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AN ABSTRACT OF A THESIS

SINGLE-LAP SHEAR TESTING TO INVESTIGATE PAN-BASED CARBON NANOFIBER AND VAPOR GROWN CARBON NANOFIBER SHEET REINFORCEMENT OF LAMINATED GRAPHITE/EPOXY COMPOSITE INTERLAMINAR SHEAR STRENGTH

Jon Rylan Cox

Master of Science in Mechanical Engineering Using carbon nanobers in an attempt to increase the interlaminar shear strength (ILSS) of laminated composites is the main focus of this research. Single-lap shear test specimens were fabricated from AS4/3501-6 graphite ber-reinforced plastic (GFRP) prepreg material using a double-vacuum box technique. Sheets of polyacrylonitrile (PAN)-based carbon nanobers (CNF) and vapor grown carbon nanobers (VGCF) were used as reinforcement in the overlap area in attempt to increase the laminated composite ILSS. Sheets were also functionalized in a 70% concentrated sulfuric, 30% concentrated nitric acid mixture, in an attempt to increase the ber/epoxy interfacial bonds. Sheet-reinforced samples were compared to nonreinforced, 0 , 45 , and 90 GFRP-reinforced specimens. Shear modulus values varied only slightly with reinforcement type. However, lap-shear strength proved highly dependent on reinforcement type. Nonreinforced specimens exhibited the highest overall average lap-shear strengths. However, PAN-based CNF-reinforced specimens displayed the highest average lap-shear strengths for reinforced specimens, with an average of 1690 psi, which was over 30% higher than the VGCF-reinforced samples. VGCF-reinforced samples displayed the lowest average lap-shear strength of 926 psi. GFRP-reinforced specimens exhibited average lap-shear strengths between that of the PAN-based CNFreinforced specimens and VGCF-reinforced specimens. The specimens reinforced with functionalized sheets exhibited lower average lap-shear strength than those reinforced with nonfunctionalized sheets. Lower strengths are most likely due to deterioration of the sheet structure during immersion in the acid mixture. It was discovered that the PAN-based CNF sheets were possibly already functionalized as-received from the manufacturer. PAN-based CNF diameters were much larger than expected, suggesting that the sheets were not fully carbonized. If the sheets were partially carbonized, they could retain functional groups from the PAN precursor material.

SINGLE-LAP SHEAR TESTING TO INVESTIGATE PAN-BASED CARBON NANOFIBER AND VAPOR GROWN CARBON NANOFIBER SHEET REINFORCEMENT OF LAMINATED GRAPHITE/EPOXY COMPOSITE INTERLAMINAR SHEAR STRENGTH

A Thesis Presented to the Faculty of the Graduate School Tennessee Technological University by Jon Rylan Cox

In Partial Fulllment of the Requirements for the Degree MASTER OF SCIENCE Mechanical Engineering

August 2007

CERTIFICATE OF APPROVAL OF THESIS

SINGLE-LAP SHEAR TESTING TO INVESTIGATE PAN-BASED CARBON NANOFIBER AND VAPOR GROWN CARBON NANOFIBER SHEET REINFORCEMENT OF LAMINATED GRAPHITE/EPOXY COMPOSITE INTERLAMINAR SHEAR STRENGTH by Jon Rylan Cox Graduate Advisory Committee: Christopher D. Wilson, Chairperson Dale A. Wilson Holly A. Stretz date date date

Approved for the Faculty: Francis Otuonye Associate Vice President for Research and Graduate Studies Date ii

STATEMENT OF PERMISSION TO USE

In presenting this thesis in partial fulllment of the requirements for a Master of Science degree at Tennessee Technological University, I agree that the University Library shall make it available to borrowers under rules of the Library. Brief quotations from this thesis are allowable without special permission, provided that accurate acknowledgment of the source is made. Permission for extensive quotation from or reproduction of this thesis may be granted by my major professor when the proposed use of the material is for scholarly purposes. Any copying or use of the material in this thesis for nancial gain shall not be allowed without my written permission.

Signature Date

iii

DEDICATION

This book is dedicated to my wife. I love you.

iv

ACKNOWLEDGMENTS

First, I thank God, who is my rock. Without Him, none of this would be possible. I thank my family, especially my wife, for their support as well. Thank you, Dr. Chris Wilson, my advisor, for pushing me. I thank Dr. Dale Wilson and Dr. Holly Stretz, my committee members, for helping me with the details. I deeply thank Richard Gregory for being a bad inuence. We had fun. Thank you, Dr. Virginia Davis and your group, for providing me with Raman spectroscopy analysis. Thank you, Gene Mullins, for helping me with the chemistry. Thank you, Dr. Crouse, for lending me chemistry equipment. Thank you, Dr. Swartling, for making glass xtures for my specimens. Thank you, Dr. Biernacki, for letting me borrow the TGA machine. Thank you, Pravin Kannan, for teaching me how to use it. Thank you, chemical engineering students, who needed to use it and let me go rst. Thank you, Vought Aircraft, for donating the prepreg material. Thanks to the TTU Manufacturing Center and Mechanical Engineering oce, for funding. Thank you, NDIA Tennessee Valley Chapter, for providing me with a fellowship. Thank you, Wayne Hawkins, for helping me with the SEM. Thank you, Mike Renfro and Joel Seber, for keeping all the computers running. Thank you, Jamie Beard, for lending me your machine shop. This material is based upon work supported by the National Science Foundation under grant no. DMR-0115961. Any opinions, ndings, and conclusions or recommendations expressed in this material are those of the author and do not neccessarily reect the views of the National Science Foundation.

TABLE OF CONTENTS

Page LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . LIST OF SYMBOLS Chapter 1. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1 2 3 4 5 7 7 7 8 11 15 15 18 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . x xii xvi

1.1 Advanced Composite Materials 1.2 Interlaminar Shear Strength 1.3 Carbon Nanomaterials

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. . . . . . . . . . . . . . . . . . . . .

1.4 Purpose of Research . . . . . . . . . . . . . . . . . . . . . . . 1.5 Thesis Outline . . . . . . . . . . . . . . . . . . . . . . . . . . 2. LITERATURE REVIEW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.1 Carbon Fiber-Reinforced Plastic Materials

2.1.1 Laminate Composites . . . . . . . . . . . . . . . . . . . . 2.1.2 Interlaminar Shear Stress . . . . . . . . . . . . . . . . .

2.1.3 Interlaminar Shear Tests . . . . . . . . . . . . . . . . . . 2.2 Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.2.1 Single-walled Carbon Nanotubes

2.2.2 Multi-walled Carbon Nanotubes . . . . . . . . . . . . . .

vi

vii Chapter 2.3 Carbon Nanobers . . . . . . . . . . . . . . . . . . . . . . . Page 20 21 23 26 27 28 31 33 34 34 36

2.3.1 Vapor-Grown Carbon Fibers . . . . . . . . . . . . . . . . 2.3.2 Polyacrylonitrile-based Carbon Fibers . . . . . . . . . . . .

2.4 Traditional Carbon Nanotube and Nanober Composites

2.4.1 Percolation Limit . . . . . . . . . . . . . . . . . . . . . . 2.4.2 Fabrication Techniques . . . . . . . . . . . . . . . . . . . 2.5 Bucky Paper Composites . . . . . . . . . . . . . . . . . . . . 2.5.1 Fabrication Techniques . . . . . . . . . . . . . . . . . . . 2.5.2 Bucky Paper Composite Properties . . . . . . . . . . . . 2.5.3 Functionalization . . . . . . . . . . . . . . . . . . . . . . 2.5.4 Functionalization Characterization . . . . . . . . . . . .

2.5.5 Functionalized CNT and CNF Composite Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6 Summary and a Look Ahead . . . . . . . . . . . . . . . . . . 3. EXPERIMENTAL PROGRAM . . . . . . . . . . . . . . . . . . . . . . 3.1 Material Properties . . . . . . . . . . . . . . . . . . . . . . . 3.2 Functionalization Process . . . . . . . . . . . . . . . . . . . . 3.3 Double Vacuum Box System . . . . . . . . . . . . . . . . . . 3.3.1 Cure Cycle Phases 3.3.2 Composite Lay-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

37 38 40 41 44 47 47 49 51 53

3.4 Preliminary Testing . . . . . . . . . . . . . . . . . . . . . . . 3.5 Test Sample Fabrication . . . . . . . . . . . . . . . . . . . .

viii Chapter 3.6 Shear Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Page 57 58 60 60 62 64 64 64 67 67 73 74 75 81 87 89 94 99 99 99

3.6.1 Physical Setup

3.6.2 Single-lap Shear Test Parameters

3.6.3 Test Sample Analysis . . . . . . . . . . . . . . . . . . . . 3.6.4 Data Analysis . . . . . . . . . . . . . . . . . . . . . . . . 4. RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1 Characterization Results 4.1.1 Measurements Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.1.2 Functionalization Results 4.1.2.1 TGA results

. . . . . . . . . . . . . . . . . . . . . .

4.1.2.2 Raman spectroscopy results . . . . . . . . . . . . . . 4.2 Shear Test Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.2.1 Extensometer Stress-Strain Curves 4.2.2 Strain Gage Stress-Strain Curves

4.3 Fracture Surface Analysis . . . . . . . . . . . . . . . . . . . . 4.3.1 Sheet Impregnation . . . . . . . . . . . . . . . . . . . . . 4.3.2 Fracture Features . . . . . . . . . . . . . . . . . . . . . . 5. CONCLUSIONS AND RECOMMENDATIONS . . . . . . . . . . . . . 5.1 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . .

5.1.1 PAN-based CNF Reinforcement . . . . . . . . . . . . . . 5.1.2 Eects of Acid Treatment

. . . . . . . . . . . . . . . . . 100

ix Chapter Page 5.2 Recommendations . . . . . . . . . . . . . . . . . . . . . . . . 101 5.2.1 Improving the Current Research Method . . . . . . . . . 101 5.2.2 Future Research . . . . . . . . . . . . . . . . . . . . . . . 103 BIBLIOGRAPHY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 APPENDICES A: SUPPLEMENTAL FUNCTIONALIZATION CHARACTERIZATION RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 B: SUPPLEMENTAL SINGLE-LAP SHEAR TEST FIGURES . . . . . . . . 120 C: SUPPLEMENTAL SINGLE-LAP SHEAR TEST RESULTS . . . . . . . . 126 D: SUPPLEMENTAL COMPACT DISC CONTENTS . . . . . . . . . . . . . 137 VITA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142

LIST OF TABLES

Table 2.1 3.1 3.2 3.3 4.1 4.2 4.3 4.4 4.5 4.6 4.7 C.1 C.2 C.3 C.4 C.5 C.6 C.7 Specic strengths of dierent materials . . . . . . . . . . . . . . . . . . Research material properties [10, 44, 73, 75] Functionalization test matrix Single-lap shear test matrix Fiber diameter statistics . . . . . . . . . . . . . . .

Page 8 42 45 56 66 76 79 79 85 88 89

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Shear test specimen overlap area statistics

Shear modulusextensometer data . . . . . . . . . . . . . . . . . . . . Shear test specimen lap-shear strength statistics . . . . . . . . . . . . . Bending moment eectsstrain gage data . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Thicknesses of specimens tested with strain gages

Shear test specimen average thicknesses . . . . . . . . . . . . . . . . . .

Data from nonreinforced specimens . . . . . . . . . . . . . . . . . . . . 128 Data from 0 CFRP-reinforced specimens . . . . . . . . . . . . . . . . . 129 Data from 45 CFRP-reinforced specimens . . . . . . . . . . . . . . . . 130 Data from 90 CFRP-reinforced specimens . . . . . . . . . . . . . . . . 131 Data from PAN-based CNF-reinforced specimens . . . . . . . . . . . . 132

Data from PAN-based CNF half-ply-reinforced specimens . . . . . . . . 133 Data from functionalized PAN-based CNF half-ply-reinforced specimens 134

xi Table C.8 C.9 Page Data from VGCF-reinforced specimens . . . . . . . . . . . . . . . . . . 135 Data from functionalized VGCF-reinforced specimens . . . . . . . . . . 136

LIST OF FIGURES

Figure 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.11 2.12 3.1 3.2 3.3 3.4 3.5 3.6 composite lamina deformation . . . . . . . . . . . . . . . . . . . . . . . ILSS failure modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Page 9 10 12 14 16 17 18 19 22 24 28 29 42 43 44 46 48 49

Composite laminates with varying amounts of porosity ( 50) [13] . . Forces and moments acting on a single-lap shear test specimen . . . . . Multi-walled nanotubes discovered by Iijima in 1991 [23] . . . . . . . .

The structure of a single-walled carbon nanotube [27] . . . . . . . . . . MWNT structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Bamboo structure of MWNT [33] . . . . . . . . . . . . . . . . . . . . VGCF morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

PAN-based CNF surface structures Percolation limit

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

The phase behavior of a rod-like polymer solution [52] . . . . . . . . . . GFRP prepreg material . . . . . . . . . . . . . . . . . . . . . . . . . .

VGCF sheet material . . . . . . . . . . . . . . . . . . . . . . . . . . . . PAN-based CNF sheet material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

The process used to functionalize CNF sheets

Degas and compaction phases [78] . . . . . . . . . . . . . . . . . . . . . The thermal cycle used to cure composite laminates [78] . . . . . . . .

xii

xiii Figure 3.7 3.8 3.9 3.10 3.11 3.12 3.13 3.14 3.15 3.16 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 Dierent layers used in the bagging process (adapted from [78]) The vacuum box used to cure composite specimens Layup of the porous teon/laminate section . . . . Page 51 52 53 54 55 57 58 59 61 62 65 66 68 69 70 72 73 75 77 78

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. . . . . . . . . . . . . . .

Shear test geometry used in this research (adapted from [17]) . . . . . . A tabbed shear test specimen with attached strain gage . . . . . . . . . Reinforcement type and orientation used in this research . . . . . . . .

Specimen imperfections . . . . . . . . . . . . . . . . . . . . . . . . . . . The test setup used for single-lap shear testing . . . . . . . . . . . . . . The setup used to measure strain by extensometer . . . . . . . . . . . . The setup used to measure strain by strain gage . . . . . . . . . . . . . Fiber diameter measurement micrographs . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

VGCF exhibiting crenulated surfaces (60,000)

Photomicrographs of preliminary test specimens . . . . . . . . . . . . . VGCF sheets functionalized for dierent amounts of time . . . . . . . . PAN-based CNF thermogram . . . . . . . . . . . . . . . . . . . . . . .

VGCF thermogram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . PAN-based CNF Raman spectroscopy results VGCF Raman spectroscopy results Stress-strain extensometer curves . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

More stress-strain extensometer curves

xiv Figure 4.11 4.12 4.13 4.14 4.15 4.16 4.17 4.18 4.19 4.20 4.21 4.22 4.23 A.1 A.2 A.3 A.4 A.5 B.1 B.2 Stress-strain strain gage curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Page 82 83 86 87 90 91 92 93 95 96 97 98 98

More stress-strain strain gage curves Strain gage and extensometer data Test specimen section thicknesses

Nonfunctionalized PAN-based CNF-reinforced fracture surface . . . . . Functionalized PAN-based CNF-reinforced fracture surface . . . . . . . Nonfunctionalized VGCF-reinforced fracture surface . . . . . . . . . . . Functionalized VGCF-reinforced fracture surface . . . . . . . . . . . . . The typical fracture mode of a single-lap shear test specimen . . . . . . Photomicrograph showing adhesive failure . . . . . . . . . . . . . . . . . . . . . . .

Photomicrograph showing mixed adhesive/cohesive failure

Cracking in a PAN-based CNF-reinforced fracture surface . . . . . . . . Pullout on VGCF-reinforced fracture surfaces . . . . . . . . . . . . . .

PAN-based CNF thermogramacid vapor suspension . . . . . . . . . . 117 PAN-based CNF thermogram2 hour immersion . . . . . . . . . . . . 117

VGCF thermogram3 hour immersion . . . . . . . . . . . . . . . . . . 118 Raman spectroscopy resultsacid vapor suspension . . . . . . . . . . . 118 Raman spectroscopy results2 hour immersion Stress-strain extensometer curves . . . . . . . . . . . . . 119

. . . . . . . . . . . . . . . . . . . . . 122 . . . . . . . . . . . . . . . . . . 123

More stress-strain extensometer curves

xv Figure B.3 B.4 Stress-strain extensometer/strain gage comparisons Page . . . . . . . . . . . 124 . . . . . . . . 125

More stress-strain extensometer/strain gage comparisons

LIST OF SYMBOLS

Symbol Symbols A d Ec Ef Em Kz L M MR P Pv Q R t V Vf Acronyms ASTM CFRP CNF CNT GFRP ILSS IR MWNT PAN SEM SWNT TGA VGCF

Description

Fluid viscosity In-plane bucky paper surface area Single-lap shear specimen nominal thickness Equivalent composite Youngs modulus Fiber Youngs modulus Matrix Youngs modulus Bucky paper z -direction permeability Bucky paper thickness Bending moment acting on reinforcement due to P Reaction bending moment acting on reinforcement due to P Load acting on single-lap shear test specimen Vacuum pressure Volume Flow rate Reaction load due to P Bucky paper infusion time Shear load due to P Fiber volume fraction

American Society for Testing and Materials Carbon ber-reinforced plastics Carbon nanobers Carbon nanotubes Graphite ber-reinforced plastics Interlaminar shear strength Infrared spectroscopy Multi-walled carbon nanotubes Polyacrylonitrile Scanning electron microscope Single-walled carbon nanotubes Thermogravimetric analysis Vapor-grown carbon nanobers

xvi

CHAPTER 1 INTRODUCTION

This research provides a study of advanced composite materials, interlaminar shear strength (ILSS), and a novel way to improve the ILSS of laminate composites using carbon nanober. This chapter introduces the research matter, denes terms, and briey states the experimental techniques used. First, terms describing composite materials are dened, and then ILSS and carbon nanomaterials are described. Next, the purpose of the researchto improve laminated composite ILSS by adding nanober sheets between composite laminais discussed. The chapter ends with a brief outline of the rest of the thesis.

