Enhancing the interfacial strength of

carbon/epoxy composites using ZnO

nanowires

A report submitted in partial fulfilment of the requirements

for the degree of Dual Degree in MFD

by

ADITYA KUMAR
(Roll No: MFD16I003)

DEPARTMENT OF ELECTRONICS AND COMMUNICATION ENGINEERING

INDIAN INSTITUTE OF INFORMATION TECHNOLOGY,
DESIGN AND MANUFACTURING, KANCHEEPURAM

March 2021
 Certificate

I, Aditya Kumar, with Roll No: MFD16I003 hereby declare that the material presented
in the Project Report titled Enhancing the interfacial strength of carbon/epoxy
composites using ZnO nanowires represents original work carried out by me in the
Department of Mechanical Engineering at the Indian Institute of Information
Technology, Design and Manufacturing, Kancheepuram during the years 2020–
2021. With my signature, I certify that:

• I have not manipulated any of the data or results.

• I have not committed any plagiarism of intellectual property. I have clearly

indicated and referenced the contributions of others.

• I have explicitly acknowledged all collaborative research and discussions.

• I have understood that any false claim will result in severe disciplinary action.

• I have understood that the work may be screened for any form of academic
misconduct.

Date: 01 March 2021

In my capacity as supervisor of the above-mentioned work, I certify that the work presented
in this Report is carried out under my supervision, and is worthy of consideration for the
requirements of Dual Degree Project work.

Advisor’s Name: Dr. Gowthaman Swaminathan

(Mail forward may be considered equivalent to guide’s signature)

i
 Abstract
This project investigates the application of Zinc Oxide nanowires (ZnO NW) to enhance
the interfacial strength of carbon/epoxy composites. ZnO NW are grown on carbon fibre
by hydrothermal method. The tensile properties of bare and ZnO NW coated carbon
fibres will be measured by single fibre fragmentation test. Improved interfacial properties
are expected by the end of this project.
Contents

Certificate i

Abstract ii

Contents iii

1 Introduction 1
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Carbon Fibres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.3 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.4 Objectives of the work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2 Literature Review 3
2.1 Improvement of Interfacial Strength . . . . . . . . . . . . . . . . . . . . . . 3
2.2 Preference of Zinc Oxide nanowires over Carbon nanotubes . . . . . . . . . 4
2.3 Single Fibre Fragmentation Test (SFFT) . . . . . . . . . . . . . . . . . . . . 4

3 Experimentation 5
3.1 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2 Specimen Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.1 Specimen Dimension . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.2 Synthesis of ZnO nanowires . . . . . . . . . . . . . . . . . . . . . . . 6
3.2.3 Preparation of specimens . . . . . . . . . . . . . . . . . . . . . . . . 7
3.3 Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.3.1 Tensile Tester . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

Bibliography 11

iii
Chapter 1

Introduction

1.1 Introduction

There has been a huge increase of the applications of fibre reinforced polymer composites
in the industries of aerospace engineering, civil engineering, development of military
equipments, etc. [1], [2]. These composites have been known to possess remarkable
properties such as light weight, very high strength to weight ratio and high corrosion
resistance [12], [13]. Nano particles such as multiwall carbon nanotubes and zinc oxide
nanowires exhibit outstanding mechanical, electrical and thermal properties. They are
known to improve the properties of composites when they are dispersed in the polymer
matrix. Zinc oxide have been aligned on carbon fibres and aramid fibres using the
hydrothermal method to improve the bonding strength between fibres and polymers [? ].

1.2 Carbon Fibres

Carbon fibres are fibres which are composed mostly of carbon atoms. They have diameters
ranging fro 5-10 µm. They are known to possess incredible properties such as low weight,
high stiffness, high tensile strength, high temperature tolerance high chemical resistance,
and low thermal expansion.
1
Chapter 1. Introduction 2

Carbon fibres are usually combined with other materials to form a composite. They form
carbon-fibre-reinforced polymers when permeated with a plastic resin and baked, which
have a very high strength-to-weight ratio, and are extremely rigid and brittle.

1.3 Motivation

The motive of this project is to gain a theoretical understanding of the applications of

zinc oxide nanowires. The aim of this project is to improve the interfacial strength of
carbon/epoxy composites by growing zinc oxide nanowires on the carbon fibre. The goal
of this project is to set a good foundation for development of products with carbon-fibre-
reinforced polymers with improved mechanical properties.

1.4 Objectives of the work

• Theoretical study of carbon-fibre-reinforced polymers and zinc oxide nano wires.

• Preparation of epoxy samples with single strand of carbon fibre.

• Preparation of epoxy samples with single strand of carbon fibre with zinc oxide grown
on it.

