ENHANCING THE PERFORMANCE OF AN EPOXY RESIN USING OLIGOMERIC

AMIDE ADDITIVES

A Dissertation by

Janet de los Reyes

Master of Science, Wichita State University, 2009

Submitted to the Department of Chemistry

and the faculty of the Graduate School of
Wichita State University
in partial fulfillment of
the requirements for the degree of
Doctor of Philosophy

May 2012

i
© Copyright 2012 by Janet de los Reyes

All Rights Reserved

ii
 ENHANCING THE PERFORMANCE OF AN EPOXY RESIN USING OLIGOMERIC
AMIDE ADDITIVES

The following faculty members have examined the final copy of this thesis for form and content,
and recommended that it be accepted in partial fulfillment of the requirement for the degree of
with a major in Chemistry.

David M. Eichhorn , Co-Chair

William T. K. Stevenson (deceased), Committee Chair

Moriah Beck, Committee Member

Denis H. Burns, Committee Member

Suresh Raju Keshavanarayana, Committee Member

Donald Paul Rillema, Committee Member

iii
 ACKNOWLEDGMENTS

First of all, I would like to thank our Maker, for I am nothing if not for Him.

I feel deeply indebted to Dr. William Stevenson for giving me an opportunity to work in

his group. I am very grateful for his guidance and intellectual inputs in this research. He will

always be cherished. I am very thankful to Dr. David Eichhorn for taking me as an advisee after

Dr. Stevenson’s death. I also extend my gratitude to the members of my committee, Dr. Moriah

Beck, Dr. Dennis Burns, Dr. Suresh Raju Keshavanarayana and Dr. Donald Rillema for their

comments and inputs for this dissertation.

I want to express my gratitude to Mrinal Agrecha, and Stacy Wolf who helped me

conduct some mechanical testings and Matt Opliger who performed some viscoelastic property

tests.

My sincere appreciation is extended to my former groupmates, Anusha Dissanayake, Dr.

Irish Gibson, Dr. Joel Flores, Dr. Rama Gandikota, Amanda Alliband, Ritu Gurung, Roxanne Uy

and Van Anh Hoang for all their help and making work enjoyable.

Finally, I would like to thank my family and friends for their constant encouragement and

support, and occasional positive distractions that helped me kept me sane as I was working on

this project. ☺

iv
 ABSTRACT

An antiplasticizer is any chemical that when added, reduces the free volume of a polymer

thereby restricting the polymeric chain motions. This type of additive usually increases the

modulus and strength but can compromise other important properties such as glass transition

temperature and thermal degradation profile.

Oligomeric amide additives, which when mixed with TGDDM and DDS, react to form

strong hydrogen bonds and reduce the free volume in the system, were synthesized. The

nonaromatic additives, especially those that have shorter methylene sequences, had low

solubility in the resin, while the mixed amide oligomer additive have better solubility. The effect

of these additives to enhance mechanical properties was tested by tensile testing and fracture

toughness measurement. Compact tension results indicated that the additives improved the

resins’ resistance to crack propagation. In general, when the additive is shorter and additive

loading is lower, the material performs better. No general conclusion can be arrived at from the

tensile testing due to the variablility of results caused by unavoidable imperfections incurred

during specimen preparation. The cure kinetics of the resin was studied using Differential

Scanning Calorimetry. Dynamic temperature scanning DSC indicated that the cure reaction was

not affected significantly by these additives. However, an increase in activation energy was

observed. TMA experiments on resins with nonaromatic additives indicated that the additives

slightly increased the softening temperature while DMA experiments on resins with mixed amide

oligomers show that the additives slightly increase the glass transition temperature. TGA

experiments on resins with mixed amide oligomers indicated that the additives did not introduce

significant changes in thermal stability.

v
 TABLE OF CONTENTS

Chapter Page

TABLE OF CONTENTS............................................................................................................... vi

LISTOF FIGURES ........................................................................................................................ ix

LIST OF TABLES........................................................................................................................ xii

LIST OF ABBREVIATIONS...................................................................................................... xiv

CHAPTER 1 ................................................................................................................................. 1

INTRODUCTION .............................................................................................................. 1

1.1 Epoxy-Amine Curing...................................................................................... 4

1.2 Free Volume ................................................................................................... 6
1.3 Hydrogen bonds .............................................................................................. 8
1.4 Related Studies ............................................................................................... 9
1.5 Controlling Average Chain Length of Oligomers ........................................ 12
1.6 Intrinsic Viscosity ......................................................................................... 13
1.7 Mechanical Properties................................................................................... 14
1.8 Overview of the Study .................................................................................. 16
CHAPTER 2 ............................................................................................................................... 19

EXPERIMENTAL............................................................................................................ 19

2.1 Introduction.................................................................................................. 19
2.2 Mixing of Resin and the Curing Agent........................................................ 19
2.3 The Additives................................................................................................ 20
2.4 Synthesis of Additives .................................................................................. 21
2.4.1 The Materials ........................................................................................... 21
2.4.2 Synthesis of Nylon-Like Oligomers ........................................................ 22
2.4.3 Synthesis of Mixed Aliphatic-Aromatic Amide Oligomers ........................ 23
2.5 Preparation of Resin with Additives............................................................. 24
2.6 The Cure Cycle ............................................................................................. 25
2.7 Intrinsic Viscosity Measurements................................................................. 25
2.8 Molecular Weight Determination ................................................................. 27
2.9 Fourier-Transform Infrared Spectroscopy .................................................... 27

vi
 TABLE OF CONTENTS (Continued)

Chapter Page

2.10 Nuclear Magnetic Resonance (NMR)........................................................... 28

2.11 Tensile Testing.............................................................................................. 28
2.12 Fracture Toughness Test ............................................................................... 30
2.13 Dynamic Mechanical Analysis ..................................................................... 32
2.14 Thermo Mechanical Analysis ....................................................................... 32
2.15 Thermogravimetric Analysis ........................................................................ 33
2.16 Differential Scanning Calorimetry................................................................ 33
CHAPTER 3 ............................................................................................................................... 36

RESULTS AND DISCUUSION: NON-AROMATIC ADDITIVES............................... 36

3.2 FTIR.............................................................................................................. 37
1
3.3 H NMR ........................................................................................................ 39
3.4 Solubility Test............................................................................................... 42
3.5 Intrinsic Viscosity ......................................................................................... 43
3.6 Curing of Resin ............................................................................................. 45
3.7 Curing with Oligomer................................................................................... 48
3.8 Tensile test .................................................................................................... 49
3.9 Tensile Testing of Resins Using New Cure Cycle ....................................... 53
3.10 Thermomechanical Analysis........................................................................ 56
3.11 Conclusion ................................................................................................... 58
CHAPTER 4 ............................................................................................................................... 59

RESULTS AND DISCUSSION: MIXED AMIDE ADDITIVES ................................... 59

4.1 Introduction................................................................................................... 59
4.2 Infrared Spectroscopy ................................................................................... 61
4.3 Proton and 13C NMR..................................................................................... 63
4.4 Intrinsic Viscosity (IV) ................................................................................. 70
4.5 Tensile Test................................................................................................... 73
4.6 Fracture Toughness....................................................................................... 82
4.7 Differential Scanning Calorimetry................................................................ 86
4.8 Dynamic Mechanical Analysis ..................................................................... 93
4. 9 Thermogravimetric Analysis ........................................................................ 95

vii
 TABLE OF CONTENTS (Continued)

Chapter Page

4.10 Conclusion .................................................................................................... 97

CHAPTER 5 ............................................................................................................................... 99

CONCLUSIONS............................................................................................................... 99

REFERENCES ........................................................................................................................... 102

APPENDICES ............................................................................................................................ 105

A. Infrared Spectra of the Additives..…...……………………………………..106

B. NMR Spectra of the Additive……..………………………………………..113
C. Intrinsic Viscosity and GPC Plots…...……………………………………..122
D. Tensile Test Results………………………………………………………...127
E. Fracture Toughness Results………………………………………………...161
F. Differential Calorimetry Plots……………………………………………...189

viii
 LISTOF FIGURES

Figure Page

Figure 1.1 The growing use of composites in aircrafts ............................................................ 2

Figure 1.2 The chemical structures of DDS and TGDDM....................................................... 3

Figure 1.3 Development of cure for an epoxy resin system.6 .................................................. 5

Figure 1.4 The reactions involved in resin curing.................................................................... 6

Figure 1.5 Dissipation of energy through disruption of hydrogen bonds. ............................... 9

Figure 1.6 Chemical Structure of EPPHAA........................................................................... 10

Figure 1.7 A Stress-Strain Curve. The slope of the straight initial part of the curve “a” is
taken as the Young’s modulus. ............................................................................ 15

Figure 2.1 Reaction of amine and acid chloride to form amide. ............................................ 21

Figure 2.2 Representative repeat unit for the 10,12 oligomer prepared using a C10 diacid
chloride and a C12 diamine. ................................................................................. 21

Figure 2.3 The chemical Structures of the diamines a. p-phenylenediamine, b. m-

phenylenediamine and c. 4,4’-methylene dianiline. ............................................. 24

Figure 2.4 The Ubbelohde dilution viscometer...................................................................... 26

Figure 2.5 Dogbone dimensions of ASTM D638 Type IV.................................................... 29

Figure 2.6 Dimensions of compact tension specimen............................................................ 31

Figure 3.1 Scheme for the synthesis of Nylon 6,6 ................................................................. 36

Figure 3.2 FTIR spectrum of nylon 6,6 Xn =6....................................................................... 38

Figure 3.3 The acid carbonyl peak in the FTIR of nylon 6,6 Xn =6...................................... 38
1
Figure 3.4 H NMR spectrum of Nylon 6,6 Xn=3.67 ............................................................ 39
13
Figure 3.6 C NMR spectrum for Nylon 6,6 Xn=3.67 .......................................................... 41

ix
 LIST OF FIGURES (Continued)

Figure Page

Figure 3.7 Solubilities of different nylon oligomers in (1) 90% formic acid (2) m-cresol (3)
DMF and (4) DMAc. (CD = completely dissolved, PD = partially dissolved and
ND = not dissolved) .............................................................................................. 43

Figure 3.8 Intrinsic Viscosity of Nylon 6,6 Xn=6.................................................................. 44

Figure 3.9 Stress-strain curves of control specimens made by Method III. ........................... 47

Figure 3.10 Linear initial part of the stress-strain curve of specimen 1 made by Method III.. 47

Figure 3.11 Comparing TMA output for nylon 10,12 Xn=3.67 and control. .......................... 57

Figure 4.1 The chemical structures of the monomers and the corresponding names of their
oligomers............................................................................................................... 59

Figure 4.2 Scheme for the synthesis of MDA10 .................................................................... 60

Figure 4.4 FTIR Spectrum of MPDA10 Xn=3.67, an enlargement of the carbonyl area. ..... 62

Figure 4.5 Proton NMR Spectrum of MPDA10 Xn=3.67 ..................................................... 64

Figure 4.6 Expansion of aromatic region of MPDA10 Xn=3.67 proton NMR spectrum...... 65

Figure 4.7 Chemical structure of MPDA10 Xn=5 with assigned carbon numbers................ 65
13
Figure 4.8 C NMR spectrum of MPDA10 Xn=3.67............................................................ 67

Figure 4.9 Expanded aliphatic region of C13NMR spectrum of MPDA10 Xn=3.67 ............. 67

Figure 4.10 Expanded aromatic region of C13NMR spectrum of MPDA10 Xn=3.67............. 68

Figure 4.11 Expanded carbonyl region of 13C NMR spectrum of MPDA10 Xn=3.67 ............ 68

Figure 4.12 Intrinsic viscosity plot for MDA10 Xn=5............................................................. 70

Figure 4.13 Gel Permeation Chromatography of MDA10....................................................... 72

Figure 4.14 Stress-strain curves of MDA10 Xn=3.67 3% ....................................................... 74

Figure 4.15 Initial portion of the stress-strain curve of Control resin specimen 1................... 74

Figure 4.16 Tensile testing curves of MPDA10 Xn=3.67 at 3 % loading. .............................. 76

Figure 4.17 Initial portion of tensile testing curve of MPDA10 Xn=3.67 3% specimen 1...... 76

x
 LIST OF FIGURES (Continued)

Figure Page

Figure 4.18 Fracture toughness test load-strain curve of control resin specimen 1. ................ 83

Figure 4.19 Plot of Control resin Degree of Cure vs. Temperature Summary......................... 87

Figure 4.20 Plot of Resin with MDA10 Xn=3.67 degree of cure vs. temperature summary... 88

Figure 4.21 Comparison of control resin and resin with MPDA10 Xn=3.67 @ 5oC/min
heating rate............................................................................................................ 88

Figure 4.22 Summary of rate of cure vs temperature for the control resin at different heating
rates. ...................................................................................................................... 89

Figure 4.23 Summary of rate of cure vs temperature for the resin containing MDA10 Xn=3.67
at 3% load at different heating rates. .................................................................... 90

Figure 4.24 Plot for ln rate of cure vs 1/T for 0.05 degree of cure of control resin. ................ 91

Figure 4.25 Activation energy vs degree of cure of Control and 3 % MDA10 Xn=3.67 ........ 92

Figure 4.26 DMA of MPDA10 Xn=3.67 3%........................................................................... 93

Figure 4.27 Comparing Tangent Delta from DMA scans. ....................................................... 94

Figure 4.28 Change of weight percent of control resin and resin with MPDA10 Xn=3.67
additive with time at 4 ºC/min heating rate. ......................................................... 96

xi
 LIST OF TABLES

Table Page

Table 1.1 Typical Tensile Strength, Elongation and Tensile Modulus of Polymers. ............. 8

Table 2.3 The dimensions of the dogbones........................................................................... 29

Table 3.1 Experimental and predicted chemical shifts for Nylon 6,6 Xn=3.67 ................... 40

Table 3.2 Corresponding MW of Nylon 2 Intrinsic viscosities and their 6,6 oligomer........ 45

Table 3.3 The calculated a parameters of the nylon 6,6 oligomers. ..................................... 45

Table 3.4 The tensile results for Control, made with and without acetone as solvent.......... 48

Table 3.5 Formulation of nylon 6,6 oligomers ..................................................................... 50

Table 3.6 Stiffness of dogbones made with different oligomer additives at 3% load. ......... 51

Table 3.7 Stress at break of dogbones made with different oligomer additives @ 3% load. 52

Table 3.8 Strain at break of dogbones made with different oligomer additives. ................. 53

Table 3.9 Stiffness of the dogbones with different nylon oligomers at 5% load. ................. 54

Table 3.10 Stress at break of the dogbones with different nylon oligomers at 5% load......... 55

Table 3.11 Strain at break of the dogbones with different nylon oligomers at 5% load......... 56

Table 3.12 Softening temperatures of control resin, resins with nylon 10,12 Xn=3.67 5% and
10% determined by TMA. .................................................................................... 57

Table 4.1 The number average degrees polymerization of MDA10 and their corresponding
reagent ratios......................................................................................................... 61

Table 4.2 Experimental and Predicted chemical shifts for MPDA10 Xn=3.67.................... 66

Table 4.3 Assignment of carbon numbers and chemical shifts in the 13C NMR of MPDA10
Xn=3.67 ................................................................................................................ 69

Table 4.4 Summary of results for intrinsic viscosity experiments........................................ 71

Table 4.5 Summary of gel permeation chromatography results. .......................................... 73

Table 4.6 Tensile testing summary for control resins........................................................... 75

xii
 LIST OF TABLES (Continued)

Table Page

Table 4.7 Tensile Testing summary for MPDA10 Xn=3.67 at 3% load. ............................. 77

Table 4.8 Formulations of resins tested. ............................................................................... 78

Table 4.9 Tensile Testing Summary for resins containing MPDA10................................... 79

Table 4.10 Tensile testing summary for resins containing MDA10. ...................................... 80

Table 4.11 Tensile Testing summary for resins containing PPDA10..................................... 81

Table 4.12 T-test calculation results ....................................................................................... 82

Table 4.13 Fracture toughness for control specimens............................................................. 83

Table 4.14 Fracture Toughness of Resins with MDA10 additives. ........................................ 84

Table 4.15 Fracture toughness tests results for resins with PPDA10 additives...................... 85

Table 4.16 Fracture toughness tests results for resins with MPDA10 additives..................... 85

Table 4.17 Comparison of the three best resins from each type of additive........................... 86

Table 4.18 Comparison of High-Temperature DMA of MDA10 and MPDA10 Xn=3.67. ... 95

Table 4.19 Summary of weight degradation for control and resins with MPDA10 Xn=3.67.96

xiii
 LIST OF ABBREVIATIONS

ASTM American Society for Testing and Materials

DBu 1, 8-diazobicycloundec-7-ene base

DDS Diaminodiphenyl sulphone

DMAc N,N - Dimethyl acetamide

DMF N,N - Dimethylformamide

DMMP Dimethyl methyl phosphate solvent

EHPC Ethyl 4-hydroxy phenyl carbamate reagent

EPPHAA Reaction product of 4-hydroxyacetanilide and 1, 2-epoxy-3-phenoxypropane

HP-3-PU 1-(4-hydroxyphenyl)-3-propyl urea

IV Intrinsic Viscosity

MDA Methylene diamine

MPDA Meta phenylene diamine

MY720 Commerical name for tetragylcidyl diaminodiphenylmethane resin

PHR Parts per hundred parts resin

PPDA Para phenylene diamine curative

TGDDM Tetraglycidyl diaminodiphenylmethane resin

VCDHAA Reaction product of vinylcyclohexene dioxide and 4-hydroxyacetanilide

VCD-EHPC Ethyl 4-(2-(7-oxa-bicyclo[4.1.0]heptan-3-yl)-2-hydroxyethoxy)phenyl carbamate

xiv
 CHAPTER 1
INTRODUCTION

Epoxy resins are widely used thermosetting plastics possessing properties that are easily

altered and tailored. For this reason they have found applications in different fields such as

adhesives, coatings, electrical and electronic, and structural applications.