1.1 Advanced Composite Materials

Because of their light weight and high strength, advanced composite materials are an important part of modern manufacturing. Examples of composite materials uses in manufacturing abound. Currently, the U.S. Army is researching new ways to fabricate advanced composites in order to replace components in their high mobility multipurpose wheeled vehicle (HMMWV) and Apache Longbow [1]. The Boeing 757 and 767 airliners use approximately 3000 lb. each of advanced composites, while the B-2 bomber uses an estimated 40,000-50,000 lb. of advanced composites [2]. Additionally, advanced composites are used in a number of sporting goods applications from tennis rackets to bicycles and are used extensively in the automobile industry. Consequently, research aimed at improving the mechanical properties of advanced composite materials has the potential to positively aect a variety of markets.

2 Composites are made up of two or more materials called constituents. Together, the constituents form a new material with properties superior to the constituents alone. Most composites are formed from a low-strength matrix material and a high-strength reinforcing material. For example, mud (matrix) mixed with straw (reinforcement) to form bricks is a composite material. Advanced composites normally employ polymer matrices, such as an epoxy resin, along with high-strength bers, such as carbon or graphite. Graphite ber-reinforced plastics (GFRP) are commonly used in the aerospace industry. One commonly-used form is the composite laminate. A composite laminate is made up of a number of sheet-like composite plys, or laminae, made of unidirectional bers or a woven cloth. The plys are layered to take advantage of the properties of each individual ply. One reason composite laminates are useful is their ability to preform to a given geometry, cutting down the cost of post-fabrication work. Another reason is that composite properties rely on the ply structure, which can be precisely tailored by the manufacturer. Therefore, composite laminates can be engineered to have specic mechanical properties depending on their intended use.

1.2 Interlaminar Shear Strength

Because of their unique ply structure, unwanted interlaminar shear stresses occur between composite laminae during loading. The measure of a laminate composite to resist failure between plys is known as interlaminar shear strength (ILSS). Interlaminar shear failure occurs in the epoxy between laminae, especially if the layers are comprised of mismatched unidirectional ply orientations. For example, adjacent plys with perpendicular ber angles have low ILSS, while adjacent plys with the same

3 ber angles have high ILSS. To increase ILSS, plys are often stacked with intermediate ber angles between perpendicular plys. ILSS is a matrix-dominated property [3]. Weakening the matrix by the introduction of voids greatly reduces ILSS [4]. One way to strengthen the matrix material is to add carbon nanomaterial as reinforcement. In fact, the fabrication and testing of nanocomposites is currently a highly researched subject because of the theoretical mechanical properties predicted for carbon nanomaterials [5].

1.3 Carbon Nanomaterials

There are a number of dierent categories of carbon nanomaterials. Carbon nanotubes (CNT) and carbon nanobers (CNF) are the two main categories described here. Both categories describe carbon-based bers with high length-todiameter aspect ratios. CNT and CNF dier in structure and size. CNT have a tube-like structure with diameters ranging from 1-100 nm and lengths as long as millimeters, while CNF have basically uniform cross sections with diameters on the order of 100 nm and lengths between 20 and 100 m [5]. CNT are conventionally split into two categories: single-walled carbon nanotubes (SWNT) and multi-walled carbon nanotubes (MWNT). SWNT have singletube structures while MWNT have concentric or scroll-like tube structures. Consequently, they possess slightly dierent mechanical properties. The two categories of CNF relevant to this research are vapor-grown CNF (VGCF) and polyacrylonitrile (PAN)-based CNF. VGCF dier in size and structure from PAN-based CNF. As a result, they also possess dierent mechanical properties.

4 Both CNT and CNF have high theoretical strengths and elastic modulus, which make them ideal reinforcement for traditional epoxy material [5]. A number of dierent methods are used to mix CNT or CNF with matrix material. The goal of these methods is to overcome the high viscosities encountered when mixing CNT or CNF with the matrix. One alternate method involves fabricating sheets of CNT (often called bucky paper) or CNF that are then impregnated with a polymer matrix [6]. However, both CNT and CNF are expensive (from $0.25 to $1900/gram depending on type and purity), rendering them impractical for use in general applications where pure CNT or CNF composites are desired [7, 8].

1.4 Purpose of Research

The purpose of this research is to increase the ILSS of graphite/epoxy composite laminates by reinforcing the epoxy between lamina using VGCF and PAN-based CNF sheets placed between composite plys. Single-lap shear tests will be used to compare lap-shear strengths of composites reinforced with CNF sheets. The sheets are to be used without prior epoxy impregnation because excess resin that exists in the material system bleeds o during the cure cycle. The sheets will be impregnated during the cure cycle, when epoxy viscosity is low, so little preparation work is needed. The sheets will be impregnated by absorbing some of the existing epoxy runo from the curing composite. If the process is successful, the CNF sheets can be used selectively at positions known to have stress-raisers, such as bolt holes or sharp corners. Using small, thin CNF sheets as selective reinforcement minimizes the amount of CNF material, and thus the cost. Because the short-term use of CNF-exclusive composites is not practical at its current cost, research that implements cost-eective

5 use of CNF is well warranted. Additionally, increasing the ILSS of composite laminates is important for the use of composites in general.

1.5 Thesis Outline

Beyond this chapter, Chapter 2 presents a review of the literature on the following subjects: carbon ber reinforced plastics (CFRP), CNT, CNF, CNT and CNF composites, and bucky paper composites. First, general composite laminates are discussed along with ILSS and the various tests used to measure ILSS. Second, CNT is discussed, detailing the dierences between SWNT and MWNT. Third, CNF are discussed, with an emphasis on VGCF and PAN-based CNF. Fourth, CNT and CNF composite fabrication is discussed along with ber functionalization techniques. Last, bucky paper composites and their properties are discussed. Chapter 3 presents the experimental program conducted in this research. First, material properties are given for each material used in this research. Second, the functionalization process is explained. Third, the double-vacuum box technique used to fabricate composite specimens is discussed. Fourth, the preliminary tests used to determine the feasibility of the research plan are discussed. Fifth, the test sample fabrication technique is discussed, along with a detailed description of test geometry. Sixth, the single-lap shear test technique used to compare ILSS is discussed, along with the physical setup and test parameters. Last, data analysis techniques are discussed. Chapter 4 presents the results of the experimental program. First, material characterization results are discussed, including microscopy and scanning electron microscope (SEM) analysis. Second, functionalization characterization results are given. Third, shear test results are presented along with stress-strain curves and other

6 data trends. Last, fracture surfaces are observed and compared to characterization and lap-shear strength results. Chapter 5 presents conclusions and recommendations based on this research. Conclusions are derived from data analyzed in Chapter 4. Recommendations include improvements to the current test method and suggestions for future research.

CHAPTER 2 LITERATURE REVIEW

Carbon nanocomposites are a highly-anticipated form of composite materials whose great commercial potential exists because of the mechanical properties of new carbon materials such as CNT and CNF. This chapter introduces carbon composites and nanocomposites and then describes fabrication and mechanical testing research in CFRP with an emphasis on ILSS. It further discusses CNT, CNF, carbon nanocomposites, and bucky paper composites.

2.1 Carbon Fiber-Reinforced Plastic Materials

CFRP are advanced composites made from carbon bers reinforced with an epoxy matrix. The extremely strong and lightweight bers bonded together with a strong but yielding matrix make CFRP novel materials for use in aerospace, automobile, and sports equipment industries. Carbon bers have strength to density ratios (specic strengths) much higher than the metals traditionally used in these industries, as shown in Table 2.1. One form of CFRP, graphite/epoxy laminated composites, are made of laminae of graphite bers impregnated with an epoxy matrix.

2.1.1 Laminate Composites

Laminated composites consist of a number of prepreg plys sandwiched together, molded to a predetermined geometry, and cured. Prepreg plys are composed of long unidirectional carbon bers impregnated with epoxy material. Unidirectional

8 Table 2.1 The specic strengths of a number of dierent materials [9, 10] Material 1018 Steel (Annealed) 4140 Steel (Quenched) Ti-50A Titanium Ti-6Al-4V Titanium 2024-T4 Aluminum 7075-T6 Aluminum AS4 Carbon Fiber Tensile Strength (ksi) 49.5 257 55.0 130 64.8 86.0 620 Density (lb/in3 ) 0.282 0.282 0.160 0.160 0.098 0.098 0.065 Specic Strength 176 911 344 813 661 878 9538

plys are laid up in a number of dierent orientations relative to each other. In this way, laminate composite properties are engineered during lay-up of the composite. For example, a multi-ply 0 (unidirectional) laminate composite with a high bending stiness may not possess adequate torsional rigidity. In this case, a stacking sequence including 45 plys is used to increase the torsional rigidity of the composite [11]. Additionally, quasi-isotropic composite materials can be formed by symmetrically varying the orientation of plys in a laminate composite about the midplane. In theory, it is possible to engineer an innite amount of ply structures and geometries. However, problems occur when mismatched plys are sandwiched together due to interlaminar shear stresses.

2.1.2 Interlaminar Shear Stress

One major problem that occurs at mismatched plys involves the deformation of plys oriented in dierent directions. As shown in Figure 2.1, ber orientation plays a major role in the deformation characteristics of composite lamina [11]. If a composite laminate is placed in tension, displacement compatibility ensures that all

Figure 2.1 The deformation of composite lamina with respect to ber orientation [11] lamina deform the same way. As a result of lamina interactions, shear stresses occur between plys. Indeed, interlaminar shear failure is one of the most common failure modes in laminate composites [3]. Interlaminar shear failure is characterized in one of four dierent ways, as shown in Figure 2.2 [3]. First, adhesive failure may occur. Adhesive failure is the failure of the bond between the adhesive (epoxy) and the substrate (graphite bers). Second, cohesive failure may occur. Cohesive failure is the failure of the adhesive itself. Third, a mixed failure may occur. Mixed failure involves both adhesive and cohesive failure. Fourth, the substrate itself may fail. Consequently, the two most important factors that inuence graphite/epoxy laminated composite ILSS are the strength of the graphite/epoxy interfacial bond and the strength of the epoxy itself.

10

Figure 2.2 Failure modes caused by interlaminar shear stress in laminate composite [3] Varma [12] researched the interlaminar shear properties of GFRP, a form of CFRP, and discovered that ILSS largely depends on the graphite/epoxy interfacial bond. By studying the temperature eects of dierent composites, it was determined that interfacial bond strength was the major cause composite failure in interlaminar shear. Additionally, he found that the wetting characteristics of the carbon ber and resin also aect the ILSS of laminate composites. The research showed that poor wetting results in voids at the ber/resin interface, which detrimentally aect the ILSS of laminate composites [12]. Lundahl [4] determined, during research on environmental eects on ILSS, that voids produced during fabrication of laminate composites are more detrimental to ILSS than even temperature and humidity eects. Voids in GFRP composites act as crack nucleation sites, which reduce epoxy strength and the ILSS of the composite.

11 Void content (a measure of the number of voids in a composite), or porosity, is classied by the percent of the material exhibiting porosity, as shown in Figure 2.3. The percent porosity in each of the gures is (a) 0%, (b) 5%, and (c) 10%. Gregory [13] measured porosity using ImagePro Plus, a program that contrasts changes in pixel color to determine porosity content. Dark areas in Figure 2.3 represent porosity.

2.1.3 Interlaminar Shear Tests

Because ILSS is such an important property of laminate composites, many dierent test methods have been devised to measure it. The American Society for Testing and Materials (ASTM) describes a number of dierent ILSS test methods including ASTM D2344-00 short beam shear test method [14], ASTM D5379-05 Vnotched beam test method [15], ASTM D7078-05 V-notched rail test method [16], and ASTM D3164-03 single-lap shear test method [17]. Hancox [18] carried out an experimental comparison of three dierent interlaminar shear test methods: the double notch method, the short beam shear method, and the torsion test method. It was determined that the double notch and short beam shear methods work well for comparison purposes, but both methods involve loading other than pure shear. He concluded that the torsion test method is the most promising and should be studied in more detail. Tarnopolskii [19] conducted a similar comparison and concluded that generating pure shear stress in specimens was practically impossible. Because generating pure shear in laminate composites is so dicult, a number of researchers have opted for the less complex single-lap shear tests to comparatively determine the adhesive strength of composites in interlaminar shear [2022]. Singlelap shear tests are described in ASTM D3164-03 as, useful for generating comparative shear strength data for joints made from a number of plastics[17]. The test requires

12

Figure 2.3 Composite laminates with varying amounts of porosity ( 50) [13]

13 two substrates bonded together with an adhesive at the joint. The specimen is then tested in tension until shear failure occurs at the joint. When a single-lap shear specimen is loaded in tension, a state of pure shear stress is not obtained, as shown in Figure 2.4, where

d = Specimen nominal thickness, P = Load on specimen, R = Reaction load due to P , M = Bending moment acting on reinforcement due to P , and V = Shear load due to P .

Because pure shear stresses are not obtained using single-lap shear tests, test results are reported as apparent shear strength, or lap-shear strength. It is inferred from Figure 2.4, that as reinforcement thickness increases, so does d and, consequently, the bending moment acting on the reinforcement. Because larger reinforcement thickness causes increased bending moments, single-lap shear test specimens joined with thicker reinforcements are expected to fail at lower loads. Regardless, the comparative values obtained from single-lap shear tests can be useful in determining the eectiveness of adhesives on laminated composite ILSS. Li [20] experimentally compared two types of glass-ber reinforced prepreg and two types of neat (nonreinforced) resin as bonding agents in single-lap shear tests. He determined that the prepreg sheets had a higher loading capacity and that ber orientation and ply stacking sequence both play major roles in determining the lap-shear strength of the joint. Shin [21] made similar conclusions when bonding

14

Figure 2.4 Forces and moments acting on a single-lap shear test specimen CFRP to steel. Sawyer [22] investigated the eects of preforming composite single-lap shear test specimen geometries at a number of dierent angles to lower shear stress concentrations inherent in traditional single-lap test specimens. It was found that increasing bond length improves lap-shear strength and reduces the preform angles related to maximum joint strength. Of the test geometries available, the single-lap shear test provides the simplest, most cost-eective way of determining comparative ILSS values for laminated composites reinforced with dierent materials. Of the reinforcements available today,

15 carbon nanomaterials may be the most promising because of their high strength and stiness values.

2.2 Carbon Nanotubes

In 1991 Sumio Iijima [23] discovered what he called, helical microtubules of graphitic carbon, or what are now called MWNT. Shown in Figure 2.5, these carbonbased nano-sized concentric tubes are composed of a hexagonal lattice of carbon atoms in sheet form with the edges rolled up and joined to form a cylinder or scroll structure. CNT have diameters between 1 and 100 nm, lengths of up to millimeters, and posses high mechanical and thermal properties [5, 2426]. Unfortunately, the high price of CNT (up to $1,900/gram) make them inaccessible to many researchers [8]. In practice, CNT are separated into two major divisions: SWNT and MWNT.

2.2.1 Single-walled Carbon Nanotubes

SWNT are quickly becoming the most anticipated material in composites research because of their high theoretical mechanical and thermal properties. However, they are very expensive (from $175 to $1,900 per gram) [8]. In his review of SWNT properties, Seetharamappa [24], using elastic modulus values, estimates SWNT tensile strength to be 150 GPa (22 Mpsi). Overney [25] calculated the elastic modulus of SWNT to be 1500 GPa (220 Mpsi). Additionally, Berber [26] estimated SWNT thermal conductivity at 6600 W/mK at room temperature. In general, the outstanding properties of SWNT are attributed to their unique graphitic structure. SWNT are composed of graphitic sheets of hexagonally spaced carbon atoms rolled up to form a perfect cylinder, as shown in Figure 2.6 [27]. As shown by

16

Figure 2.5 Multi-walled nanotubes discovered by Iijima in 1991 [23] Iijima [23], graphitic sheets can be rolled at a number of dierent angles, called helical angles, to form carbon nanotubes. In his review of SWNT composites, Coleman [5] stated that SWNT exhibit dierent thermal and electrical properties depending on their helical angles. However, Gao [28], in his study of the molecular mechanics and dynamics of SWNT, predicts that the elastic modulus of SWNT varies little with helical angle. Though theoretical strengths for single SWNT are large, especially when compared to values found in Table 2.1, these strengths have yet to be veried in laboratory

17

Figure 2.6 The structure of a single-walled carbon nanotube [27] testing. Ironically, it is their highly praised structure that causes diculties in determining SWNT strength. Because they are so small, and tend to aggregate into bundles, SWNT are tested in bulk. In his research on SWNT composites, Zhu [29] reviewed the weaknesses inherent in the bulk structure of SWNT. He states that the atomically smooth structures of SWNT give them extremely low interfacial bonding characteristics. In a similar review, Coleman [6] states that SWNT bundles are only weakly bound by van der Waals forces. Consequently, when tested in bulk, SWNT tend to slip out of bundles causing the structures to fail prematurely, so tensile strengths of SWNT tested in bundles remain well below their theoretical values. In experimental research on SWNT bundle tensile strength, Yu [30] measured values between 10 Gpa and 52 GPa (1.5 Mpsi and 7.5 Mpsi). Though still present, the problems that plague SWNT research are not as prevalent in MWNT research because MWNT grow much larger than SWNT and, therefore, are easier to test individually.

18

Figure 2.7 (a) Concentric MWNT structure and (b) Scroll MWNT structure [31] 2.2.2 Multi-walled Carbon Nanotubes

MWNT are known to possess slightly lower mechanical and thermal properties than SWNT [5]. Lower properties are due to dierences in size and cylindrical structure. Atomically, MWNT are similar to SWNT in their graphitic structure. However, as described by Iijima, MWNT are comprised of a number of SWNT layers in either concentric or scroll-like formation, as shown in Figure 2.7 (a) and (b), respectively. Iijima observed MWNT with layers ranging from two (double-walled CNT) to fty. Because experimental diculties arising from small MWNT sizes, their exact structure is still debated among researchers studying the topic [31, 32]. Iijima observed only concentric MWNT structures in his initial research [23]. Bandow [31], in a study on thermal expansion of MWNT, proposed that thick layered MWNT should tend to conform to scroll structures because of their radial thermal expansion characteristics. Wu [32], in a study of high temperature treatment of MWNT, suggests that MWNT display dierent structural characteristics depending on size and heat treatment. At diameters over 50 nm, Wu found that heat treated

19

Figure 2.8 Bamboo structure of MWNT [33] MWNT tend to polygonize, while under 50 nm, MWNT exhibit scroll-like characteristics [32]. Another unique MWNT structure, described by Olek [33] as bamboo MWNT and shown in Figure 2.8, have ridges on the surface that may help decrease bundle slippage. Regardless of their exact structure, MWNT are known to have larger diameters and lower mechanical properties than SWNT. However, because they are somewhat larger than SWNT and easier to fabricate (with costs on the order of $110 to $515 per gram), more experimental data is available on individual MWNT [8]. In an experimental analysis on double-walled CNT strands, Li [34] recorded strand tensile strengths between 0.62 and 2.6 GPa (90 ksi and 380 ksi) and elastic modulus between 10 and 23 GPa (1.5 Mpsi and 3.3 Mpsi). Similar to SWNT research,

20 individual double-walled carbon nanotubes exhibited bundle pullout, which reduced the strength of the strands. Yu [35] performed stress-strain measurements on single MWNT inside an electron microscope and recorded tensile strengths of between 11 and 63 GPa (1.6 Mpsi and 9.1 Mpsi) and elastic modulus between 270 and 950 GPa (39 Mpsi and 140 Mpsi). In his research, Yu observed failure at the outermost tube with inner tubes pulling out in a telescopic, or sword and sheath manner, which would suggest concentric MWNT structure. In summary, though the properties of CNT are impressive, especially when compared to the values found in Table 2.1, their cost and dicult fabrication techniques make them unavailable to many researchers. Additionally, their small sizes limit research possibilities in terms of current technology capabilities. In many instances, CNF make a good substitution for CNT in terms of size and mechanical properties. Though dierent structurally, CNF give insight to the mechanics of nanomaterials in general and are easier to fabricate and use than CNT.

