PHA Bioplastics Synthesis and Material Properties

PHA Bioplastics Synthesis and Material Properties

PHA Bioplastics Synthesis and Material Properties University of Queensland (Australia) and AnoxKaldness (Sweden) UQ: S. Pratt, B. Laycock, L. P. Halley, P. Lant, Luigi Vandi Current PhD students: Montao-Herrera, Syarifah Nuraqmar Syed Mahamud, C. Chen. Industry Partners: M. Arcos-Hernndez, P. Magnusson, P. Johansson, A. Werker. Some context Desired characteristic PHA PLA Starch Degradable PE Industrially relevant Biodegradable Non oil-based Non food-based Manufactured Intracellularly Yes Yes Yes Yes Yes Yes Yes Yes NO

NO Yes Yes Yes NO NO Yes Slowly NO Yes NO But PHB, and to a lesser extent PHBV, is stiff and brittle PHBV suffers from aging PHBV is challenging to process / narrow processing window PHBV is expensive to make Overview Bioprocesses 3. Options? Feedstock 2. Pure Culture Bioreactors 2. Mixed Culture Downstream processing

Biomass Harvesting and Treatment Extraction and Recovery Product Dry PHA 1. Properties? 1. What are the properties? How are they set? 2. Does it matter if pure or mixed cultures are used for PHA production? Material Balance: Mixed culture production opens the door to using waste streams as feedstocks but how much feedstock is needed? Overview our background in PHBV PHA-Wood Bioprocesses 3. Options? Feedstock Wastewater Methane Biosolids 2. Pure Culture Block

Polymers Bioreactors Distribution / Blends 2. Mixed Culture Accumulatio n in AS Composites Downstream processing Biomass Harvesting and Treatment Crystallisati on Extraction and Recovery Solvent Extraction Degradation Dry PHA Thermal

Degradation 1. Properties? Mechanical Properties 1. PHA properties and how are they set? A: Polymerisation B: PHA granule (Rehm (2013)) C: PHA polymer chain D: Semi crystalline polymer E: AFM of a PHBV film F: Plastic product Processing and mechanical properties Core mechanical properties for commodity applications: Elongation at break Youngs modulus Tensile strength Synthesis PHB, and to a lesser extent PHBV, is stiff and brittle because of high crystallinity HB-HV Crystallinity PHA-PHA Blends

MW Microstructure Properties Processing and mechanical properties P(3HB) P(3HB) Biomer 240 Mirel P1001 P(3HBV) P(3HBV) ENMAT BioC 1000 PolyProp Our PHBV Melt Flow (g/10min) 5-7 10-12 Density (g/cm3)

1.17 Crystallinity (%) 60-70 Tensile Strength (MPa) 18-20 28 36 30-40 40 Elongation (%) 10-17 6 5-10 2.5-6 100 3-60 1.4

2.5-3 2 0.8-3 170-175 140-170 80/170 1.39 Flexural Modulus Melt Temp 17 1.22 <1 50-60 Tensile Modulus (GPa) Flexural Strength 1.25 46 61 3.2 1.4 147 From Shen et al in Laycock et al. Composition Incorporation of HV units can drop stiffness and brittleness and increases elongation to break. Why? Inclusion of HV units effects / disrupts crystallinity. HBHV Crystallinity PHA-PHA Blends MW Microstructure Properties PHB PHBV HBHV

Crystallinity Crystallinity PHA-PHA Blends MW Microstructure But Isodimorphic: Properties Copolymers exist together in the crystal structure high degree of crystallinity across the range Pseudoeutectic Crystallinity - Aging Microstructure Block copolymers HBHV Crystallinity PHA-PHA Blends MW Microstructure

