Characterization of Bark Derived PF Resin from Mountain-Pine Beetle Infested Lodgepole Pine Yong Zhao +, Ning Yan +, Martin Feng* + University of Toronto * FPInnovations-Forintek 6/20/2010 FPS, 2010, Y.Zhao, U of T 1
Outline Introduction Methodology Results Conclusions Acknowledgement 6/20/2010 FPS, 2010, Y.Zhao, U of T 2
Introduction Bark Materials Waste residue used as hog fuel or dispose without recovery Low heating value Renewable biomass, low carbon footprints No impact on human and animal feed system Similarity in composition to wood, except extractives, polyphenol, and suberin Good Candidate for higher value applications 6/20/2010 FPS, 2010, Y.Zhao, U of T 3
Adhesive Application of Biomass Lignin, bark, bark extractives as a replacement of petroleum-based phenol to synthesize PF resins Feasibility demonstrated in previous studies Inconsistency in performance due to low reactivity and high variability in structures Chemical modification e.g. liquefaction or phenolation However, Curing behavior & curing kinetics Bark from Beetle infested trees 6/20/2010 FPS, 2010, Y.Zhao, U of T 4
Beetle Infestation Mountain Pine Beetle (Dendroctonus ponderosae Hopkins) Sources:British Columbia Ministry of Forests and Range/L. Maclaughlan 6/20/2010 FPS, 2010, Y.Zhao, U of T 5
Chemical Composition of Barks % Ethanol-Toluene extractives Dicholormethane extractives Hot water soluble * 1% NaOH solubles Holocellulose α-cellulose Klason lignin Ash Beetle-Infested Pine Bark 17.7 (0.5) 14.2 (0.5) 7.5 (1.2) 68.1 (0.5) 46.7 (1.2) 20.5 (1.1) 42.6 (0.7) 4.0 (1.8) Non-infested Pine Bark 18.2 (0.4) 14.7 (0.8) 3.9 (1.2) 61.9 (0.3) 46.5 (0.4) 24.9 (3.2) 45.1 (0.6) 4.1 (2.8) * After Ethanol-Toluene extraction. Number in bracket is standard deviation. 6/20/2010 FPS, 2010, Y.Zhao, U of T 6
Beetle Infestation Mountain Pine Beetle (Dendroctonus ponderosae Hopkins) Change in chemical composition, physical and mechanical properties after infestation Suitability of application after beetle infestation is unknown 6/20/2010 FPS, 2010, Y.Zhao, U of T 7
Methodology Bark powder (BI, GP) Phenolation Residue filtered by Whattman Millipore. Oven dry Phase separation Adhesive synthesis and Characterization (TGA, DSC, Lap- shear test) BI: Mountain Pine Beetle infested lodgepole pine bark; GP: Non-infested lodgepole pine bark 6/20/2010 FPS, 2010, Y.Zhao, U of T 8
Adhesive Synthesis Liquefied lodgepole pine bark (150, Solvent/bark=3, 120min, 3%catalyst) Formaldehyde (37%) Sodium hydroxide (40%, 1/3 of total weight) Reaction temperature 65, kept for 10 min 2/3 of NaOH was added and reaction temperature increased to 85 kept for 60min Lab PF and commercial PF as comparison. 6/20/2010 FPS, 2010, Y.Zhao, U of T 9
Adhesive Characterization Mw, Mn and Mw/Mn were measured by MALDI/TOF/TOF. Dynamic DSC scans were made with the heating rates of 5 /min,10 /min, 15 /min, 20 /min, respectively. Kissinger method was applied to calculated the activation energy. Isothermal DSC scans were made at 110, 120, 130, 140, 150, respectively. TGA of cured resins with heating rate of 10 /min, from room temperature to 700, N 2 atmosphere. 6/20/2010 FPS, 2010, Y.Zhao, U of T 10