2.3 Carbon Nanobers

CNF are nano-sized, carbon-based bers with slightly lower mechanical properties than CNT [5]. The major dierence between CNT and CNF is the ber structure itself [36]. CNF are not tube-like and are usually larger in diameter (on the order of 100 nm) than CNT, with lengths between 20 and 100 m [5]. Accordingly, individual CNF do not possess the mechanical properties of CNT. However, carbon nanobers, such as VGCF and PAN-based carbon nanobers, are cheaper ($0.25 per gram for VGCF) and easier to manufacture than their CNT counterparts and give important insight to the mechanics of carbon nanomaterials in general [7].

21 2.3.1 Vapor-Grown Carbon Fibers

VGCF diameters can range from 20 nm to tens of m, with larger sized bers no longer falling under the category of CNF [3739]. VGCF are produced by decomposing gases such as methane, ethane, or coal gas in the presence of a catalyst, hydrogen sulde, and ammonia [40]. The gases decompose into carbon and hydrogen, which is then conveyed to a reactor furnace. VGCF grow in the reactor furnace in only a few milliseconds. They are then transported to a basin where they are debulked for sale or further processing [40]. Using scanning electron microscopy, Hashishin [41] studied the morphological eects of large ( 4 12 m diameters) VGCF on tensile strength. He observed that VGCF are formed of both cylindrical and polygonal layers, with rotating orientations, surrounding an amorphous core, as shown in Figure 2.9. For the cross section of a VGCF, the central gray circle indicates the amorphous core, dotted circular lines indicate circular carbon layers, and polygonal solid lines indicate platelet carbon layers. He also observed external ber characteristics naming three VGCF morphologies: VGCF with smooth side surfaces, fused VGCF, and VGCF with granulated surfaces. VGCF with smooth side surfaces had no surface irregularities. Fused VGCF were the result of two laments fusing together during fabrication. VGCF with granulated surfaces included spherical growths protruding from VGCF surfaces. Studying similar sized bers, Van Hattum [39] observed external characteristics of VGCF and their relation to VGCF tensile strength. The research focused on three dierent morphologies: perfect cylinder, crenulated, and quasi-perfect cylinder. Perfect cylinder VGCF have no surface irregularities and are similar to those described by Hashishin. Crenulated VGCF are similar in structure to bamboo MWNT with

22

Figure 2.9 A cross-section diagram of VGCF showing three dierent morphologies (adapted from [41]) more random surface irregularities. Quasi-perfect VGCF are a mix between perfect cylinder and crenulated VGCF, with less pronounced surface irregularities. Regarding tensile properties, Hashishin [41] observed a wide scatter in terms of VGCF diameter (ranging from 4 12 m), but a denite trend regarding surface morphology. Using a tensile tester to measure individual laments, he found that VGCF with smooth side surfaces lead to the best tensile strengths of 0.7 to 3.7 GPa (100 ksi to 540 ksi). Tensile strength deteriorated with granulated surface VGCF from 0.5 to 1.5 GPa (73 ksi to 220 ksi) and fused VGCF from 0.6 to 0.7 GPa (87 ksi to 100 ksi). Van Hattum [39] observed a change in tensile strength with respect to both ber length and morphology. For perfect cylinder morphology and 5 mm length, he measured a tensile strength of 2.9 GPa (420 ksi). Tensile strengths decrease with increasing ber length down to 1.3 GPa (190 ksi) for 40 mm bers. Additionally, Van Hattum found a decreasing tensile strength when transitioning from perfect cylinder

23 VGCF to quasi-perfect and crenulated VGCF to a minimum of 0.75 GPa (110 ksi) at 40 mm. Van Hattum also measured elastic modulus and found a dependence on ber diameter [39]. For bers with a mean diameter of 18.3 m, a 110 GPa (16 Mpsi) elastic modulus was measured. For bers with a mean diameter of 11.7 m, a 140 GPa (20 Mpsi) elastic modulus was measured. If this trend of increasing elastic modulus continues, nano-sized bers, with diameters between 100 and 200 nm should have even larger elastic modulus values. Because the bers have lengths of m instead of mm, nano-sized VGCF should exhibit higher tensile strength values as well. Much like VGCF, similarly sized PAN-based carbon bers have been shown to exhibit outstanding tensile strength and elastic modulus values.

2.3.2 Polyacrylonitrile-based Carbon Fibers

PAN-based carbon bers are similar in size and mechanical properties to VGCF, though with dierent internal structures. Klinklin [42] observed cross sections of PAN-based carbon bers in a transmission electron microscope and found three dierent structures at ber surfaces. Fiber surface structures are composed of layers of carbon distinguished by their orientation. The three structures are as follows: layers parallel to the surface of the ber, layers perpendicular to the surface of the ber, and layers exhibiting mixed characteristics. The three structures are shown in Figure 2.10. Klinklin found the three structures existing simultaneously on each of the bers studied [42]. According to both Isaac [43] and Ko [44], the two values that most eect PANbased carbon ber properties are precursor material type and fabrication technique. Isaac states that the three most commonly used divisions of PAN-based carbon bers

24

Figure 2.10 A cross-section diagram of PAN-based bers showing three dierent surface structures (adapted from [42]) are high strength (HS or HT), high modulus (HM), and intermediate modulus (IM) bers, each dependent on fabrication technique [43]. Additionally, in testing precursor materials of various ber diameters, it was found that dierences in ber diameter yield dierences in tensile strength and elastic modulus. By hot stretching precursor materials during fabrication, Isaac signicantly decreased the nal diameters of PAN-based carbon bers. At a ber diameter of 4.3 m, Isaac measured maximum tensile strength and elastic modulus of 5.02 GPa and 527 GPa (730 ksi and 76 Mpsi), respectively. At a ber diameter of 5.3 m, he measured maximum tensile strength and elastic modulus of 5.41 GPa and 548 GPa (780 ksi and 79 Mpsi), respectively. Finally, at a ber diameter of 8.3 m, he measured maximum tensile strength and elastic modulus of 3.73 GPa and 467 GPa (540 ksi and 68 Mpsi), respectively [43]. The 5.3 m diameter bers most likely exhibited higher strength and elastic modulus

25 values because they were stretched further during fabrication and had a larger percent diameter reduction than the other two ber types. In general, tensile and elastic modulus values increase with decreasing ber diameter. Ko [44] observed changes in ber diameter, density, tensile strength, and elastic modulus of PAN-based carbon bers when using dierent temperatures during precarbonization of precursor materials. According to Ko, carbonization is the process of thermally decomposing precursor materials, eliminating non-carbon species, thus producing a relatively pure carbon ber. The non-carbon elements are removed as volatiles, yielding a nal carbon ber with a mass about half that of the original precursor bers. Using precursor bers with diameters from 8.5-10.5 m, Ko used temperatures from 450-700 C during precarbonization to produce nal carbon ber diameters of 7-8 m, with carbon wt% between 95% and 97%. For nal-product carbon bers, elastic modulus increased continually from 138 GPa to 187 GPa (20 Mpsi to 27 Mpsi) while tensile strength peaked at 2.43 GPa (350 ksi) at a precarbonization temperature of 550 C. With improved fabrication techniques, PAN-based CNF is now available with diameters ranging from 200-600 nm, as reported by Kim [45], though the morphological structure is yet unknown. If the structure of larger diameter PAN-based bers can be applied to nano-sized bers, the morphological structure should be similar to that shown in Figure 2.10. As in the case of VGCF, if trends in increasing tensile strength and elastic modulus with decreasing ber size are applied to PAN-based CNF, then mechanical properties should be outstanding. It is because of these highly anticipated tensile and elastic modulus values that CNF is sought as an additive in composite materials.

26 2.4 Traditional Carbon Nanotube and Nanober Composites

Because of their high strength and elastic modulus values, CNT and CNF are being used as reinforcement in composite materials [5, 46]. Estimates of CNT and CNF composite mechanical properties via rule of mixtures and similar methods reveal high strength and stiness at low CNT and CNF wt% [5]. The rule-of-mixtures is a way of predicting composite properties using constituent properties alone. It follows a simple formula, shown in Equation 2.1, using Youngs modulus as the estimated composite property:

Ec = (Ef Em )Vf + Em

(2.1)

where

Ec = composite modulus, Ef = ber modulus, Em = matrix modulus, and Vf = ber volume fraction.

However, the rule-of-mixtures has a number of assumptions. First, bers are assumed to be well-aligned and span the length of the specimen. Additionally, bers are assumed to be well-bonded to the matrix material and equally strained under tension. Unfortunately, CNT and CNF do not conform to any of these assumptions. Therefore, the modied rule-of-mixtures, Halpin-Tsai equations, and other formulations are required to accurately predict CNT and CNF composite properties [5, 47,

27 48]. Often, even the most conservative equations can overestimate the composite properties. Overestimation is due, in part, to previously stated problems concerning the structure of CNT and CNF: their smooth surfaces and tendency to aggregate to bundles. Self-evident from [5, 47, 4951], the two most dicult obstacles in creating CNT and CNF reinforced composites are good ber dispersion and good ber/epoxy stress transfer. Both of these obstacles are partly due to the low percolation limit of CNT and CNF in solution.

2.4.1 Percolation Limit

CNT and CNF composites are expected to exhibit excellent mechanical properties at low ber wt%, due in part to the low percolation limit of CNT and CNF in solution. The percolation limit, as depicted in Figure 2.11, is the statistical chance that all bers in a matrix are interconnected. When the ber/epoxy mixture reaches the percolation limit and all the bers are interconnected, load sharing occurs among the bers, yielding a stronger composite material. Because of their size and high length to width ratios, CNT and CNF have very low percolation limits [52]. For example, Song [53] measured a percolation limit in MWNT/epoxy resin composites of 0.5 wt%. Zhang [54] found a percolation of 1.5 wt% for SWNT in high density polyethylene. Potschke [55] observed percolation limits between 1 and 2 wt% for MWNT in polycarbonate. In contrast, Lozano [38] found a percolation limit of 9-18 wt% of VGCF in polypropylene, probably due to the larger size of VGCF bers. In a review of the properties of SWNT, Davis [52] discussed the phase behavior of rod-like polymer solutions. The polymer solution, Shown in Figure 2.12, passes

28

Figure 2.11 Percolation limit: bers (a) under percolation limit (b) over percolation limit through a number of dierent phases as ber content reaches and surpasses the percolation limit. First, the polymer transitions from a dilute solution to semi-dilute, where the rotation ability of rods is prohibited. Once the rod concentration approaches the percolation limit, it becomes an isotropic concentrated solution in which rod rotation and translation are inhibited. At higher concentrations, the solution becomes biphasic (two separate phases in equilibrium), where the isotropic concentrated solution is in equilibrium with a liquid crystalline phase. Finally, the system becomes fully liquid crystalline. At this point, polymer viscosity becomes the limiting factor in fabricating high wt% CNT and CNF composites. Davis states that 6 wt% SWNT mixed in 102% sulfuric acid has a viscosity roughly one million times that of water with negligible reduction when heated [52].

2.4.2 Fabrication Techniques

Because of high viscosity levels at low ber content, fabricating CNT and CNF test specimens is something of a challenge. For example, Zhu [29] encountered processing problems when fabricating 4 wt% SWNT composites, citing viscosity problems resulting in voids. Though not quantied, Gojny [51] describes the enormous shear forces required to mix 0.1 wt% double-walled CNT into an epoxy matrix using

29

Figure 2.12 The phase behavior of a rod-like polymer solution [52] a calander. Choi [56] tested VGCF composites with 3-20 wt% bers and found that maximum strength and elastic modulus was obtained for VGCF composites containing 5 wt% bers. Dispersion quality and void content were both cited as reasons for low mechanical properties at higher VGCF content. Consequently, a number of dierent techniques have been developed to obtain well dispersed CNT and CNF in polymer matrix. The simplest way to decrease the diculties of dispersing CNT and CNF into epoxy matrices and to reduce the cost of working with CNT and CNF, is to use low ber content. A number of researchers have experimented on CNT composites with ber concentrations of 5% [29, 47, 51, 53, 57]. Other researchers, working with CNF composites, report increasing mechanical properties with higher ber concentrations of 5-31 wt% [56, 58, 59]. Despite decreasing ber content, dispersing CNT and CNF within a matrix is still a problem. Consequently, other techniques are used to achieve well-dispersed bers in CNT and CNF composites. Currently, there are three main methods of dispersing CNT and CNF in epoxy composites: heated mixing, solution-evaporating by sonication, and fabricating CNT or CNF sheets. A common practice, in both heated mixing and solution-evaporating

30 by sonication, is to mix the matrix material with a low-viscosity liquid such as ethanol or acetone to reduce the matrix viscosity. CNT or CNF is then added to the mixture. CNT and CNF sheet fabrication is a process used to disperse bers by mixing them in a low-viscosity liquid, then ltering the solution, leaving a thin sheet of CNT or CNF material. Some researchers use more than one method in an attempt to better disperse CNT and CNF in epoxy matrix [57, 60]. Heated mixing involves three variables: time, temperature, and mixing speed. Lozano [61] reported adequate dispersion after mixing VGCF in polyethylene at 190 C, 65 rpm for 15 minutes. Morales-Teyssier [36] also successfully mixed VGCF in polymer material using cam-type rotors at 190 C, 75 rpm for 15 minutes. Gojny [51] achieved dispersion by mixing double-walled CNT at room temperature for 2 minutes at speeds up to 180 rpm. Solution-evaporating by sonication involves dispersing CNT or CNF in an easily evaporating solvent and then using high frequency vibrations to disperse the bers. The solution is then added to the matrix material and the process is repeated to disperse further the CNT or CNF bers and to evaporate the solvent. Song [53] used this technique to disperse MWNT into an epoxy resin. The MWNT were rst dispersed in ethanol under sonication for 2 hours. The ethanol solution was then mixed with the epoxy resin. The mixture was sonicated again for 1 hour at 80 C and then kept in a vacuum oven to evaporate the ethanol. A hardener was then added to the MWNT/epoxy mixture and stirred for 15 minutes under sonication. Gao [62] used the solution-evaporating by sonication method to disperse VGCF into polycarbonate. The VGCF and polycarbonate were separately mixed with chloroform and sonicated both solutions until the polycarbonate was dissolved completely. The VGCF solution was then added to the polycarbonate solution and the resulting mixture was further

31 sonicated for varying amounts of time (0.5-24 hours). The mixed solutions were then poured into molds and left until the chloroform evaporated, leaving VGCF composite lms.

2.5 Bucky Paper Composites

Numerous researchers have shown that heated mixing and sonication are proven techniques used to disperse CNT and CNF in polymers, as previously discussed. However, use of CNT and CNF sheet material to make composites may provide the best option because dispersion occurs before integration into the polymer, eliminating problems arising from high viscosity due to liquid crystalline phase described by Davis [52]. A number of researchers have already used this technique with success [6, 6365]. Unfortunately, little research is based on the mechanical properties of CNF sheets and their composites. However, SWNT sheets (commonly called bucky paper) are very similar and are used more often to reinforce polymers. The process used to make bucky paper composites mainly involves mixing bers in a solution, then passing the solution through a very ne lter. The bers left on the lter are then dried and washed to form the paper. Bucky paper composites are formed by impregnating the papers with an epoxy. Impregnation then becomes the main obstacle in forming bucky paper composites because of the nanoscale pore structure of the sheets [6, 64]. Often, diluted epoxy, at increased temperatures is used, since the viscosity of pure epoxy is too high to impregnate the sheets alone. Wang used Darcys law to determine the z -direction permeability of bucky paper [64]:

Kz =

QL Ab Pv

(2.2)

32 where

Kz = z -direction permeability, Q = ow rate, = uid viscosity, L = bucky paper thickness, Pv = vacuum pressure, and A = in-plane bucky paper surface area.

The minimum time required to fully impregnate the papers by using 1-D Darcys law was also found:

t=

L2 K z Pv

(2.3)

where

t = infusion time, = uid viscosity, L = thickness of bucky paper, Kz = z -direction permeability, and Pv = vacuum pressure.

As shown, Darcys law states that vacuum pressure (related to sheet porosity) and sheet thickness also eect the permeability of CNT and CNF sheets. Since sheet

33 permeability is a problem, research is usually limited to thin sheets with high porosities [63, 65].

2.5.1 Fabrication Techniques

Coleman [6] produced bucky paper by dispersing SWNT in water using a surfactant. The solution was ltered and the remaining bers annealed under owing argon at up to 1000 C to remove any contaminants, producing around 75% porous bucky paper sheets. The bucky paper was then soaked in deionized water-diluted polymer solutions for various amounts of time then dried in ambient conditions for approximately 8 hours. Using approximately 85% porous sheets, Coleman achieved maximum polymer wt% bucky paper composites of roughly 27%, leaving 58% free volume (voids) in the composite. Gou [63] made bucky paper composites by mixing bers in sulfuric acid, heating, then ltering under vacuum pressure to remove the acid. The remaining bers left on the lter were dried and washed with acetone to restore neutral pH values. The resulting network of bers formed the bucky paper, resulting in roughly 15 m thick, 53% porous sheets. Composites were formed by introducing diluted epoxy in the paper through vacuum pressure for over two hours, then hot-pressing to produce the nal composite. In this manner, Gou observed composites with approximately 47 wt% SWNT well dispersed in epoxy matrix. The bucky sheets were fully impregnated and contained uniform dispersion of SWNT. Wang [64] fabricated bucky paper by dispersing SWNT into water with the aid of a surfactant and sonication. The solution was then passed through a lter to form the bucky papers. Using Equation 2.3, the pure resin impregnation time was calculated to be over 60 hours, so an acetone diluted resin was used instead. With

34 reduced viscosity, projected impregnation time was 2 hours. Once impregnated, a hot press molding process was used to cure the composite samples. Wangs procedure produced nanocomposites with SWNT loading up to 39 wt%, adequately infused with epoxy matrix.

