Electrospinning of Lignin as a Carbon Fiber Precursoe

Amir Hamzah Siregar, Saharman Gea, Aditia Warman, Mahyuni Harahap,

Grace Nainggolan and Dellansyah

Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Sumatera Utara, Medan, Indonesia

Keywords: Lignin, Precursor, Electrospinning, Pyrolysis, Carbon Fibre.

Abstract:

Electrospinning is a valuable method for polymeric to produce the nanoscale of fibres. This technique has

significant attention due to its simple and efficient. To realize these more advanced functional carbon fibre,

how that polymer affects the electrospinning process is essential. In this study, 10% PVA in deionised water

was prepared using reflux at 25 ºC for 2 hours and mixed with 0.5, 1.0, 1.5, 2.0, and 2.5 gram of lignin. The

addition of lignin to the PVA solution decreased the conductivity and increased the viscosity. The polymer

solution was then electrospun with distance 13 cm, flow rate 0.2 ml/h, voltage 19 kV at 24 ºC. Using The

Fourier Transform Infrared (FTIR) and Scanning electron microscopy (SEM), respectively the functional

group and spun of fibre morphology were characterised. The result showed that it formed beads-fibres.

1 INTRODUCTION

Carbon fibre was produced by carbonization of

carbon precursors (Gindl-altmutter et al., 2019).

The different part carbon, there are carbon fibre that

contain 92% of carbon based on that weight, based

on pyrolysis process (Deng et al., 2013). Carbon

fibre is a lightweight with a tensile frame, high

strength and low density. Therefore significant

benefits in development of precursors for carbon

fibre, obtained renewal from biobased such as lignin.

Lignin, a plant-based biopolymer, has three

dimensional polyphenolic polymer and available in

the plant cell walls (Chemistry, 2019; Poursorkhabi

et al., 2015). Aromatic structure of lignin, supported

the graphization during the carbonization process

(Ago et al., 2012). There are literature study reported

that applied of lignin Kraft and organosolv as a

carbon fibre precursor after obtaining thermal

stabilization and carbonization (Dalton et al., 2018).

Lignin-based carbon fibre offers potentially

attractive manufacturing cost advantages over

current technology, estimated costs on a commercial

scale of around $4/Ib - $6/Ib compared to production

for petroleum-based carbon fibre $10/Ib (Milbrandt

& Booth, 2016).

Table 1: Cost-saving figures for carbon fibre dependent on

lignin compared with traditional PAN carbon fibre.

Process Cost

Category

PAN-Based

Carbon Fibre

Cost Estimate

(

S9.88/Ib

)

Lignin-Based

Carbon Fibre

Cost Estimate

(

$3.71/Ib

)

Precursors $5.04 $0.50

Stabilization

and oxidation

$1.54 $0.99

Carbonization

and

hitization

$2.32 $1.48

Surface

treatment

$0.37 $0.33

Spooling and

acka

$0.61 $0.41

The polymer should have the specifications to

form a fibre, linear molecular structure, high carbon

content, low polydispersity, higher molecular

density, compact structure, lower crystallinity and

molecular orientation (Ko, F.K., Wan, 2014).

Electrospinning was commonly employed in the

manufacture of nanofibre sheets, which are applied

in various fields such as Nano sensors, ultrafiltration

membranes and nanocomposites (Akgul et al., 2018;

Chen et al., 2014; Choi et al., 2019; Ko et al., 2015;

Zhang et al., 2019).

There are parameter that affect the diameter of

nanofibres including high voltage and flow rate

(Abbas et al., 2016). The electrospinning fabrication

258

Hamzah Siregar, A., Gea, S., Warman, A., Harahap, M., Nainggolan, G. and Dellyansyah, .

Electrospinning of Lignin as a Carbon Fibre Precursor.

DOI: 10.5220/0010142700002775

In Proceedings of the 1st International MIPAnet Conference on Science and Mathematics (IMC-SciMath 2019), pages 258-262

ISBN: 978-989-758-556-2

process, the diversity of materials, the unique

associated with fibres result, can be used for various

application such as biomedical, drug delivery, tissue

engineering, wound dressing, filter, membrane,

energy and electronics (Bellan, 2008) and produced

nanometre size of fibres diameters accuracy

(Poursorkhabi et al., 2015).