• Testing of samples by single fibre fragmentation test under a microscope.

• Running a 3D simulation to gain a numerical understanding of the mechanical

properties of the composite.
Chapter 2

Literature Review

2.1 Improvement of Interfacial Strength

Karger et al. [3] demonstrated that the interfacial strength of fibre reinforced plastics
(FRPs) can be tailored through strategies like (i) fibre functionalization (by
sizing/polymer coating of fibres) and (ii) fibre modification (by creation of hierarchical
fibres using nanostructures). Pittman et. al. [4] explains that the fibre sizing modifies
the morphology of the fibre surface and enhances the chemical reactivity with matrix
materials. They involve extensive treatments and depend on the type of matrix used and
may not offer a universal process for enhancing the interfacial strength of composite [? ],
[? ], [? ]. The alternate approach to improve interfacial adhesion is by modifying the
fibre with nanoscale materials like carbon nanotubes (CNTs) and zinc oxide nanowires
(ZN NWs). Karger et al. [3] mentions that the advantages of this fiber modification
include enhancement of the fiber surface area, possibility of mechanical
interlocking,capillary wetting by the matrix and local reinforcement of the interphase.
Thostenson et al. [8] modified the carbon fibres by growing CNTs on them by the
method of chemical vapour deposition. They tested the single fibre composites and they
observed that the nanocomposite reinforcement improved the interfacial load transfer by
15%.

3
Chapter 2. Literature Review 4

Sager et al. [9] investigated the properties of carbon-fibre-reinforced epoxy composite

with CNT coated on carbon fiber through the process of chemical vapour deposition
process and observed that there was a significant reduction of tensile strength of the
carbon fibre.

2.2 Preference of Zinc Oxide nanowires over Carbon

nanotubes

Zinc Oxide nanowires are preferred over Carbon nanotubes for the following reasons:

• Low synthesis temperature.

• Does not damage the fibre.

• Does not alter the mechanical properties of the fibre.

• Cheaper to synthesize.

2.3 Single Fibre Fragmentation Test (SFFT)

Single Fibre Fragmentation Test has been extensively used to characterize the interfacial
properties and damage process at the constituent level. The interfacial shear strength
will be measured using SFFT where the interfacial adhesion will be determined by the
Kelly-Tyson model equation under the assumption of constant shear stress.
Chapter 3

Experimentation

3.1 Materials

• Carbon fibers without any surface treatments are used as substrates for growing of
ZnO NW.

• The seed materials used for synthesis of ZnO NW are Zinc acetate dihydrate (ACS
reagent ≥ 98%, Sigma-Aldrich) and Sodium hydroxide reacted within ethanol.

• The growth materials are Zinc nitrate hexahydrate (98%, Sigma-Aldrich) and
Hexamethylene tetramine (ACS reagent ≥ 99%, Sigma-Aldrich).

• Single fiber composites are made using DGEBA based epoxy resin and cyclo aliphatic
amine curing agent. The resin and curing agent mixing ratio was 100:40. The curing
time is 48hrs.

5
Chapter 3. Experimentation 6

3.2 Specimen Manufacture

3.2.1 Specimen Dimension

A dogbone shaped epoxy specimen is used for the tensile test. The dimensions of the
specimen are 2 mm width, 2 mm thickness and 16 mm gauge length.

Figure 3.1: Dogbone shape of specimen for fragmentation test

3.2.2 Synthesis of ZnO nanowires

ZnO NW are grown on fibers as mentioned in [10] using low temperature hydrothermal
method which consists of two steps – ZnO seed layer deposition and ZnO NW growth.

• ZnO seed layer deposition:

– 1.3 mmol of zinc acetate dihydrate is dissolved in 80 mL of ethanol under

magnetic stirring at 50◦ C for 5 min.

– 2mm of sodium hydroxide is dissolved separately in 100 mL of ethanol under

magnetic stirring at 50◦ C for 5 min.

– After cooled to room temperature, 40 mL of zinc acetate solution and 40 mL

of sodium hydroxide solution were mixed with 320 mL of ethanol and 100 mL
of ethanol, respectively.
Chapter 3. Experimentation 7

– These solutions were heated separately to 65◦ C, then mixed and vigorously
stirred at 65◦ C for 30 min.

– Before subjected to dip coating, tow of glass fibers were rinsed in ethanol and
dried in hot air oven at 100◦ C for 10 min.

– Then, the fibers were dipped in the as prepared ZnO seed solution and dried
at 150◦ C for 2 min. This process was repeated for seven times to have total
annealing time of 15 min.

• ZnO NW growth:

– An equimolar of 25 mM zinc nitrate hexahydrate and hexamethylene tetramine

were dissolved in 500 mL of deionized water and heated to 90◦ C under vigorous
stirring.

