Synthesis, Characterization, and Flow Behavior of

Biomaterial-based Microfibers

Kaitlyn McHugh
Ning Wattana
Osuji Group

August 6, 2021
 Goal: Synthesis of high-quality natural microfibers
1

1 m = 1,000,000 μm
Microfibers are materials on the order of 106 times smaller than a meter in diameter
➢ Fiber properties, including diameter, length, mechanical strength, and elasticity can
be controlled during synthesis

Important tool in medical applications

➢ Structure provides a scaffold for alignment and movement of cells in tissue Alginate microfiber
engineering
➢ Surface modification allows use in drug delivery
➢ Therapeutics can be encased in hollow fibers

Microfibers in tissue engineering Microfibers in drug delivery

Drug

Polymer precursor Fibers Surface-modified

Fiber production (wet spinning) Fiber scaffold Cell-scaffold composite fiber

He, C. J. Mater. Chem. 2014, 2, 7828-7848.

Xu, B. RSC Adv. 2015,5, 42705-42713.
Introduction Materials Methods Results Conclusion
Goal: Synthesis of high-quality natural microfibers
1

1 m = 1,000,000 μm
Microfibers are materials on the order of 106 times smaller than a meter in diameter
➢ Fiber properties, including diameter, length, mechanical strength, and elasticity can
be controlled during synthesis

Important tool in medical applications

➢ Structure provides a scaffold for alignment and movement of cells in tissue Alginate microfiber
engineering
➢ Surface modification allows use in drug delivery
➢ Therapeutics can be encased in hollow fibers

Microfibers are often made using synthetic polymers, like polyacrylonitrile

(PAN), due to their better mechanical properties
Synthetic fibers are less biocompatible and biodegradable than natural fibers

We investigate the synthesis, characterization, and flow behavior of natural alginate and nanocellulose
fibers as a potential replacement for synthetic PAN fibers

Introduction Materials Methods Results Conclusion

 Biomaterials as a replacement for acrylic fibers
2

Synthetic
Polyacrylonitrile (PAN)
● Petroleum and coal-derived
polymer used to manufacture
acrylic fibers
● Detrimental to the environment
● Strong mechanical properties

Yang, X. ACS Nano 2020, 14, 1, 724–735.

Introduction Materials Methods Results Conclusion
 Biomaterials as a replacement for acrylic fibers
2

Synthetic
Polyacrylonitrile (PAN)
● Petroleum and coal-derived
polymer used to manufacture
acrylic fibers
● Detrimental to the environment
● Strong mechanical properties
Natural
Cellulose Nanofibers (CNF)
● Derived from disintegration of
plant cells to individual
cellulose nanofibrils
● 3-15 nm in diameter and 1-3
μm in length
● Biocompatible

Yang, X. ACS Nano 2020, 14, 1, 724–735.

Introduction Materials Methods Results Conclusion
 Biomaterials as a replacement for acrylic fibers
2

Synthetic Natural
Polyacrylonitrile (PAN) Cellulose Nanofibers (CNF) Sodium alginate (SA)
● Petroleum and coal-derived ● Derived from disintegration of ● Obtained from brown algae
polymer used to manufacture plant cells to individual ● Salt of alginic acid, also forms
acrylic fibers nanofibrils calcium salt
● Detrimental to the environment ● 3-15 nm in diameter and 1-3 ● Non-toxic
● Strong mechanical properties μm in length ● Low cost
● Biocompatible

Yang, X. ACS Nano 2020, 14, 1, 724–735.

Introduction Materials Methods Results Conclusion
 Biomaterials as a replacement for acrylic fibers
2

Synthetic Natural
Polyacrylonitrile (PAN) Cellulose Nanofibers (CNF) Sodium alginate (SA)
● Petroleum and coal-derived ● Derived from disintegration of ● Obtained from brown algae
polymer used to manufacture plant cells to individual ● Salt of alginic acid, also forms
acrylic fibers cellulose nanofibrils calcium salt
● Detrimental to the environment ● 3-15 nm in diameter and 1-3 ● Non-toxic
● Strong mechanical properties μm in length ● Low cost
● Biocompatible

Yang, X. ACS Nano 2020, 14, 1, 724–735.