Properties Extend material property range, rapid crystallisation, limited embrittlement with aging (secondary crystallisation) Long chain block copolymer BBBBBBBBBB VBVB VVVVV BBB B VV Short chain block copolymer VVVV BVVBB BBBBB V B B VVVV V Random copolymer BVBBVBVVVVBBVBBBBBVVBVVVBVBVVVVVBBB BVVBVBBV Manipulating microstructure A Feeding Microstructure HAc:HPr 50:50 Random copolymers HAc:HPr 70:30

D 2.3-3.0 R 0.8-1.0 B HAc (4h) then HPr (4h) A-B diblocks and/or A-B-A triblock, blended with random copolymer 5.6 0.6 C HAc (1.0h) alternating HPr (0.5h) A-B diblocks and/or A-B-A triblock and/or or possible (A-B)n repeating multiblocks 20.0 0.44 Characterising microstructure Quantitative 13C NMR

Analyse diad and V-centred triad peak intensities Compare distributions with statistically random copolymerisation and blends D value >1.5, R value <1 = blocky copolymer or bimodal (or more) blend of random copolymers B3 B2 B4 V3 B1 V2 V4 V5 V1 Manipulating microstructure A Feeding Microstructure HAc:HPr 50:50 Random copolymers HAc:HPr 70:30 B

HAc (4h) then HPr (4h) A-B diblocks and/or A-B-A triblock, blended with random copolymer C HAc (1.0h) alternating HPr (0.5h) A-B diblocks and/or A-B-A triblock and/or or possible (A-B)n repeating multiblocks Elongation (%) Youngs Mod. MPa 5-6.5 850-950 3 2000 58 800 Microstructure and macroscale architecture

Blocky Random Blocky (C1 Fr2) Random 10 10 m a) b) c) 10 m d) a) and b) AFM images and c) and d) POM images on crystallisation of blocky (left) and random (right) copolymeric PHBV. Manipulating microstructure Increased elongation for blocky copolymer retained over > 4 months Result has been reproduced However, most materials produced have properties similar to low HV content PHAs (low elongation to break) its not straightforward to make high performance PHBV materials. HBHV PHA-PHA blends

MW We make PHBV copolymers but how homogeneous is the product? 50% HV 50% HV V V B V B V V V V B V B B V

V V V B B B V V B B B V B B V B B B B

V V V V V B B V B B V B As produced P(3HB)-based copolymers have been fractionated to give a series of fractions with narrow compositional distribution. B Same substrate and the same organism in the same conditions two different groups of PHA copolymers (Yoshi and Inoue). PHA-PHA blends Mn Mw

g mol-1 g mol-1 x 10-5 x10-5 52% 2 40% 63% 77% HV %Cmol Sample Material A4 and B1 fractionated into >3 distinct copolymers (based on composition) A4 Fraction Asproduced 1 2

3 R B1 Asproduced 1 2 3 R %Mass by fraction by NMR GC/MS 100 42 42 16 38% 55% 71% PDI D R 5.9 2.9

2.6 0.9 1.7 1.5 1.3 5.3 4.7 4.6 3.1 3.1 3.6 8.7 0.4 1.6 0.7 1 1.1 65% 2.5 5.5 2.2 2.9

0.8 45% 51% 91% 1.9 2.1 1.6 5.5 5.4 5.4 3 2.6 3.3 6.7 2.6 2 0.56 0.85 0.9 95 100 18 21 61 94

33% 49% 89% PHA-PHA blends (DSC) Properties controlled by more rapidly crystallising components Blends Macroscale architecture Synthesis Properties are a function of macroscale architecture HBHV MW macroscale architecture 2. PHA synthesis PHA biotechnology is relatively expensive: Requirement for refined substrates Requirement for sterilisation Opportunity for mixed culture production: Waste organics as a feedstock No requirement for sterilisation Process into bioplastic

