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Characterization of Biochar Sourced from Lignin Used to Tune the Electrical and Mechanical Properties of Biodegradable Polymer Blends Seth Kane Jesse Arroyo, Stephan Warnat, Cecily Ryan [email protected] Biochar & Bioenergy July 3, 2019 PLA PHBV Carbon Black e- PLA PHBV Biochar 1

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Page 1: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Characterization of Biochar Sourced from Lignin Used to Tune the Electrical

and Mechanical Properties of Biodegradable Polymer Blends

Seth KaneJesse Arroyo, Stephan Warnat, Cecily Ryan

[email protected]

Biochar & BioenergyJuly 3, 2019

PLA

PHBV

Carbon Black

e-PLA

PHBV

Biochar

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Page 2: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Motivation

https://www.epa.gov/smm/sustainable-materials-management-basicshttps://www.epa.gov/smm/sustainable-materials-management-basics

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Page 3: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

MotivationComposite materials allow for the

tuning of material properties to the desired application

Composite materials are not commonly recycled

Nanofilled composites enable the creation of electrically semi-conductive materials

https://www.rockwestcomposites.com/

Ryan Lab Group, Unpublished 2019

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Page 4: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Why add biochar to bioplastics?3D printable, biodegradable, electrically

semi-conductive plastics!

Promising alternative to carbon black

Beneficial at end of life

https://www.blackmagic3d.com/

Biochar from lignin

Carbon black Vulcan XCMAX22

Arroyo, J., & Ryan, C. (2018). https://doi.org/10.3390/polym10121371

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Page 5: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Why use a lignin sourced biochar?Waste product

High percentage carbon

https://en.wikipedia.org/wiki/LigninRyan Lab Group, Unpublished 2019

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Page 6: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Biodegradable polymersPoly(3-hydroxybutyrate-co-3- hydroxyvalerate) (PHBV)

Ryan Lab Group, Unpublished 2019

Polylactic acid (PLA)

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Page 7: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Why use a polymer blend?

Ryan, C., Unpublished, 2018

Nanofiller

occupies A or B

Nanofiller

localizes to A

Nanofiller

localizes to B

Nanofiller localizes

to interfaceArroyo, J., & Ryan, C. (2018). https://doi.org/10.3390/polym10121371

PLA

PHBV

Nanofiller

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PHBV

PLA

Nanofiller

Page 8: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Why use a polymer blend?

Ryan, C., Unpublished, 2018

Nanofiller

occupies A or B

Nanofiller

localizes to A

Nanofiller

localizes to B

Nanofiller localizes

to interfaceArroyo, J., & Ryan, C. (2018). https://doi.org/10.3390/polym10121371

PLA

PHBV

Nanofiller

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PHBV

PLA

Nanofiller

Page 9: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Why use a polymer blend?

Below c At/Above c

Percolation threshold c

Onset of connectivity

Add nanofiller

Change blend ratio

e-

e-

Ryan, C., Unpublished, 2018

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Page 10: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Why use a polymer blend?

Below c At/Above c

Percolation threshold c

Onset of connectivity

Add nanofiller

Change blend ratio

e-

e-

Ryan, C., Unpublished, 2018

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Arroyo, J., & Ryan, C. (2018). https://doi.org/10.3390/polym10121371

Page 11: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Arroyo, J., & Ryan, C. (2018). https://doi.org/10.3390/polym10121371

Challenges for composite processing

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Page 12: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Research ObjectivesCharacterize the reaction occurring between biochar and biodegradable

polymers

Investigate how this reaction might be mitigated or eliminated via different sourcing or preprocessing

Characterize properties of resulting composite

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Page 13: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Biochar Production VariablesFeedstocks:

Ryan Lab Group, Unpublished 2019

Ryan Lab Group, Unpublished 2019

Pretreatment:Ball milled to ~1-10 µmDried at 110°C for >24 hrs

Alkaline Lignin Dealkaline Lignin Wheat Stems

Alkaline Lignin Pre-milled

Alkaline Lignin Milled

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Page 14: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Biochar Production VariablesHighest Treatment Temperature:700 °C, 900 °C, and 1100 °C

▪ Nitrogen flow▪ Heat at 10 °C/min to HTT▪ Hold 1 hr▪ Ramp down

Ryan Lab, Unpublished 2019

Biochar Production Tube Furnace

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Page 15: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Thermogravimetric Analysis: PHBV and Lignin

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Page 16: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Differential Scanning Calorimetry: PHBV & Biochar

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Page 17: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Differential Scanning Calorimetry: PHBV & Biochar

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Page 18: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Differential Scanning Calorimetry: PHBV & Biochar

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Page 19: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Differential Scanning Calorimetry: PHBV & Biochar

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Page 20: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Differential Scanning Calorimetry: PHBV & Biochar

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Page 21: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Differential Scanning Calorimetry: PHBV & Biochar

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Page 22: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Differential Scanning Calorimetry: PHBV & Biochar

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Page 23: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Differential Scanning Calorimetry: PHBV & Biochar

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Page 24: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Similar trends seen in TGA of PLA…

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Page 25: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Initial ConclusionsReduction in thermal degradation temperature responsible for the

behavior seen

Present with biochar from multiple lignin feedstocks and wheat stems

Arroyo, J., & Ryan, C. (2018). https://doi.org/10.3390/polym10121371

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Page 26: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Next StepsCharacterize the reaction between biochar and plastics

How can we avoid this reaction?

Characterize the properties of resulting materialElectrical conductivity, mechanical properties, life cycle analysis

Biochar in other biodegradable plastic blends

Nanofiller

localizes to

interface

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Page 27: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Expected SignificanceA biodegradable replacement for carbon black would be highly

desirable as the market share of biodegradable plastics increases

Long termFully biodegradable and 3D printable semi-conductive materials

https://www.blackmagic3d.com/

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Page 28: Characterization of Biochar Sourced from Lignin Used to ... Seth.pdfFeedstocks: Ryan Lab Group, Unpublished 2019 Ryan Lab Group, Unpublished 2019 Pretreatment: Ball milled to ~1-10

Thank you!

Questions?

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[email protected]