SF5) (SF5) (SF5) 10992 10992 10992 (SF5) 10992 Nyglos 8- Nyglos Nyglos12- Nyglos20- Nyglos 4W- Nyglos
Composition: Braskem PP Copolymer & 20% Mineral
24 2017 Polyolefin Conference North America Test Results - Wollastonite
Brightness Neat Surface Treated 100 82.0 79.4 81.2 78.6 76.8 79.5 80 72.4 75.7 60
CIE, L* CIE, 40 20 Nyglos 8 Nyglos Nyglos 12 Nyglos 20 Nyglos Nyglos 4W Nyglos
Composition: Braskem PP Copolymer & 20% Mineral
Wollastonite Findings Increase in reinforcement & impact strength with surface treatment (↑ by 10-19% & 50% respectively) Effect of aspect ratio (for surface treated grades) ↑ higher aspect ratio yields ↑ Modulus. Higher reinforcement (↑ 10%) compared to talc or mica (2450 vs. 2200 Mpa) Impact decreases with increase in particle length/diameter (coarser products); overall inferior to talc Superior brightness Boost with surface treatment Finer grades overall better
25 2017 Polyolefin Conference North America Test Results - CLTE
CLTE of Talc, Mica, Wollastonite and Chopped Glass Fiber
180 167 168 // ┴ 160 139 138 140 135
120 109 103 104 99 100 95 95 98 98 95 95 100 92 91 93 87 87 87 86 83 80 72 CLTE (10^-6°C) CLTE 60 51
40 HAR T84 HAR JetFil T290 JetFil JetFine3CC JetWhite 6C JetWhite 5C JetWhite Chopped GF Chopped Suzorite 80-SF Suzorite Suzorite 150-S Suzorite Nyglos 8-10992 Nyglos Suzorite 325-HK Suzorite Nyglos 20-10992 Nyglos Nyglos 4W 10992 4W Nyglos Neat Braskem HICP Braskem Neat
Composition: Braskem PP Copolymer & 20% Mineral
26 2017 Polyolefin Conference North America Performance Comparison (Talc/Mica/Wollastonite/GF)
Mineral selection/grade largely Performance Grid for 20% Mineral in 20MFI PP Copolymer dependent on CTQ, end Chopped Property Talc Mica Wollastonite performance requirements GF along with price (overall cost to Modulus/Stiffness ++ ++ ++½ ++++ performance) Impact – Notched Izod ++++ ++ +++ + Impact – Multiaxial Impact ++++ + +++ ++ Talc, generally mineral of choice if stiffness/impact Rheology – Melt Flow +++ ++ ++++ + Color/Brightness +++ ++ ++++ balance is key; commonly used HDT ++½ ++½ ++ ++++ with olefins/automotive Shrinkage +++ +++ ++ +++½ formulations CLTE +++ +++ ++ +++½ Mica & Wollastonite more Scratch Resistance ++½ + ++ +++ prevalently used with Nucleation of PP +++ ++ Surface Treatment + +++ +++ +++ engineered resins (PA6, 6/6) Each mineral has its own This Study Prior Study/Knowledge unique strengths/weaknesses
27 2017 Polyolefin Conference North America Conclusions
Various Talc, Mica, Wollastonite grades evaluated versus chopped glass fiber Process Optimization – Critical to establish for each mineral Chopped Glass Fiber – Highest reinforcement Best modulus/strength; workhorse in many applications in which impact is less critical Does have limitations/challenges (impact, flow, wear, surface aesthetic, etc.) Stiffness/Impact balance inferior to talc & Wollastonite Talc – Excellent stiffness/impact balance Best performance with finer grades (Increase in stiffness/impact with lower psd) Color influenced by ore body & purity ‒HAR for maximum stiffness & low shrinkage/CLTE ‒Jetfine 3CW for optimum balance of stiffness/impact & impact ductility at -30°C ‒Jetfine 3CC for optimum scratch resistance & stiffness/impact balance ‒JetWhite for color sensitive high bright applications ‒Nicron 674 for moderate reinforcement
28 2017 Polyolefin Conference North America Conclusions
Mica – High reinforcement/inferior impact retention Highest reinforcement with coarser grades (increase in stiffness with higher particle size) Impact considerably lower than talc or Wollastonite ‒Grades available for maximum stiffness & high brightness ‒Surface treatment possible (but not evaluated in study) Wollastonite – Excellent reinforcement, highest brightness (exceeds talc/mica), impact inferior to talc; Best stiffness/impact with surface treated product Good flow & high brightness ‒Surface treated Nyglos 4W – for good reinforcement & impact retention ‒Surface treated Nyglos 8, 12 and 20 – for maximum reinforcement; some loss in impact
29 2017 Polyolefin Conference North America Thank you for your attention !
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