Introduction Materials Methods Results Conclusion
Project Outline: From precursor to characterization
3

1. Precursor synthesis

2. Wet spinning

3. Controlling Fiber
Dimensions

4. Characterization

Introduction Materials Methods Results Conclusion

 Precursor Synthesis
4

Polyacrylonitrile (PAN), sodium alginate (SA), and cellulose nanofibers (CNF) were used for precursor synthesis
➢ Fiber precursors are polymers dissolved in solvent

Different wt % CNF Different ratios SA:CNF

3 wt % PAN 2 wt % SA
(2, 1.1, 0.55) (2:0.55, 1:0.55, 1:1)

➢ Solvent: ➢ Solvent: water ➢ Suspended in water ➢ Solvent: water

dimethylformamide ➢ Polymer slowly added ➢ 1.1 wt % CNF stock ➢ SA and CNF solution
(DMF) until 2% wt was solution was dried were mixed to give
➢ Polymer added until reached using rotary desired % wt
reaching 3 wt % ➢ Stirred at 800 rpm and evaporator until ➢ Solutions were
➢ Mixed until fully heated at 55°C for 1 reaching 2% wt refrigerated for ≥3
dissolved hour until fully ➢ 1.1 wt % CNF was days before extrusion
dissolved diluted with water until
0.55 wt %

Introduction Materials Methods Results Conclusion

 Fiber Synthesis: Wet Spinning Process
5

Precursor of polymer dissolved in solvent is extruded into a coagulation bath of nonsolvent to form fibers
Precursor solution

Nonsolvent/coagulant

Fibers
Syringe pump

Precipitation Polymerization Method Ion exchange method

PAN/DMF extruded into H2O Sodium alginate/CNF/water extruded into CaCl2

➢ Harsh organic solvents are required to dissolve ➢ SA is soluble in water, calcium alginate is not
PAN (DMF in this case) ➢ SA/water precursor enters CaCl2 coagulation
➢ PAN is extruded into water, but it is insoluble bath and ion exchange occurs
➢ PAN precipitates to form fibers ➢ Calcium alginate precipitates to form fibers

Phan, S. Science and Food. 2013.

Xu, B. RSC Adv. 2015,5, 42705-42713.
Introduction Materials Methods Results Conclusion
Fiber Synthesis: Controlling Fiber Dimensions
6

Diameter of fibers was controlled by flowing the precursor at different rates through the extrusion needle
➢ Measurements were obtained under optical microscope
➢ Most precursors follow the pattern: slower rate = smaller diameter

PAN requires slower rates to

yield target fiber size (≤200 μm)
Alginate fibers can be pumped at
faster rates to yield target fiber
2% SA:0.55% CNF at
size
3% PAN at 0.02 mL/min 2% SA at 0.1 mL/min
0.25 mL/min ➢ 0.1, 0.25, 0.5, 1 and 5
mL/min are successful

Differences in viscosity may

impact how fibers are extruded
through the needle

Introduction Materials Methods Results Conclusion

Fiber Synthesis: Controlling Fiber Dimensions
7

Length of SA/CNF fibers was changed by “cutting” with air during extrusion
Air
➢ Precursor and air were pumped at different rates using separate syringe pumps 2 mL/min

➢ Air intersects at T connector to create a patterned flow of precursor and air

Addition of CNF to SA precursor favors shorter lengths

➢ Indicates that air intersects CNF precursors more frequently/easily
Precursor
➢ CNF may change the crosslinking structure in SA fibers 0.05 mL/min

2% SA 2% SA:0.55% CNF 1% SA:0.55% CNF 1% SA:1% CNF

Introduction Materials Methods Results Conclusion

 Precursor Characterization: Viscosity
8

Viscosity (η) is determined by shearing the precursor solution with cone and plate geometry, using a
.
rheometer to track stress (σ) as a function of shear rate (γ)
➢ Newtonian fluids: viscosity is constant with different shear rates (ex: water)
➢ Non-Newtonian fluids: viscosity changes with different shear rates (ex: honey)

Viscosity of Precursor Solutions

Cone and plate geometry. Cone applies pressure to the

precursor solution by rotating on the plate at desired rates.

3% PAN (η=0.019) and 2% sodium alginate (η=0.077) show

Newtonian behavior
Adding CNF results in deviations from Newtonian behavior
➢ Viscosity is not constant - shear thinning with yield stress occurs

Rheology - Theory and Applications. Boston Rheology Training. TA Instruments.

Introduction Materials Methods Results Conclusion
 Precursor Characterization: Viscosity
8

Viscosity (η) is determined by shearing the precursor solution with cone and plate geometry, using a
.
rheometer to track stress (σ) as a function of shear rate (γ)
➢ Newtonian fluids: viscosity is constant with different shear rates (ex: water)
➢ Non-Newtonian fluids: viscosity changes with different shear rates (ex: honey)

Viscosity of Precursor Solutions

Cone and plate geometry. Cone applies pressure to the

precursor solution by rotating on the plate at desired rates.