The most important application of epoxy resins in the aerospace industry is in the

fabrication of fiber reinforced composites for use in structural applications. They constitute the

matrix in long fiber reinforced composites. They are used as such for the following reasons: they

are light-weight, impregnation of reinforcing fiber is easy, and it has excellent adhesion to the

reinforcing fiber.

Figure 1.1 shows that the use of composites in both military and commercial aircrafts is

steadily growing.1 They are much preferred over other structural components such as metals

because of the following properties: they are lightweight, have high strength compared to weight,

are corrosion resistant, have low thermal conductivity which makes them good insulators, are

non-electrically conductive, and have dimensional stability which means they are resistant to

expansion and contraction due to temperature changes. They are also radar transparent. This

property plays a key role in stealth bombers.2

The military aircrafts V-22 and Eurofighter, which presently have the highest composite

percentage of 80%, are lightweight and very agile. On the other hand, the Boeing 787, formerly

known as Boeing 7E7, which was first launched in 2009 has a composition of 50% composite

(the highest among the commercial planes), 20% aluminum, 15% titanium, 10% steel, and 5%

other materials.3 It uses 20% less fuel than an aircraft with a comparable size making it very

economical.

1
Figure 1.1 The growing use of composites in aircrafts

Although the resin matrix in a composite may appear to have unimportant mechanical

properties due to the presence of reinforcing fibers, matrices are also subjected to tensile stresses.

Since the matrix is what holds the fibers together in a composite, when it fails the whole

composite’s strength and performance are greatly affected and could cause the whole composite

to fail. Since epoxy resins are inherently brittle, much research has been conducted on improving

their resistance to mechanical failures.

Many epoxy composites used in the aerospace industry are based on N,N,N’,N’-

tetraglycidyl-4,4’-diaminodiphenylmethane (TGDDM) resin and diaminodiphenyl sulphone

(DDS) curative (Figure 1.2) as matrix components. These composites have high mechanical

properties and can be used at high temperatures due to their high glass transition temperatures.

TGDDM, commercially known as MY720 resin, is a semi-solid and therefore requires only

minor modifications to obtain good physical properties in the prepreg. DDS is used as the

2
aromatic amine curative because the electron-withdrawing sulfone group provides latency,

molecular fit and relatively stable epoxy/amine links,4-5 which, when combined with TGDDM,

give excellent initial mechanical properties.

O O
S

H 2N NH 2

4,4-Diamino diphenyl sulfone or DDS (resin curing agent)

O N N O

O O

N,N,N’,N’-tetraglycidyl-4,4’-diaminodiphenylmethane or TGDDM or MY720

Figure 1.2 The chemical structures of DDS and TGDDM

Even though TGDDM/DDS systems provide high mechanical properties due to a high

crosslink density, they are inherently brittle materials and have poor resistance to crack

propagation. They are known to fail by the growth of internal flaws and micro voids that

consolidate into cracks. TGDDM/DDS based composites also have been recorded to have very

low fracture toughness values. Various chemical additives have been developed that would

improve the fracture toughness and the tensile strength of these systems without having adverse

effects on other properties such as the glass transition temperature (Tg) and solvent resistance.

Compounds having terminal amine functionality are often used as additives as they can easily

react with the epoxide groups of the resin.

3
1.1 Epoxy-Amine Curing

The process of curing epoxy resins involves reaction of monomeric or oligomeric

polyfunctional epoxide molecules with a curing agent (which is usually an amine compound) and

catalyst, to form a highly crosslinked, rigid structure. The curing takes place in stages.6 The first

stage involves combining the epoxy resin and curing agent. The resin is a viscous liquid and the

curing agent is either a liquid or a low-temperature melting solid. When combined and after a

catalyst is added and heated, the curing agent and resin react, accompanied by release of

additional heat which helps to increase the speed of reaction. The second stage results in the

formation of linear chains of combined curing agent and epoxy resin. At this stage, the material

is still liquid but its viscosity increases rapidly. Continued heating causes the linear chains to

crosslink to form a network with a very high molecular mass. At this stage of cure (third stage),

the material is a strong solid gel. The final stage is carried out at a more elevated temperature to

push the crosslinking process to completion. The product is a very strong, chemically resistant

material. A representation of the curing process is shown in Figure 1.3.

4
 Figure 1.3 Development of cure for an epoxy resin system.6
The mechanism of epoxy-amine curing has been widely studied. There are three basic

reactions 4,7-8 (Figure 1.4) First is (1) attack of the primary amine lone pair on the least hindered

methylene of the epoxide, opening the ring and producing a secondary amine and a hydroxyl

group; (2) the secondary amine reacts further with another epoxide to form a tertiary amine and

another hydroxyl group; (3) the hydroxyl groups of the products in reactions (1) and (2) react

with any excess epoxide to form an ether linkage.

1) Epoxy – Primary Amine

O OH
NH2 +
H2C CH NH CH2 CH

5
 2) Epoxy-Secondary Amine

OH
O
NH +
H2C CH N CH2 CH

3) Etherification

CH2 CH CH2
CH2 CH CH2
O
+ O
OH H2 C CH

HO H2C CH

Figure 1.4 The reactions involved in resin curing.

Reaction 2 is slower than reaction 1 due to steric factors in the secondary amine. The

tendency of the etherification reaction to take place depends on the temperature and the basicity

of the diamine and increases with the initial ratio of epoxy/amine.7 It is insignificant if the

reactants are mixed in stoichiometric amounts or with an excess of the amine. It occurs at high

temperatures and advanced degrees of cure, especially if the epoxy is in excess in the mixture.

This leads to a more brittle resin, therefore this reaction is unwanted.

1.2 Free Volume

Chain flexibility is a major factor in establishing polymer properties such as stiffness,

strength, glass transition and melting temperature, and thermal stability. The more flexible the

polymer chains are, the easier it is for the segments to acquire translational motion. If the

polymer chains are stiff, the bulk polymer will have high stiffness, glass transition and melting

temperature and will be more thermally stable. With an appropriate packing of polymer chains,

intermolecular forces of attraction can exert an effect on holding the chains together and thus

6
help make the chains less flexible. Good packing occurs when the polymer chains have structural

regularity, symmetry, compactness and a certain degree of flexibility. 9

The influence of packing on the properties of polymers can be explained by the concept

of free volume. Free volume may be considered as the unoccupied volume by the atomic species

of the material. The bigger the free volume, the bigger the space for polymer segment mobility

and the easier it is for polymer molecules to slip from one another. Therefore free volume

determines any physical or mechanical property of a polymer that is dependent on the ability of a

polymer to physically respond or move in response to external stress.10

This has led to the idea of antiplasticizing polymers by using small compounds as

additives to fill the free volume or introduce attractive forces such as hydrogen bonds to make

polymer chains less mobile, and therefore improve stiffness and tensile strength. The early

attempts at antiplasticization involved adding low molecular weight compounds to

polycarbonates, polyesters, and poly(sulfone ether) as reported by Jackson and Caldwell in 1967.
10-13

When a low molecular weight material is added to a polymer the resultant free volume of

the system, f, can be described by the relationship

f = V1f1 + V2f2 + KV1V2

where V1 is the volume fraction of the polymer and f1 is the fractional free volume of the

polymer, while V2 and f2 refer to the additive. K is an interaction parameter.12-14 The free volume

decreases when f2 is small and K is a large negative number which coincides with the additive as

a stiff polar molecule able to form strong interactions with the polymer. In such a case

antiplasticization occurs, thereby stiffening the polymer.

7
1.3 Hydrogen bonds

As mentioned before, secondary forces have influence on flexibility and therefore play a

significant part in the polymer’s properties. Polar functionalities in polymer chains or side groups

can lead to interchain secondary bonding. These forces can result in a higher tensile strength and

melting point. These hydrogen bonds are the reason for the high tensile strength and melting

point of polyacrylic acid, nylon 6, and polyamide-imide. (Table 1.1) Polyamide-imide and nylon

6 both contain amide and carbonyl groups and polyacrylic acid contains hydroxyl groups that can

form hydrogen bonds between adjacent chains.14

Table 1.1 Typical Tensile Strength, Elongation and Tensile Modulus of Polymers.

Ultimate Tensile Strength Elongation Tensile Modulus

Polymer Type
(MPa) (%) (GPa)

Acrylonitrile Butadiene Styrene 40 30 2.3

Polyacrylic Acid 70 5 3.2

Nylon 6 70 90 1.8

Polyamide-Imide 110 6 4.5

Polycarbonate 70 100 2.6

Polyethylene, HDPE 15 500 0.8

Polyethylene Terephthalate (PET) 55 125 2.7

Polypropylene 40 100 1.9

Polystyrene 40 7 3

To propagate a crack in a polymeric material, energy must be available to at least equal

the surface energy of the two new surfaces produced by the growth of the crack.15 If attractive

8
 forces such as hydrogen bonds are present, part of the available crack energy G will also be

dissipated to break the hydrogen bonds. This means to increase the crack length, a greater

amount of crack energy is needed because part of it, which is equal to the hydrogen bonding

energy, H, is spent to disrupt the hydrogen bonds. (Figure 1.5)

N C
Crack N C H O
Energy G Crack
H O
Q = H bonding energy Energy G - Q
O H
C N O H
C N

Figure 1.5 Dissipation of energy through disruption of hydrogen bonds.

1.4 Related Studies

Since epoxy resins are brittle yet used as matrices for composites, several studies about

improving their mechanical properties have been conducted. Modifying polymers by the use of

an additive is more cost effective and flexible than switching to a more expensive polymer due to

the range of additives that can be formulated. Therefore, numerous studies have been conducted

to develop additives that improve the physical and mechanical properties of epoxy resins. Many

antiplasticizer additives first reported were characterized by their bulky, stiff structure due to the

idea that stiffening is governed by the ability to fill free volume, thereby reducing chain mobility.

Haldankar reported that a compound that has a flat, compact structure and has a polar

group like the phthalimide group in N-(2,3-epoxypropyl) phthalimide is an effective

antiplasticizer in the diglycidyl bisphenol-A (DGEBA, EPON 828) – methylenediamine resin

system because it can facilitate good packing.16 In the same paper, the dependence of modulus

9
on free volume of the epoxy resin system was reported. The modulus increased as the free

volume decreased. The free volume was calculated as the difference between specific volume

and occupied volume, with the occupied volume being determined by the extrapolation of the

rubbery coefficient of thermal expansion data to zero Kelvin.

McLean reported successful development of a range of additives that improve the

strength (up to 60%) and stiffness (up to 70%) of amine cured epoxy resins, as well as improving

the ability of the specimens to yield before fracture using EPPHAA (Figure 1.6) as a

representative of the series, which is a reaction product of epoxyphenoxy propane and 4-

hydroxyacetanilide.17 However, there were decreases of glass transition temperatures in the

epoxy resins. The fracture toughness values for EPPHAA-containing samples were strongly

strain-rate dependent. There was a significant increase in the toughness at low testing rates

however.

NH

O O

OH

Figure 1.6 Chemical Structure of EPPHAA

In another paper, Garton, et al. reported that EPPHAA and VCDHAA (a reaction product

of vinylcyclohexene dioxide and 4-hydroxyacetanilide) increase the tensile modulus of

conventional epoxy-amine systems by over 60% and tensile strength by over 50% while

producing a ductile mode of failure.18 They found a reduction in the free volume by adding these

compounds to the resin system at low strains and that such hinders polymer segmental motion

10
and so increases the modulus. However, resin systems also exhibit a very low Poisson’s ratio and

strains about 5% cause an increase in free volume sufficient that ductile failure can occur. It was

also reported that the coefficients of thermal expansion and water uptake of the resins were

reduced.

However, it was reported by Zerda that a small, non-aromatic molecule, dimethyl methyl

phosphate (DMMP) was still capable of enhancing mechanical properties of the diglycidyl ether

of bisphenol-A (EPON 825 from Shell) through antiplasticization.19 It was found that 10 pph

yielded maximum mechanical properties enhancements. Both the tensile strength and modulus

increased by 2%. It was also reported that the introduction of DMMP resulted in flammability

enhancements.

On the other hand, Don described an antiplasticization behavior in the polycaprolactone

(PCL)/polycarbonate (PC) – modified epoxy system, cured with an aromatic amine up to 15

parts modifier.20 This means that a high molecular weight polymer can also serve as an

antiplasticizer in the same manner as a low molecular weight compound. The initial modulus

increased and the fracture toughness and the elongation at break decreased with the addition of

the PCL/PC modifier with only a slight decrease in glass transition temperature with modifier

content up to 15 phr.2 It is found in his research that the formation of hydrogen bonding between

the carbonyl groups of PCL/PC and the hydroxyl groups in the epoxy leads to antiplasticization.

It is thought that a strong interaction is probably leading to a decrease in the free volume of the

matrix. The FTIR analysis indicated appreciable hydrogen bonding between the carbonyl groups

not only in PC but also in PCL with the hydroxyl groups in the epoxies.

In general, an additive, no matter how small or large, bulky or not can still act as an

antiplasticizer as long as it either has strong interaction toward the polymer or can fill the free

11
volume. And also, unfortunately, improving one property of a resin can be achieved sometimes

only at the expense of another.15,16 Usually, the use of an additive is very property-specific in

nature.

1.5 Controlling Average Chain Length of Oligomers

Synthesizing oligomeric additives with multi-hydrogen bonding capable functionalities of

different lengths can be achieved by using a concept introduced by Carother in step-growth

polymerization. The average chain lengths of polymers or oligomers can be controlled by

adjusting the stoichiometric mole ratios of the reactants.

In a linear polymer composed of equimolar mixtures of two monomers, the number

average degree of polymerization, X n (which relates to average chain length) is given by the

Carother’s equation9:

1
Xn = (1)
1− p

where p is the extent of reaction. If one of the monomers is stoichiometrically in excess, the

relationship between the extent of stoichiometric imbalance (r) and X n , for this type of reaction

is given by the modified Carother’s equation:

1+ r
Xn = (2)
1 + r − 2rp

where r is the mole ratio of functional groups of monomers or reactants. If p 1, that is the

reaction approaches completion or loss of all of one type functional group, the modified

Carother’s equation relating X n to r simplifies to

1+ r
Xn = (3)
1− r

12
 Based on this equation, the average chain length can be estimated by adjusting the

stoichiometric imbalance, r.

The number average molecular weight, M n of the polymer is calculated by multiplying

the number average degree of polymerization by the molecular weight, M o , of the repeating unit.

M n = X nMo (4)

If a diamine and a dicarbocylic acid or diacid chloride are used as monomers in a

condensation reaction, using this idea, oligomeric amides of different lengths can be made.

1.6 Intrinsic Viscosity

The viscosity of a polymer solution is dependent on the concentration and the average

molecular size of the sample and therefore the molecular weight of the polymer.

The intrinsic viscosity, also known as limiting viscosity number [η ] , of a polymer gives a

measure of the volume of the solvated polymer coil. It constitutes an accepted marker of chain

length which may be converted to an absolute value of molecular weight if Mark-Houwink-

Sakurada constants are available.21

The viscosity average molecular weight, M v , is related to viscosity through the Mark-

Houwink equation, [η ] = KM vα , where [η ] is intrinsic viscosity for the polymer/solvent system

and the α and K are empirical constants for the particular system where α is dependent on the

polymer-solvent pair and temperature.22

The intrinsic viscosity number is the limiting value of the specific viscosity/concentration

ratio extrapolated to zero concentration. To measure it, viscosities at different concentrations are

determined and then viscosity at zero concentration is extrapolated.

13
 Experimentally, [η ] can be determined by measurements of flow times of solvent (to)

with a series of dilute polymers of known concentration (tc) in a viscometer. Specific viscosity is

calculated as follows:9

ηc − ηo tc − to
η sp = = (1)
ηo to

Based on the Huggin’s equation

η sp 2
= [η ] + k 1 [η ] c (2)
c

where c is the concentration of dilute polymer solution and k1 is a positive constant. The intrinsic

η sp
viscosity can be determined by plotting against c and extrapolating to zero concentration.
c

When [η ] is determined, the Mv can then be calculated using the Mark-Houwink equation

if the empirical constants are known. However, based on the equation, even without knowing the

values of these constants, it can be said that when [η ] increases Mv of the polymer also increases.

1.7 Mechanical Properties

How a resin matrix in a composite responds to external stress is a huge concern in the

aerospace industry. Mechanical testing includes, amongst other tests, the measuring of ultimate

strength, Young’s modulus and fracture toughness. Ultimate strength is defined as the maximum

tensile stress which a material is capable of developing. Stress is defined as the intensity

(measured per unit area) of the internal distributed forces, or components of force, which resist a

change within a body.23 It may be calculated based on the original dimensions of the cross

section of the body. The modulus of elasticity or Young’s modulus, E, a measure of stiffness, is

the ability of a material to resist deformation when stress is applied. It is represented by the slope

of the initial straight segment of the stress-strain curve obtained from a uniaxial tension test.

14
(Figure 1.7) Strain is the deformation of a material’s dimensions when stress is applied or

simply, elongation.