2.5.2 Bucky Paper Composite Properties

To date, more emphasis has been given to impregnating bucky paper with epoxy matrix and characterizing the ber distribution than testing the mechanical characteristics of the nished composite itself. However, Coleman reported increased bucky paper tensile strength and elastic modulus from 6.29 MPa and 2.3 GPa (0.91 ksi and 330 ksi) to 57 MPa and 6.9 GPa (8.3 ksi and 1,000 ksi), respectively, after impregnation with epoxy matrix. Additionally, the toughness values increased by a factor of 30. Frizzell [65] fabricated bucky paper composites in a similar manner described previously by Coleman [6]. At 17 vol% an increase in tensile strength was observed from 4.3 MPa to 24.7 MPa (0.62 ksi to 3.6 ksi) and an increase in elastic modulus from 0.91 GPa to 3.26 GPa (130 ksi to 470 ksi). Additionally, the toughness values increased by a factor of 26.

2.5.3 Functionalization

The two main obstacles in creating CNT and CNF composites are (1) ber dispersion and (2) ber/epoxy interfacial bond. Each of the dispersion methods previously discussed deals with the rst obstacle in a number of complex ways. Functionalization provides a relatively simple way to address interfacial bonding issues [36, 66]. In general, functionalization is the process of covalently attaching or

35 growing functional groups on the surface of CNT. Tasis [66] describes a number of various procedures used to functionalize CNT. In most cases, the bers were functionalized by immersion in dierent chemical solvents. Sinnot [67] also describes chemical functionalization of CNT in a review of CNT functionalization methods. Many approaches involve mixing CNT in acid solutions at increased temperature to both purify and functionalize CNT surfaces. Morales-Teyssier [36] studied the eects of nanober functionalization on dispersion and mechanical properties of nanocomposites. VGCF was functionalized in a peroxide then mixed the solution in polystyrene for 15 minutes using a Brabender torque rheometer mixing chamber. Samples were then extracted and compression molded to form test specimens. It was found that functionalization increased both the tensile strength and elastic modulus of VGCF nanocomposites. In addition, by viewing fracture surfaces in a SEM, it was determined that functionalized samples yield better ber dispersion. Chen [68] functionalized MWNT in a mixture of concentrated sulfuric and 70% nitric acids. The MWNT were sonicated in the acid mixture for one hour and then stirred for three hours at room temperature. After acid treatment, the solution was washed exhaustively in deionized water and then mixed with hydrochloric acid to complete the functionalization process. The nal solution was again washed with deionized water until near neutral pH values were reached. The functionalized MWNT were sonicated and mixed in epoxy matrix to form composite test samples.

36 2.5.4 Functionalization Characterization

It is important to quantify the degree of functional groups present on ber surfaces following functionalization. Three techniques are primarily used to characterize the degree of functionalization of CNT and CNF: Raman spectroscopy, infrared spectroscopy (IR), and thermogravimetric analysis (TGA). The rst method, Raman spectroscopy, is based on light scattering. As a beam of light passes through a nonabsorbing medium it loses intensity and some of its energy is scattered into the surrounding area [69]. The measurable energy loss associated with light scattering provides information about the vibration of the molecules on the sample surface. There are two important active vibrational features for graphitic materials: an inplane mode at 1580 cm1 and a vibrational feature near 1355 cm1 associated with disorder on the surface of the graphite sample [69]. As the degree of surface disorder increases, so does the ratio of the 1355 cm1 to the 1580 cm1 vibrational bands. When bers are functionalized, their surfaces become more disordered with the addition of functional groups. By comparing the 1355 cm1 and 1580 cm1 ratios for control and functionalized samples, the degree of functionalization is obtained. The second method used to determine the degree of functionalization, IR, is also dependent on molecular vibrations [70]. In the case of IR, samples absorb infrared radiation, which excites molecules into higher-energy vibrational states. Like Raman spectroscopy, IR compares light intensities as a function of wavelength to determine molecular vibrational characteristics. IR is especially helpful for characterizing functional groups because the groups vibrate at nearly the same frequencies in any molecular environment. For example, methylene has distinct vibrational

modes from 3000 cm1 to 2800 cm1 , 1500 cm1 to 1300 cm1 , and 800 cm1 to 700 cm1 [70]. In contrast to Raman Spectroscopy, where the vibrational modes of

37 unmodied graphitic materials are characterized, IR directly characterizes the functional groups themselves. The last method, TGA, is used to determine composition and thermal stability of polymeric materials [71]. TGA measures the mass of bers in a controlled atmosphere with increasing temperature. Specimens are put in ceramic or platinum holders placed on a microbalance in a specialized furnace. The furnace is heated to a predetermined temperature and samples lose some of their weight content in stages. Each stage represents a unique mechanism for decomposition. TGA results are plotted on a wt% vs. temperature graph known as a thermogram. The section of a thermogram associated with a sudden drop in wt% is known as thermal decomposition. The thermal stability of a sample is found by determining the temperature associated with the onset of thermal decomposition [71]. Thermal decomposition onset temperature is found by extending the thermally stable section of the thermogram out until a 5 wt% drop is observed between the extension and the true thermogram [72]. The temperature associated with the 5 wt% drop is the onset temperature. Additionally, TGA has successfully been used to determine the presence of functional groups on CNT and CNF surfaces [60, 68]. As the temperature increases, functional groups burn o quicker than the bulk sample; yielding dierent mass vs. temperature plots for control and functionalized samples. Percent functionalization is determined by comparing the two thermograms.

2.5.5 Functionalized CNT and CNF Composite Mechanical Properties

With the design of a number of novel fabrication techniques and functionalization processes, researchers have found increases in epoxy properties with the addition of small amounts of functionalized CNT and CNF. For example, Chen [68]

38 observed an increase from 51 MPa to 110 MPa (7.4 ksi to 16 ksi) in exural strength of functionalized MWNT/epoxy composites over neat epoxy with an addition of only 3 wt% MWNT. Additionally, it was found that the MWNT-reinforced epoxy tensile strength could increase by over 3 by functionalizing bers. Zhu [29] measured an increase from 83 MPa to 104 MPa (12 ksi to 15 ksi) with the addition of 1 wt% functionalized SWNT. Morales-Teyssier observed a 25% increase in tensile strength and a 27% increase in elastic modulus when comparing functionalized and nonfunctionalized VGCF with the same ber loading [36].

2.6 Summary and a Look Ahead

Interlaminar shear failure is one of the most common failure modes in laminated composites [3]. Because three of the four major interlaminar fracture modes, shown in Figure 2.2, depend on the strength of the matrix material and the ber/matrix interfacial bond, research aimed at improving the matrix strength is warranted. Though many dierent methods exist to test composite ILSS, the single-lap-joint test is the simplest and most cost-eective. One proven way to improve the strength of neat epoxy resins involves introducing CNF bers into the resin itself [5, 46]. However, mixing carbon nanomaterial into epoxy resins becomes dicult even at low ber wt% because of extreme viscosity eects, which are shown to cause porosity in the nished product [29]. Therefore, preformed sheets of CNT are used as epoxy reinforcement because they provide good ber dispersion with no required mixing [63]. Additionally, functionalization is often performed to increase ber/epoxy interfacial bond strength [36]. With the information found in the literature review in mind, the purpose of this research was to increase laminated composite interlaminar shear strength with

39 the addition of PAN-based CNF and VGCF sheets. Single-lap shear test specimens were fabricated with both functionalized and nonfunctionalized CNF sheet reinforcement. The lap-shear strength of each specimen was determined along with the shear modulus. Finally, fracture surfaces were studied and characterized. The experimental program is provided in Chapter 3.

CHAPTER 3 EXPERIMENTAL PROGRAM

The goal of this research is to increase the ILSS of graphite/epoxy composite laminates by reinforcing the epoxy between lamina using VGCF and PAN-based CNF sheets placed between composite plys. This research focuses on testing reinforcements in laminate composites without incorporating complex techniques. Using the testing technique described here, laminate composites are made in an out-of-autoclave double vacuum box, using two types of CNF as reinforcement between lamina: PAN-based CNF sheets and VGCF sheets. The sheets are used because of their useful form and handling characteristics and because they do not alter the chemical makeup of the composite itself: the composite remains carbon-based. PAN-based CNF and VGCF sheets should increase the ILSS of the composite material by increasing the weakest part of the composite structure: the matrix bonding the plys together, especially plys with dierent orientations. As discussed in Chapter 2, the addition of CNF to a thermoset epoxy increases the strength and elastic modulus of the epoxy. Additionally, two favorable outcomes are immediately obvious following the integration of CNF sheets in GFRP composites. First, the successful integration of CNF sheets into GFRP composites provides an immediate use for carbon nanomaterial because much smaller quantities are required to reinforce composite lamina than to create the same size composite made solely from the material itself. Second, integration of thin CNF sheets allows selective reinforcement. In other words, it is not essential to cover the entire area of a composite with reinforcement material.

40

41 This chapter describes the experimental program used during this research. First, material properties are discussed along with the process used to functionalize the CNF sheets. Second, the fabrication technique is described. Third, single-lap shear testing is discussed. Fourth, a brief discussion of data analysis is presented.

3.1 Material Properties

The GFRP prepreg material used in this research was donated to TTU by Vought Aircraft in Milledgeville, GA. It consists of Hexcel Composites PAN-based Magnamite R AS4 carbon ber [10] along with 3501-6 amine cured thermoset epoxy resin [73] in unidirectional prepreg form. The prepreg sheets, shown in Figure 3.1, are 0.006 in. thick and consist of approximately 63.5% AS4 carbon bers and 36.5% 3501-6 epoxy resin. The prepreg is hand-cut to size at TTU from a ve-foot wide roll of material. Material properties for the prepreg constituents are shown in Table 3.1. The VGCF material used in this research was purchased from Applied Sciences, Inc. [74]. It consists of as-grown Pyrograf R -III PR-25 XT randomly oriented VGCF, with diameters ranging from 70 to 200 nm and lengths from 20 to 200 m, in sheet form [74]. VGCF sheets, shown in Figure 3.2, are approximately 0.008 in. thick and 90% porous. The sheets contain a small amount of iron content leftover from fabrication, though all Pyrograf R -III materials are greater than 98% pure [75]. Material properties for the VGCF are shown in Table 3.1. The PAN-based material used in this research was purchased from eSpin Technologies, Inc. [37]. It consists of randomly oriented, continuous PAN-based CNF, with diameters ranging from 20 to 200 nm, in sheet form. The sheets, shown in Figure 3.3, are approximately 0.003 in. thick and 30% porous [76]. Material properties for the PAN-based CNF sheets are shown in Table 3.1. eSpin Technologies, Inc., gave no

42

Figure 3.1 GFRP prepreg material Table 3.1 Research material properties [10, 44, 73, 75] Tensile Strength Modulus Density (ksi) (ksi) (lb/in3 ) 3501-6 Epoxy 6.6 615 0.0457 AS4 Carbon Fiber 620 33,100 0.0646 PR-25 XT VGCF 1015 87,000 0.0632 PAN-based CNF 305 21,800 0.0641 Note: PAN-based CNF tensile data based on 6.5 m diameter bers specic information on ber material properties; instead, the properties are estimated from sources found in literature for larger-diameter (6.5 m) PAN-based carbon bers. Material

43

Figure 3.2 VGCF sheet material Scanning electron microscope (SEM) analysis, using a Quantum FEI 2000 environmental scanning electron microscope, was performed on CNF sheets to determine sheet properties. The SEM uses EDAX x-ray microanalysis software. Each of the material samples was sputter coated with gold before viewing in the SEM. Properties of interest include ber diameter and any irregularities present in the material. Pictures were taken at a number of dierent magnications and are shown in Chapter 4.

44

Figure 3.3 PAN-based CNF sheet material 3.2 Functionalization Process

Additional single-lap shear tests were carried out using functionalized PANbased CNF and VGCF as reinforcement in an attempt to generate a stronger ber/epoxy bond. The functionalization process used was prescribed by both Dr. Holly Stretz [72] of Tennessee Technological University and Dr. Virginia Davis [77] of Auburn University and is comparable to that performed by Chen [68], though sonication was not performed in order to avoid damaging the sheets. Both PAN-based CNF and VGCF sheets were functionalized using a mixture of 70% concentrated sulfuric and 30% concentrated nitric acids at 50 C to attach functional groups to the surface of the bers.

45 Table 3.2 Reinforcement PAN-based CNF PAN-based CNF PAN-based CNF VGCF VGCF Functionalization test matrix Time, hours Medium Used as Reinforcement 6 Acid Vapor No 1 Acid Immersion No 6 Acid Immersion Yes 3 Acid Immersion No 1 Acid Immersion Yes

Two dierent variables were used during functionalization: time and media. Functionalization time ranged from 1 to 6 hours. The two functionalization media were acid vapor and immersion in the acid itself. A functionalization test matrix is shown in Table 3.2. Functionalization test setup is shown in Figure 3.4. The acid is held in a sealed reaction vessel over a heater unit at 50 C. The CNF sample is held in the vapor or immersed using glass xture supports. Acid fumes were condensed using a condenser connected to a water faucet that runs cool water through the condenser. The water exits the condenser at the top and ows into a drain beneath the faucet. The reaction vessel is sealed using silicone-based sealant. The entire setup is located under a hood that vents any acid fumes escaping through the condenser. The PAN-based CNF sheets were functionalized rst and initially held in the acid vapors for 6 hours. The PAN-based CNF was suspended in the acid vapors in order to preserve the sheet form of the bers. However, since no strong evidence of functionalization was found after characterization, sheets were thereafter immersed in the acid solution for various amounts of time. The PAN-based CNF sheets were more resistant to acid treatment than VGCF sheets, which is why they were immersed for longer periods of time. After acid treatment, immersed PAN-based CNF and VGCF sheets were transferred to a beaker containing distilled water and allowed to rinse for approximately

46

Figure 3.4 The process used to functionalize CNF sheets 10 minutes. The sheets were then placed on lter paper over a vacuum and rinsed repeatedly with distilled water for approximately 10 minutes. The sheets were left to dry overnight and afterward stored in plastic zip-lock bags. For functionalization characterization, TGA was used to determine onset of thermal decomposition and degree of functionalization. Excluding one PAN-based

47 sample that was tested in an argon atmosphere, samples were tested in an air atmosphere in ceramic holders. Temperature was increased at a rate of 10 C/min. up to 600 C. Additionally, Raman spectroscopy was used to characterize the degree of functionalization of the CNF sheets. TGA was performed at TTU and Raman spectroscopy was performed at Auburn University by Dr. Virginia Davis group [77].

3.3 Double Vacuum Box System

Next, single-lap shear test specimens were fabricated using a novel out-ofautoclave double vacuum process, originally designed by Sherwin [78]. The double vacuum process employed is similar to that used by Gregory in controlled porosity research [13]. The rst vacuum is produced with a conventional vacuum bag over the specimen. The second vacuum is produced by a steel outer box. There are two phases to the cure cycle. The rst phase is the staging process, which produces a partially cured laminate. The staged laminate is then placed in storage or fully cured immediately. The second part is the nal cure, which completes the curing process.

3.3.1 Cure Cycle Phases

Two separate phases comprise the staging process: degas and compaction. A diagram of the fabrication setup during the degas and compaction stages are shown in Figure 3.5. During the degas phase, a 27-in. Hg vacuum is applied to both the vacuum bag and the steel outer box. Having two vacuums insures that no pressure gradient exists on the specimen being cured and allows any volatiles to freely escape the laminate. If preserved in the laminate, the volatiles create porosity, which is detrimental to composite strength.

48

Figure 3.5 Degas and compaction phases [78] During compaction, the steel outer box is vented and a vacuum is kept on the specimen being cured. Fully venting the steel outer box to the atmosphere creates a pressure gradient on the specimen, which forces the laminate layers together. Since most of the gases escape during degas, the composite is no longer in danger of forming excessive porosity. Using a heater blanket, elevated temperatures are employed during the degas and compaction stages to decrease the viscosity of the epoxy resin. Low viscosity enables the resin to bind the laminate layers together as well as impregnate the nanober material. However, the temperatures are kept low enough that full cure does not take place during the staging process. After degas and compaction, nal cure takes place. The temperature is elevated to full cure temperature and maintained until the laminates are fully cured. Sherwins [78] curing cycle is shown in Figure 3.6.

49

Figure 3.6 The thermal cycle used to cure composite laminates [78] 3.3.2 Composite Lay-up

The bagging process is similar to that developed by Sherwin [78] and used by Gregory [13]. Sherwins bagging process is needed to ensure adequate volatile removal and resin ow. A number of dierent layers and kinds of materials are used, as shown in Figure 3.7. Bagging materials are described from the baseplate up. A compositebacked honeycomb structure is used as a base to maintain a sti foundation that will not warp under the temperature and pressure of the curing process. Fiberglass N10 breather cloth is used to provide pathways to ease the passage of volatiles out of the

50 system. A 120 Volt, 1680 watt Heatcon heater blanket is used to provide thermal energy to the system. Porous teon and nonporous release lm are used to protect the heater blanket from the viscous ow of the epoxy resin. A thin aluminum caul sheet is used to support the specimen and give it a better surface nish. Adhesive backed nonporous teon is attached to the caul sheet to keep the epoxy resin from sticking to it. The layers of porous and nonporous teon surrounding the laminate help control resin run-o. The adhesive back nonporous teon, caul sheet, and berglass N10 perform the same duties as their counterpart materials below the laminate. The vacuum bagging applied over the top of the lay-up is sealed to the baseplate using vacuum bag sealant tape. A two-piece vent base is used to evacuate air from the lay-up through the pump. The bottom piece remains under the vacuum bagging. A hole is punctured in the bagging where the top piece screws into the bottom piece. A seal between the pieces prevents air from escaping between them. The top piece is attached to a vacuum pump which evacuates the air from the lay-up. A second vacuum pump is attached to the steel outer box. The double vacuum box with a fully laid-up specimen is shown in Figure 3.8. For this research, a slightly dierent porous teon/laminate layup was used to support the single-lap shear test geometry, as shown in Figure 3.9. To support the specimen geometry, previously cured composite lamina, with thicknesses equal to that of the test specimen, were placed on each side of the shear test specimen, sandwiched between two sheets of porous teon. The supports ensured the pressure gradient during compaction did not damage the single-lap shear specimen structure used in this research.