3% PAN (η=0.019) and 2% sodium alginate (η=0.077) show

Newtonian behavior
Adding CNF results in deviations from Newtonian behavior
➢ Viscosity is not constant - shear thinning with yield stress occurs

Rheology - Theory and Applications. Boston Rheology Training. TA Instruments.

Introduction Materials Methods Results Conclusion
 Precursor Characterization: Viscosity
8

Viscosity (η) is determined by shearing the precursor solution with cone and plate geometry, using a
.
rheometer to track stress (σ) as a function of shear rate (γ)
➢ Newtonian fluids: viscosity is constant with different shear rates (ex: water)
➢ Non-Newtonian fluids: viscosity changes with different shear rates (ex: honey)

Viscosity of Precursor Solutions

Cone and plate geometry. Cone applies pressure to the

precursor solution by rotating on the plate at desired rates.

3% PAN (η=0.019) and 2% sodium alginate (η=0.077) show

Newtonian behavior
Adding CNF results in deviations from Newtonian behavior
➢ Viscosity is not constant - shear thinning with yield stress occurs

Rheology - Theory and Applications. Boston Rheology Training. TA Instruments.

Introduction Materials Methods Results Conclusion
 Precursor Characterization: Viscosity
8

Viscosity (η) is determined by shearing the precursor solution with cone and plate geometry, using a
.
rheometer to track stress (σ) as a function of shear rate (γ)
➢ Newtonian fluids: viscosity is constant with different shear rates (ex: water)
➢ Non-Newtonian fluids: viscosity changes with different shear rates (ex: honey)

Viscosity of Precursor Solutions

Cone and plate geometry. Cone applies pressure to the

precursor solution by rotating on the plate at desired rates.

3% PAN (η=0.019) and 2% sodium alginate (η=0.077) show

Newtonian behavior
Adding CNF results in deviations from Newtonian behavior
➢ Viscosity is not constant - shear thinning with yield stress occurs

Rheology - Theory and Applications. Boston Rheology Training. TA Instruments.

Introduction Materials Methods Results Conclusion
Fiber Characterization: Tensile Measurement
9

Young’s Modulus (E) is determined by stretching fibers until they break, using a rheometer to track the
stress (σ) as a function of strain (ε)
➢ Tells us how easily a material stretches before irreversible change
Tensile Measurement of Fibers

Material E (MPa)

3% PAN 0.0136

2% SA 0.0225

2% SA 0.5% CNF 0.1122

1% SA 0.5% CNF 0.0032

Rheometer configuration for tensile
1% SA 1% CNF 0.0043 measurement of 3% PAN fiber.

➢ 3% PAN fibers are more stiff and break faster

➢ 2% SA and 2% SA 0.5% CNF fibers are more elastic

Guinea, G. V. J Exp Biol. 2005, 208 (1), 25–30.

Introduction Materials Methods Results Conclusion
 Conclusions: Factors that influence fiber characteristics
10

Many factors can influence size, structure, mechanical properties, and overall production of fibers

Extrusion rate
Length
Extrusion needle size
Diameter
Precursor composition
Mechanical properties
Precursor viscosity

➢ Sodium alginate and cellulose nanofibers were wet
spun into fibers of comparable diameter to PAN
➢ PAN fibers were more stiff, while alginate fibers were
more elastic
➢ Differences in viscosity and extrusion rate can
impact the final fiber morphology
➢ Low η precursors make shorter fibers and
require slower rate to reach small diameter
(≤200 μm) fibers
➢ High η precursors make longer fibers and can
use faster rates to make small diameter fibers

Future Directions
Biocompatibility and degradation of natural and synthetic fibers for medical applications
➢ For in vivo processes, degradation products of fibers must also be non-toxic to living tissue
➢ Tissue engineering/scaffolds require the degradation rate to be similar to the target tissue
Bhattarai, D. Membranes. 2018, 8, 3 62.
Introduction Materials Methods Results Conclusion
Acknowledgements
11

Thank you to my mentor Ning for all of her help and

collaboration on this project. Thanks to my PI Dr. Osuji and all
the Osuji group members for all of their support throughout this
program. Thank you Dr. Jeong and the CEMB for making this
presentation possible.
Synthesis, Characterization, and Flow Behavior of
Biomaterial-based Microfibers

Kaitlyn McHugh
Ning Wattana
Osuji Group

August 6, 2021