These properties can be measured by stress-strain tests, the most common of which is the

uniaxial tensile test. In stress-strain tests the buildup of force is measured as the material is being

deformed at a constant rate. The tensile test used in this research is described in the American

Society for Testing and Materials (ASTM) D638 -02 (Type IV) method.24
Stress

Yield Stress

Strain

Figure 1.7 An example of a stress-strain Curve. The slope of the straight initial part of
the curve “a” is taken as the Young’s modulus.

In general, plastics that are:

a. Soft, weak – have low modulus of elasticity, yield point and elongation at break.

b. Hard, brittle – have high modulus of elasticity, no well defined yield point and low

strain at break.

15
 c. Soft, tough – have low modulus of elasticity, low yield point and high strain at break

d. Hard, strong – have high modulus of elasticity, yield point and moderate stress and

strain at break

e. Hard, tough – have high modulus of elasticity, yield point, stress and strain at break.

Brittle failure, otherwise known as fracture starts from nucleation and propagation of

imperfections such as micro and macro cracks. These cracks can propagate, that is, to increase its

surface area if there is sufficient energy to form new surfaces. The energy needed to form new

surface is called fracture energy.20 The fracture energy needed for the formation of a new

fracture surface is defined as

δτ = GδS (1)

Where G is the energy released per unit area of the crack (rate of elastic strain energy release)

and δS the crack growth increment. .

There are different techniques used to measure fracture toughness and each uses a

different geometry. They are the double-cantilever beam, impact test and compact tension. This

research employed the use of compact tension for measuring mode-1 fracture toughness (opening

mode).

1.8 Overview of the Study

The goal of this research was to synthesize additives that can enhance the mechanical

properties of the MY720-DDS resin system. The additives would have functional groups which

can form hydrogen bonds. It was expected that these additives will fill free volume and that

added hydrogen bonds would yield additional attractive forces to the hydroxyl group of the

epoxies thereby antiplasticizing the resin system. It was also hoped that these hydrogen bonds

16
would act as energy absorbers during crack propagation thereby increasing the fracture

toughness of the resin system.

The type of compounds that were explored were short chain amide oligomers since the

amide functional group has a carbonyl and N-H group that can form hydrogen bonds. The

additives were designed to be amine terminated so that they could react with the epoxies of the

resin.

The first part of the research was spent on exploring amine-terminated nylon-like

oligomers produced from reacting non-aromatic diacid chlorides and diamines while the second

part was spent on exploring mixed oligomeric amides produced from reacting non-aromatic

diacid chlorides and aromatic diamines. This is the general structure of the additives that were

used in this research:

where n= 3-9.

Different types of oligomers were made by varying the monomers used and different

oligomer lengths were made by adjusting the stoichiometric imbalance of the monomers. The

additives were characterized by FTIR and NMR. The variation of average chain lengths and

average molecular weight were verified via intrinsic viscosity experiments and gel permeation

chromatography, respectively.

The effects of the additives on modulus and strength were studied, as well as how the

properties change at various loads through tensile testing and on fracture toughness through

compact tension. The glass transition temperatures and softening temperatures of the resins were

studied by dynamic mechanical analysis and thermomechanical analysis. The degradation of the

17
resins with temperature was conducted through thermogravimetric analysis. And lastly, how the

additives affect the kinetics of the resin curing was studied by differential scanning calorimetry.

18
 CHAPTER 2
EXPERIMENTAL

2.1 Introduction

The properties of additive-containing resins were compared to those of a control resin.

This control resin is made from MY720 and the curing agent DDS. The formulation was based

on a commercial resin called 934 Resin, which was known to contain MY720, DDS and traces of

the catalyst, BF3. The DDS in 934 Resin is slightly in excess to make sure all epoxy

functionalities in the resin are reacted to form a network, and also to prevent etherification

reactions. The 934 Resin contains a catalyst, BF3, which enables the resin to cure at a fast rate

even at low temperatures. Since in this study, there was no need to cure the resins at low

temperatures, BF3 was not used but higher curing temperatures were employed. The properties of

the cured resin proved to be similar to those of the resin cured with a catalyst. It is stiff, has high

glass transition temperature and is somewhat brittle.

2.2 Mixing of Resin and the Curing Agent

It was necessary that the base resin mixture was formulated in order to achieve best

properties so that a proper comparison can be made with the additive enhanced resin mixture. In

this research, three methods of preparing the base resin (control resin) were attempted over a

large number of experiments.

1. The DDS powder was added to the resin in a paddle mixer and the mixture was heated.

2. The DDS powder was added to the resin in a high shear mixer and the mixture was heated.

3. The DDS powder was dissolved in acetone and added to the warmed resin in a high shear

mixer. A stir bar was then added, and the mixture was stirred and warmed in a heated oil bath

19
 under vacuum. The temperature of the resin was raised to keep the mixture fluid as acetone

was lost by vacuum pumping. Acetone was chosen to be the solvent in this method because it

is the only low boiling point solvent in which it would dissolve.

It was observed in Methods 1 and 2 that the DDS did not mix homogeneously with the

resin. Resins made from Method 1 and 2 have undissolved particles which would act as nuclei

for crack propagation. On the other hand, it was observed that Method 3 produces a

homogeneous mixture and at 140 oC it is flowing and can be poured into a mould. Method 3,

therefore, was used as the mxing method for all resins in this study.

2.3 The Additives

The molecules that were synthesized to be used as additives were aliphatic amide nylon-

like oligomers and mixed aliphatic-aromatic amide oligomers. Their linkages, -CONH- can

hydrogen bond and they can be synthesized in a way that they are going to be amino group-

terminated (-NH2) so that they could react with the epoxy groups of the resin.

The additives synthesized in this research were based on the reaction product of diamines

and aliphatic linear diacid chlorides. The peptide linkage may be produced in a number of ways.

However, the reaction between an aliphatic amine and an acid chloride is one of the simplest and

easiest to control experimentally. The reagents are simply mixed at room temperature with

solvent and a strong bulky base to remove the HCl by-product. The reaction is inexpensive, a

low temperature reaction and yields hydrogen bonding capable and thermally stable amide

oligomers. The reaction is illustrated in Figure 2.1 below.

20
 O

C H2N

Cl

(-HCl)

O H

C N

Figure 2.1 Reaction of amine and acid chloride to form amide.

A representative of the additives made for this work - the reaction product of a C10

diacid chloride, i.e. a diacid chloride with ten carbon atoms, and a C12 diamine, that is a diamine

with twelve carbon atoms - is reproduced below in Figure 2.2. This additive is classified as a

saturated oligomer 10,12 where m is the number of repeating units.

[
O H

H
N

H O
N
[ N

H
H

m
Figure 2.2 Representative repeat unit for the 10,12 oligomer prepared using a C10
diacid chloride and a C12 diamine.

2.4 Synthesis of Additives

2.4.1 The Materials

The materials used in the additive syntheses are the following: 1,6-diaminohexane (98%,

Acros Organics), 1,8-diaminooctane (98%, Acros Organics), 1,10-diaminododecane (97%,

Aldrich), 1,12-diaminododecane (98%, Aldrich), p-phenylenediamine (99%, Acros Organics),

m-phenylenediamine (98%, Aldrich), methylenedianiline (97%, Acros Organics), adipoyl

chloride (98%, Acros Organics), sebacoyl chloride (97%, Aldrich), 1,12-dodecanedioyl

21
dichloride (98%, Acros Organics), N,N-dimethylacetamide (99%, Acros Organics) and 1,8-

diazabicyclo[5.4.0]undec-7-ene (98%, Aldrich).

2.4.2 Synthesis of Nylon-Like Oligomers

The system was flushed with nitrogen to remove water and water vapor. The diamine was

dissolved in an aprotic solvent, N,N-dimethylacetamide (DMAc) in a flask. A bulky base, 1,8-

diazabicyclo[5.4.0]undec-7-ene (DBU) was added. The diacid chloride in the same solvent was

added slowly with stirring. The reaction was allowed to proceed for at least an hour. Finally, the

reaction mixture was removed and added to a large excess of acidified distilled water to

precipitate the product. The product was filtered off and added to fresh water, then stirred

overnight to remove impurities, then filtered and vacuum dried.

The diamine was always in excess so that the oligomer was amine terminated and can

easily react into the polymerizing resin mixture. The number of moles of the deficient

functionality , in this instance, diacid chloride in the reaction flask is denoted as “A” and the

number of moles of diamine, the excess functionality, is “B”. Assuming that the reaction has

proceeded to completion, the relationship between the extent of stoichiometric imbalance (r) and

1+ r
their theoretical average chain length, X n , for this class of reaction is X n = , as discussed in
1− r

Chapter 1.5 .The average molecular weight is calculated as, M n = X n × M o , where Mo is the

average of the masses of the reacting monomers.

e.g. If A= 1 and B= 1.25

r = A/B = 0.8

and therefore, Xn= 9

22
 The nylon-like oligomers synthesized are listed in Table 2.1 below with their

corresponding theoretical average chain lengths and their theoretical average molecular weights.

Table 2.1 List of nylon-like oligomers used as additives.

#C in moles moles
#C in r theoretical Theoretical
material Diacid diacid diamine
Diamine (=A/B) Xn Mn
Chloride "A" "B"
(1+r)/(1-r) Xn*Mo

oligomer 6,6 6 6 1 1.75 0.57 3.67 415.25

oligomer 6,6 6 6 1 1.5 0.67 5 565.74

oligomer 6,6 6 6 1 1.4 0.71 6 678.89

oligomer 6,8 6 8 1 1.5 0.67 5 635.87

oligomer 10,8 10 8 1 1.5 0.67 5 776.13

oligomer 6,12 6 12 1 1.75 0.57 3.67 569.68

oligomer 6,12 6 12 1 1.5 0.67 5 776.13

oligomer 10,12 10 12 1 1.75 0.57 3.67 672.63

oligomer 10,12 10 12 1 1.5 0.67 5 916.39

oligomer 12,12 12 12 1 1.75 0.57 5 724.11

oligomer 12,12 12 12 1 1.5 0.67 5 986.52

2.4.3 Synthesis of Mixed Aliphatic-Aromatic Amide Oligomers

The mixed aliphatic-aromatic oligomers were made in the same way as the aliphatic

oligomers were synthesized except for PPDA which had to be mixed with the solvent DMAc and

heated to dissolve because it was less soluble in the chosen solvent.

The diacid chloride used was sebacoyl chloride (C10) and there were three diamine

compounds used to react it with, namely, p-phenylenediamine (PPDA), m-phenylenediamine

(MPDA) and 4,4’-methylenedianiline (MDA). See Figure 2.3 for their chemical structures.

23
a. b. c.
H2N NH2
H2N NH2

H2N NH2

Figure 2.3 The chemical Structures of the diamines a. p-phenylenediamine, b. m-

phenylenediamine and c. 4,4’-methylene dianiline.

The mixed amide oligomer additives that were synthesized are listed in Table 2.2 below.

Table 2.2 Synthesized mixed amide oligomers.

#C in moles moles
r theoretical Theoretical
Additive Diacid diacid diamine
(=A/B) Xn Mn
Chloride "A" "B"
(1+r)/(1-r) Xn*Mo
MPDA10 10 1 1.75 0.57 3.67 503.41
MPDA10 10 1 1.5 0.67 5 685.84
PPDA10 10 1 1.75 0.57 3.67 503.41
PPDA10 10 1 1.5 0.67 5 685.84
PPDA10 10 1 1.25 0.57 9 1234.51
MDA10 10 1 1.75 0.80 3.67 668.77
MDA10 10 1 1.5 0.67 5 911.14
MDA10 10 1 1.25 0.80 9 1640.04

2.5 Preparation of Resin with Additives

It was found that the additives did not easily dissolve into the resin mixtures. To ensure

dissolution, the MY720 resin, additive and acetone (solvent) were mixed at room temperature

using a high shear mixer for about one hour. Once the additive was mixed thoroughly with the

resin to form a homogenous mixture, the curing agent, DDS, was added and the mixture was

stirred again using the high shear mixer. Then the mixture was heated in an oil bath under rotary

pump vacuum to remove acetone. The temperature of the mixture was gradually increased so

that the mixture remained fluid as acetone was being pumped out. Once the temperature reached

140 oC, the resin was poured into a mould and cured.

24
2.6 The Cure Cycle

After the resin and curing agent have been mixed and heated, the mixture is then poured

into a stainless steel mould and then cured.

As discussed in Chapter 1, the epoxy-amine reaction involves two main reactions. First,

is the reaction of a primary amine with an epoxy group to form a secondary amine and the

second one is the reaction of the secondary amine with an epoxy group which is a slower

reaction and needs a higher temperature to form the network. The cure cycle of the resin used

two heating steps at substantially higher temperatures.

Two cure cycles were tried in this research. The first one was carried out by an initial

cure cycle of 2 h @ 140oC followed by 2h @ 200oC in a programmable, digital, forced air oven.

It was shown by DSC that it only cures the resin to 90%. The cure percentage did not meet the

acceptable degree for stability purposes which is around 95%26 so another cure cycle was

attempted, which was 2 hrs at 140oC and the second heating step was still at 200oC but prolonged

for 4 hrs. This cure cycle resulted in 97% resin cure and thus was used in all subsequent

φuncured − φ cured
experiments. The % cure was calculated using the following formula: x100 = %
φuncured

cure, where Фuncured (535.6 J/g) is the heat required to fully cure an uncured resin and Фcured is the

residual heat of cure determined by DSC (53.9 J/g for resin cured at 2 hours at 140 oC and 2

hours at 200 oC and 17.1 J/g for resin cured for 2 hours at 140 oC and 4 hours at 200 oC).

2.7 Intrinsic Viscosity Measurements

In order to determine whether or not there was some control achieved over the average

molecular weight of the polyamide oligomer by adjusting the ratio of diacid to diamine, oligomer

fractions were characterized by dilute solution viscometry.

25
 About 1 g of sample was dissolved in either filtered 90% formic acid (for nylon-like) or

filtered m-cresol (for aromatic additives) in a 25 mL volumetric flask. The flask of solution along

with a stock solution of 90% formic acid and Ubbelohde viscometer (Figure 2.4) were then

placed in a water bath held at 25oC. A 10 mL portion of the solution was placed in the

viscometer through tube 1. Tube 3 was then covered, while the solution was sucked from tube 2

using a rubber bulb until the solution filled the bulb above line A. The stopper at tube 3 was then

released and at the same time, the suction from tube 2 was released. The solution flows back

down and flow time of the solution from line A to line B, t, was taken. This process was done in

three trials and the average flow time was calculated.

The solution in the viscometer was then diluted by adding 2 ml of the solvent

quantitatively. The solution was allowed to mix and the temperature to equilibrate by blowing air

using a rubber bulb. The same process of elution was done in three trials and the average flow

time was calculated. The solution was successively diluted with 2 ml of solvent and for each

dilution the time of flow was measured for 3-4 times to determine the average flow time at

different concentration of additive.

1 2 3

Figure 2.4 The Ubbelohde dilution viscometer.

26
2.8 Molecular Weight Determination

The molecular weight and polydispersity index, that is, a measure of molecular weight

distribution of polymers and oligomers can be determined by GPC. This technique involves

separating the polymers or oligomers based on their hydrodynamic size. The sample solution is

passed through a column packed with a porous material. The smaller molecules can penetrate

more into the pores and therefore are more retained and eluted at a longer time. The larger

molecules on the other hand, can penetrate less into the pores and therefore passes through the

column in a less hindered route and are eluted faster.

This technique is done by first performing a calibration using a series of standards of

known molecular weight. The retention time for these standards is then used to create a

calibration curve. The standard used in the GPC was polystyrene. The additives were studied via

GPC using DMAc with 5 g/L LiBr as eluent, with PSS GRAM 10:m, 30Å, 8x50mm as

precolumn, PSS GRAM, 10:m, 30 Å, 8x300mm, PSS GRAM, 10:m, 100 Å, 8x300mm and PSS

GRAM, 10:m, 3000 Å, 8x300mm as columns, with temperature held at 70 oC and flow rate at

1.0 mL/min.

2.9 Fourier-Transform Infrared Spectroscopy

Infrared spectroscopy can often give an idea of what functionalities are present in

additives. The presence of the amide I band, the amide carbonyl peak (a strong peak that usually

appears around 1640 cm-1) and amide II band (the C-N stretching peak for an amide, a medium

band which appears around 1540 cm-1) were all sought to confirm the formation of amide

groups. This technique can also determine if there were unreacted monomer reactants. If

unreacted acid chloride exists a peak around 1815-1770 cm-1 would be observed or if hydrolyzed

unreacted acid chloride is present, a peak around 1640 cm-1 would be observed.

27
 About 3 mg of additive was mixed with 300 mg of pre-dried KBr. The mixture was

pressed into a disc then subjected to FTIR using a Nicolet Avatar 360 FTIR.

2.10 Nuclear Magnetic Resonance (NMR)

NMR is an important tool in elucidating chemical structures of organic compounds. The

synthesized additives are fairly large, thus insoluble in most NMR solvents. However, the

additives were soluble in trifluoroacetic acid-d1 and thus this solvent was used for all H-NMR

and CNMR runs.

Approximately 0.1 mg of additive was dissolved in about 1.0 mL of deuterated

trifluoroacetic acid and analyzed in a Varian Mercury 300MHz instrument. Samples were

subjected to both 1H and 13C NMR spectroscopy. The results were compared to those generated

by the NMR spectra predictor, ACD/Labs. The chemical structure is drawn using the software

and the NMR spectra can be predicted by the software using HOSE code and neural net

algorithms to provide the most chemical shifts. It can also predict positions of chemical shifts in

different solvents.

2.11 Tensile Testing

Tensile testing is considered as the most fundamental type of mechanical test that can be

performed on a material. It is simple and relatively inexpensive. By pulling, the material reacts to

forces being applied in tension and its strength and its extension can be measured.