51

Figure 3.7 Dierent layers used in the bagging process (adapted from [78]) 3.4 Preliminary Testing

During preliminary testing, feasibility samples were prepared with and without PAN-based CNF reinforcement, using the same layup and curing process for both types. The feasibility samples were fabricated in order to determine if the PAN-based CNF and VGCF bers could be fully impregnated with matrix material between laminae being reinforced and to determine the amount of porosity introduced by the addition of the reinforcement. The feasibility PAN-based CNF reinforced preliminary samples measured 2 in. 2 in. and had a quasi-isotropic stacking sequence of [0/45/90/ 45]S . 1 in. 1 in. PAN-based CNF sheets were placed between the

52

Figure 3.8 The vacuum box used to cure composite specimens two 45 plys at the center of the composite. Additionally, a VGCF specimen was fabricated using the shear test geometry that will be described in Section 3.5. After curing, the samples were cut with an MK Diamond Products, Inc. tile saw and mounted in epoxy for microscopy. The microscopy samples were ground and polished then viewed under an optical microscope. Additional preliminary samples included two sample types for interlaminar shear testing. First, sixteen control specimens were fabricated without reinforcement. Second, eight specimens were fabricated with PAN-based CNF reinforcement. During preliminary test sample fabrication, PAN-based CNF sheets delaminated after

53

Figure 3.9 Layup of the porous teon/laminate section cutting, usually leaving two half-layer samples. A full layer of PAN-based CNF sheet was used during preliminary testing. Later testing employed only a half-thickness sheet of PAN-based CNF. Shear test specimens were fabricated using the single-lap shear test geometry.

3.5 Test Sample Fabrication

Because of low lap-shear strengths found in preliminary testing using the fulllayer of PAN-based CNF sheets, half layer sheets were used for the main body of tests. The full PAN-based CNF layer specimens were especially dicult to manufacture because they delaminated immediately, causing the test specimens to slide apart during layup. For PAN-based CNF and VGCF-reinforced specimens, adhesion diculty was the main obstacle encountered during fabrication, and the cause of some manufacturing discontinuities, as discussed later in this section.

54

Figure 3.10 Shear test geometry used in this research (adapted from [17]) Shear test specimens were fabricated using the single-lap-joint test geometry, shown in Figure 3.10. As stated in Chapter 2, this test geometry is similar to that described in ASTM D 3164-03 [17]. While ASTM D 3165-00 is the preferred test geometry for laminates, a simpler method was desired [79]. The test geometry was chosen because it does not require complicated test xtures and the specimens are easy to fabricate and require a minimum amount of reinforcement material. Major divergences from ASTM D 3164-03 include desired specimen material type, a larger reinforcement surface area, and a longer specimen total length. Specimens were precut to their specic lengths then laid up individually for fabrication. Eight specimens were fabricated in each batch. Two batches of each reinforcement type were fabricated, except for where otherwise noted. After fabrication, test specimens were tabbed to avoid damage from the test machine grips. A cured and tabbed test specimen with attached strain gage is shown in Figure 3.11. The shear test specimen substrates are comprised of four unidirectional (0 , running along the axis) GFRP plys. Two lengths of substrate were connected using

55

Figure 3.11 A tabbed shear test specimen with attached strain gage an overlap area of 1 in2 , as shown in Figure 3.11. The overlap area was reinforced with a number of dierent materials, as described in Table 3.3. Overlap lengths were selected as 1 in. each. The substrates were 6 in. each, yielding a total specimen length of 11 in. During preliminary testing, the specimens were put in tension causing the composite to fail in shear between the two overlapping pieces.

56 Table 3.3 Single-lap shear test matrix Reinforcement Nonreinforced 0 GFRP 45 GFRP 90 GFRP PAN-based full sheet PAN-based half sheet PAN-based half sheet Func. VGCF VGCF Func. Count 20 16 16 16 8 16 16 16 8 Designation S1-S20 S37-S44, S69-S76 S53-S60, S85-S92 S45-S52, S77-S84 S21-S28 S29-S36, S61-S68 S109-S124 S93-S108 S125-S132

To produce a wide variety of test data, a number of dierent reinforcements were used to strengthen the test specimen overlap area. GFRP-reinforced specimens were fabricated using one ply of prepreg oriented in three dierent directions. 0 GFRP reinforcement is parallel to the axis of the shear test specimen. The 45 GFRP reinforcement is oriented at a 45 angle from the test specimen axis. The 90 GFRP reinforcement is perpendicular to the test specimen axis. PAN-based CNF-reinforced shear test specimens were fabricated using the half layer of the PANbased CNF sheet produced when the reinforcement delaminated. VGCF-reinforced specimens were reinforced with a square-inch of VGCF sheet material. Functionalized versions of each of the nanober-reinforced specimens were also produced for testing. An illustration of test specimen reinforcement orientation is shown in Figure 3.12. When laying up the CNF-reinforced composites, it was dicult to align the mating halves of the single-lap shear test specimen. The CNF sheets bonded to the prepreg material; however, the sheets were fragile and came apart when moving them from the setup table to the vacuum box. Consequently, the sections were aligned on the vacuum box without the help of reference lines, which caused slight imperfections,

57

Figure 3.12 Reinforcement type and orientation used in this research as shown in Figure 3.13 (a), in a small number of the shear test specimens. Other imperfections arose from the fabrication process itself, shown in Figure 3.13 (b).

3.6 Shear Testing

After fabrication, test samples were measured using Mitutoyo digital calipers. The calipers are accurate to the nearest 0.001 in. The lengths measured correspond to the overlap lengths found in Figure 3.10, along with the overlap area thickness and

58

Figure 3.13 Specimen imperfections: (a) slight misalignment in a specimen, (b) ber spreading during fabrication the thickness of the sections to each side of the overlap area. After measurement, the specimens were tested in tension to failure.

3.6.1 Physical Setup

Single-lap shear test specimens were tested using a 20,000-pound capacity MTS Systems Corp. MTS 810 servo-hydraulic tensile test machine, using a 2,000-pound load range. If the specimen exceeded the 2,000 pounds, the full 20,000-pound capacity was used. An MTS force transducer model number 661.20E-03, accurate to the nearest 1% of the load capacity, was used to measure the force applied by the MTS

59

Figure 3.14 The test setup used for single-lap shear testing test machine. Serrated grips were used to hold the specimen during testing. A picture of the test setup is shown in Figure 3.14. Three physical setups were used when testing shear specimens. First, specimens were tested using an extensometer to measure strain across the overlap area, as shown in Figure 3.15. A MTS Systems Corp. extensometer model 632.25B-20 with a 2 in. gage length was used. Four specimens out of every batch were tested with an extensometer. Second, strain gage specimens were set up to measure strain in the overlap area on both sides of the specimen, as shown in Figure 3.16. Vishay Micro-Measurements model CEA-13-240UZ-120 general purpose student strain gages

60 were used. These strain gages have a grid resistance of 120 ohms and a gage factor of 2.100 at 24 C. Strain was measured using a Vishay Micro-Measurements P3 strain indicator with multiple channels. One out of every eight specimens was set up with strain gages to measure strain on both sides of the overlap area. The remaining three specimens from each batch were tested without an extensometer or strain gage, to determine if the extensometer or strain gage setup introduced any adverse stresses on the test specimens, causing specimens to fail at lower loads.

3.6.2 Single-lap Shear Test Parameters

The MTS test machine was controlled using MTS TestStar software on a Compaq P4 computer. Force transducer and extensometer values were recorded directly onto the computer. Displacement (stroke) control was used during testing at a rate of 0.05 in. per minute to a maximum of 1 in. The test machine was programmed to end the test if the force dropped 5% of maximum value. Strain gage values were recorded at 100 pound intervals. A preload of 20 pounds was given to all specimens upon clamping to ensure the test machine did not put the specimens in compression. After testing, sample halves were placed in zip-lock bags and stored for SEM analysis.

3.6.3 Test Sample Analysis

After testing, CNF-reinforced samples were analyzed in SEM to determine fracture type, CNF characteristics, and CNF sheet impregnation by epoxy matrix. Preliminary feasibility samples (which were not tested in shear) were cut and mounted for microscopy and SEM analysis to determine in-composite sheet thickness, porosity

61

Figure 3.15 The setup used to measure strain by extensometer levels, and CNF sheet impregnation by epoxy matrix. Preliminary single-lap shear specimens were tested to determine load levels and fracture characteristics.

62

Figure 3.16 The setup used to measure strain by strain gage 3.6.4 Data Analysis

Stress-strain curves developed using an extensometer for strain measurement were plotted and analyzed to determine shear modulus and lap-shear strength. Stressstrain curves developed using a strain gage for strain measurement were plotted and

63 analyzed to determine stress levels on both sides of the specimen. Further analysis of strain gage data was performed using Microsoft Excel to determine shear modulus. TGA and Raman results were plotted and analyzed to determine the degree of functionalization of the sheet surfaces. All plots were created using MatLab. Data les from Microsoft Excel were imported and plotted using MatLab plotting tools. SEM analysis of fracture surfaces along with statistical analysis of nanober measurements was carried out using EDAX x-ray microanalysis software and Microsoft Excel, respectively. The porosity content of preliminary specimens was compared by visual inspection.

CHAPTER 4 RESULTS

In Chapter 3, the experimental program was discussed in detail. CFRP laminated composites were fabricated and tested using a single-lap shear test geometry. VGCF and PAN-based CNF sheets were used as reinforcement. Both functionalized and nonfunctionalized sheets were used. The current chapter provides results obtained during material characterization and shear testing.

4.1 Characterization Results

First, VGCF and PAN-based CNF diameters were measured to compare with the values given by their respective manufacturers. After test sample fabrication, microscopy was performed to determine if the VGCF and PAN-based CNF were well-impregnated with matrix. Additionally, shear test specimen overlap area was determined for use later in nding lap-shear stresses. Finally, the VGCF and PANbased CNF sheets were acid-treated and then characterized using TGA and Raman spectroscopy.

4.1.1 Measurements Results

VGCF and PAN-based CNF diameter measurements were made from photomicrographs similar to those shown in Figure 4.1. PAN-based CNF diameter

measurements are based on photomicrographs similar to Figure 4.1 (a) (6,000); VGCF ber diameter measurements are based on photomicrographs similar to Figure 4.1 (b) (20,000). Granules were observed on ber surfaces, as shown in Figure 4.1 64

65

Figure 4.1 Basic PAN-based CNF and VGCF micrographs used for measuring ber diameters (b). The granules are thought to be either iron content left over from manufacturing or VGCF granulated surfaces as described by Hashishin [41]. As shown in Figure 4.2, VGCF bers also exhibited crenulated surfaces similar to those reported by Van Hattum and the bamboo MWNT structures observed by Olek [33, 39]. Fiber diameter statistics are displayed in Table 4.1. For each set of measurements, three dierent micrographs were analyzed using EDAX x-ray microanalysis software. For PAN-based CNF diameters, 45 separate measurements were taken. For VGCF diameters, 60 separate measurements were taken. PAN-based CNF diameters are much larger (1.5-14) than maximum diameter specied on the eSpin Technology, Inc. website [37]. This dierence suggests that the PAN precursor bers were not fully carbonized during the manufacturing process. On the other hand, VGCF show good agreement with diameters specied on the Applied Sciences, Inc., website, with maximum measured ber diameter roughly 1.5 larger than advertised [74].

66

Figure 4.2 VGCF exhibiting crenulated surfaces (60,000) Table 4.1 Fiber diameter statistics Fiber Type Max Min Mean nm nm nm PAN-based CNF 1050 280 510 VGCF 313 83.0 162 Std. Dev. nm 148 156

After ber diameters were measured, preliminary tests were performed to determine sheet impregnation. In preliminary tests, nonreinforced, PAN-based CNFreinforced, and VGCF-reinforced composite laminates were fabricated. After fabrication, the specimens were cut and mounted for microscopy. Micrographs, shown in Figure 4.3, were taken using an optical microscope. In Figure 4.3 (b) and (c)

67 the central layer is the reinforcement. Micrographs showed that nonreinforced (Figure 4.3 (a)) and PAN-based CNF-reinforced (Figure 4.3 (b)) composites have little to no porosity, which suggests good PAN-based CNF sheet impregnation. However, the VGCF sheet reinforced composite (Figure 4.3 (c)) exhibited high amounts of porosity. After porosity was discovered, thinner VGCF sheet material was purchased from Applied Sciences, Inc., in an attempt to obtain better sheet impregnation. Sheet thickness reported in Section 3.1 is based on the thinner VGCF sheets. Further impregnation analysis is given in Section 4.3.

4.1.2 Functionalization Results

Both PAN-based CNF and VGCF sheets were acid-treated to add functional groups to the bers. Initially, a PAN-based CNF sheet was suspended in acid vapor in order to maintain sheet integrity. However, both TGA and Raman spectroscopy analysis gave inconclusive evidence of functionalization, so the sheets were immersed in the acid mixture instead. PAN-based CNF sheets showed no deterioration after being immersed for up to 6 hours in the acid mixture. Unfortunately, as shown in Figure 4.4 (left), after 3 hours of immersion in the acid mixture the VGCF sheets showed signicant deterioration. Careful immersion in the acid solution for 1 hour produced sheets similar to the one shown in Figure 4.4 (right). Two sheets out of four, immersed for 1 hour each, were satisfactory for use in shear test specimens, leaving eight shear test samples. 4.1.2.1 TGA results. After PAN-based CNF and VGCF sheets were acid-

treated, they were dried and subjected to TGA and Raman spectroscopy. TGA was used to determine the onset of thermal decomposition and degree of functionalization

68

Figure 4.3 Photomicrographs of (a) nonreinforced, (b) PAN-based CNF-reinforced, and (c) VGCF-reinforced laminated composites (200)

69

Figure 4.4 VGCF sheets functionalized for dierent amounts of time for control and acid-treated samples. A thermogram of PAN-based CNF (immersed for 6 hours in acid solution) plotted with a control sample is shown in Figure 4.5. Two distinct drops in slope are found in both plots in Figure 4.5. The rst drop, between 30 C and 100 C, is thought to be due to moisture absorbed by the specimen and incompletely removed during the drying process. The moisture content represents approximately 7 wt% of the specimens. The second drop, between 400 C and 600 C, is attributed to thermal decomposition of the PAN-based CNF material. Based on the second drop, the thermal decomposition of the control specimen is approximately 470 C, while the thermal decomposition of the acid-treated specimen is approximately 490 C. The dierence in slopes suggests that the character of the char produced by the acid-treated specimen was changed, most likely due to the presence of functional groups.

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Figure 4.5 Thermogram for PAN-based CNF control and acid-treated sheets (air atmosphere) A thermogram of VGCF (immersed for 1 hour in acid solution) plotted with a control sample is shown in Figure 4.6. Additional thermograms diering in functionalization and characterization method are shown in Appendix A. Three distinct slope drops are found in the acid-treated VGCF plot. The rst distinct drop, between 30 C and 100 C, is most likely due to the evaporation of moisture content. The moisture content represents approximately 5 wt% of the acid-treated specimen. The second drop, between 160 C and 280 C, is most likely due to the addition of functional groups attached to the VGCF sheets. This drop represents approximately

71 9 wt% of the acid-treated specimen. Based on this intermediate drop, the thermal decomposition onset temperature of the functional groups is approximately 170 C. The third drop, beginning at around 500 C, is likely due to thermal decomposition of the acid-treated VGCF material. Based on the second drop, the thermal decomposition onset temperature of the acid-treated VGCF material is approximately 570 C. The VGCF control sample has only one distinct drop between 450 C and 600 C, due to thermal decomposition of the material. Based on this decrease in slope, the thermal decomposition onset temperature of the VGCF control sample is approximately 510 C. Both thermograms of acid-treated specimens in Figures 4.5 and 4.6 show greater mass loss at lower temperatures than the control specimens. Maximum wt% dierence for both samples occurred at around 400 C. The acid-treated PAN-based CNF sample exhibited roughly 10 wt% mass reduction from the control at 400 C, while the acid-treated VGCF sample exhibited roughly 14 wt% mass reduction. The percent mass reduction is reduced to 9% if the moisture content, which was not found in the control sample, is taken into account. For the PAN-based CNF material, acid treatment increased the onset of thermal decomposition of the nanomaterial by 20 C (4.3%). For the VGCF material, acid treatment increased the onset of thermal decomposition of the nanomaterial by 60 C (12%). The change in thermal decomposition onset temperature of the bers between the functionalized and nonfunctionalized specimens suggests that the sheets were fundamentally dierent after acid treatment, possibly due to the addition of functional groups. The acid treatment aected both materials; however, TGA results suggest that each material was aected dierently. The VGCF sheets were aected more dramatically, with signicantly higher increase in the onset of thermal decomposition and

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100 90 80 70 60 Wt% 50 40 30 20 10 0 0 Control 1 hr. Immersed 100 200 300 400 Temperature (C) 500 600

Figure 4.6 Thermogram for VGCF control and acid-treated sheets (air atmosphere) comparable mass reduction at reduced acid treatment time. The VGCF sheets exhibited an intermediate slope drop suggesting the decomposition of a functional group. It appears that both materials were functionalized during acid treatment, with VGCF sheets functionalized to a higher degree when acid treatment time is considered. However, it is possible that the PAN-based CNF sheets were already functionalized. The measurement analysis showed larger ber diameters than expected, which suggests that the sheets were not fully carbonized during fabrication. If the sheets were not

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Figure 4.7 Raman spectroscopy plots for control and acid-treated PAN-based CNF sheets fully carbonized, it is likely that the bers retained functional groups from the PAN precursor material. 4.1.2.2 Raman spectroscopy results. As stated in Section 3.2, Raman

spectroscopy was performed by Dr. Daviss group at Auburn University [77]. A Raman plot for a PAN-based CNF control specimen, along with one immersed in acid for 6 hours, is shown in Figure 4.7. The ratio for the 1355 cm1 and 1580 cm1 vibrational bands remained unchanged, at 0.89, for the PAN-based CNF control and acid-treated specimens.