Adhesive Characterization Bondability-Lap shear Tests Poplar veneer: 3 mm thickness Resin solid: 0.025~0.035g/cm 2 Hot press condition: 160, 4.5mm thickness control, 3min. Zwick universal test machine at 1.3 mm/min crosshead speed. Dry test, Water-soak-and-dry test, boiling water test. 25.4mm 25.4mm 3 mm 108mm 6/20/2010 FPS, 2010, Y.Zhao, U of T 11
Results Properties of the resins ph Solids content (%) Viscosity (cps) Gel time at 120 (s) Mn (Da) Mw (Da) Mw/Mn Commercial PF 11.16 59.0 200 172 212.09 386.48 1.82 LBI PF 12.07 52.97 125 152 325.57 619.49 1.89 LGP PF 11.96 52.35 150 161 437.17 849.24 1.95 Lab PF 11.93 48.87 25 173 258.95 327.27 1.25 LBI PF: Liquefied mountain pine beetle infested pine bark PF resin; LGP PF: Liquefied green pine bark PF resin 6/20/2010 FPS, 2010, Y.Zhao, U of T 12
Dynamic DSC curve of bark-derived PF resin (non infested) Heat Flow (mw) 10 0-10 -20 5 /min 10 /min 15 /min 20 /min -30 Exo Up -40 0 50 100 150 200 250 Temperature( ) 6/20/2010 FPS, 2010, Y.Zhao, U of T 13
Resin Cure Temperatures LBI PF LGP PF Commercial PF PF (Lab made) Heating Onset Peak Onset Peak Onset Peak Onset Peak rate Temp Temp Temp Temp Temp Temp Temp Temp ( /min) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) 0 * 98.86 133.93 99.34 133.29 98.11 127.76 95.86 136.00 5 103.66 140.57 104.9 139.81 105.54 134.35 103.89 143.74 10 113.43 151.45 113.66 151.47 113.94 143.66 112.53 155.74 15 117.97 159.89 119.38 158.67 122.21 151.35 120.66 164.79 20 123.03 164.73 124.78 164.51 128.81 156.85 128.6 171.23 * Extrapolated values from the intercept of the plots of the onset temperatures and peak temperatures versus the heating rate. 6/20/2010 FPS, 2010, Y.Zhao, U of T 14
-9 0.0022 0.00225 0.0023 0.00235 0.0024 0.00245 0.0025-9.2-9.4 Ln(f/Tp^2) -9.6-9.8-10 -10.2-10.4 LBI PF LGP PF Commercial PF PF(Lab made) -10.6 1/Tp E (kj/mol) A (s -1 ) Kinetic Equation LBI PF 78.12 2.08X10 9 d α 9400 = 2.08 10 exp(- )(1- α ) dt T LGP PF 77.60 1.85X10 9 d α 9338 = 1.85 10 exp(- )(1- α ) dt T PF (Lab) 70.22 1.59X10 8 d α 8450 = 1.59 10 exp(- )(1- α ) dt T COM PF 82.23 1.18X10 10 d α 9895 = 1.18 10 exp(- )(1- α ) dt T LBI PF: Liquefied mountain pine beetle infested pine bark PF resin; LGP PF: Liquefied green pine bark PF resin 9 0.84 9 0.75 8 0.64 10 0.56 6/20/2010 FPS, 2010, Y.Zhao, U of T 15 r 0.99 0.99 0.99 0.99
Bark-derived PF resin (Beetle infested) Conversion rate(/s) 0.025 0.02 0.015 0.01 n th order 110 120 130 140 150 LBI PF Autocatalyti c 0.005 0 0 10 20 30 40 50 60 70 80 90 100 Conversion(%) 6/20/2010 FPS, 2010, Y.Zhao, U of T 16
Bark-derived PF resin (Non infested) 0.02 LGP PF Conversion rate (/s) 0.015 0.01 0.005 110 120 130 140 150 0 0 10 20 30 40 50 60 70 80 90 100 Conversion (%) 6/20/2010 FPS, 2010, Y.Zhao, U of T 17
Lab made PF resin 0.016 0.014 Lab PF Conversion rate (/s) 0.012 0.01 0.008 0.006 0.004 0.002 110 120 130 140 150 0 0 10 20 30 40 50 60 70 80 90 100 Conversion (%) 6/20/2010 FPS, 2010, Y.Zhao, U of T 18
Commercial PF resin 0.05 0.045 Commercial PF Conversion rate (/s) 0.04 0.035 0.03 0.025 0.02 0.015 0.01 0.005 110 120 130 140 150 0 0 10 20 30 40 50 60 70 80 90 100 Conversion (%) 6/20/2010 FPS, 2010, Y.Zhao, U of T 19
Bark-derived PF resin (Beetle infested) 100 90 80 70 Conversion(%) 60 50 40 30 20 10 LBI PF 110 120 130 140 150 0 0 5 10 15 20 25 30 35 40 Time (min) 6/20/2010 FPS, 2010, Y.Zhao, U of T 20
Bark-derived PF resin (Non infested) 100 90 80 70 Conversion(%) 60 50 40 30 20 10 LGP PF 110 120 130 140 150 0 0 5 10 15 20 25 30 35 40 Time (min) 6/20/2010 FPS, 2010, Y.Zhao, U of T 21