In preparing tensile specimens, the heated uncured resin (refer to Chapter 2.3) was

poured into a dogbone-shaped stainless steel mould, which was pre-treated with silicone mould

release agent and cured (refer to Chapter 2.5). The dimensions of the dogbones are shown in

Figure 2.5 and Table 2.3, in accordance with ASTM D638 Type IV.25

28
 .

Figure 2.5 Dogbone dimensions of ASTM D638 Type IV.

Table 2.3 The dimensions of the dogbones.

Dimensions mm

W- Width of the narrow section 6

L – Length of the narrow section 33

WO – Width overall 19

LO – Length overall 115

G – Gauge length 25

D – Distance between grips 65

R – Radius of fillet 14

RO 25

T - Thickness 3

The sides of the dogbones were smoothened using very fine aluminum oxide sandpaper

to achieve uniformity on their surfaces and eliminate imperfections especially on their thin

29
bodies. The width and thickness of the narrow section were measured using a vernier caliper.

The dogbone specimen was pulled using an Instron Tensile Tester machine. A clip-on strain

extensometer was used to measure strain. The specimen was stretched at a speed of 5 mm/min

[about 0.2 in. /min] in accordance with ASTM D638-02. Force and elongation were measured

and used to calculate stress (σ) and strain (ε). Stress (σ) was calculated by dividing the force at

each time step by the cross sectional area of the narrowest section of the specimen. Strain (ε) was

obtained by measuring the extension of a gage length of 1 inch.

2.12 Fracture Toughness Test

Fracture toughness is a material’s property which describes the ability of a material to

resist fracture. It is indicated by the amount of energy required to propagate a preexisting flaw. It

is very important since flaws are not completely unavoidable in the processing and flaws lead to

premature fracture.

To determine the fracture toughness of the resins, compact tension specimens were made.

The resins were cured the same way as the tensile specimen but cured in a rectangular mould

with a thickness of 1/4 inch. The cured resins were then cut using a band saw and press drilled to

form rectangular-like specimens as shown in Figure 2.6 using the same dimensions described by

Cottington.27

30
 Thickness: 0.64- 1 cm, 0.3 ≤ a/W ≤ 0.7 cm, hole diameter: 0.4 -0.5 cm

Figure 2.6 Dimensions of compact tension specimen.

The specimens were tested using the same Instron Tensile tester for tensile testing but

using fixtures at a testing rate of 0.5 in/min .The force at break of each specimen was recordeded

to calculate the fracture energy in J/m2 using the equation below.

Y 2 P@a
FractureEnergy (G ) =
EW 2b 2

Where Y - Geometrical factor

P - load at break in pascals (N/m2)

a - Crack length in meters

E - Elastic modulus in pascals (determined from tensile test)

W- Hole to edge distance in meters

b - Thickness in meters

31
The fracture toughness was then calculated as (√(E*G)) with units of Pa*m1/2.

2.13 Dynamic Mechanical Analysis

Dynamic mechanical analysis is a thermo analytical technique that can be used to study

viscoelastic properties of a material. The sample is subjected to a low sinusoidal stress and the

resulting strain is measured. The storage modulus and loss modulus can be determined as a

function of temperature or time as the polymer is deformed under the oscillating force. The shear

elastic modulus (G’) is used to determine the stiffness of the material.28 The shear loss modulus

(G”) sheds light on the viscous damping and energy dissipation properties of the material. DMA

is also used to determine the glass transition temperature or α transition of a material.

Cured samples were shaped into 1 inch by 0.25 inch and were sent to National Institute

for Aviation Research (NIAR) for DMA. The samples were tested using TA DMA Q800 with a

test fixture of 20 mm, 3-point bent clamp with 15 micrometers oscillating amplitude. Samples

were tested at 1 Hz at a ramp rate of 5 ºC/min from 100 ºC to 300 ºC to determine the alpha

transition and -140 ºC to 30 ºC to determine the beta transition. In DMA, an oscillating force is

applied to a sample of material and the resulting displacement of the sample is measured.

The sample deforms under the load. From this, the stiffness of the sample can be

determined, and the sample modulus can be calculated. By scanning the temperature during

DMA, the abrupt change in modulus due to the transition from glassy to rubbery state, the glass

transition temperature is determined.

2.14 Thermo Mechanical Analysis

Thermo Mechanical Analysis is used to determine the glass transition temperature and

thermal expansion coefficients of materials. It measures the physical dimension change of a

sample due to thermal expansion or indentation at the softening point as a function of

temperature and time. The glass transition (Tg) of a polymer corresponds to the thermal transition

32
of the material from a brittle glassy state at lower temperature to a rubbery state at higher

temperatures. By interpolating the straight line portions of the graph, a value for Tg can be

obtained.

Samples of the cured resin were sent to National Institute for Aviation Research. The

samples were shaped into little squares with the dimensions of 0.25 in. x 0.25 in. and tested using

TA TMA Q400 at a constant load of 1 N and ramped from 100-280 oC, at 5 oC/min.

2.15 Thermogravimetric Analysis

It is important to study how a material degrades with temperature in order to determine

the range of temperatures at which the material is stable. The effect of the additives on the

degradation pattern of the resin was studied by thermogravimetric analysis (TGA). In this

method, the weight of a sample is measured as the material is heated. The percentage weight loss

is recorded against sample temperature. The weight loss curve can be easily differentiated to

achieve a vs T rate curve.

The samples were prepared by pulverizing using a cryogenic grinder and were sent to

NIAR for TGA. Each sample was tested by placing on a basket-shaped platinum pan and heated

from 30 oC to 750 oC at heating rates of 1, 2, 4, 7 and 10 oC/min under nitrogen atmosphere.

2.16 Differential Scanning Calorimetry

Differential Scanning Calorimetry (DSC) measures the heat flow that accompanies phase

transitions and chemical reactions. In this research, DSC was used to study the kinetics of resin

cure by determining the relationship between degree of cure (α) and the rate of cure (dα/dt) of

the samples as a function of temperature and calculating the activation energy for the cure

reaction (Ea).

The general formula for rate of reaction for epoxy cure is;28

33
 dα
(1) = kf (α )
dt

where α is the degree of cure, t is the reaction time, k is the reaction constant and f(α) is a

function of degree of cure. Usually, k shows an Arrhenius type temperature dependence

 − Ea 
 
 RT 
(2) k = Ae

where A is the pre-exponential factor, Ea is the activation energy of cure, R is the universal gas

constant (8.314 J/mol K) and T is the temperature in Kelvin.

Therefore,

 − Ea 
dα  
= A f (α )e  RT 

(3) dt

However,

dα dα
(4) =Φ
dt dT

where Φ is the heating rate. Substituting equation 4 into 3 gives,

− Ea
dα
(5) Φ = Af (α )e RT
dT

Taking the logarithm of the above variables results gives,

dα E
(6) ln{Φ } = (ln A + ln f (α )) − a
dT RT

dα
At a constant α, ( lnA + ln f (α) ) is a constant and ln{Φ } becomes proportional to 1/T.
dT

dα
Therefore in ln{Φ } vs 1/temperature plots, m= -Ea/R
dT

The activation energy of cure can then be estimated for values of α from 0.05 to 0.95, thus can

show any changes in the reaction mechanism at different α’s.

34
 The effect of the additives on the kinetics of the curing of the resin was studied. About 7-

10 mg of the uncured resin was loaded in a T-Zero aluminum DSC pan and sealed with T-Zero

aluminum lid. For all DSC experiments the sample was equilibrated at 30 oC and then ramped

from 30 oC to 350 oC at a specific rate using TA Q2000, which was pre-calibrated with a

sapphire calibration disc. This process was done for the following heating rates ranging from 1-

20 oC/min. To verify whether the resin was fully cured after the first heating, the resin sample

was cooled down to 30 oC at a rate of 30 oC/min and reheated to 400 oC at 10 oC/min. No excess

exotherm was observed for all samples, so it was concluded that all resins were fully cured after

the first heating.

TA universal analysis software was used to analyze DSC results. The degree of cure (α)

was calculated by dividing the area of the cure exotherm at that point by the total exotherm area

times 100. The degree of cure intervals of 0.05 was differentiated with respect to time using

Origin software, which yielded rate of cure at that value of α. Plots of rate of cure vs temperature

were constructed for each heating rate using Microsoft Excel. Summary graphs for degree of

cure (α) and rate of cure vs temperature were then generated using Microsoft Excel to determine

the effect of heating rate on the above two factors. Logarithms of rate of cure vs 1/temperature

plots for each degree of cure ranging from 0.05 to 0.95 were constructed. Activation energy of

the curing at different values of α was then calculated using the gradients of these plots.

35
 CHAPTER 3
RESULTS AND DISCUUSION: NON-AROMATIC ADDITIVES

3.1 Synthesis of Oligomers

The first additives synthesized in this research were a set of nylon-like molecules based

on the reaction products of aliphatic linear diamines and aliphatic linear diacid chlorides. The

oligomers were synthesized by using the following representative scheme shown in Figure 3.1.

Cl
+
H 2N DMAc
Cl
NH 2
DBU
o

N
H 2N H H
N N + DBU•HCl
H H

O n

Figure 3.1 Scheme for the synthesis of Nylon 6,6

The amine reactant added to the reaction mixture was in slight excess. Hence, the

oligomer products were amine terminated at both ends. Since control over stoichiometry was a

crucial aspect of the reaction, the conditions of the synthesis were controlled in such a way that

none of the monomers would be lost to side reactions.

Since one of the monomers is a diamine and the other monomer is a diacid chloride,

using a protic solvent in the synthesis was not an option. The acidic hydrogen of the solvent

would react with the amine and the diacid choride is very sensitive towards nucleophiles. The

solvent used DMAc, is an aprotic polar solvent. DMAc was a good choice since it hydrolyzes in

acidified water and therefore can be washed away easily from the oligomer product.

36
 The addition of base, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was needed to react

with HCl produced in the reaction to prevent the amino groups from reacting with the HCl so

produced to form salts that will not react with the acid chloride. Furthermore, if the amine chain

ends are present as the salts, this would also prevent the oligomers from eventually reacting with

epoxy groups in the resin. The DBU base is very bulky and its basic nitrogen is sufficiently

sterically hindered that it will not itself react with the diacid chloride. The use of a smaller bulky

base such as triethylamine (TEA) was attempted, however the oligomers precipitated out in the

middle of the reaction leading to poor control over molecular weight. The solubility of the

oligomers in DMAc/DBU mixture was better compared with DMAc/TEA.

The oligomer produced in the reaction was isolated by precipitation by addition of

acidified water with stirring. DBU was washed off by filtering the precipitated oligomer-

acidified water mixture and additional washing with acidified water.

3.2 FTIR

The IR spectrum for nylon 6,6 Xn =6 oligomer, reproduced in Figure 3.2 (all other

spectra are shown in Appendix A) reveals a strong carbonyl amide I band at 1637 cm-1 and

medium amide II band at 1539 cm-1, which is due to C-N bending. The large peak at 3320 cm-1

also confirms the presence of N-H stretching of the amides. The medium absorption peak at 3295

cm-1 is due to amide hydrogen bonded N-H, further confirming this hypothesis.

An enlargement of the carbonyl section shows a little hump around 1750 cm-1 (Figure

3.3) This means that the additive has a negligible amount of acid impurity which was a product

of the hydrolysis of the diacid chloride. This also means that the oligomer is not acid-terminated,

and therefore, is amine-terminated.

37
 Nylon 6,6 Xn=6

2.50

2.00
Amide I
1.50
absorbance

Amide II
1.00

0.50

0.00
4000 3500 3000 2500 2000 1500 1000 500
-
wavenumber (cm )

Figure 3.2 FTIR spectrum of nylon 6,6 Xn =6.

Nylon 6,6 Xn=6

2.50

2.00

1.50
absorbance

1.00
Acid C=O

0.50

0.00
1800 1750 1700 1650 1600 1550 1500
-
wavenumber (cm )
Figure 3.3 The acid carbonyl peak in the FTIR of nylon 6,6 Xn =6.

38
 1
3.3 H NMR
13
The proton and C spectra obtained for Nylon 6,6 Xn=3.67, are reproduced below in

Figure 3.4 and Figure 3.6. All other NMR spectra are given in Appendix B.

Trifluoroacetic acid

NH

1
Figure 3.4 H NMR spectrum of Nylon 6,6 Xn=3.67

Shifts observed in the NMR spectra were compared to modelled shifts generated using

ACDLABS (9.0) software. Figure 3.5 shows the structure of Nylon 6,6 Xn=3.

O
16
9 7 5 NH 11 13 15 18 20 22 NH2
H2 N 8 6 4 3 2 12 14 NH 19 21 23 24
10 17
O
1

Figure 3.5 Chemical structure of Nylon 6,6 Xn=3 with numbered atoms.

39
 Table 3.1 Experimental and predicted chemical shifts for Nylon 6,6 Xn=3.67

Carbon number Chemical shift generated Chemical shift observed

assignment on Figure 3.5 by ACD software/ ppm experimentally in Figure
3.4/ ppm
6, 20 1.30 1.55
8,22 1.50 1.80
5,19 1.58 1.90
12 1.69 2.65
11,14 2.21 2.75
9,23 2.54 3.40
4,18 3.07 3.60

It was observed that the spectra predicted from ACD software and those that were

observed experimentally were similar, however, the peaks show up more downfield in the

experimentally determined one. However, the chemical shifts obtained using ACD software were

predicted using methanol-D as the solvent while the samples were dissolved in trifluoroacetic

acid which is a more polar solvent than chloroform and therefore the peaks were observed

further downfield.

Seven prominent peaks, excluding the peak at 11.7 ppm, which is from the solvent

deuterated trifluoroacetic acid, were observed in the experimental spectrum and are consistent

with the ACD predicted spectrum. The small broad NH peak observed at 6.85 ppm is way

downfield compared to the one predicted in ACD which is at 5.25 ppm. This is probably

observed because the NH groups in the additive forms hydrogen bonds with the solvent.

Small peaks found at 2.2, 3.5, and 3.8 ppm indicates the presence of traces of DBU.

40
 The 13C NMR spectrum (Figure3.6) of nylon 6,6 Xn = 3.67 was difficult to interpret. See

Figure 3.6, Based on the structure in Figure 3.5 the 8 methylene carbon atoms are expected to be

seen in the spectrum. However, the sample was a mixture of nylon 6,6 oligomers. The Xn was

3.67 but this is only the theoretical average length. This means longer and shorter chains are

present in the mixture. And the presence of longer chains result in the appearance of quite a

number of peaks in the spectrum. However it can still be pointed out that the sample has a

carbonyl peak at 181 ppm which is quite high compared to a normal amide carbonyl. The

downfield shift is caused by extensive hydrogen bonding among the carbonyl groups. The peak

at 44.96 ppm is the peak for carbon atoms next to nitrogen atoms and the peak at 36.21 ppm is

the peak for the carbon atom next to a carbonyl. The peaks at 50 ppm and 55 ppm are due to the

pressence of DBU which means that DBU was not completely removed by washing.

Nylon 6,6 Xn=3.67

4000

3500

3000 Trifluoroacetic
acid
2500
absorbance

DBU
2000

1500

1000

500

0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
Figure 3.6 C NMR spectrum for Nylon 6,6 Xn=3.67

41
3.4 Solubility Test

Nylon polymer is known to be insoluble in most solvents. Its solubility is suppressed by

the polar amide groups. Molecular dissolution requires strong interaction between the solvent

and the amide groups to disrupt the inter-chain hydrogen bonding of the amide groups.

Moreover, the hydrophobic interactions of the methylene sequences must also be loosened. The

most common solvents for nylon 6,6 are strong oxy-acids such as H2SO4 and formic acid and

solvents having solubility parameters close to its own like phenols (e.g. phenol and cresols).

Nylon 6,6 possesses solubility parameters29 (Hildebrand) of δd=18.62, δp=5.11, and δh=12.28 (δ

in MPa1/2). Solubility parameters for m-cresol are δd=18.0, δp=5.1, and δh=12.9.

Because the synthesized oligomers have a range of lengths of methylene sequences and

low molecular weights they might not have the same solubility as long chain nylon 6,6.

Therefore, solubility had to be tested before performing experiments which would require

dissolution, such as intrinsic viscosity (IV). The solubility of nylon-like oligomers in 90% formic

acid and m-cresol were tested. These two are commonly used in IV experiments for nylon 6,6.

Solubility in DMF and DMAc were also of interest since DMAc was used as the solvent in the

synthesis and DMF is a close relative. All oligomers were soluble in m-cresol. This means that

the solubility parameters of the other oligomers must also be close to the parameters of m-cresol.

The solubility in 90% formic acid decreases as the methylene sequences gets longer (Figure 3.7).

The same behavior was also observed concerning the solubility of the additives in DMAc and

DMF. It is commonly known that as the polymer chain length increases, in order to maintain

solubility, the difference in solubility parameter between the polymer and solvent must be

lessened.

42
 CD CD PD PD CD CD PD PD
1 2 3 4 1 2 3 4

a. Nylon 6,6 b. Nylon 6,8

CD CD PD PD PD CD ND ND
1 2 3 4 1 2 3 4

c. Nylon 6,12 d. Nylon 10,12

PD CD ND ND
1 2 3 4

e. Nylon 12,12

Figure 3.7 Solubilities of different nylon oligomers in (1) 90% formic acid (2) m-cresol
(3) DMF and (4) DMAc. (CD = completely dissolved, PD = partially dissolved
and ND = not dissolved)

3.5 Intrinsic Viscosity

Intrinsic viscosity (IV) experiments were conducted to determine whether there was some

control of the oligomer length by adjusting the mole to mole ratio of diacid chloride to diamine.