74 Three possible conclusions are inferred from the unchanged vibrational bands. First, the PAN-based CNF material was unaected by the acid treatment, which is unlikely when TGA results are taken into consideration. Second, the sheets were puried by the acid treatment, resulting in more structured surfaces, then functionalized, resulting in disordered surfaces. The results were oset due to the dual nature of the acid treatment. However, it seems unlikely that the sheets were puried and functionalized to the same degree. Last, it is possible that the sheets remained unchanged because they were already functionalized, as suggested by TGA results and measurement analysis. A Raman plot for VGCF immersed in acid for 1 hour is shown in Figure 4.8. Here, the ratio of the 1355 cm1 band to the 1580 cm1 changes from 0.72 for the control to 0.76 for the acid-treated specimen. However, the change toward unity favors a more ordered ber surface, suggesting that the sheets were puried during the acid treatment. It is possible that the bers were also functionalized, but to a lesser degree. Ultimately, Raman spectroscopy results were inconclusive for both PAN-based CNF and VGCF acid-treated sheets.

4.2 Shear Test Results

Before shear testing, test specimens were measured using electronic calipers. Measurement statistics are shown in Table 4.2. On average, sample overlap areas were slightly over the 1 in2 target. The overlap area of each specimen was used to calculate lap-shear stress.

75
5500 5000 4500 4000 3500 Counts 3000 2500 2000 1500 1000 500 0 1200 1250 1300 1350 1400 1450 1500 Raman Shift (1/cm) 1550 1600 1650 1700 Control 1 hr. Immersed

Figure 4.8 Raman spectroscopy plots for control and acid-treated VGCF CNF sheets 4.2.1 Extensometer Stress-Strain Curves

Stress-strain curves were derived using both extensometer and strain gage data. Extensometer stress-strain curves were used to determine shear modulus. Stressstrain curves obtained from extensometer data are presented in Figures 4.9 and 4.10. For the sake of space, only half of the extensometer data is supplied in the gures. One set of data for each specimen batch is presented. The rest of the extensometer gures are contained in Appendix B.

76 Table 4.2 Shear test specimen overlap area statistics Reinforcement Nonreinforced 0 CFRP 45 CFRP 90 CFRP PAN-based Full Sheet PAN-based Half Sheet PAN-based Half Sheet Func. VGCF Sheet VGCF Sheet Functionalized Max in2 1.154 1.127 1.141 1.112 1.074 1.094 1.078 1.059 1.062 Min in2 1.022 0.975 1.025 0.975 0.993 0.975 0.927 0.978 0.965 Mean in2 1.063 1.067 1.073 1.072 1.019 1.015 1.004 1.021 1.009 Std. Dev. in2 0.034 0.044 0.036 0.032 0.025 0.036 0.034 0.023 0.028

Shear modulus statistics are shown in Table 4.3. The modulus values were found using Microsoft Excel trendlines. Each R2 value was 0.99 and above. The only major discrepancy in the modulus data (evident by the high standard deviation) occurs in the 0 CFRP-reinforced data. Most specimen types were fabricated in two batches, with eight specimens per batch. The second 0 CFRP-reinforced batch showed 12% lower average modulus than the rst batch. Upon further inspection, the lap-shear strength, shown in Table 4.4, was 17% lower on average for the second batch. The average lap-shear strength and shear modulus for the rst batch were 1740 psi and 1090 ksi, respectively. The average lap-shear strength and modulus for the second batch were 1440 psi and 960 ksi, respectively. The dierence in strength and modulus suggests problems during fabrication for the second batch, though no errors during fabrication were noticed. Furthermore, one of the specimens in the second batch cracked during tabbing, which further suggests problems during fabrication. However, because no denite proof of fabrication error was found, the results were not discarded. The VGCF-reinforced specimens also exhibited a high standard deviation. The VGCF-reinforced specimens failed at much lower lap-shear strengths than

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Figure 4.9 Stress-strain curves for non-reinforced and CFRP-reinforced specimens other reinforced shear specimens. It is thought that the VGCF-reinforced specimens exhibited high amounts of scatter because of problems impregnating the sheets. As will be discussed in Section 4.3, some VGCF sheets seemed well impregnated, while others showed signs of loose bers and porosity. VGCF reinforcement also exhibited poor ber/epoxy interfacial bonds. Less than 5% dierence in lap-shear strength was found between any other specic shear test specimen batches.

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Figure 4.10 Stress-strain curves for nanober-reinforced specimens

79 Table 4.3 Shear test specimen shear modulus statisticsextensometer data Reinforcement Nonreinforced 0 CFRP 45 CFRP 90 CFRP PAN-based Full Sheet PAN-based Half Sheet PAN-based Half Sheet Func. VGCF Sheet VGCF Sheet Func. Spec. Designation S5,S6,S14-17 S38-41,S70-73 S54-57,S86-89 S46-49,S78-81 S22-25 S30-33,S62-65 S110-113,S118-121 S94-97,S102-105 S126-129 Table 4.4 Shear test specimen lap-shear strength statistics Reinforcement Nonreinforced 0 CFRP 45 CFRP 90 CFRP PAN-based Full Sheet PAN-based Half Sheet PAN-based Half Sheet Func. VGCF Sheet VGCF Sheet Func. Max psi 2780 2140 2050 1660 1780 2100 1950 1290 1230 Min psi 1720 1360 1240 1310 1280 1410 1190 985 709 Mean psi 2140 1590 1500 1460 1470 1690 1550 1140 926 Std. Dev. psi 285 222 191 127 149 193 218 84.0 168 Max ksi 1050 1130 1050 1080 1060 1090 1030 1030 1010 Min ksi 949 937 937 922 977 993 919 812 901 Mean ksi 995 1030 984 961 1010 1040 996 962 977 Std. Dev. ksi 39.1 74.1 44.7 31.4 37.2 34.4 33.2 75.2 51.8

PAN-based CNF-reinforced shear test specimens exhibited the highest shear modulus values, with an average shear modulus of 1040 ksi. The lowest average shear modulus values were exhibited by VGCF-reinforced and 90 CFRP-reinforced specimens at approximately 960 ksi each, which is approximately 8% lower than the PAN-based CNF-reinforced shear test specimens. For shear test specimens, the shear modulus showed dependence on reinforcement type, evident from the decrease of

80 shear modulus from the 0 CFRP-reinforced specimen to the 45 CFRP-reinforced specimen, to the 90 CFRP-reinforced specimen. However, the changes were relatively small. Lap-shear strength was measured for every single-lap shear test specimen in a batch and is based on nal loads before failure. For strain gage specimens, load was increased at intervals of 100 lb., while the strain from each channel was recorded. Stresses from strain gage data represent the highest load before failure. Lap-shear strength statistics are shown in Table 4.4. The nonreinforced specimens exhibited over 25% higher average lap-shear strength than the PAN-based half-sheet reinforced specimens, which were the strongest of the reinforced test specimens. PAN-based CNF half-sheet-reinforced specimens displayed approximately 45% higher average lap-shear strength than the VGCFreinforced specimens and 6% higher lap-shear strength than the 0 CFRP-reinforced specimens, which were the second strongest reinforced specimens. Functionalized VGCF-reinforced specimens had the lowest average lap-shear strength at 926 psi, which was over 20% lower than non-functionalized VGCF-reinforced specimens, and 35% lower than the next highest average lap-shear strength, exhibited by the 90 CFRP-reinforced specimens. As expected, the CFRP-reinforced specimens decreased in average lap-shear strength from the 0 CFRP-reinforced specimens, to the 45 CFRP-reinforced specimens, to the 90 CFRP-reinforced specimens. As discussed in the next section, the drop in average lap-shear strength from the nonreinforced specimens to the 0 CFRPreinforced specimens and from the PAN-based half sheet-reinforced specimens to the PAN-based CNF full sheet-reinforced specimens was also expected. However, the

81 decrease in average lap-shear strength from the nonfunctionalized reinforced specimens to the functionalized reinforced specimens was unexpected. Functionalized PAN-based CNF-reinforced specimens failed at approximately 8% lower lap-shear stress than nonfunctionalized specimens. Functionalized VGCF-reinforced specimens failed at approximately 20% lower lap-shear stress than nonfunctionalized specimens. Decreased lap-shear strength after acid treatment suggests that the acid treatment damaged the nanober sheet structure instead of functionalizing the bers, or possibly that the damage caused by the acid treatment outweighed the benets of functionalization. Further analysis of acid-treated sheets vs. pristine sheets is given in Section 4.3.

4.2.2 Strain Gage Stress-Strain Curves

Stress-strain curves based on strain gage data were used to measure the stressstrain discrepancy caused by shear-induced bending moments on each side of the shear test specimen. A number of specimens were rotated 180 in the test grips to ensure that the dierences in stress-strain plots were not caused by eccentricities in the test machine setup. In each case, strains were dierent depending on orientation, suggesting the test machine was operating correctly. A diagram of the forces and moments acting on a single-lap shear test specimen is shown in Figure 2.4 in Section 2.1.3. Shear-induced bending moments on each side of the test specimen cause strain to vary across the specimen cross section. One moment is additive, the other is subtractive. The variable that has the greatest eect on the bending moments, evident from Figure 2.4, is the nominal thickness, d. Curves plotted from strain gage data are shown in Figures 4.11 and 4.12.

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Figure 4.11 Strain gage stress-strain curves for nonreinforced and CFRP-reinforced specimens The nominal thickness of shear test specimens is dependent on reinforcement thickness. For example, nonreinforced and 0 CFRP-reinforced shear test specimens have identical ber alignment in the overlap area. The only dierence between the two specimens is the nominal thickness due to the CFRP reinforcement. It is hoped that the dierence is negligible in relation to the shear stress present in the specimen. However, looking at Table 4.4, this trend is not the case. The average lap-shear strength of the 0 CFRP-reinforced shear test specimens are 25% lower than the nonreinforced

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Figure 4.12 Strain gage stress-strain curves for nanober-reinforced specimens

84 specimens. The same concept can be applied to the PAN-based CNF reinforcement. The average lap-shear strength of the PAN-based CNF full-sheet reinforced specimens is 15% lower than the half-sheet reinforced specimens. To determine the exact eect of bending moments on lap-shear strength, strains on each side of the specimen were averaged. The bending moments are in equilibrium, so the average strain is assumed to be the actual strain on the specimen due to shear forces. The dierence between the average strain and the measured strain is assumed to be the strain due to bending moments. The strain due to the bending moments is compared to the average strain to obtain a percent change in shear strain due to bending moments acting on the test specimen. Since the stress-strain relationship is linear for the specimens tested, the percent change in shear strain can be directly related to the percent change in shear stress with a 1:1 ratio. Plots of the average strain from strain gage data along with the extensometer data from a sample within the same batch is shown in Figure 4.13. As shown in Figure 4.13, the average of the two strain gage channels exhibits lower modulus than the extensometer data. For example, for the half-sheet PAN-based CNF reinforced specimens, the average strain gage data is 25% lower than the extensometer data. This drop is most likely due to dierences in gage length. Extensometer results are partially based on strain occurring above and below the overlap area. For the strain gage data obtained, lap-shear strength, average strain, strain due to bending moments, and percent bending is shown in Table 4.5. Strain at fracture is used to estimate percent bending. For specimens with identical reinforcement, those with higher percent dierence in strain fail at lower lap-shear strengths. The two specimens that do not t this trend are the 45 and 90 CFRP-reinforced specimens, most likely due to scatter in the data.

Table 4.5 The eects of bending moments on strain gage test specimens Reinforcement % Bend. 4.5 14 33 42 7.8 17 7.2 31 12 5.8 1.7 35 20 31 17 8.4

Spec. Designation

2 13 37 69 53 85 45 77 21 29 61 109 117 93 101 125

Lap-shear Avg. Strain psi Nonreinforced 1840 2260 Nonreinforced 1770 2250 0 CFRP 1590 1680 0 CFRP 1470 1640 45 CFRP 1670 2280 45 CFRP 2050 2740 90 CFRP 1650 2240 90 CFRP 1670 2020 PAN-based Full Sheet 1780 2200 PAN-based Half Sheet 1640 1910 PAN-based Half Sheet 2100 2840 PAN-based Half Sheet Func. 1510 1620 PAN-based Half Sheet Func. 1760 2040 VGCF Sheet 1190 1390 VGCF Sheet 1280 1490 VGCF Sheet Func. 1230 1480 Note: Strain gage data is accurate to 5

Bending Strain 102 323 544 682 178 457 162 625 264 112 49.5 560 406 434 259 124

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Figure 4.13 Average strain gage data and extensometer data for a PAN-based CNF-reinforced specimen (half sheet) As discussed, the value that should determine bending moments is the nominal thickness, d, from Figure 2.4. The thicknesses measured correspond to the three specimen sections found in Figure 4.14. Sections A and B are comprised of four unidirectional CFRP plys. The overlap section is comprised of eight unidirectional plys with reinforcement placed at the midplane. The half-thickness of each four-ply section was subtracted from the total thickness of the overlap area to nd the nominal thickness. Nominal thickness values ranged from 0.021 to 0.029 in. For most specimens, nominal thickness did not correspond to bending moment values or even reinforcement thickness, as shown in Table 4.6. Inconsistencies in nominal thickness and reinforcement thickness are probably due to the buildup of epoxy on the surface of the specimens during curing, which were not sanded before they were measured. Most likely, thicker reinforcements absorbed more epoxy, leading

87

Figure 4.14 Test specimen section thicknesses to less buildup on the overlap surface. Inconsistencies may also be attributed to the accuracy of the calipers in measuring such small lengths. Average thicknesses for all the specimens tested are shown in Table 4.7. Supplemental single-lap shear test results are contained in Appendix C. A closer estimation of nominal thickness was made, however, since nanober and CFRP sheet thicknesses are known. The VGCF sheets were approximately 1.3 thicker than the CFRP plys and approximately 5.3 thicker than the PAN-based CNF half-sheets. The CFRP plys were approximately 4.0 thicker than the PANbased CNF half-sheets. The relative thickness of the VGCF sheets in comparison with the CFRP and PAN-based CNF sheets sheds some light on the low lap-shear strength values obtained for VGCF sheets during testing. However, these values are relative and provide limited information about the true bending stresses seen by the reinforcements. The percent bending strain does not suggest that the VGCFreinforced specimens received larger bending stresses than other samples.

4.3 Fracture Surface Analysis

Fracture surface analysis was performed to determine two specimen characteristics: sheet impregnation and fracture mode. Both characteristics are quantied

Table 4.6 Thicknesses of specimens tested with strain gages Reinforcement % Bend. 4.5 14 33 42 7.8 17 7.2 31 12 5.8 1.7 35 20 31 17 8.4

Spec. Num.

2 13 37 69 53 85 45 77 21 29 61 109 117 93 101 125

Reinf. Thick. Sec. A Overlap Sec. B in in in in Nonreinforced 0 0.025 0.045 0.024 Nonreinforced 0 0.024 0.048 0.025 0 CFRP 0.006 0.023 0.048 0.023 0 CFRP 0.006 0.023 0.047 0.022 45 CFRP 0.006 0.023 0.047 0.023 45 CFRP 0.006 0.023 0.048 0.023 90 CFRP 0.006 0.022 0.047 0.021 90 CFRP 0.006 0.023 0.048 0.023 PAN-based Full Sheet 0.003 0.023 0.047 0.023 PAN-based Half Sheet 0.0015 0.024 0.049 0.023 PAN-based Half Sheet 0.0015 0.022 0.046 0.022 PAN-based Half Sheet Func. 0.0015 0.023 0.047 0.024 PAN-based Half Sheet Func. 0.0015 0.023 0.047 0.023 VGCF Sheet 0.008 0.023 0.048 0.023 VGCF Sheet 0.008 0.022 0.046 0.018 VGCF Sheet Func. 0.008 0.023 0.047 0.023 Note: measurement data is accurate to 0.001 in.

Nom. Thick. in 0.021 0.024 0.025 0.024 0.025 0.025 0.025 0.025 0.024 0.026 0.024 0.024 0.024 0.025 0.026 0.024

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89 Table 4.7 Shear test specimen average thicknesses Section A Overlap Section B Nom. Thick. in in in in Nonreinforced .023 .046 .023 .023 0 CFRP .022 .047 .022 .025 45 CFRP .023 .047 .023 .024 90 CFRP .022 .047 .021 .025 PAN-based Full Sheet .023 .046 .023 .023 PAN-based Half Sheet .023 .046 .022 .023 PAN-based Half Sheet Func. .023 .047 .023 .024 VGCF Sheet .023 .047 .022 .025 VGCF Sheet Func. .023 .049 .023 .026 Note: measurement data is accurate to 0.001 in. visually and by the SEM for four dierent test specimens: one each of nonfunctionalized and functionalized PAN-based CNF-reinforced and VGCF-reinforced specimens. Reinforcement

4.3.1 Sheet Impregnation

A typical fracture surface of a nonfunctionalized PAN-based CNF-reinforced specimen is shown in Figure 4.15. A number of dierent characteristics are displayed in this photomicrograph. First, the top left portion of the gure shows the top surface of the reinforcement material where graphite ber pullout is seen. This region suggests some adhesive failure in the specimen. An exposed surface of the substrate layer is seen at the bottom right side of the photomicrograph. Some loose bers are present, also suggesting graphite ber pullout. The center section of the gure shows good impregnation through the thickness of the PAN-based CNF sheet. However, the upper right section of the gure shows some loose CNF (small strands) along with matrix cracking, suggesting inadequate sheet impregnation or localized porosity. The

90

Figure 4.15 A nonfunctionalized PAN-based CNF-reinforced fracture surface (800) cracking could also be the product of matrix shrinkage after the nal cure. It is possible that the impregnated sheets shrank while cooling down, separating the sheet layer from the substrate. The sheet was otherwise fully impregnated and exhibited strong CNF/epoxy interactions, which corresponds well with the relatively high lapshear strengths found for the PAN-based CNF-reinforced specimens. A functionalized PAN-based CNF-reinforced fracture surface is shown in Figure 4.16 (a) 400 and (b) 1,500. The functionalized PAN-based CNF-reinforced specimens show the same impregnation characteristics as the nonfunctionalized test specimens. The sheets were impregnated well over a large area, as shown in Figure 4.16 (a). The sheets were also impregnated through the thickness, with no sign of loose bers, as shown in Figure 4.16 (b). However, the network of bers on the surface

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Figure 4.16 A functionalized PAN-based CNF-reinforced fracture surface at (a) 6,000 and (b) 1500 of the reinforcement layers, with no visible matrix damage, is further evidence of matrix shrinkage after curing. It is possible that the matrix-impregnated sheets shrank away from the substrate after curing, causing poor contact between the substrate and the reinforcement layer. Nevertheless, as with the non-reinforced specimens, full sheet impregnation and strong ber/epoxy interaction corresponds well with the lap-shear strength data obtained for the PAN-based CNF-reinforced specimens. A nonfunctionalized VGCF-reinforced fracture surface is shown in Figure 4.17, (a) 150, (b) 400, (c) 800, and (d) 13,000. From these micrographs, it appears that the nonfunctionalized VGCF was also well impregnated over a large area and through the sheet thickness. Additionally, from Figure 4.17 (d), VGCF seem to be well-coated with matrix material, suggesting favorable VGCF/epoxy interaction. As seen in (a) and (b), the top of the reinforcement layer, as well as the substrate below the layer, is predominantly characterized by graphite ber pullout. Additionally, no

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Figure 4.17 A nonfunctionalized VGCF-reinforced fracture surface at (a) 150, (b) 400, (c) 800, and (d) 13,000 evidence of matrix shrinkage is found. However, as will be shown in Section 4.3.2, fracture surface analysis shows that the bers did not bond well with the epoxy matrix material.