– Once the growth solution reached 90◦ C, the seeded glass fibers were immersed
in this preheated solution continuously for 5 h.

– Finally, the fibers were rinsed with deionized water to remove accumulated
precipitates on the fibers.

– In an alternate method, the growth solution was refreshed at the intervals of

1.5 and 3 h.

– After 5 h, the fibers were rinsed with deionized water to remove accumulated
precipitates on the fibers.

3.2.3 Preparation of specimens

• PLA moulds were 3D printed for making specimens.

• Single fibers were aligned by vertical suspension in-between the mold at the required
height (1 mm). The fibers were pre-strained and carefully placed inside the mold to
account for shrinkage during curing.

• The epoxy resin/hardener mixture was prepared and degassed to avoid air bubbles.
Chapter 3. Experimentation 8

Figure 3.2: 3D printing of moulds

• The mixture is then filtrated into the molds without disturbing the fibers. The molds
were then allowed to cure at room temperature for 48 h.

Figure 3.3: Specimens with Carbon Fibre

Chapter 3. Experimentation 9

Figure 3.4: Specimen without Carbon Fibre

Chapter 3. Experimentation 10

3.3 Testing

3.3.1 Tensile Tester

Single fibre fragmentation test is performed using custom made low cost tensile tester
designed to pull one of the specimen slowly apart. This results in a uniform tensile stress
distribution in the gauge section of the specimen. This apparatus is placed on top of
an x-y-table and a holder is mounted on the back to connect the apparatus to the light
microscope.

Figure 3.5: Tensile Tester loaded with specimen

Bibliography

[1] B. M. K. F. P. . L. K. Mouritz, A. P., “Review of applications for advanced three-

dimensional fibre textile composites,” Part A: applied science and manufacturing,
vol. 30, no. 12, pp. 1445–1461, 1999.

[2] G. E. B. P. . C. Mouritz, A. P., “Review of advanced composite structures for naval

ships and submarines,” Composite structures, vol. 53, no. 1, pp. 21–42, 2001.

[3] P. A. Karger-Kocsis J, Mahmood H, “Recent advances in fiber/matrix interphase

engineering for polymer composites,” Prog Mater Sci., vol. 73, pp. 1–43, 2015.

[4] W. B. Pittman CU, He GR, “Chemical modification of carbon fiber surfaces by nitric
acid oxidation followed by reaction with tetraethylenepentamine,” Carbon, vol. 35,
no. 3, 1997.

[5] K. M. Drzal LT, Rich MJ, “Adhesion of graphite fibers to epoxy matrices: Ii. the
effect of fiber finish,” J Adhes., vol. 16, no. 2, pp. 133–152, 1983.

[6] F. O. Delamar M, Desarmot G, “Modification of carbon fiber surfaces by

electrochemical reduction of aryl diazonium salts: application to carbon epoxy
composites,” Carbon, vol. 35, no. 6, pp. 801–807, 1997.

[7] G. Y. Feller JF, “Coupling ability of silane grafted poly (propene) at glass
fibers/poly(propene) interface,” Appl Sci Manuf., vol. 35, no. 1, pp. 1–10, 2004.

[8] W. D. Thostenson ET, Li WZ, “Carbon nanotube/carbon fiber hybrid multiscale

composites,” Appl Phys., vol. 91, no. 9, pp. 6034—-6037, 2002.

11
Bibliography 12

[9] L. D. Sager RJ, Klein PJ, “Effect of carbon nanotubes on the interfacial shear strength
of t650 carbon fiber in an epoxy matrix.” Compos Sci Technol, vol. 69, no. 7, pp. 898–
904, 2009.

[10] G. C. G. H. . C. U. Gowthaman Swaminathan, Chandrakumar Palanisamy,

“Enhancing the interfacial strength of glass/epoxy composites using zno nanowires,
composite interfaces,” Composite Interfaces, vol. 25, no. 2, pp. 151–168, 2018.

[11] B. M. K. F. P. . L. K. Mouritz, A. P., “Review of applications for advanced three-

dimensional fibre textile composites,” Part A: applied science and manufacturing,
vol. 30, no. 12, pp. 1445–1461, 1999.

[12] G. E. B. P. . C. Mouritz, A. P., “Review of advanced composite structures for naval

ships and submarines,” Composite structures, vol. 53, no. 1, pp. 21–42, 2001.

[13] E. G. . S. H. A. Lin, Y., “Increased interface strength in carbon fiber composites

through a zno nanowire interphase,” Advanced functional materials, vol. 19, no. 16,
pp. 2654––2660, 2009.