The nylon 6,6 aditive was soluble in 90% formic acid and thus this solvent was used for IV

experiments.

Figure 3.8 shows the plot of specific viscosity divided by concentraion versus

concentration for nylon 6,6, where the y-intercept of the equation of the curve was taken as the

intrinsic viscosity of the oligomer.

43
 Nylon 6,6 Xn=6

30
Intrinsic Viscosity
25
y = 866.63x + 10.664
2
R = 0.9736
20
nsp/C

15

10

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018
C (g/ml)

Figure 3.8 Intrinsic Viscosity of Nylon 6,6 Xn=6

Since the Mark-Houwink-Sakurada parameters of Nylon 6,6 in formic acid at

25oC are known from the literature (K= 11.0 x 10-2 mL/g and a = 0.72),29 the molecular weights

of the oligomers can be estimated by using the Mark-Houwink equation, [η ] = KM va as discussed

in Chapter 1.5. However, this is not going to give the true average mass since the parameter is

experimentally determined for nylon polymers of high average masses. The α parameter gets

closer to the value of theta (θ), 0.5, as the polymer chain length is reduced. Theta is a condition at

which the polymer coils act like ideal chains, assuming exactly their random walk coil

dimensions. Corresponding molecular weights calculated from the equation using the parameters

for nylon 6,6 and the molecular weights when α =0.5 and α =0.72 are listed in Table 3.2.

Formula weight is calculated as X n x Mo, where Mo is the weight of the repeating unit.

44
 Table 3.2 Corresponding MW of Nylon 2 Intrinsic viscosities and their 6,6 oligomer.

IV MW/g MW/g Formula

Oligomer Xn (mL/g) (α=0.72) (α=0.72) Weight
Nylon 6,6 3.67 2.9283 708.67 95.38 415
Nylon 6,6 5 5.1931 2228.78 211.37 565
Nylon 6,6 6 10.6640 9398.42 574.20 678

From the results it is apparent that when either a value is used the average polymer

molecular weight or chain length increases with the theoretical X n . Therefore, we are exerting a

modicum of control over average molecular weight, M n , by adjusting the ratio of the diamine to

diacid chloride in the additive synthesis reactor.

When the α values are calculated from the intrinsic viscosities and the formula weight it

can be noted that the α parameter does approach 0.5 (Table 3.3). This further proves that

adjusting the monomer ratio indeed controls the average chain length of the oligomers. As the

X n is reduced, the α value approaches its theta (θ) value of 0.5.

Table 3.3 The calculated a parameters of the nylon 6,6 oligomers.

Oligomer Xn IV (g/ml) Formula Weight Calculated a

Nylon 6,6 3.67 2.9283 414.71 0.54
Nylon 6,6 5 5.1931 565 0.60
Nylon 6,6 6 10.664 678 0.70

3.6 Curing of Resin

Making dogbones was not a straightforward process. Sometimes the cured specimens

contained bubbles and these specimens had to be discarded. It was thought that the bubbles were

caused by residual acetone, the solvent that was used in mixing the resin and curative,

evaporating as the resin is cured in the mould. This would mean that acetone was not completely

removed by vacuum pumping prior to curing. To address this issue, three alternative methods of

45
preparing the resin mixture were tested as described in Chapter 2.2. In Method I, the MY720

resin and the DDS were heated and mixed in a paddle mixer - upon reaching 140 oC, the resin

mixture was poured into a mould. Method II uses a shear mixer instead of a paddle mixer. And

lastly, in Method III, the resin and the DDS are dissolved in acetone then heated and mixed. (See

Chapter 2.2 for more detailed procedure.) After achieving a homogeneous mixture, the acetone

was pumped off while heated until the temperature is 140 oC, poured into a mould and then

cured.

Mixing the curing agent DDS with the MY720 without a solvent turned out to be difficult

even with heating and the use of a paddle mixer or shear mixer. The mixture could not be

homogenized. The cured dogbones made by these methods had some observable undissolved

curing agent. Mixing was much easier when solvent was used (Method III). The mixture with

acetone was heated and stirred. When the temperature of the oil bath reached 140 oC and the

acetone was pumped off, the mixture became viscous but could still be poured into the mould.

The cured dogbone resin looked clear and free from undissolved particles. Tensile tests were

performed on these dogbones and their stress-strain curves were generated. An example of these

plots are shown on Figure 3.9 which are generated using the dogbones that were made using

Method III.

The slopes of the initial straight line of the curves (slope from 0% to 0.5% straight

arbitrarily chosen) were taken as the moduli and the average modulus was calculated. An

example of this is shown in Figure 3.10, i.e. from the initial part of the curve of specimen 1 of

control resin made by Method III.

46
 Tensile Testing Curves for Control Resin (Method III)

6.00E+07

5.00E+07
sp 1
sp2
4.00E+07
sp3
stress (Pa)

sp4
3.00E+07

2.00E+07

1.00E+07

0.00E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
strain (%)

Figure 3.9 Stress-strain curves of control specimens made by Method III.

Control Resin Specimen 1 (Method III)

2.00E+07

1.80E+07
1.60E+07 y = 33944286.6692x + 361418.5040
2
1.40E+07 R = 0.9997

1.20E+07
stress (Pa)

1.00E+07

8.00E+06
6.00E+06
4.00E+06
2.00E+06

0.00E+00
0.00 0.10 0.20 0.30 0.40 0.50
strain (%)

Figure 3.10 Linear initial part of the stress-strain curve of specimen 1 made by Method
III.

47
 The averages of the tensile results for the dogbones are listed on Table 3.4.

Table 3.4 The tensile results for Control, made with and without acetone as solvent.

Average
Stress at % Average Std. % Average %
Break Std.Dev change Stiffness Dev Change Strain Std. Dev Change
(Mpa) (MPa) (Mpa) (Mpa) to Break
Material
Control
Method 0.0159 0.00126
III 34.0856 1.4112 48.5179 1.6434 (1.590%) (0.126%)

Control 0.00928 0.00200

Method I 34.5058 0.7034 1.2328 30.6917 5.5058 -36.7415 (0.928%) (0.200%) -41.6352

The undissolved particles in the resin cured without the use of solvent (Method I) had

become nuclei for crack formation, thus the resins failed at a low stress. Its stiffness is 36.7% and

strain to break is 41.6% lower than the ones made using Method III. No resins made using

Method II were tested because none of the dogbones made were suitable for testing. Some were

already broken in the mould.

It is apparent that the use of acetone in mixing of the resin made things easier and

resulted in specimens with better properties. So even though this method sometimes produced

bubbles in the specimens, it is still used for all succeeding experiments. Samples containing

bubbles in the test zone were discarded. Those that had few surface bubbles were recovered by

surface smoothing with sandpaper.

3.7 Curing with Oligomer

The amine to epoxy mole to mole ratio was kept constant at 1.1:1 for all resin systems

including systems with additive. The amount of amine terminated additive loaded to the resin

was also taken into account when adjusting stoichiometry.

48
 There were some issues regarding the solubility of oligomers with shorter methylene

segments, namely nylon 6,6, nylon 6,8 and nylon 10,8 in the base resin. These oligomers did not

completely dissolve during mixing with the base resin, DDS, and acetone prior to curing even at

140 oC. As a result cured resins made with the previously mentioned additives possessed some

visible particles throughout the cured resin. However, mixtures made using nylon 6,12, nylon

10,12 and nylon 12,12 oligomers were more homogeneous. These longer segment oligomers

produced a more homogenous cured resin. These resins were a little opaque but with no visible

particles. It was also observed that the longer the oligomer (keeping the structure fixed) the more

opaque was the final cured resin. In some instances, we were completely unable to mix resin

with additive. For example, mixing powdered nylon 6,6 oligomers with resin dissolved in

acetone overnight prior to adding the DDS curative was attempted. With heating or without

heating the nylon 6,6 type would not dissolve.

3.8 Tensile test

The first resins prepared for tensile test were cured using the cure cycle 2 hours at 140oC

and 2 hours at 200 oC because it was not known yet that this cure cycle only cured about 90% of

the resin. The resins prepared in this cure cycle are listed in Table 3.5 and their formulations are

also given in the same table.

49
Table 3.5 Formulation of nylon 6,6 oligomers.

g additive/
moles moles theoretical Amine
g DDS/ g 1g of
material diacid diamine r (=A/B) Xn N-
MY720 MY720
"A" "B" (1+r)/(1-r) H/epoxy

MY720-DDS 0.6472 0 1.1

nylon 6,6 Xn=3.67 1 1.75 0.57 3.67 0.6173 0.05 1.1
nylon 6,6 Xn=5 1 1.5 0.67 5 0.6253 0.05 1.1
nylon 6,6 Xn=6 1 1.4 0.71 6 0.6289 0.05 1.1
nylon 6,8 Xn=5 1 1.5 0.67 5 0.6277 0.05 1.1
nylon 10,8 Xn=5 1 1.5 0.67 5 0.6308 0.05 1.1
nylon 6,12 Xn=3.67 1 1.75 0.57 3.67 0.6254 0.05 1.1
nylon 6,12 Xn=5 1 1.5 0.67 5 0.6312 0.05 1.1

nylon 10,12 Xn=3.67 1 1.75 0.57 3.67 0.6287 0.05 1.1

nylon 10,12 Xn=5 1 1.5 0.67 5 0.6337 0.05 1.1

nylon 12,12 Xn=3.67 1 1.75 0.57 3.67 0.6301 0.05 1.1

nylon 12,12 Xn=5 1 1.5 0.67 5 0.6346 0.05 1.1

Stress-strain curves for these resins are shown in Appendix B.

The results of the tensile tests are given in Tables 3.6-3.8. In general, the stiffness of the

resin increased when fortified with the nylon additives. It can be noted in Table 3.6 that as the

theoretical Xn increases, the stiffness decreases, see results for resins #2, #3, and #4 for nylon

6,6, resins #7 and #8 for nylon 6,12 and resins #9 and #10 for nylon 10,12. However, resins #11

and #12 nylon 12,12 have an opposite trend.

50
Table 3.6 Stiffness of dogbones made with different oligomer additives at 3% load.

Xn Stiffness
(Theoretical) Average Standard Stiffness %
Material (1+r)/(1-r) (MPa) deviation (MPa) Change
1 Control X 31.3225 0.9334 X
2 Nylon 6,6 3.67 33.4132 0.5452 6.6748
3 Nylon 6,6 5 30.4412 1.3864 -2.8136
4 Nylon 6,6 6 30.2533 0.0593 -3.4135
5 Nylon 6,8 5 32.2860 1.2824 3.0761
6 Nylon 10,8 5 31.7545 1.1859 1.3792
7 Nylon 6,12 3.67 34.0990 1.7906 8.8642
8 Nylon 6,12 5 33.9584 1.6408 8.4153
9 Nylon 10,12 3.67 33.8266 0.8405 7.9946
10 Nylon 10,12 5 33.4612 0.3593 6.8280
11 Nylon 12,12 3.67 32.1563 0.2433 2.6534
12 Nylon 12,12 5 32.1751 0.2574 2.7220

Resins #2-6 failed at stresses a lot lower than that of the control resin (Table 3.7). It was

expected that these resins would fail at a lower stress than the control because of the presence of

undissolved particles in the cured resin. These particles served as nuclei for crack formation.

However, generally, for resins #7-12, which had better dissolution in the resin mixture, those

with Xn =3.67 oligomers failed at stresses higher than those which are fortified with Xn =5 and

that of the control. This shows that the oligomers with higher methylene content have a positive

effect on the resin in terms of strength. However, increasing the theoretical chain length had an

adverse effect. We believe that this is related to solubility issues. The longer the theoretical

average chain lengths the less soluble the oligomer is in the resin mixture.

51
Table 3.7 Stress at break of dogbones made with different oligomer additives @ 3%
load.

Xn Stress at Break
(Theoretical) Standard % Change
Material (1+r)/(1-r) Average (MPa) Deviation (Mpa)
1 Control X 67.6899 5.9206
2 Nylon 6,6 3.67 37.0206 5.3071 -45.308532
3 Nylon 6,6 5 25.1346 0.7279 -62.86802
4 Nylon 6,6 6 26.0263 2.2538 -61.550689
5 Nylon 6,8 5 19.8043 2.6305 -70.742607
6 Nylon 10,8 5 40.6702 3.2257 -39.916856
7 Nylon 6,12 3.67 76.8637 10.3891 13.5527
8 Nylon 6,12 5 69.4538 0.7230 2.6059
9 Nylon 10,12 3.67 84.3584 8.8296 24.624796
10 Nylon 10,12 5 66.9616 8.3421 -1.0759
11 Nylon 12,12 3.67 75.3148 13.7355 11.2645
12 Nylon 12,12 5 65.6532 5.3717 -3.0089

The results for strain-to-break tensile experiments summarized in Table 3.8 show

congruence with stress at break. Resins #2-5 in Table 3.8 exhibit lower strains compared to the

control while resins #7, 9 and 11 which were all resins with Xn =3.67 had extended longer than

the control when they failed and are higher compared to their analogs with Xn =5. We believe

that this is again solubility related. Due to the presence of the undissolved particles, resins #1-6

do not take long to elongate before they break.

52
 Table 3.8 Strain at break of dogbones made with different oligomer additives.

Xn
Material (Theoretical) Strain at Break Standard Deviation % Change
(1+r)/(1-r)
1 Control X 0.02 70 (2.702%) 0.003399 (0.3399%)

2 Nylon 6,6 3.67 0.01 40 (1.400%) 0.001414 (0.414%) -48.1481

3 Nylon 6,6 5 0.0 120 (1.20%) 0.007482 (0.748%) -55.5556

4 Nylon 6,6 6 0.0 123 (1.23%) 0.007307 (0.731%) -54.4444

5 Nylon 6,8 5 0.00 59 (0.590%) 0.000781 (0.0781%) -78.1481

6 Nylon 10,8 5 0.0 137 (1.37%) 0.001155 (0.116%) -49.2593

7 Nylon 6,12 3.67 0.0 277 (2.77%) 0.002887 (0.289%) 2.5926

8 Nylon 6,12 5 0.026 (2.6%) 0.0002828 (0.0283%) -3.7037

9 Nylon 10,12 3.67 0.0 333 (3.33%) 0.005686 (0.569%) 23.3333

10 Nylon 10,12 5 0.024 19 (2.419%) 0.003965 (0.396%) -10.4074

11 Nylon 12,12 3.67 0.02 908 (2.93%) 0.007578 (0.758%) 7.7037

12 Nylon 12,12 5 0.02 448 (2.45%) 0.002602 (0.260%) -9.3333

3.9 Tensile Testing of Resins Using New Cure Cycle

Since it was found out previously that oligomers of nylon 10,12 and nylon 12,12 have

some positive effects on the mechanical properties of the MY720 resin, dogbone resins fortified

with 5% of these oligomers were made using the new cure cycle, 2 hours at 140 oC and 4 hours

at 200 oC and then tensile testing was performed. Table 3.9 shows the stiffness of the resin with

additives. Stiffness decreased by a small percentage apart from nylon 12,12 Xn=3 at 5% load.

No general pattern can be concluded in terms of the effect of Xn of the oligomer.

53
Table 3.9 Stiffness of the dogbones with different nylon oligomers at 5% load.

stiffness
Stiffness
material standard %
average deviation change
(MPa) (MPa)
MY720-DDS control 34.0856 1.4112

Nylon 10,12 Xn=3 5% 32.2651 0.4462 -5.3410

Nylon 10,12 Xn=3.67 5% 33.4695 0.8089 -1.8075

Nylon 10,12 Xn=5 5% 33.9174 0.0535 -0.4936

Nylon 12,12 Xn=3 5% 34.7467 1.3209 1.9395

Nylon12,12 Xn=3.67 5% 31.8300 0.2477 -6.6173

Nylon 12,12 Xn=5 5% 32.8598 0.6410 -3.5962

The effect of the additives on stress at break is shown in Table 3.10. It can be seen that all

of the resins with additive broke at stresses higher than that of the control with nylon 10,12

Xn=3.67 improving the resin by 57.9%. However, no general trend could be concluded based on

the results.

54
Table 3.10 Stress at break of the dogbones with different nylon oligomers at 5% load.

stress at break
stress at
material standard break %
average deviation change
(MPa) (MPa)
control 48.5179 1.6434
Nylon 10,12
Xn=3 5% 67.3995 3.4096 38.9168
Nylon 10,12
Xn=3.67 5% 76.5965 7.8769 57.8727
Nylon 10,12
Xn=5 5% 62.8425 7.7879 29.5244
Nylon 12,12
Xn=3 5% 72.6986 1.6213 49.8387
Nylon12,12
Xn=3.67 5% 65.1828 8.0533 34.3478
Nylon 12,12
Xn=5 5% 68.1505 7.1093 40.4646

The results for the comparison of strain at break are shown on Table 3.11 The extensions

at break of the resins with additive were higher than that of the control. This means that the resin

had become less crack sensitive. Nylon 10,12 Xn=3.67 increased the strain at break by 92.4%.

Again no trend can be concluded in terms of the effect of structure of additive or Xn .