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Figure 4.18 A functionalized VGCF-reinforced fracture surface showing (a) poor impregnation and (b) loose bers A functionalized VGCF-reinforced fracture surface is shown in Figure 4.18 (a) 1500 and (b) 2000. These micrographs show fracture surfaces much dierent from those found earlier. A number of loose bers are found in both micrographs indicating either ber pullout during fracture or poor impregnation. In Figure 4.18 (a), the VGCF sheet shown seems to be partially impregnated through part of the sheet thickness (right side of micrograph), but poorly impregnated through the rest (left side of the micrograph). In contrast, as shown in Figure 4.18 (b), parts of the VGCF sheet seem to be well impregnated, but with poor VGCF/epoxy bonds, evident by the loose bers laying on the surface of the epoxy. Loose bers laying on the surface are an indication of VGCF pullout from the matrix during fracture. Further evidence of pullout is found in Section 4.3.2. Poor impregnation and ber/epoxy interaction further solidies the low lap-shear strengths found for functionalized VGCF-reinforced specimens.

94 4.3.2 Fracture Features

Four dierent shear-induced fracture modes were presented in Figure 2.2. As briey discussed in the previous section, many test specimens exhibited adhesive or mixed adhesive-cohesive failure. A typical fractured specimen is shown in Figure 4.19. The specimens generally exhibited through-thickness adhesive fracture at some point in the overlap area. This type of mixed adhesive/cohesive failure mode was expected since bending stresses were present during testing. It is also possible that matrix shrinkage led to poor contact between the impregnated reinforcement and the specimen substrate, as mentioned below. A few specimens exhibited a small amount of substrate failure, though these were not the majority. Microanalysis of fracture surfaces was performed to determine fracture modes. A through-thickness adhesive fracture line from a nonfunctionalized PANbased CNF-reinforced fracture surface is shown in Figure 4.20. Additional adhesive failure of the epoxy/CFRP bond is seen below and above the fracture line. Some substrate failure is also seen below the fracture line. Mixed adhesive/cohesive failure is shown in Figure 4.21 for a nonfunctionalized PAN-based CNF-reinforced specimen. Cohesive failure is evident from the cracks and missing pieces in the reinforcement layer. Cracking on a functionalized PAN-based CNF-reinforced fracture surface is shown in Figure 4.22 (a) 800 and (b) 3,000. Cracking across bers implies good load transfer from the matrix to the bers, which is further evidence of good ber/epoxy interfacial bonds. However, the central area of (a) exhibits shrinkage eects, as discussed in the previous section. The areas aected by shrinkage may act as small, thin voids which reduce the strength of the specimen. Nonetheless, relatively high lapshear strengths for PAN-based CNF-reinforced material were most likely a result of

95

Figure 4.19 The typical fracture mode of a single-lap shear test specimen superior load transfer between the CNF and the epoxy matrix material. Surprisingly, no benets from functionalization were observed. In most cases, through-thickness cohesive failure of PAN-based CNF-reinforced specimens was dominated by ber fracture as well as matrix fracture with some evidence of matrix shrinkage. However, the situation for VGCF-reinforced fracture surfaces was quite dierent. As shown in Figure 4.23, ber pullout dominates the cohesive fracture mode of both (a) nonfunctionalized and (b) functionalized VGCF-reinforced fracture surfaces. Both fracture surfaces exhibit similar ber pullout, suggesting poor ber/epoxy interfacial bonds. In most cases, the through-thickness cohesive failure was dominated by purely matrix fractures. Poor lap-shear strengths for VGCF-reinforced specimens are

96

Figure 4.20 Adhesive failure in a PAN-based CNF-reinforced fracture surface (200) most likely due to inadequate load sharing between the VGCF and the matrix as well as poor impregnation of the functionalized specimens, as discussed in the previous section.

97

Figure 4.21 Mixed adhesive/cohesive failure in a PAN-based CNF-reinforced fracture surface (160)

98

Figure 4.22 Cracking in a functionalized PAN-based CNF-reinforced fracture surface at (a) 800 and (b) 3,000

Figure 4.23 Evidence of pullout on (a) nonfunctionalized and (b) functionalized VGCF-reinforced fracture surfaces (8,000)

CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS

This chapter presents the conclusions and recommendations determined from research. First, the conclusions regarding PAN-based CNF reinforcement are presented. Next, conclusions about the eect of acid treatment on the VGCF sheets are presented. After the conclusions are discussed, the recommendations are presented. Recommendations include suggestions for improving the current research method and suggestions for future research.

5.1 Conclusions

The purpose of this research was to improve laminated composite ILSS by the introduction of PAN-based CNF and VGCF sheets between composite plys. Unfortunately, the nonreinforced specimens exhibited the highest lap-shear strengths; however, one of the reinforcements produced promising results. Two main conclusions were determined from the analysis of this research. First, of all reinforcements tested, PAN-based CNF sheets are the most promising. Second, acid treatment most likely functionalized the VGCF themselves, but harmed the VGCF sheet structure. The details of these conclusions are discussed below.

5.1.1 PAN-based CNF Reinforcement

The PAN-based CNF sheets are a promising reinforcement for laminated composites and were possibly already functionalized as received from the manufacturer. First, PAN-based CNF sheets provided the best reinforcement for single-lap shear 99

100 test specimens. The PAN-based CNF-reinforced test specimens exhibited a lap-shear strength of 1690 psi, which was 6% higher than the 0 CFRP-reinforced specimens the second strongest reinforced specimens. PAN-based CNF-reinforced specimens exhibited over 30% higher lap-shear strength than the VGCF nonfunctionalized specimens. Additionally, both functionalized and nonfunctionalized PAN-based CNF reinforced specimens exhibited good impregnation and ber/epoxy interfacial bonds, as shown in Figures 4.15 and 4.22. Sheets were fully impregnated and cracking was seen through bers, suggesting adequate load sharing between the bers and epoxy matrix material. However, some matrix shrinkage eects were observed, which may have aected the lap-shear strength of the PAN-based CNF-reinforced specimens. A possible reason that the PAN-based CNF-reinforced specimens exhibited good ber/epoxy load sharing was that they were already functionalized as received from the manufacturer. PAN-based CNF diameters were much larger than expected from the manufacturers website, suggesting that the bers were not completely carbonized. The partially carbonized sheets may have retained functional groups on the CNF from the PAN precursor material. If the bers were already functionalized, it is likely that they formed stronger ber/epoxy interfacial bonds than any of the other reinforcement types. Additionally, the PAN-based CNF sheets exhibited no benet from acid treatment, further suggesting that the bers were already functionalized before acid treatment.

5.1.2 Eects of Acid Treatment

Acid treatment of the VGCF sheets most likely functionalized the bers themselves, but severely deteriorated the sheet structure, resulting in signicantly lower lap-shear strengths. TGA suggests that the VGCF sheets were functionalized after

101 acid treatment, as shown in Figure 4.6. However, acid treatment proved detrimental to VGCF sheet structure, as shown in Figure 4.4. Acid treatment of VGCF reinforcement also decreased VGCF-reinforced specimen lap-shear strength. Acid-treated VGCF-reinforced specimens failed at approximately 20% lower lap-shear strengths than specimens that were not subjected to acid treatment. Furthermore, the VGCF fracture surfaces showed that acid-treated specimens exhibited large amounts of ber pullout, as well as large sections that were not impregnated with matrix material. Deterioration of the sheet structure, relatively low lap-shear strength, poor sheet impregnation, and ber pullout all suggest that the harmful eects of acid treatment outweighed any benets of functionalization.

5.2 Recommendations

A few of the resulting insights of this research are applicable to current manufacturing processes. However, as with most research, better methods and new applications were conceived after testing was complete. This section provides recommendations for improving the current research method, as well as ideas for future research.

5.2.1 Improving the Current Research Method

Though ASTM D3164-03 [17] is the simplest technique for testing lap-shear strength, ASTM D3165-00 [79] is tailored more for laminated composites, and should be used in future research. A smaller test specimen overlap area should be used, as recommended by the standard [79]. Smaller overlap area will also reduce the amount

102 of material needed for testing. Additionally, test specimens should be sanded before measuring thickness to reduce epoxy buildup on the specimen surface. Using dierent shear tests, such as ASTM D2344-00 short-beam shear test [14], ASTM D5379-05 v-notched beam test [15], or ASTM D7078-05 V-notched rail test [16], would be useful for obtaining a wider scope of shear strength data for CNF-reinforced laminated composites. Using dierent reinforcement types, such as bucky paper and MWNT sheets, is also recommended. In future testing, VGCF should be functionalized before the sheets are fabricated. Functionalizing before fabrication will eliminate the possibility of acid damage to the sheet structure. Varying the duration of acid treatment and the acid mixture itself may produce more favorable functionalization results. Due to the sometimes inconclusive nature of functionalization characterization techniques, IR analysis should be performed as well as TGA and Raman spectroscopy. As stated in subsection 2.5.4, IR analysis directly characterizes functional groups. It is recommended that extra epoxy material be placed on the specimen overlap area during fabrication to ensure the sheets have an adequate amount of epoxy material to absorb. Extra epoxy material may reduce the shrinkage eects observed in the PAN-based CNF-reinforced test specimens. Additional research should be conducted to determine the amount of additional epoxy required to fully impregnate the reinforcement. Another method recommended to increase the amount of epoxy available for impregnation involves using prepreg with lower ber content. Prepreg with as low as 50-55% ber content are commonly used in the aerospace industry. Using similar prepreg should provide more excess matrix material for absorption by CNF reinforcement sheets.

103 Last, dierent sheet reinforcements should used in single-lap shear testing. For example, bucky paper or sheets of MWNT may produce favorable results. Uniform CNF sheet thicknesses should be used in order to make fair lap-shear strength comparisons. CNF sheets should be as thin as possible to reduce shear-induced bending moments on the specimen. Thinner sheets should also require less epoxy to impregnate.

5.2.2 Future Research

A study of the eect of PAN carbonization on ber/epoxy interfacial bonds is strongly recommended. More specically, it is important to determine if partially carbonized PAN-based CNF retain functional groups of the surface of the bers. It would be of great benet to engineer pre-functionalized CNF for use in nanocomposites. General research in PAN-based CNF sheet-reinforced composites, such as composite tensile strength and modulus, would also be helpful. Likewise, more research on VGCF sheet-reinforced composites is needed. Current sheet impregnation techniques are rudimentary and need to be rened. Research on VGCF sheet fabrication techniques in order to produce thinner sheets would also be useful. Furthermore, a study of the morphological attributes of PAN-based CNF and VGCF is necessary to determine if they possess the same attributes as larger diameter bers. More accurate CNF tensile strength and modulus values are also needed. Research in CNF tensile test techniques would be useful in determining ber mechanical properties. Hopefully, the current research provides a stepping stone for future work. By using PAN-based CNF sheets, the two greatest obstacles in fabricating nanober

104 composites were eliminated: ber distribution and ber/epoxy interfacial bonding. Future work should concentrate on fabricating stronger PAN-based CNF and PANbased CNF composites along with CNF/GFRP hybrid composites. PAN-based CNF seem to provide the easiest way to study nanocomposites and the best way to achieve practical use of nanocomposites in the near future.

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APPENDICES

114

APPENDIX A: SUPPLEMENTAL FUNCTIONALIZATION CHARACTERIZATION RESULTS

115

116 This appendix provides supplemental information on the characterization of functionalized sheets. Both TGA and Raman spectroscopy results are provided. A thermogram of a PAN-based CNF sheet suspended in acid vapor for 6 hours along with a control specimen is shown in Figure A.1. TGA of the suspended sheet was performed in an air atmosphere with temperature increasing 10 C/min. up to 600 C. A thermogram of a PAN-based CNF sheet immersed in acid for 2 hours along with a control specimen is shown in Figure A.2. TGA of the immersed sheet was performed in an argon atmosphere with temperature increasing 10 C/min. up to 800 C. A thermogram of a VGCF sheet immersed in acid for 3 hours along with a control specimen is shown in Figure A.3. TGA of the VGCF sheet was performed in an air atmosphere with temperature increasing 10 C/min. up to 600 C. Raman spectroscopy results of a PAN-based CNF sheet suspended in acid vapor for 6 hours along with a control specimen is shown in Figure A.4. Raman spectroscopy results of a PAN-based CNF sheet immersed in acid for 6 hours along with a control specimen is shown in Figure A.5.

117
100 90 80 70 60 Wt% 50 40 30 20 10 0 0 Control 6 hr. Vapor 100 200 300 400 Temperature (C) 500 600

Figure A.1 Thermogram of PAN-based CNF control sheet and one suspended in acid vapor for 6 hours (air atmosphere)
100 90 80 70 60 Wt% 50 40 30 20 10 0 0 Control 2 hr. Immersed 100 200 300 400 500 Temperature (C) 600 700 800

Figure A.2 Thermogram of PAN-based CNF control sheet and one suspended in acid vapor for 2 hours (argon atmosphere)

118
100 90 80 70 60 Wt% 50 40 30 20 10 0 0 Control 3 hr. Immersed 100 200 300 400 Temperature (C) 500 600

Figure A.3 Thermogram of VGCF control sheet and one immersed in acid for 3 hours (air atmosphere)

6000

5000

4000 Counts

3000

2000

1000 Control 6 hr. Vapor 0 1200 1250 1300 1350 1400 1450 1500 Raman Shift (1/cm) 1550 1600 1650 1700

Figure A.4 Raman plots of PAN-based CNF control sheet and one suspended in acid for 6 hours

119

15000

10000 Counts 5000

Control 2 hr. Immersed 0 1200 1250 1300 1350 1400 1450 1500 Raman Shift (1/cm) 1550 1600 1650 1700

Figure A.5 Raman plot of PAN-based CNF control sheet and one immersed in acid for 2 hours

APPENDIX B: SUPPLEMENTAL SINGLE-LAP SHEAR TEST FIGURES

120

121 This appendix provides supplimental stress-strain plots formed from both extensometer and strain gage data. Plots based on extensometer data for dierent types of reinforcement are shown in Figures B.1 and B.2. Averages of the two strain gage channels plotted with extensometer data for the next specimen in a batch is shown in Figures B.3 and B.4.

122

2500 S5 S6 2000

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Figure B.1 Stress-strain curves based on extensometer data for non-reinforced and CFRP-reinforced specimens

123

2500 S62 S63 S64 S65

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Figure B.2 Stress-strain curves based on extensometer data for CNF-reinforced specimens

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2500 S13 SG Avg. S14 2000

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3000

3500

(c) PAN-based CNF-reinforced

(d) Functionalized PAN-based CNF-reinforced

Figure B.3 Strain gage averages plotted against extensometer strain data for dierent specimens

125

2500 S109 SG Avg. S110 2000

2500 S93 SG Avg. S94 2000

Stress (psi)

1000

Stress (psi) 0 500 1000 1500 2000 Strain () 2500 3000 3500

1500

1500

1000

500

500

500

1000

1500 2000 Strain ()

2500

3000

3500

(a) Functionalized PAN-based CNF-reinforced


2500 S101 SG Avg. S102 2000 2000 2500

(b) VGCF-reinforced
S125 SG Avg. S126

Stress (psi)

1000

Stress (psi) 0 500 1000 1500 2000 Strain () 2500 3000 3500

1500

1500

1000

500

500

500

1000

1500 2000 Strain ()

2500

3000

3500

(c) VGCF-reinforced

(d) Functionalized VGCF-reinforced

Figure B.4 More strain gage averages plotted against extensometer strain data for dierent specimens

APPENDIX C: SUPPLEMENTAL SINGLE-LAP SHEAR TEST RESULTS

126

127 This appendix provides supplemental measurements and results for single-lap shear test specimens. Tables are distinguished by reinforcement type. Specimen information includes: specimen number, testing mode (extensometer, strain gage, or none), thickness of section A, thickness of the overlap area, thickness of section B, nominal thickness, overlap area, load at fracture, shear-lap strength, and shear modulus. Thickness values correspond to those found in Figure 4.14.

Table C.1 Mode Shear Mod. ksi 780

Num.