What does mixed culture synthesis mean for polymer properties? Broad and dynamic distribution of populations of PHA accumulating organisms So how does the community variability influence biopolymer synthesis? What does mixed culture synthesis mean for polymer properties? Multiple populations metabolising substrates at different rates. (Lemos et al, and Albuquerque et al, and UQ-Anox) Individual populations shift metabolic state. (UQ-Anox) Potential for: Complex substrate-monomer relationships. PHA-PHA blends broad compositional distribution. Flux in community PAP Description Y(PHA/S) 20 hr (gPHA/gVSS)

(gCOD PHA/ gCOD VFA) 100% HAc 0.56 0.04 0.48 0.02 100% HAc 0.48 0.06 0.38 0.04 100% HPr 0.40 0.04 0.31 0.03 100% HPr 0.48 0.03 0.40 0.07 50/50 HAc/HPr 0.48 0.06 0.39 0.03

50/50 HAc/HPr 0.52 0.03 0.45 0.03 Alt HAc/HPr 0.59 0.03 0.52 0.03 Alt HAc/HPr 0.52 0.06 0.49 0.03 Alt HAc/HPr 0.53 0.04 0.59 0.02 Little effect on accumulation performance. HV profile reproducible with feed strategy PHA Accumulation Potential relatively stable Overall PHA yields were similar Substrate-monomer relationships HB Unit Unit

HV Acetate HB Propionate HV (mainly) and HB Substrate to monomer Evolution of instantaneous molar 3HV fraction with respect to total PHA in mixed cultures under conditions of negligible or low cell growth rate. (Jiang, Hebly et al. 2011; Pardelha, Albuquerque et al. 2014; ArcosHernandez, Laycock et al. 2013). 1.0 0.8 ) PHA/mol3HV (mol inst 0.6 0.4 %3HV Generally HV synthesis is consistent but not

always... 0.2 0.0 0 2 4 6 Time (h) 8 10 12 Metabolic states Active biomass Polymer composition HV HB GLUM 38 9,11 8,10 37

HPr HAc PrAcCoA NH3 AcAcCoA GLUT 2 R1,5P E4P 36 AcCoA PrCoA 27 6 1 7 NADPH

4 5 26 ISC F6P 25 G3P 3PG 24 23 PEP 14 13 2 NADPH G6P KGKG NADP+ 2832

2 NADP+ PYR 12 21 SucCoA 18 15 GOX 19 33 NADH NAD+ OAA 22 20 MAL 34 FADH

SUC 16 17 FAD+ NADP+ NADPH What does (mixed culture) synthesis mean for polymer properties? Multiple populations metabolising substrates at different rates. Synthesis HBHV MW Individual populations shift metabolic state. Complex substrate-monomer relationships. PHA-PHA blends broad compositional distribution. macroscale architecture

Material balance for PHA production Company name Carbon Substrate Product name Production (t/a) DaniMer Scientific / Meredian Canola oil SelumaTM 15,000 Metabolix/Antibiticos Switchgrass, camelina, sugar Mirel, MveraTM 10,000 TianAn Biologic Material Co Corn/cassava starch ENMAT 10,000 Tianjin GreenBio

Corn starch SoGreenTM 10,000 Bio-on Beet or sugar cane Bio-onTM 10,000 PHB Industrial Sugar cane BiocycleTM 2,000 Kaneka Vegetable oil AONILEX 1000 Biomer Sugar (sucrose)

Biomer PTM 1,000 Newlight Technologies Waste methane AirCarbonTM >500 Challenge: Design for PHA production capacity of > 10,000 t/a How much feedstock is needed? Material balance for PHA production Accumulation Yield PHA Content Growth Yield Material balance for PHA production Challenge: Design for PHA production capacity of > 10,000 t/a How much

feedstock is needed? > 60% of C as CO2 > 20% of C as CO2 Material balance for PHA production Challenge: Design for PHA production capacity of > 10,000 t/a < 20% of C as PHA How much feedstock is needed? Biomass? Methane? So need > 50,000 t/a of organics (less than the waste organics from a large paper mill) Alternative carbon sources? Techno-economics for PHA from CH4 Material balance for PHA production

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