55
Table 3.11 Strain at break of the dogbones with different nylon oligomers at 5% load.

strain at break extension at

material
Control
Nylon 10,12 Xn=3 5%
Nylon 10,12 Xn=3.67 5%
Nylon 10,12 Xn=5 5%
Nylon 12,12 Xn=3 3%
Nylon 12,12 Xn=3.67 5%
Nylon 12,12 Xn=5 5%
break %
Average standard deviation change
0.01590 (1.590%) 0.01260 (0.1260%)
0.02530 (2.523%) 0.001959 (0.195%) 59.1195
0.03059 (3.059%) 0.005296 (0.53%) 92.3899
0.02249 (2.249%) 0.004031 (0.403%) 41.4465
0.02674 (2.674%) 0.001725 (0.172%) 68.1761
0.02417 (2.417%) 0.003571 (0.357%) 52.0126
0.02497 (2.497%) 0.004972 (0.497%) 57.0440

In general the addition of nylon 10,12 and nylon 12,12 oligomers improved the properties

of the resin. Both the stress at break and extension at break were increased with a minimal

decrease in stiffness except for nylon 12,12 Xn=3 at 3% load because it improved all three

properties studied. No general trend could be established and this could be because it was hard to

control uniformity of the specimens. Achieving perfect specimens was hard because most of the

times the specimens would contain gas bubbles.

3.10 Thermomechanical Analysis

Thermomechanical analysis (TMA) can determine the softening temperature of a

material. The TMA results for the cured resin, resins with 5% load and 10% load of nylon 10,12

Xn =3.67 are shown in Figure 3.12. It was determined that the softening temperature of the

fortified resins were higher than that of the control.

Softening temperature is affected by the strength of the intermolecular forces of attraction

in the material. The stronger the forces the higher the temperature required to soften. The

additives in the resin are capable of hydrogen bonding which is the strongest among all

intermolecular forces. So these hydrogen bonds were responsible for making the resin more

resistant to softening.

56
 It is interesting that the softening temperatures of the resin with 5% and 10% additive

were about the same. This might be brought about by the opposing effect of the decrease in

crystallinity of the resin when more of the additive is loaded. Although the additives are creating

hydrogen bonds, the crystallinity of the material decreases as more of the additive is added.

TMA: Resins with Nylon 10,12 Xn=3.67 vs Control Resin

200

-200
Control
µm

-400
Nylon 10,12 Xn=3.67 5%

-600 Nylon 10,12 Xn=3.67 10%

-800

-1000
0 50 100 150 200 250 300 350 400
Temperature (°C)

Figure 3.11 Comparing TMA output for nylon 10,12 Xn=3.67 and control.

Table 3.12 Softening temperatures of control resin, resins with nylon 10,12 Xn=3.67 5%
and 10% determined by TMA.
TMA (Tm)
Dimension Change
Sample # Tm [°C] Tm [°F]
Control Resin 326.58 619.84
Resin with Nylon 10,12 Xn=367 5% 331.28 628.30
Resin with Nylon 10,12 Xn=367 10% 330.81 627.46

57
3.11 Conclusion
The additives synthesized are amide oligomers and are amine terminated as suggested by

FTIR and NMR results. The length of the oligomers can be somewhat controlled by adjusting the

mole ratio of the reacting monomers. The additives did not easily homogenize with the resin

especially the additives that contain monomers with shorter methylene sequences, resulting in

deterioration of mechanical properties of the resin.

Nylon 10,12 and Nylon 12,12 additives improved the tensile strength and increased the

strain to break of the resin. It can be said that these nylon oligomers apparently did create

hydrogen bonds as reflected by the increase in the softening temperature and the increase in

tensile strength of the resin when compared to control.

Because of the low solubility of the additives in the resin, the research went into the

direction of exploring additives with lesser crystallinity but with some bulky groups that may

help make the resin stiffer. These oligomers are going to be discussed in the next chapter.

58
 CHAPTER 4
RESULTS AND DISCUSSION: MIXED AMIDE ADDITIVES

4.1 Introduction

In chapter 3, it was concluded that the nylon-like oligomers were too crystalline and thus

solvating in the resin was a problem. To address this issue, the research went into the direction of

using less crystalline oligoamides. As dicussed in Chapter 3, it was determined that the longer

the methylene sequence in the oligomer, the more soluble the oligomer becomes in the resin,

resulting in a cured resin with better mechanical performance. Based on those ideas, the new set

of oligomers explored were mixed oligoamides made from a diacid chloride with long methylene

sequence, sebacoyl chloride (C10) and aromatic diamines, namely methylenedianiline (MDA),

p-phenylenediamine (PPDA) and m-phenylenediamine (MPDA). These aromatic diamines have

bulky and rigid rings that makes the additive less crystalline. The nomenclature of their

corresponding oligomers is shown in Figure 4.1.

O
a. + Cl MDA10
Cl
H2N NH2
O
MDA Sebacoyl Chloride

H2N NH2 O
b. MPDA10
+ Cl
Cl

O
MPDA Sebacoyl Chloride

O
c. H2N NH2 + Cl
Cl PPDA10

O
PPDA Sebacoyl Chloride

Figure 4.1 The chemical structures of the monomers and the corresponding names of
their oligomers.

59
Synthesis of Oligomers

The synthesis scheme for MDA10, as a representative for this new set of oligomers is

shown in Figure 4.2. The synthesis is very similar to the synthesis of nylon-like oligomers in

Chapter 3. N.N-dimethylacetamide is still used as the solvent and DBU is still used as base to

neutralize HCl produced in the reaction.

O
Cl DMAc
+ Cl DBU
H2N NH2
O

DBU•HCl +
O
HCl NH NH H
H2N NH
O
Where n= 2.67, 4 and 8 n

Figure 4.2 Scheme for the synthesis of MDA10

The different number average degrees of polymerization ( Xn ) or simply the theoretical

chain lengths of the additive were made by adjusting the monomer ratios. For MDA10, for

example, see Table 4.1. The corresponding theoretical molecular masses are also listed below.

The number average molecular weight (Mn) was also calculated by multiplying Xn with Mo,

where Mo is the average mass of the two monomers sebacoyl chloride and the diamine. Different

theoretical chain lengths of MPDA10 and PPDA10 oligomers were also preapared in the same

manner.

60
Table 4.1 The number average degrees polymerization of MDA10 and their
corresponding reagent ratios.

Oligomer Moles Sebacoylc Moles Ratio Theoretical Theoretical

Chloride (A) MDA (B) r=A/B Xn Mn = Xn *M0
MDA10 1 1.75 0.57 3.67 661.49
MDA10 1 1.5 0.67 5 901.21
MDA10 1 1.25 0.80 9 1162.18

4.2 Infrared Spectroscopy

Figure 4.3 below is a representative IR spectrum of the additives. All other spectra are

given in Appendix A. The MDA10 Xn=3.67 IR spectrum reveals a carbonyl amide I band at

1660 cm-1 and medium amide II band at 1540 cm-1, which is due to C-N bending.. The medium

absorption peak at 3295 cm-1 is due to amide hydrogen bonded N-H. This showed that the

additive has an amide functionality. Enlargement of the carbonyl area in Figure 4.4 shows the

absence of a band around 1750 cm-1 which means that the product was free from acid impurity, a

hydrolysis of the diacid chloride. This also means that the oligomer is not acid-terminated. The

large peak around 1610 cm-1 is due to carbon to carbon aromatic double bond.

61
 1.20 IR Spectrum of MPDA10 Xn=3.67

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
4000 3600 3200 2800 2400 2000 1600 1200 800 400
wavenumber (cm-)

Figure 4.3 FTIR Spectrum of MPDA10 Xn=3.67

IR Spectrum of MPDA10 Xn=3.67

1.20

1.00

0.80

0.60
absorbance

No Acid C=O

0.40

0.20

0.00
1800 1700 1600 1500
-
wavenumber (cm )

Figure 4.4 FTIR Spectrum of MPDA10 Xn=3.67, an enlargement of the carbonyl area.

62
4.3 Proton and 13C NMR

The 1H NMR spectrum of MPDA10 Xn =3.67 in deuterated trifluoroacetic acid is

reproduced in Figure 4.5. The spectrum shows three prominent peaks in the aliphatic region and

bunched up peaks in the aromatic region which is expanded in Figure 4.6. The spectrum was

compared to the one predicted by ACDLabs NMR simulator for MPDA10 Xn=5 (Figure 4.7).

The experimental and predicted spectra were comparable despite the fact that the simulation was

predicted in methanol-d. The chemical shifts of the experimental result were more downfield

because trifluoroacetic acid is more polar than methanol. Their chemical shifts are listed in

Table 4.2. Peaks at 2.754 ppm are due to protons 11, 18, 31 and 38 which are closest to electron

withrawing carbonyl groups. Protons 13, 14, 15, 16, 33, 34, 35 and 36 have have about the same

high field chemical environments and thus their peaks are bunched up at 1.484 ppm. The peak

for protons 12, 17, 32 and 37 is at 1.890 ppm. The NH peaks are shifted to very low field region.

The experimental NMR spectrum shows two faint peaks around 9.037 and 9.379 ppm, which are

due to the NH groups, while the software’s prediction is at 5.14 ppm. The large downfield shift

shows that there is extensive hydrogen bonding interaction between the solvent and the oligomer.

Of the two NH peaks, the one that is more deshielded should be due to the NH that is involved in

the amide bond.

63
 Proton NMR Spectrum of MPDA10 Xn=3.67

12 11 10 9 8 7 6 5 4 3 2 1 0
ppm

Figure 4.5 Proton NMR Spectrum of MPDA10 Xn=3.67

ACD HNMR predictor software indicates that there are seven peaks in the aromatic

region of the ACD spectrum. These correspond to the seven peaks observed in the experimental

spectrum. The CH groups belonging to the terminal benzene rings appear more upfield than

those from the central aromatic group. This is because the terminal benzene rings are connected

to highly electron donating NH2 groups, whereas the central aromatic ring is connected to two

amide groups that are less electron donating. When considering the terminal benzene rings of our

additive, the ortho and para positions (with respect to NH2) are negatively charged due to the

mesomeric effect of the NH2 and NHCO groups attached to it. Therefore those CH groups

resonate at a position more upfield when compared to the CH group in the meta position. This

trend is observed in the chemical shifts observed for the ACDLABS generated spectrum as well.

When considering the central benzene ring of the prepared additive, NHCO is electron donating

and therefore the ortho and para positions in relation to the two substituted positions have high

electron density making them more upfield than the meta CH. This trend is again similar in the

spectrum predicted by ACDLABS.

64
 Proton NMR Spectrum of MPDA10 Xn=3.67 (expanded aromatic region)

9 8 7
ppm

Figure 4.6 Expansion of aromatic region of MPDA10 Xn=3.67 proton NMR spectrum.
5 46
6 4 O O 47 45
10 40
1 3 9 12 14 16 18 NH 23 NH 31 33 35 37 39 42 44
H2N 2 N 11 13 15 17 19 21 22 24 28 29 32 34 36 38 NH 43 NH2
7 8 41 48
H O 27 25 O
8a 20 26 30

Figure 4.7 Chemical structure of MPDA10 Xn=5 with assigned carbon numbers.

65
Table 4.2 Experimental and Predicted chemical shifts for MPDA10 Xn=3.67

Carbon/Nitrogen Chemical shift Experimental

numbers From generated by ACD Chemical shift
Figure 4.7 software (ppm) (ppm)
13, 16, 33, 36 1.38 1.484
14, 15, 34, 35 1.34 1.484
12, 17, 32, 37 1.82 1.890
18, 31 2.19 2.754
11, 38 2.23 2.754
2, 43 6.43 7.435
6, 45 6.99 7.438
4, 47 7.00 7.500
5, 46 7.15 7.520
25, 27 7.28 7.560
26 7.39 7.900
23 7.96 8.131
7, 48 5.14 9.073
8, 21, 28, 41 5.14 9.379

In the aliphatic region of the spectrum of MPDA10 Xn=3.67 there are also peaks at 3.523

and 3.665 ppm due to the methyl groups of incompletely removed DMAc solvent. These 2 peaks

confirm trace amounts of DMAc present in the mixture (which can be confirmed by the carbonyl

peak in the 13C NMR spectrum). The small peaks with chemical shifts 2.23, 2.31, 3.50, 3.64 and

3.71 ppm are due to incompletely removed DBU.

13
The experimental C spectrum for MPDA10 Xn=3.67 additive is shown in Figure 4.8,

the aliphatic region is expanded in Figure 4.9 and the expanded aromatic region is shown in

Figure 4.10.

66
 CNMR Spectrum of MPDA10 Xn=3.67

200 180 160 140 120 100 80 60 40 20 0

ppm

13
Figure 4.8 C NMR spectrum of MPDA10 Xn=3.67

CNMR Spectrum of MPDA10 Xn=3.67 (Expnaded Methylene Region)

40 39 38 37 36 35 34 33 32 31 30 29 28 27 26 25
ppm

Figure 4.9 Expanded aliphatic region of C13NMR spectrum of MPDA10 Xn=3.67

67
 CNMR Spectrum of MPDA10 Xn=3.67 ( Expanded Aromatic Regoin)

15000

10000

5000

0
140 135 130 125 120 115
ppm

Figure 4.10 Expanded aromatic region of C13NMR spectrum of MPDA10 Xn=3.67

Expanded Carbonyl Region of C13 Spectrum of MPDA10 Xn=3.67

15000

10000

5000

0
185 184 183 182 181 180 179 178 177 176 175
ppm

Figure 4.11 Expanded carbonyl region of 13C NMR spectrum of MPDA10 Xn=3.67

68
Table 4.3 Assignment of carbon numbers and chemical shifts in the 13C NMR of
MPDA10 Xn=3.67

Carbon numbers in Predicted Chemical shift Experimental Chemical

Figure 4.7 generated by ACD software shift observed (ppm)
1, 44 139.22
(ppm) 139.896
2, 43 117.79 119.675
3, 44 138.80 133.205
4, 47 114.70 124.002
5. 46 130.02 131.008
6, 45 114.70 125.230
9, 39 171.68 180.943
19. 29 171.68 180.380
11, 18, 31, 38 37.63 37.986
12, 17, 32, 37 25.60 28.074
13, 16, 33, 36 29.43 30.835
14, 15, 34, 35 27.56 30.657
22, 24 138.80 137.741
23 117.79 119.859
25, 27 129.62 125.8
26 130.02 132.669

The observed experimental chemical shifts correlate to those predicted by ACD software.

Observed shifts are slightly more downfield due to the fact that samples were dissolved in highly

polar trifluoroacetic acid. Shifts from ACD C13NMR predictor software were predicted in

methanol as solvent. The experimental spectrum indicates traces of impurities. The tiny peak at

176.963 ppm is most likely due to DMAc. The two peaks at 180.943 and 180.380 ppm are due to

the oligomer’s carbonyl groups. The aromatic region of the experimentally obtained spectrum

shows 10 peaks, which is consistent with the structure. The most downfield of these are C1 and

C44 which give a peak at 139.896 ppm. The remainder of the aromatic peaks and their chemical

shifts are listed in Table 4.3.

The peak at 39.644 ppm observed in the experimentally obtained spectrum could be due

to methyl groups attached to the nitrogen atom of DMAc. The peak at 19.108 ppm is due to the

methyl group attached to the carbon of DMAc. The peak at 37.986 ppm is the most deshielded

69
carbon of the oligomer and it is due to carbons 11, 18, 31,38 of Figure 4.7. All the other peaks

can be attributed to DBU and DMAc that is present in the mixture.

The NMR spectra of the other oligomers are given in Appendix B.

4.4 Intrinsic Viscosity (IV)

The reduced specific viscosity plot obtained for MPDA10 Xn=5 is shown in Figure 4.12.

All other IV plots are given in Appendix C. By extrapolating the plot to C=0, the intrinsic

viscosity is estimated to be 16.482 mL/g of oligomer. The intrinsic viscosity experiments for

MPDA10 and MDA10 additives were done using filtered m-cresol as the solvent since the

additive is not very soluble in 90% formic acid.

Intrinsic Viscosity Plot for MPDA10 Xn=5

26

24
y = 153.82x + 16.482
22 2
R = 0.9824
nsp/C

20

18

16

14

12

10
0.000 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040 0.045 0.050

C (g/ml)

Figure 4.12 Intrinsic viscosity plot for MDA10 Xn=5

The intrinsic viscosity values obtained for the additives are summarized in Table 4.4

below.

70
Table 4.4 Summary of results for intrinsic viscosity experiments.

Additive Xn Intrinsic viscosity (mL/g)

MPDA10 3.67 14.327

5 16.482
9 16.844
MDA10 3.67 19.808
5 22.112
9 27.165

It is apparent that there is a control over the intrinsic viscosity by adjusting the theoretical

number average degree of polymerization, Xn. The intrinsic viscosity increases with Xn. This

indicates that by controlling the molar ratio of reactants, the oligomer can be lengthened or

shortened. No intrinsic viscosity experiments were performed on PPDA10 additives due to

difficulty of finding a suitable solvent. They are only partially soluble in m-cresol and in 90%

formic acid.

4.4 Gel Permeation Chromatography

The gel permeation chromatography results support our conclusion from intrinsic

viscosity experiments. GPC chromatograms of MDA10 additives are shown in Figure 4.13 while

GPC chromatograms for the MPDA10 additives are shown in Appendix C. PPDA10 additives

were not sent for GPC since a good solvent was not found.

The chromatograms show the mass distribution of the three additives. There is a shift

towards higher masses as Xn increases.