This study aims to electrospun lignin to obtain

fine fibre as a carbon fibre precursor.

2 EXPERIMENTAL

2.1 Materials

Lignin alkali, with partially soluble 13.4 wt, % loss

on heating 316ºC, with pH: 6.5 (25ºC, 5% aqueous

solution, d: 1.3 g/mL at 25

C, the PVA, fully

hydrolyzed (Mw approx. 60000) with viscosity 20ºC

(4%; water), degree of hydrolysis ≥98.0% was

purchased from Sigma Aldrich, USA. The lignin and

PVA were used as received. The aqueous solutions

were prepared using distilled water.

2.2 Preparation of PVA/lignin

The PVA 10% was prepared by dissolving for 4

hours 10 g of PVA in 100 mL in aquatic reflux. This

process results a colorless and thick PVA solution

which was mixed with amount of lignin 0.5, 1.0. 1.5,

2.0, and 2.5 g using ultrasonic (hemasonic) for 6

hours at room temperature, then calculated the

conductivity and the viscosity value of the polymer

solution that was analyzed.

2.3 Preparation of PVA/lignin Nano

Fibre via Electrospinning

For the electrospinning process PVA/lignin solution

was prepared and carried out in a horizontal

electrospinning machine (syringe SP20, high voltage

power supplies PS-35PV and speed controller with

drum collector ESD-30S, NLI) on substrate material.

The prepared 1 mL volume solutions were loaded

into a 10 ml of syringe with an 18 G needle and

were electrospun at 18-20 kV voltage, 0.2 mL/h feed

rate of, and 13 cm tip-to-collector size. The

electrospun nanofibers electrospun were then dried

out for 24 hours at room temperature. Figure 1.

Demonstrates the PVA/lignin cycle fabricated using

electrospinning system.

Figure 1: Process of electrospinning PVA/lignin.

2.4 Characterization

2.4.1 Conductivity and Viscosity

The samples were prepared in five different

concentrations of PVA/lignin and one sample of

PVA aqueous as basic parameter test. Isolv AC780-

Conductivity Meter determined the electrical

conductivity of polymer solutions.

The viscosity solutions was determined by

viscometer redwood. The step to calculated are

homogenized the solution and put into viscometer

tank at room temperature in Kohlrausch flask below

of viscometer. The test repeated for three times. The

viscosity of samples can determined by the formula:















175.1

00260.0µ

Noted:

µ = dynamics viscosity of sample (Nm/s

)

t = times of dropped

y = density of samples (kg/m

)

µ = (0.00260t – 1.175) y

2.4.2 Scanning Electron Microscopy

The morphology surface of electrospun was

observed by scanning electron microscopy (SEM) at

an accelerating voltage EHT of 20.00 kV, probe =

101 Pa and signal A = SE1. The morphology of the

samples was examined with a scanning electron

microscope. The samples was placed on an

adhesive-backed carbon tape and secured to the

specimen. The sample was sputter-coated with a thin

layer of gold alloy (SC 500 emscope) to reduce the

charging during analysis. that the word “Table” is

spelled out.

2.4.3 Fourier Transform Infrared

The Fourier Transform Infrared Spectroscopy

(FTIR) analized the functional sample groups within

Electrospinning of Lignin as a Carbon Fibre Precursor

259

the range of 4000 cm

-1

-400 cm

-1

with 4cm

-1

resolution.

3 RESULT AND DISCUSSION

3.1 Viscosity

The amount of lignin added affects the viscosity of

solution, because the interaction between solute and

solvent in solution. The solution preparation such as

concentration of component, stirring intensity,

duration of stirring before mixing have important

effect on the viscosity of the blends. The viscosity of

polymer solutions measured at 24ºC was shown in

Figure 2.

Figure 2: The viscosity of 10% PVA in deionized

water/lignin.

According to figure 2, the viscosity of PVA

solution with the addition of lignin. It was 3.023

Nm/s

, and improved to 5.942 Nm/s

, 9.497 Nm/s

11.552 Nm/s

, 13.331 Nm/s

, 25.731 Nm/s

, with the

amount of lignin 0.5 g, 1.0 g, 1.5 g, 2.0 g, 2.5 g

respectively. It might be due to the presence of

macromolecular solute increased the solution’s

viscosity, because the large molecules affect fluid

flow at great distances (Tissos et al., 2014).