Batch

950 1000

S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 S17 S18 S19 S20

1 1 1 1 2 2 2 2 2 2 2 2 3 3 3 3 3 3 3 3

NS SG NS NS EXT EXT NS NS NS NS NS NS SG EXT EXT EXT EXT NS NS NS

Data from nonreinforced specimens Sec.A Lap Thck. Sec.B Nom. Thck. Lap Area Frac. Load Lap Str. in in in in in2 lb psi 0.024 0.044 0.023 0.021 1.103 1740 1580 0.025 0.045 0.024 0.021 1.089 2000 1840 0.023 0.045 0.023 0.022 1.061 1700 1600 0.023 0.045 0.023 0.022 1.123 1920 1710 0.022 0.045 0.023 0.023 1.154 2820 2440 0.022 0.046 0.023 0.024 1.077 2370 2200 0.022 0.045 0.022 0.023 1.077 2520 2340 0.023 0.046 0.024 0.023 1.026 2400 2340 0.023 0.046 0.022 0.023 1.058 2030 1920 0.023 0.046 0.023 0.023 1.060 2050 1930 0.023 0.045 0.023 0.022 1.051 1810 1720 0.024 0.046 0.023 0.023 1.084 2610 2410 0.024 0.048 0.025 0.024 1.073 1900 1770 0.022 0.045 0.022 0.023 1.022 1970 1930 0.022 0.046 0.022 0.024 1.097 2080 1900 0.022 0.045 0.022 0.023 1.042 2380 2280 0.022 0.044 0.022 0.022 1.026 1980 1930 0.022 0.044 0.022 0.022 1.027 2210 2150 0.023 0.046 0.022 0.024 1.046 2910 2780 0.023 0.047 0.022 0.024 1.084 2350 2170 Note: NS = No strain data, SG = Strain gage, EXT = Extensometer

740 1000 950 1020 1050

128

Table C.2 Mode Shear Mod. ksi 890 1100 1060 1130 1080

Num.

Batch

S37 S38 S39 S40 S41 S42 S43 S44 S69 S70 S71 S72 S73 S74 S75 S76

6 6 6 6 6 6 6 6 10 10 10 10 10 10 10 10

SG EXT EXT EXT EXT NS NS NS SG EXT EXT EXT EXT NS NS NS

Data from 0 CFRP-reinforced specimens Sec.A Lap Thck. Sec.B Nom. Thck. Lap Area Frac. Load Lap Str. in in in in in2 lb psi 0.023 0.048 0.023 0.025 1.072 1700 1590 0.022 0.047 0.022 0.025 1.056 1790 1690 0.022 0.047 0.022 0.025 1.049 1820 1730 0.023 0.048 0.023 0.025 1.127 1800 1760 0.023 0.047 0.022 0.025 1.149 1890 1800 0.022 0.047 0.023 0.025 1.017 2180 2140 0.023 0.048 0.022 0.026 0.975 1810 1850 0.024 0.052 0.023 0.029 1.011 1370 1360 0.023 0.047 0.022 0.024 1.086 1600 1470 0.022 0.047 0.022 0.025 1.106 1680 1520 0.022 0.046 0.022 0.024 1.127 1680 1490 0.023 0.046 0.021 0.024 1.119 1530 1370 0.022 0.046 0.022 0.024 1.081 1550 1440 0.022 0.047 0.022 0.025 1.100 1500 1340 0.022 0.047 0.022 0.024 1.101 1660 1510 0.022 0.046 0.022 0.024 1.105 1510 1360 Note: NS = No strain data, SG = Strain gage, EXT = Extensometer

840 940 950 980 990

129

Table C.3 Mode Shear Mod. ksi 730 940 950 940 960

Num.

Batch

S53 S54 S55 S56 S57 S58 S59 S60 S85 S86 S87 S88 S89 S90 S91 S92

8 8 8 8 8 8 8 8 12 12 12 12 12 12 12 12

SG EXT EXT EXT EXT NS NS NS SG EXT EXT EXT EXT NS NS NS

Data from 45 CFRP-reinforced specimens Sec.A Lap Thck. Sec.B Nom. Thck. Lap Area Frac. Load Lap Str. in in in in in2 lb psi 0.023 0.047 0.023 0.025 1.138 1700 1900 0.022 0.046 0.022 0.024 1.141 1790 1600 0.022 0.046 0.022 0.024 1.104 1820 1690 0.023 0.047 0.023 0.024 1.114 1800 1460 0.023 0.047 0.022 0.025 1.052 1890 1570 0.022 0.046 0.022 0.024 1.038 2180 1490 0.022 0.046 0.022 0.024 1.042 1810 1420 0.024 0.048 0.023 0.024 1.085 1370 1680 0.023 0.048 0.023 0.025 1.071 1600 2200 0.023 0.048 0.023 0.025 1.025 1680 1270 0.024 0.048 0.023 0.025 1.043 1680 1750 0.024 0.047 0.022 0.024 1.042 1530 1550 0.023 0.048 0.023 0.025 1.055 1550 1590 0.022 0.047 0.023 0.025 1.063 1500 1390 0.023 0.047 0.023 0.024 1.089 1660 1710 0.022 0.047 0.022 0.025 1.071 1510 1550 Note: NS = No strain data, SG = Strain gage, EXT = Extensometer

750 1050 1010 980 1040

130

Table C.4 Mode Shear Mod. ksi 740 960 970 920 940

Num.

Batch

S45 S46 S47 S48 S49 S50 S51 S52 S77 S78 S79 S80 S81 S82 S83 S84

7 7 7 7 7 7 7 7 11 11 11 11 11 11 11 11

SG EXT EXT EXT EXT NS NS NS SG EXT EXT EXT EXT NS NS NS

Data from 90 CFRP-reinforced specimens Sec.A Lap Thck. Sec.B Nom. Thck. Lap Area Frac. Load Lap Str. in in in in in2 lb psi 0.022 0.047 0.021 0.025 1.092 1800 1650 0.022 0.047 0.021 0.025 1.093 1470 1350 0.022 0.047 0.021 0.025 1.078 1470 1360 0.022 0.047 0.021 0.025 1.112 1470 1320 0.022 0.046 0.021 0.025 1.102 1490 1360 0.022 0.046 0.021 0.025 1.099 1450 1310 0.022 0.046 0.021 0.025 1.070 1500 1400 0.022 0.046 0.021 0.025 1.077 1790 1660 0.023 0.048 0.023 0.025 1.080 1800 1670 0.021 0.046 0.022 0.024 1.075 1430 1330 0.022 0.048 0.022 0.026 1.072 1650 1540 0.022 0.047 0.022 0.025 0.975 1570 1610 0.021 0.046 0.022 0.025 1.057 1530 1450 0.021 0.046 0.021 0.025 1.062 1530 1440 0.022 0.046 0.021 0.025 1.062 1490 1410 0.022 0.046 0.021 0.025 1.041 1510 1450 Note: NS = No strain data, SG = Strain gage, EXT = Extensometer

790 950 950 1030 970

131

Table C.5 Mode SG EXT EXT EXT EXT NS NS NS Shear Mod. ksi 810 990 980 1010 1060

Num.

Batch

S21 S22 S23 S24 S25 S26 S27 S28

4 4 4 4 4 4 4 4

Data from PAN-based CNF-reinforced specimens Sec.A Lap Thck. Sec.B Nom. Thck. Lap Area Frac. Load Lap Str. in in in in in2 lb psi 0.023 0.047 0.023 0.024 1.013 1700 1590 0.022 0.046 0.023 0.024 1.023 1790 1690 0.023 0.047 0.023 0.024 1.074 1820 1730 0.023 0.045 0.023 0.023 0.993 1800 1760 0.022 0.046 0.023 0.024 1.003 1890 1800 0.022 0.046 0.023 0.023 0.999 2180 2140 0.022 0.045 0.022 0.023 1.018 1810 1850 0.023 0.045 0.022 0.023 1.024 1370 1360 Note: NS = No strain data, SG = Strain gage, EXT = Extensometer

132

Table C.6 Mode Shear Mod. ksi 810 1040 1030 1050 1010

Num.

Batch

S29 S30 S31 S32 S33 S34 S35 S36 S61 S62 S63 S64 S65 S66 S67 S68

5 5 5 5 5 5 5 5 9 9 9 9 9 9 9 9

SG EXT EXT EXT EXT NS NS NS SG EXT EXT EXT EXT NS NS NS

Data from PAN-based CNF half-ply-reinforced specimens Sec.A Lap Thck. Sec.B Nom. Thck. Lap Area Frac. Load Lap Str. in in in in in2 lb psi 0.024 0.049 0.023 0.026 1.037 1700 1590 0.024 0.045 0.024 0.021 1.014 1910 1690 0.023 0.045 0.023 0.022 1.006 1640 1730 0.023 0.045 0.023 0.022 0.975 1940 1760 0.023 0.045 0.023 0.022 0.975 1640 1800 0.023 0.045 0.023 0.022 0.977 1730 2140 0.023 0.045 0.023 0.023 0.996 1630 1850 0.023 0.046 0.022 0.024 0.979 1650 1360 0.022 0.046 0.022 0.024 1.094 2300 1470 0.024 0.048 0.024 0.024 1.015 1430 1520 0.022 0.046 0.022 0.025 1.030 1540 1490 0.022 0.046 0.021 0.025 1.074 1760 1370 0.022 0.047 0.023 0.024 0.999 1480 1440 0.022 0.046 0.023 0.023 1.035 1920 1340 0.022 0.046 0.022 0.024 0.998 1670 1510 0.022 0.046 0.021 0.025 1.040 1510 1360 Note: NS = No strain data, SG = Strain gage, EXT = Extensometer

740 990 1090 1000 1070

133

Table C.7 Shear Mod. ksi 870 990 1010 1010 1010

Num.

Batch

S109 S110 S111 S112 S113 S114 S115 S116 S117 S118 S119 S120 S121 S122 S123 S124

15 15 15 15 15 15 15 15 16 16 16 16 16 16 16 16

Data from functionalized PAN-based CNF half-ply-reinforced specimens Mode Sec.A Lap Thck. Sec.B Nom. Thck. Lap Area Frac. Load Lap Str. in in in in in2 lb psi SG 0.023 0.047 0.024 0.024 0.927 1400 1510 EXT 0.024 0.046 0.023 0.023 1.078 1760 1630 EXT 0.023 0.047 0.023 0.024 1.005 1660 1650 EXT 0.023 0.047 0.023 0.024 1.045 1250 1190 EXT 0.023 0.047 0.023 0.024 1.029 1800 1750 NS 0.023 0.047 0.023 0.024 0.971 1420 1470 NS 0.023 0.046 0.023 0.023 1.007 1630 1620 NS 0.023 0.046 0.023 0.024 0.992 1370 1380 SG 0.023 0.047 0.023 0.024 1.024 1800 1760 EXT 0.023 0.047 0.023 0.025 1.006 1280 1270 EXT 0.023 0.047 0.023 0.024 0.967 1500 1550 EXT 0.023 0.048 0.023 0.025 1.010 1380 1370 EXT 0.023 0.047 0.023 0.024 1.020 1990 1950 NS 0.023 0.046 0.023 0.023 0.997 1330 1340 NS 0.023 0.047 0.023 0.024 1.007 1480 1470 NS 0.023 0.047 0.023 0.024 0.982 1850 1890 Note: NS = No strain data, SG = Strain gage, EXT = Extensometer

820 1000 1000 920 1030

134

Table C.8 Mode Shear Mod. ksi 790 900 810 970 970

Num.

Batch

S93 S94 S95 S96 S97 S98 S99 S100 S101 S102 S103 S104 S105 S106 S107 S108

13 13 13 13 13 13 13 13 14 14 14 14 14 14 14 14

SG EXT EXT EXT EXT NS NS NS SG EXT EXT EXT EXT NS NS NS

Data from VGCF-reinforced specimens Sec.A Lap Thck. Sec.B Nom. Thck. Lap Area Frac. Load Lap Str. in in in in in2 lb psi 0.023 0.048 0.023 0.025 1.011 1400 1200 0.022 0.048 0.023 0.025 1.050 1760 1230 0.023 0.047 0.023 0.025 1.031 1660 1190 0.024 0.049 0.023 0.026 1.005 1250 1110 0.023 0.047 0.023 0.025 1.003 1800 1080 0.023 0.047 0.022 0.025 0.978 1420 1120 0.024 0.049 0.023 0.025 1.007 1630 1090 0.029 0.048 0.022 0.022 1.055 1370 1130 0.022 0.046 0.018 0.026 1.019 1800 1300 0.022 0.046 0.023 0.024 1.016 1280 1110 0.022 0.047 0.023 0.025 0.991 1500 1110 0.022 0.047 0.022 0.025 1.044 1380 1030 0.023 0.047 0.023 0.024 1.028 1990 1100 0.023 0.048 0.023 0.025 1.027 1330 1270 0.023 0.047 0.023 0.024 1.059 1480 1300 0.023 0.046 0.023 0.024 1.020 1850 1310 Note: NS = No strain data, SG = Strain gage, EXT = Extensometer

790 1020 1030 1030 970

135

Table C.9 Mode SG EXT EXT EXT EXT NS NS NS Shear Mod. ksi 770 1010 900 990 1010

Num.

Batch

S125 S126 S127 S128 S129 S130 S131 S132

17 17 17 17 17 17 17 17

Data from functionalized VGCF-reinforced specimens Sec.A Lap Thck. Sec.B Nom. Thck. Lap Area Frac. Load Lap Str. in in in in in2 lb psi 0.023 0.047 0.023 0.024 1.060 1300 1230 0.024 0.050 0.023 0.027 0.965 670 710 0.023 0.052 0.022 0.029 1.016 720 710 0.023 0.048 0.023 0.025 0.991 910 920 0.023 0.048 0.023 0.025 0.999 960 960 0.023 0.049 0.022 0.026 1.062 950 890 0.023 0.048 0.023 0.025 1.042 1000 960 0.023 0.048 0.023 0.025 1.003 1030 1020 Note: NS = No strain data, SG = Strain gage, EXT = Extensometer

136

APPENDIX D: SUPPLEMENTAL COMPACT DISC CONTENTS

137

138 Directory Tree Structure Supplemental Data Excel Spreadsheets Individual Stress-strain Curves Inverted Microscope MatLab Files PowerPoint Diagrams Presentation Files SEM Fiber Measurements PAN-based CNF Diameters VGCF Diameters PAN-based CNF Functionalized PAN-based CNF Nonfunctionalized PAN-based CNF PAN-based CNF Sheet Structure PAN-based CNF Fracture Surfaces Functionalized PAN-based CNF Fracture Nonfunctionalized PAN-based CNF Fracture Preliminary Microscopy VGCF VGCF Sheet Structure VGCF Fracture Surfaces Functionalized VGCF Fracture Nonfunctionalized VGCF Fracture Preliminary VGCF Fracture Test Setup Pictures TeXnicCenter Files Thesis Figures Diagrams Extensometer and Strain Gage Average Extensometer Figures Literature Review Figures Raman Spectroscopy SEM Micrographs Strain Gage Figures Test Pictures TGA Figures

139 Description of subfolder contents Supplemental Data Top Level Folder. Contains all subfolders and Thesis.pdf le. Excel Spreadsheets Data records in Excel spreadsheets. Includes extensometer data, strain gage data, ber diameters, Raman spectroscopy, TGA, and compiled specimen data. Individual Stress-strain Curves Individual specimen stress-strain plots from both extensometer and strain gage data. Ch1, Ch2, and Avg. denote strain gage data. Inverted Microscope Contains a micrograph for both VGCF and PAN-based CNF-reinforced specimens. MatLab Files All data les used to create gures in MatLab (.pdf gures), including stress-strain plots, thermograms, and Raman spectroscopy plots. PowerPoint Diagrams PowerPoint les used to create many of the diagrams presented in this research. Presentation Files All les used to compile masters defense presentation. SEM Contains subfolders with supplemental SEM gures and a SEM micrograph displaying GFRP pullout from matrix material. Fiber Measurements Contains subfolders of CNF diameter measurements. PAN-based CNF Diameters Micrographs used to make PAN-based CNF diameter measurements. VGCF Diameters Micrographs used to make VGCF diameter measurements. PAN-based CNF Contains subfolders of PAN-based CNF SEM micrographs. Functionalized PAN-based CNF Micrographs of functionalized PAN-based CNF. Nonfunctionalized PAN-based CNF Micrographs of nonfunctionalized PANbased CNF.

140 PAN-based CNF Sheet Structure Micrographs of PAN-based CNF sheet thicknesses showing sheet structure. PAN-based CNF Fracture Surfaces Contains subfolders of PAN-based CNF fracture surfaces for functionalized and nonfunctionalized specimens. Functionalized PAN-based CNF Fracture Contains micrographs of fracture surfaces from functionalized PAN-based CNF-reinforced specimens. Nonfunctionalized PAN-based CNF Fracture Contains micrographs of fracture surfaces from nonfunctionalized PAN-based CNF-reinforced specimens. PAN-based CNF Preliminary Microscopy Contains preliminary SEM micrographs of PAN-based CNF-reinforced specimens used to verify impregnation. VGCF Contains subfolders of VGCF SEM micrographs. VGCF Sheet Structure Micrographs of VGCF sheet thicknesses showing sheet structure. VGCF Microscopy Micrographs of VGCF. VGCF Fracture Surfaces Contains subfolders of VGCF fracture surfaces. Functionalized VGCF Fracture Micrographs of functionalized VGCF-reinforced specimen fracture surfaces. Nonfunctionalized VGCF Fracture Micrographs of nonfunctionalized VGCFreinforced specimen fracture surfaces. Preliminary VGCF Fracture Micrographs of preliminary VGCF-reinforced specimen fracture surfaces (VGCF sheet reinforcement with 0.015 inch thickness). Test Setup Pictures Various pictures of specimens and dierent test setups and equipment. TeXnicCenter Files Files used to build thesis including .aux, .bbl, .bib, .bst, .lof, .lot, .log, .out, .toc, .tps, LaTeX packages, LaTeX documents, and TeXnicCenter project les. Thesis Figures Contains subfolders of gures found in thesis.

141 Diagrams Contains diagrams found in thesis. Extensometer and Strain Gage Average Contains stress-strain plots of the average of two strain gage channels for a specimen along with the extensometer data taken from the next available specimen. Extensometer Plots Each le contains stress-strain plots derived from extensometer data for four specimens (except for nonreinforced, which contains only two). Literature Review Figures Contains both adapted and unmodied pictures from the literature review. Raman Spectroscopy Raman spectroscopy plots used in the thesis. SEM Micrographs SEM micrographs used in the thesis. Strain Gage Plots Each le contains stress-strain plots of two channels from two dierent specimens derived from strain gage data. Test Pictures Various pictures of test setup, specimens, and materials. Thermograms TGA plots used in the thesis.

VITA

Jon Rylan Cox was born on December 6, 1981, in Montreal, Canada. He attended East Ridge High School in East Ridge, Tennessee, where he graduated top ten in May of 2000. He began college at Freed-Hardeman University, where he met his wife, Sheree Cox. They were married in August 2003. He then transferred to Tennessee Technological University where he graduated 11th in his class in December of 2005, with a degree in Mechanical Engineering. He remained at TTU to pursue his Masters Degree.

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