71
 GPC for MDA10
1.00
0.90 MDA10 Xn=3.67
0.80 MDA10 Xn=5
0.70 MDA10 Xn=9

0.60
W(log M)

0.50
0.40
0.30
0.20
0.10
0.00
1.00E+01 1.00E+02 1.00E+03 1.00E+04 1.00E+05 1.00E+06
Molar Mass (Da)

Figure 4.13 Gel Permeation Chromatography of MDA10

The average molecular weight, Mw (or weight average molecular weight) of the MDA10

and MPDA10 additives are listed in Table 4.5.The results show that adjusting the theoretical Xn

indeed controls the molecular weight of the additives. The polydispersity index, D of each type

of oligomer, which relates to the range of distribution of weights, is also given in the table. All of

them are above 2 which are typical for condensation polymerization. The chromatogram of

MDA10 Xn=5 looks like it has more low molecular weight species (most probably due to DBU

and DMAc impurities) compared to the other two. Since it has more impurities, its dispersity

index is higher than the rest of the additives.

72
Table 4.5 Summary of gel permeation chromatography results.

Oligomer Xn Mw (Dalton) D

3.67 5115 4.41

MDA10 5 8770 7.34

9 9551 3.06

3.67 6320 2.17

MPDA10 5 7830 2.87

9 15200 3.11

4.5 Tensile Test

Stress-strain curves such as Figure 4.14 were plotted and the stress at break, strain to

break and moduli which were taken from the slope of the initial portion of the curves such as

Figure 4.15, were determined. All other plots are given in Appendix D. Four control resins were

tested and the summary of results are given in Table 4.6.

73
 Tensile Testing Curves for Control Resin

6.00E+07

5.00E+07
sp 1

sp2
4.00E+07
sp3
stress (Pa)

sp4
3.00E+07

2.00E+07

1.00E+07

0.00E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8

strain (% )

Figure 4.14 Stress-strain curves of MDA10 Xn=3.67 3%

Control Resin Sample 1

2.00E+07

1.80E+07

1.60E+07 y = 33944286.6692x + 361418.5040

2
1.40E+07 R = 0.9997
stress (Pa)

1.20E+07

1.00E+07

8.00E+06

6.00E+06

4.00E+06

2.00E+06

0.00E+00
0.00 0.10 0.20 0.30 0.40 0.50

strain (% )

Figure 4.15 Initial portion of the stress-strain curve of Control resin specimen 1.

74
Table 4.6 Tensile testing summary for control resins.

Specimen modulus (MPa) Strain to failure (%) stress at break (MPa)

1 33.9443 1.676 50.2620
2 33.2176 1.567 47.5573
3 36.1218 1.421 46.7422
4 33.0587 1.696 49.5101
Ave 34.0856 1.590 48.5179
Stdev 1.4112 0.126 1.6434
% RSD 4.1402 7.931 3.3872

The low average ultimate strength to break from the above experiments indicates that

MY720 and DDS forms a brittle material. The percentage relative standard deviation (RSD) for

the modulus and stress at break are fairly low, indicating a consistent sample preparation.

However, the strain to failure shows a high %RSD and this could be due to imperfections such as

bubbles on the specimens that would affect crack formation.

The tensile curves of resin specimens containing MPDA10 Xn=3.67 at a loading of 3%

are shown in Figure 4.16 and the initial portion of the first specimen is shown in Figure 4.17.

The summary of results is given in Table 4.7. All other tensile testing plots and results are given

in Appendix D.

75
 Tensile Testing Curves of MPDA10 Xn=3.67 3% Specimens
7.0E+07

6.0E+07
sp1
5.0E+07 sp2
sp3
stress (Pa)

4.0E+07 sp4

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.5 1 1.5 2 2.5
strain %

Figure 4.16 Tensile testing curves of MPDA10 Xn=3.67 at 3 % loading.

Initial Portion of MPDA10 Xn=3.67 3% Specimen 1

2.0E+07
1.8E+07
y = 35,686,956.1411x + 608,338.3224
1.6E+07
R2 = 0.9997
1.4E+07
stress (Pa)

1.2E+07
1.0E+07
8.0E+06
6.0E+06
4.0E+06
2.0E+06
0.0E+00
0 0.1 0.2 0.3 0.4 0.5
strain %

Figure 4.17 Initial portion of tensile testing curve of MPDA10 Xn=3.67 3% specimen 1.

76
Table 4.7 Tensile Testing summary for MPDA10 Xn=3.67 at 3% load.

Specimen Modulus (MPa) Strain to Failure (%) Stress at Break (MPa)

1 35.6870 1.691 54.0702
2 35.9517 2.020 63.4879
3 33.8357 1.530 48.2066
4 36.0078 1.719 55.1947
Ave 35.3705 1.740 55.2398
Stdev 1.0328 0.2044 6.2946

MPDA10 Xn=3.67 at 3% loading gives a 3.77% improvement on modulus, 13.85%

improvement on stress at break and gives a 9.43% increase on strain to failure when compared to

control. This suggests that the material has become stronger and less brittle upon addition of the

additive.

The resins listed in Table 4.8 were tested. The formulations of the resins tested are given

in the same table. The amount of curing agent added is adjusted to the type of oligomer and

oligomer loading used.

77
Table 4.8 Formulations of resins tested.

g
moles moles Theoretical g N-H in
r additive/
material diacid diamine Xn DDS/g additive
(=A/B) g of
"A" "B" (1+r)/(1-r) MY720 /epoxy
MY720

MY720-DDS control
w/ solvent 0.6472 0 1.1
MPDA10 XN=3.67 3% 1 1.75 0.57 3.67 0.5729 0.03 1.1
MPDA10 XN=3.67 5% 1 1.75 0.57 3.67 0.5768 0.05 1.1
MPDA10 XN=5 3% 1 1.5 0.67 5 0.5768 0.03 1.1
MDA10 Xn =3.67 3% 1 1.75 0.57 3.67 0.5765 0.03 1.1
MDA10 XN=3.67 5% 1 1.75 0.57 3.67 0.5689 0.05 1.1
MDA10 XN=3.67 10% 1 1.75 0.57 3.67 0.5504 0.10 1.1
MDA10 Xn=5 3% 1 1.5 0.67 5 0.5795 0.03 1.1
MDA10 Xn=5 5% 1 1.5 0.67 5 0.5740 0.05 1.1
MDA10 Xn=9 3% 1 1.25 0.8 9 0.5831 0.03 1.1
MDA10 Xn=9 5% 1 1.25 0.8 9 0.5801 0.05 1.1
MDA10 Xn=9 10% 1 1.25 0.8 9 0.5725 0.10 1.1
PPDA10 Xn=3.67 3% 1 1.75 0.57 3.67 0.5729 0.03 1.1
PPDA10 Xn=3.67 5% 1 1.75 0.57 3.67 0.5630 0.05 1.1
PPDA10 Xn=3.67 10% 1 1.75 0.57 3.67 0.5384 0.10 1.1
PPDA10 Xn=5 3% 1 1.5 0.67 5 0.5768 0.03 1.1
PPDA10 Xn=5 5% 1 1.5 0.67 5 0.5696 0.05 1.1
PPDA10 Xn=5 10% 1 1.5 0.67 5 0.5515 0.10 1.1
PPDA10 Xn=9 3% 1 1.35 0.8 9 0.5817 0.03 1.1
MDA10 XN=9 5% 1 1.25 0.8 9 0.5776 0.05 1.1

The tensile test results for resins with MPDA10 additives are given in Table 4.9.

Attempts to prepare several resins with MPDA10 additives were made, however only resins

containing MPDA10 Xn=3.67 at 3% and 5% loading and MPDA10 Xn=5% were successfully

made. The others have imperfections not tolerable for testing. Moreover, it was decided not to

pursue attempting to prepare again the resins that were unsuccessfully made because based on

the results the mechanical property deteriorates as % load and Xn are increased.

78
Table 4.9 Tensile Testing Summary for resins containing MPDA10.

Stiffness stress at break Strain at break

No of
% % %
Material samples Ave StDev Ave StDev
change change Ave StDev change
tested (MPa) (MPa) (MPa) (MPa)

MY720-
DDS 0.01590 0.00126
control w/ 34.0856 1.4112 48.5179 1.6434 (1.590%) (0.126%)
solvent 4
MPDA10 0.0174 0.00204
Xn=3.67 35.3705 1.0328 3.7696 55.2398 6.2946 13.8545 (1.74%) (0.204%) 9.4340
3% 4
MPDA10 0.01301 0.00305
Xn=3.67 35.21 0.8260 3.2976 42.2310 8.1233 -12.9579 (1.301%) (0.305%) -18.1761
5% 4
0.01170 0.00371
MPDA10 35.1162 1.3063 3.0236 38.2780 9.8276 -21.1054 (1.1697%) (0.3708%) -26.4969
Xn=5 3% 3

Among the three resins containing MPDA10, the Xn=3.67, with 3% loading is the only

one that shows improvement. There was a 3.77 % increase in modulus, 13.85% in stress at break

and 9.34% in strain at break. This means that the material has become stronger and stiffer.

However, the resins with 5% MPDA10 Xn=3.67 and 3% MPDA10 Xn=5 show improvement

only in modulus and show deterioration in stress at break and strain at break.

The results for resins with MDA10 additives are given in Table 4.10. Resin MDA10

Xn=9 at 5% loading gave the best result. The additive has improved 1.59% in modulus, 56.61%

stress at break and 58.30% strain at break. It can be noted that resins with 5% loading gave the

most improvement for all three Xns. This could be because resins having 5% additive have more

hydrogen bonds than those that only have 3% and resins having 10% additives have solubility

issues. Undissolved additive can act as nucleus that starts crack propagation. As for the effect of

the Xn, no conclusion can be arrived at since there is no consistent pattern; either increasing or

decreasing property measurement is observed.

79
 Table 4.10 Tensile testing summary for resins containing MDA10.

Stiffness stress at break strain at break

No of
% %
Material samples Ave StDev Ave StDev % change
change ave StDev change
tested (MPa) (MPa) (MPa) (MPa)

MY720-
DDS control 0.0159 0.0126
w/ solvent 4 34.0856 1.4112 48.5179 1.6434 (1.59%) (0.126%)
0.01367 0.00159
MDA10 34.1093 0.8667 0.0695 43.1459 3.8543 -11.0722 (1.367%) (0.159%) -14.1139
Xn=3.67 3% 7
0.02128 0.002865
MDA10 32.7234 0.5060 -3.9964 59.9588 6.3819 23.5808 (2.128%) (0.287%) 33.8634
Xn=3.67 5% 4
MDA10 0.01234 0.00178
Xn=3.67 34.6935 1.9574 1.7835 40.0822 5.3990 -17.3868 (1.234%) (0.178%) -22.3899
10% 5
0.01335 0.001067
MDA10 36.4544 1.1120 6.9496 44.6762 1.1815 -7.9181 (1.335%) (0.011%) -16.0377
Xn=5 3% 3
0.0163 0.00347
MDA10 34.5855 0.5098 1.4666 47.8403 8.1951 -1.3966 (1.53%) (0.347%) -3.7736
Xn=5 5% 4
0.01418 0.00222
MDA10 34.9359 1.3248 2.4946 45.3621 1.9981 -6.5044 (1.418%) (0.222%) -10.8176
Xn=9 3% 3
0.02517 0.00368
MDA10 34.6280 2.5493 1.5913 75.9837 2.5167 56.6096 (2.517%) (0.368%) 58.3019
Xn=9 5% 4
0.01872 0.00491
MDA10 34.7171 2.0688 1.8527 55.9826 10.955 15.3855 (1.872%) (0.491%) 17.7358
Xn=9 10% 5

The results for resins with PPDA10 additives are shown in Table 4.11. The resins that

gave the best results among them are those that contain 5% PPDA10 Xn=3.67 and 5% PPDA10

Xn=5, showing increase in modulus, stress at break and strain to failure. The resin with PPDA10

Xn=9 at 5% loading had greater stress at break and strain at break improvement than the Xn=5,

however the material is less stiff. The resins that showed improvement on tensile strength also

showed an increase in strain-to-failure which indicates that the additives have a toughening

effect. The PPDA10 additives are consistent with the MDA10 additives that resins with 5%

additives are best in all three Xns. And as expected, resins with 10% loading of additive show

80
 very poor mechanical properties due to solubility issues. As for the effect of Xn on the three

mechanical properties, no general trend can be arrived at.

Table 4.11 Tensile Testing summary for resins containing PPDA10.

Number Stiffness stress at break strain at break

stress at Extension
of Stiffness
Material average Standard Average standard break % Standard at break
samples % change average
(MPa) deviation (MPa) deviation change deviation % change
tested
(MPa) (MPa)
MY720- 0.0159 0.0126
DDS control 4 34.0856 1.4112 48.5179 1.6434 (1.59%) (0.126%)
0.01881 0.00196
PPDA10 33.7534 1.3193 -0.9747 55.2709 3.388851 13.9187 (1.881%) (0.196%) 18.3019
Xn=3.67 3% 5
0.0187 0.00335
PPDA10 35.4719 0.5827 4.0670 57.7422 7.747524 19.0121 (1.87%) (0.335%) 17.6101
Xn=3.67 5% 4
PPDA10 0.01132 0.00017
Xn=3.67 35.5554 0.7181 4.3120 38.4683 1.332717 -20.7131 (1.132%) (0.017%) -29.9874
10% 3
0.01823 0.00492
PPDA10 33.5802 1.5652 -1.4828 53.6544 9.556974 10.5868 (1.823%) (0.492%) 14.6541
Xn=5 3% 5
0.02001 0.0001
PPDA10 34.7140 1.6147 1.8436 59.7335 1.3237 23.1164 (2.001%) (0.01%) 25.8491
Xn=5 5% 4
0.01597 0.00472
PPDA10 35.0071 1.0232 2.7035 49.7156 3.4654 2.4686 (1.597%) (0.472%) 0.4403
Xn=5 10% 4
0.01458 0.00421
PPDA10 35.0655 1.0791 2.8749 46.4452 10.30997 -4.2721 (1.458%) (0.421%) -8.3019
Xn=9 3% 4
0.02023 0.006130
PPDA10 33.5841 0.6073 -1.4173 56.9832 13.1904 14.8558 (2.022%) (0.613%) 27.1698
Xn=9 5% 4

Among all the resins tested the MDA10 Xn=9 at 5% loading gave the best mechanical

property improvement.

To determine whether the percent changes listed in Tables 4.9-4.11 are significant, the

results were analyzed through T-test at 95% confidence interval. The values were calculated and

listed in Table 4.12.

81
Table 4.12 T-test calculation results

Calculated t
t (table stress at strain-to-
Resin with: DF value) Stiffness break failure
MPDA10 Xn=3.67 3% 6 1.9432 1.4695 2.0665 1.2512
MPDA10 Xn=3.67 5% 6 1.9432 1.3753 1.5171 1.7515
MPDA10 Xn=5 3% 5 2.0150 0.9848 2.1132 2.1639
MDA10 Xn=3.67 3% 9 1.8331 0.0350 2.6075 2.3906
MDA10 Xn=3.67 5% 6 1.9432 1.6661 3.4721 3.4379
MDA10 Xn=3.67 10% 7 1.8946 0.5195 2.9794 3.3625
MDA10 Xn=5 3% 5 2.0150 2.3861 3.4076 2.1115
MDA10 Xn=5 5% 6 1.9432 0.6663 0.1621 0.2167
MDA10 Xn=9 3% 5 2.0150 0.8083 2.3035 1.317
MDA10 Xn=9 5% 6 1.9432 0.3723 18.2755 4.7664
MDA10 Xn=9 10% 7 1.8946 0.5183 1.3325 1.1126
PPDA10 Xn=3.67 3% 7 1.8946 0.3643 3.6231 2.5581
PPDA10 Xn=3.67 5% 6 1.9432 1.8160 2.3294 1.5646
PPDA10 Xn=3.67 10% 5 2.0150 1.6258 8.6184 6.1072
PPDA10 Xn=5 3% 7 1.8946 0.5019 1.0483 0.9118
PPDA10 Xn=5 5% 6 1.9432 0.5861 10.5299 6.5034
PPDA10 Xn=5 10% 6 1.9432 1.0573 0.6246 0.0287
PPDA10 Xn=9 3% 6 1.9432 1.1032 0.3971 0.6007
PPDA10 Xn=9 5% 6 1.9432 0.6529 1.2737 1.3838

Note: Results in red are greater than t (table value) and therefore the difference of these results

from the control are significant.

4.6 Fracture Toughness

The load-strain plot for the first control specimen and the summary table for the

calculation of fracture toughness are shown in Figure 4.18 and Table 4.13. The rest of the plots

for the control resin are in Appendix E.

82
 Control Resin Specimen 1

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03
Crosshead Displacement (cm)

Figure 4.18 Fracture toughness test load-strain curve of control resin specimen 1.

Table 4.13 Fracture toughness for control specimens.

hole
to
Fracture crack elastic edge fracture fracture
geometrical load P length a modulus E dist W thickness energy toughness
control factor, Y (N) (m) (Pa) (m) b (m) (J/m2) (Mpa*m1/2)
1 23.14615 207.32 0.0026 34085597.75 0.025 0.0064 1498679.19 1.5322
2 23.14615 208.87 0.0024 34085597.75 0.025 0.0064 1266426.78 1.4879
3 23.14615 230.05 0.0028 34085597.75 0.025 0.0064 1749935.54 1.7610
4 23.14615 227.95 0.0027 34085597.75 0.025 0.0064 1630029.55 1.7198
5 23.14615 205.16 0.0030 34085597.75 0.025 0.0064 1509593.72 1.6256
6 23.14615 193.39 0.0034 34085597.75 0.025 0.0064 1499269.52 1.6313
Average 1.6263
STDEV 0.10
% RSD 6.4

The average fracture toughness of the control was found to be 1.6263 MPa*m1/2 The

fracture toughness results of the resins with MDA10 additives are given in Table 4.14. All resins

with MDA10 additive tested showed improvement in fracture toughness. The additive that

improved the resin’s fracture toughness the most is MDA10 Xn=3.67 at 3% load, increasing the

fracture toughness by 26.62%. Fracture toughness of resins with additives with 3% additive load

83
have higher fracture toughness compared to the ones with 5% load. It can be observed from the

resin with 5% additives that the fracture toughness decreases with Xn.