3.2 Conductivity

The solution of PVA/lignin resulted different of

electrical conductivity. The electrical conductivity of

polymer solution has the ability to deliver an electric

current, because of the ions contained in solution

(Irwan & Afdal, 2016). Based on the data showed

that the conductivity of PVA solution increased with

the addition of 0.5 g lignin from 154.1 S/cm

-1

255.5 S/cm

-1

. However, the higher the amount of

lignin the lower its conductivity. This result was the

same as Mahyuni’s research (Harahap, 2018). The

conductivity of PVA/lignin electrospun solution was

illustrated in Figure 3.

Figure 3: The conductivity of PVA 10% in deionized

water/lignin.

3.3 Scanning Electron Microscopy

Morphology

Figure 4 shows the morphology of the spun-fibres,

with reference of the bead-fibres was produced

during electrospinning. It is being the low

compatibility of lignin with PVA. In addition the

diameter of spun-fibres decreased with the

increasing of conductivity. The electrical

conductivity of polymer solutions influenced the

diameter fibre electrospun. It can happen because an

electric current carried by cations and anions in a

colution and increased the movement of ions in

solution, so the conductivity of solution increased

(Irwan & Afdal, 2016). When the conductivity value

is strong, the jet elongation between the tip of the

needle and the collector is weaker, leading to the

making of thicker fibers (Harahap, 2018). Table 2

Summarizes the diameter of the spun-fibres.

Table 2: Electrical conductivity of PVA/lignin solutions

and the fibre diameter.

Sample

PVA/lignin

(% wei

ht)

Electrical

Conductivity

S/cm

-1

Fibre

Diameter

(nm)

0 154.1 114.76

5 291.2 63.38

10 286.8 84.63

15 275.4 64.20

20 260.7 55.13

25 255.5 48.38

IMC-SciMath 2019 - The International MIPAnet Conference on Science and Mathematics (IMC-SciMath)

260

Figure 4: SEM images of PVA 10% (w/v) contained of

lignin (a) 0 g (b) 0.5 g, (c) 1.0 g (d) 1.5 g, (e) 2.0 g, (f) 2.5

3.4 Fourier Transform Infrared

Analysis

The spectrum of FTIR lignin commercial, PVA, and

PVA/lignin was illustrated in Figure 6.

Figure 5: FTIR spectrum of lignin commercial,

PVA/lignin, PVA.

The FTIR has been used to classify the groups of

functions present in the materials used in this

analysis. The reference disk was used to obtain the

FTIR spectrum in context.

The chemical of lignin represents spectrum

revealed with the literature. We can see the presence

of a large peak at 3433.29 cm

-1

linked to the

stretching of O-H from the intermolecular hydrogen

bonds. This peak decreased after the electrospinning

lignin/PVA solution. The peaks observed at 2848

-1

-2939 cm

-1

are respectively related to the

symmetric stretching vibrational of C-H from alkyl

groups. The another peak, showed at 1604 cm

-1

indicated be assigned to the aromatic C=C stretching

group, peaks at 1373 cm

-1

related to the S=O group,

and the peak at 817 cm

-1

related to the C-O-S bonds

(Rodrigues et al., 2002).

The FTIR analysis of PVA showed at 3425.58

-1

is consistent with the O-H of hydrogen bonds,

the peak observed at 2916.37 cm

-1

stretching

vibrational of C-H that alkyl group, the peak at 1651

-1

C=C be assigned to the aromatic group. There

are another peak of 1327 cm

-1

is S=O group, and

peak at 842 cm

-1

can be related to C-O-S bond

(Awada & Daneault, 2015).

4 CONCLUSIONS

The fabrication of lignin as a carbon fibre using

electrospinning method has been successfully

demonstrated. The morphology of lignin-PVA spun

fibres was rough due to the inhomogeneous of lignin

with the polymer solution. The diameter fibers of

PVA 10% (w/v) contained lignin (0g; 0.5g; 1.0g;

1.5g; 2.0g; 2.5g are 114.76; 63.38; 84.63; 64.20;

55.13; 48.38.

ACKNOWLEDGEMENTS

Financial support was received from Talenta USU

2019.

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