Lab made PF resin 100 90 80 70 Conversion (%) 60 50 40 30 20 10 Lab PF 110 120 130 140 150 0 0 5 10 15 20 25 30 35 40 Time (min) 6/20/2010 FPS, 2010, Y.Zhao, U of T 22
Commercial PF resin 100 90 80 Conversion (%) 70 60 50 40 30 20 10 Commercial PF 110 120 130 140 150 0 0 5 10 15 20 25 30 35 40 Time (min) 6/20/2010 FPS, 2010, Y.Zhao, U of T 23
Thermal Stability of Cured Resins 100 90 80 LBI-PF LGP-PF PF (Lab made) Commercial PF Weight (%) 70 60 50 N% : 11.52% in Commercial PF 40 0 100 200 300 400 500 600 700 Temperature ( ) LBI PF: Liquefied mountain pine beetle infested pine bark PF resin; LGP PF: Liquefied green pine bark PF resin 6/20/2010 FPS, 2010, Y.Zhao, U of T 24
Shear strength of board prepared by different adhesives 4 Shear strength (Mpa) 3.5 3 2.5 2 1.5 1 Dry WSDT BWT/Wet 0.5 0 LBI PF LGP PF Lab PF Com WSAD: specimens were soaked in water at room temperature for 24h,, and then dried for 24h at room temperature, then for test. BWT/Wet: specimens were boiled in water for 4h, dried for 20h at 63 ± ±2,boiled in water again for 4h, then cooled down with tap water and for test. 6/20/2010 FPS, 2010, Y.Zhao, U of T 25
Conclusions Bark-derived PF resins have larger Mw, PI and shorter gel time. All the resins exhibit both n-th order and autocatalytic cure mechanism. The post curing thermal stability of the BPF resins was similar to Lab PF but differed significantly from commercial PF resins. BPF resins showed highest wet bonding strengths. Beetle infestation was shown to have no negative effect on the bonding properties of the BPF resins. Bark from the mountain pine beetle infested lodgepole pine is a suitable material to partly replace phenol to synthesize phenolic resins. 6/20/2010 FPS, 2010, Y.Zhao, U of T 26
Acknowledgement Prof. Ning Yan & Martin Feng. FP Innovation Forintek Division Gireesh Gupta and Tony Ung for lap-shear test Syed Abthagir Pitchai Mydeen for kindly help. Lab-mates for suggestions and discussions. 6/20/2010 FPS, 2010, Y.Zhao, U of T 27
Thanks! Any Questions? 6/20/2010 FPS, 2010, Y.Zhao, U of T 28
Backup slides 6/20/2010 FPS, 2010, Y.Zhao, U of T 29
10000 9000 LBI PF 8000 176 199 Monomers & Dimers 7000 Trimers 6000 343 5000 4000 165 154 207 220 313 3000 2000 189 283 449 479 Tetramers 1000 0 117 419 555 617 586 0 200 400 600 800 1000 1200 Mass/Charge Pentamers & Hexamers 722 839 6/20/2010 FPS, 2010, Y.Zhao, U of T 30
10000 9000 Monomers & Dimers LGP PF 8000 177 199 313 Trimers 7000 6000 154 207 5000 342 4000 3000 189 221 283 Tetramers 2000 1000 0 117 229 389 419 449 479 556 533 585 608 Pentamers & Hexamers 0 200 400 600 800 1000 1200 Mass/Charge 6/20/2010 FPS, 2010, Y.Zhao, U of T 31
10000 9000 8000 199 Monomers & Dimers PF 7000 6000 5000 4000 177 221 3000 154 Trimers 2000 343 Tetramers 1000 0 137 207 243 283 313 365 449 479 419 607 620 583 0 200 400 600 800 1000 1200 Mass/Charge Pentamers & Hexamers 6/20/2010 FPS, 2010, Y.Zhao, U of T 32
Mass Possible Structures Mass Possible Structures 117 199 OH OCH 3 OH CH 2 OH 137 OH CH 2 OH 207 OH C H 2 OH OCH 3 154 H 3 CO CH 2 OH 221, 229 H 3 C O OH C H 2 OH OCH 3 OH CH 2 OH CH 2 OH OH 165, 177 H 3 CO OR CH 2 OH HOCH 2 OH CH 2 OH 243 H 3 C O OR C H 2 OH HOCH 2 OH CH 2 OH CH 2 OH Monomers Dimers 6/20/2010 FPS, 2010, Y.Zhao, U of T 33