Table 4.14 Fracture Toughness of Resins with MDA10 additives.

ave fracture toughness no. of

material (MPa*m1/2) %RSD % change specimens
control 1.6263 6.44 6
MDA10 Xn=3.67 3% 2.0592 7.33 26.62 4
MDA10 Xn=3.67 5% 2.0471 5.52 25.87 4
MDA10 Xn=5 3% 1.9783 7.30 21.64 3
MDA10 Xn=5 5% 1.8529 10.81 13.94 4
MDA10 Xn=9 5% 1.8362 7.83 12.91 6

The fracture toughness test for resins containing PPDA10 additives are given in Table

4.15. All PPDA10 additives also showed improvements. Just like the resin-MDA10 additives

series, the PPDA10 Xn=3.67 at 3% load gave the greatest improvement, increasing the fracture

toughness by 33.93%. Resins with Xn=3.67 and Xn=9 additives also follow the same trend as

the resins with MDA10 additives where the fracture toughness of resins with 3% additive have

higher average fracture toughness than the corresponding resins with 5% load. For resins with

3% load, fracture toughness decreases with additive Xn. The result for resins with PPDA10

Xn=5 at 5% showed an increase of 29.88%, which is inconsistent with trend.

84
Table 4.15 Fracture toughness tests results for resins with PPDA10 additives.

ave fracture toughness % no. of

material (MPa*m1/2) %RSD change specimens
control 1.6263 6.44 6
PPDA10 Xn=3.67 3% 2.1781 8.63 33.93 6
PPDA10 Xn=3.67 5% 1.9658 4.06 20.88 4
PPDA10 Xn=5 3% 1.8726 4.87 15.14 6
PPDA10 Xn=5 5% 2.1122 5.08 29.88 4
PPDA10 Xn=9 3% 1.8246 7.32 12.19 6
PPDA10 Xn=9 5% 1.7886 2.57 9.98 5

Compact tension specimens were also made for resins with MPDA10 additives that were

tested for tensiles. The results are given in Table 4.16.

Table 4.16 Fracture toughness tests results for resins with MPDA10 additives.

ave fracture toughness no. of

material (MPa*m1/2) %RSD % change specimens
control 1.6263 6.44 6
MPDA10 Xn=3.67 3% 1.9567 8.80 20.32 5
MPDA10 Xn=3.67 5% 1.8906 6.73 16.25 6
MPDA10 Xn=5 3% 1.8381 5.04 13.02 3

MPDA10 Xn=3.67 at 3% load gave the most improvement among the three additives

showing 20.32% increase in fracture toughness. The average fracture toughness of resins with

3% Xn=3.67 is higher than the resins with 5% additive load and resins with 3% of MPDA10

Xn=5. .

The results show that the additives indeed introduce secondary forces of attraction

between chains in the resin causing the fracture toughness to increase. Two general trends can be

observed. First, increasing the additive load decreases the fracture toughness. This is attributed to

the solubility of the additive in the resin. The additives are not very soluble at higher loads. So

the higher percentage additive the more likely it is that a fraction of the additive will not

85
dissolve. Undissolved particles can act as nuclei in crack propagation and thus leads to the

decrease in fracture toughness. A second observation is that fracture toughness decreases with

Xn. This observation can be attributed to decrease in resin crosslink density as well as the

decrease of solubility of the additves in the resin as the size of the additives increase.

Comparison of resins containing MDA10, MPDA10 and PPDA10 all having an Xn=3.67

and at 3% load are given in Table 4.17. PPDA10 Xn=3.67 at 3% load gave the greatest

improvement among the three. The PPDA10 is less bulky compared to MDA10 and has a more

linear structure than MPDA10 and thus creates a better fit for formation of hydrogen bonds.

Table 4.17 Comparison of the three best resins from each type of additive.

ave fracture
toughness no. of
material (MPa*m1/2) %RSD % change specimens
control 1.6263 6.44 6
MDA10 Xn=3.67 3% 2.0592 7.33 26.62 4
MPDA10 Xn=3.67 3% 1.9567 8.80 20.32 5
PPDA19 Xn=3.67 3% 2.1781 8.63 33.93 6

4.7 Differential Scanning Calorimetry

Data generated from dynamic temperature scanning were used to construct plots for the

degree of cure (α) as a function of temperature over a range of heating rates from 1 °C/min to 20

°C/min. A summary of plots of α vs T obtained for the control resin is shown in Figure 4.19. The

cure reaction shifts to higher temperatures at higher heating rates. At slower heating rates such as

1 and 2 ºC/min the cure is complete by 230 ºC. At higher heating rates such as 20 ºC/min, curing

is not completed until 286.1 ºC.

At slower heating rates, the molecules have sufficient time to unravel, rearrange

themselves and react. However, at faster heating rates molecules are not given sufficient time

therefore will need to be heated to higher temperatures in order to react and form a network.

86
 Similar curves were plotted for resin containing MDA10 Xn=3.67 at a 3% load. Again,

the area percentage values generated by the DSC instrument for plots of heat flow vs temperature

were used to calculate the degree of cure. Plots of degree of cure as a function of temperature at

different heating rates (1 ºC/min to 20 ºC/min) were constructed. These plots are summarized in

Figure 4.20.

The cure reaction also shifts to higher temperatures as the heating rate increases. At lower

heating rates of 1 ºC/min, the cure reaction is completed by 243 ºC. However, at higher heating

rates, 20 ºC/min for instance, the temperature must be raised up to 293.1 ºC to completely cure

the resin mixture. These temperatures are not very different from those obtained for the control

resin. A comparison plot in Figure 4.21 shows the additive has no significant effect on the

ultimate curing temperatures.

Control Resin Degree of Cure vs Temperature Summary

1.2

1
1C/min
2C/min
3C/min
0.8
4C/min
Degree of Cure

5C/min
0.6 7C/min
10C/min
15C/min
0.4 20C/min

0.2

0
100 120 140 160 180 200 220 240 260 280 300
Temperature (ºC)

Figure 4.19 Plot of Control resin Degree of Cure vs. Temperature Summary

87
 Resin with MDA10 Xn=3.67 Degree of Cure vs Temperature Summary

1.2

1C/min
1
2C/min

3C/min
0.8
4C/min
Degree of Cure

5C/min
0.6 7C/min
10C/min

0.4 15C/min
20C/min

0.2

0
100 120 140 160 180 200 220 240 260 280 300
Temperature (ºC)

Figure 4.20 Plot of Resin with MDA10 Xn=3.67 degree of cure vs. temperature summary.

Degree of cure vs Temperature of Control Resin

and Resin with MDA10 Xn=3.67 @ 20 ºC/min
1.2

1
control
Degree of Cure

0.8 with additive

0.6

0.4

0.2

0
100 150 200 250 300 350
Temperature (ºC)

Figure 4.21 Comparison of control resin and resin with MPDA10 Xn=3.67 @ 5oC/min
heating rate.

88
 Using the software, Origin, the plots for degree of cure vs temperature were differentiated

dα
with respect to time to construct plots of rate of cure as a function of temperature. A
dT

summary of rate of cure vs temperature plots obtained for the control resin at heating rates

ranging from 1 ºC/min to 20 ºC/min is shown in Figure 4.22.

Control Rate of Cure vs Temperature Summary

4.00E-01

3.50E-01
1cmin
3.00E-01 2cmin
3cmin
4cmin
2.50E-01
Rate of Cure

5cmin
7cmin
2.00E-01
10cmin
15cmin
1.50E-01 20cmin

1.00E-01

5.00E-02

0.00E+00
100 120 140 160 180 200 220 240 260 280 300
Temperature (ºC)

Figure 4.22 Summary of rate of cure vs temperature for the control resin at different
heating rates.

It is observed that the rate of cure increases with heating rate. It can also be observed

from the plot that the maximum shifted to higher temperature at higher heating rates. Figure 4.23

summarizes the rate of cure as a function of temperature at heating rates ranging from 1 ºC/min

to 20 ºC/min for control resin containing MDA10, Xn=3.67 additive at 3% load. The rate of cure

profile is very similar to that of the control resin. The rate of cure increases as the heating rate is

increased. The temperature at which the highest cure rate is achieved also increases with

89
increasing heating rate. This means that the additive MDA10, Xn=3.67 at 3% load does not alter

the rate of cure significantly.

Resin Containing MDA10 Xn=3.67 at 3% load Rate of Cure vs

Temperature Summary

4.00E-01

3.50E-01 1C/min
2C/min
3.00E-01 3C/min
4C/min
2.50E-01 5C/min
Rate of Cure

7C/min
2.00E-01 10C/min
15C/min
1.50E-01 20C/min

1.00E-01

5.00E-02

0.00E+00
100 120 140 160 180 200 220 240 260 280 300
Temperature (ºC)

Figure 4.23 Summary of rate of cure vs temperature for the resin containing MDA10
Xn=3.67 at 3% load at different heating rates.

Using the data above, plots of ln (rate of cure) against 1/temperature (K) were

constructed at different degrees of cure ranging from 0.05 to 0.95. A typical plot of ln rate of

cure vs 1/temperature for the control resin is reproduced in Figure 4.24. The remaining plots are

given in Appendix F.

90
 ln Rate of Cure vs. 1/T for 0.05 Degree of Cure
0

-1

-2
ln rate of cure

-3

-4
y = -7,687.090x + 13.718
-5 2
R = 0.987

-6
0.0021 0.00215 0.0022 0.00225 0.0023 0.00235 0.0024 0.00245
1/T (1/K)

Figure 4.24 Plot for ln rate of cure vs 1/T for 0.05 degree of cure of control resin.

The slope of each graph was multiplied by the gas constant (8.314 J/mol K) to obtain the

activation energy for each degree of cure. The calculated activation energies were plotted against

degree of cure for each resin system (Figure 4.25).

91
 Activation Energy Comaprison

140000

120000
Acivation Energy (J/mol)

100000

80000

60000

40000
control
20000
with 3% MDA10 Xn=3.67
0
0 0.2 0.4 0.6 0.8 1

Degree of Cure

Figure 4.25 Activation energy vs degree of cure of Control and 3 % MDA10 Xn=3.67

The activation energy of the control slightly decreases during the curing process. This is

because during the curing process hydroxyl groups are formed and these hydroxyl groups

catalyze the process. However, towards the end of the curing process, the activation energy

increases because at this point the resin is already very viscous and has already formed a network

Therefore, it would be harder for the reacting functional groups to meet and react.

The comparison suggests that addition of the additive increases the activation energy of

the curing process. This is probably due to the secondary forces brought by the additives. The

interchain attraction brought by the additive makes it more difficult for chains to move and

functional groups to meet and react.

92
4.8 Dynamic Mechanical Analysis

The storage modulus, G’ was plotted on a linear scale to observe the drop off in G’ at

higher temperatures. Tan (δ) max is an easier method of determining Tg and is more accurate.

Figure 4.26 compares the storage modulus of resin systems containing MPDA10 Xn=3.67 and

MDA10 Xn=3.67 additives with fixed chain lengths, Xn=3.67. The storage modulus vs

temperature is compared against that measured for the control resin. Resins with additives at 3%

have higher storage moduli at lower temperatures than the control. However at higher

temperatures their storage moduli are about the same.

Comparing Storage Modulus

3010
Storage Modulus (MPa)

Control
2510
MPDA10 Xn=3.67
3%
2010 MDA10 Xn=3.67
3%
1510 MDA10 Xn=5 3%

1010

510

10
0 50 100 150 200 250 300 350 400
Temperature (°C)

Figure 4.26 DMA of MPDA10 Xn=3.67 3%

93
Figure 4.27 compares the tangent delta values of resin system containing MPDA10 and MDA10

additives with fixed chain lengths, Xn=3.67.

Comparing Tangent Delta

1
0.9
0.8
0.7 Control
Tangent Delta

MPDA10 Xn=3.67 3%
0.6
MDA10 Xn=3.67 3%
0.5 MDA10 Xn=3.67 5%

0.4
0.3
0.2
0.1
0
140 160 180 200 220 240 260 280 300
Temperature (C)

Figure 4.27 Comparing Tangent Delta from DMA scans.

The results of Figure 4.26 and Figure 4.27 are summarized in Table 4.18. Addition of an

additive slightly increased the glass transition temperature of the control resin. The percent

change ranges from 0.70-1.41 are too low and insignificant from application stand point.

However, the slight increase in Tg suggests that the additives have slightly decreased the resin’s

free volume. MPDA10 Xn=3.67 has a slightly greater effect than MPDA10 Xn=3.67. This is

because MPDA10 has a less bulky structure than MDA10 and therefore can form a more

94
crystalline structure with the resin. As the loading of MDA10 Xn=3.67 is increased, the cross

link density of the resin decreases causing a minimal decrease in the Tg.

Table 4.18 Comparison of High-Temperature DMA of MDA10 and MPDA10 Xn=3.67.

Onset Storage Modulus Peak of Tangent Delta

% Change % Change
(Based on (Based on
Tg Tg Tg in Tg Tg Tg in
Sample [°C] [°F] Celcius) [°C] [°F] Celcius)
Control 234.88 454.78 251.7 485.06
MDA10 Xn=3.67 3% 236.52 457.74 0.70 253.62 488.52 0.76
MDA10 Xn=3.67 5% 236.35 457.43 0.63 253.57 488.43 0.74
MPDA10 Xn=3.67 3% 238.19 460.74 1.41 253.71 488.68 0.80

4. 9 Thermogravimetric Analysis

TGA plots for the control and resin containing MPDA10 Xn=3.67 at loadings of 3%, 5%,

and 10% and were constructed in Figure 4.28, obtained using a heating rate of 4 ºC/min and inert

atmosphere.

TGA MPDA10 Xn=3.67 (4C per min)

120

100
control
3%
80
Weight Percent (%)

5%
10%
60

40

20

0
0 100 200 300 400 500 600 700 800

Temperature (Celcius)

95
Figure 4.28 Change of weight percent of control resin and resin with MPDA10 Xn=3.67
additive with time at 4 ºC/min heating rate.

The onset and endset temperatures of degradation for the control resin, heated at 4

ºC/min, were found to be 325.57 ºC and 393.49 ºC respectively. During this degradation a weight

change of 41.54% was observed. Upon heating resin mixtures containing MPDA10, Xn=3.67 at

loadings of 3%, 5% and 10% at the same heating rate, the degradation onset temperatures were

found to be 313.90 ºC, 305.55 ºC and 307.57 ºC with weight degradation of 39.13%, 39.61%

and 43.41% respectively. The results are summarized on Table 4.19

Table 4.19 Summary of weight degradation for control and resins with MPDA10
Xn=3.67.

MPDA10 Xn=3.67 Heating Rate = 4 C/mim

Onset Endset
Additive Load Temperature Temperature Degredation
TO [°C] TO [°F] TE [°C] TE [°F] ∆ Weight (%)
Control (0%) 325.57 618.03 393.49 740.28 41.54
3% 313.90 597.02 399.22 750.60 39.13
5% 305.55 581.99 401.96 755.53 39.61
10% 307.57 585.63 418.34 785.01 43.41

The onset of degradation has been shifted towards lower temperatures, lowering the

thermal stability of the resin mixture. This is probably due to the decrease of crosslink density of

the resin as the percentage of additive is increased. The percentage weight change also remains

approximately the same as that of the control resin, indicating that no new degradation processes

occur by the addition of the additive to the resin.

96
4.10 Conclusion

MDA10, MPDA10 and PPDA10 oligomers were synthesized and characterized. From

FTIR and NMR results the oligomers were proven to contain amide groups. Intrinsic viscosity

experiments and GPC show that there was some control over the chain length of the oligomer by

adjusting the ratio of reacting monomers.

Fracture toughness tests show that all oligomers tested improved the toughness of the

resin suggesting that the hydrogen bonds of the amide groups added resistance towards crack

propagation. It is observed that the resins containing 3% have greater fracture toughness than the

resins containing 5% additive. The decrease in toughness can attributed to the solubility of the

additives into the resin since they are not very soluble at higher loading.

From the tensile tests, it can be observed that the best resins from the tests have a

moderate load of additive, which is at 5%. From 3% to 5% the mechanical performance

improves which suggests that the more hydrogen bonds (from the additive) introduced, the

stronger and stiffer the resin becomes. However, when the load is at 10%, the mechanical

performance deteriorates. Again this behavior is attributed to solubility of the additives to the

resin additives. At 10% loading, some of the additives are not dissolved in the resin and will

initiate crack propagation during the testing

The additives slightly increase the glass transition temperature of the resin based on

dynamic mechanical analysis results. This suggests that the additives are causing the resin

molecules to be more compact thus, decreasing the free volume and becoming less mobile. This

most likely was caused by formation of hydrogen bonds by the amide groups in the oligomer.

The increase in the glass transition temperature is only minimal, however, the goal of using

97
additives that does not decrease the glass transition temperature of the resin was at least

achieved.

From the thermal degradation analysis, it can be concluded that the additives do not lead

to new degradation processes. Even though addition of the additives slightly decreases the onset

of degradation temperatures, the change is insignificant and the percentage weight change also

remains approximately the same as that of the control resin.

The results from differential scanning calorimetry suggest that addition of additive

increases the activation energy of the curing process. This is most likely caused hydrogen bonds

of the amide groups of the additive. The hydrogen bonds gave the material more rigid and less

resistant to movements making the resin more viscous during the curing process making it more

difficult for the reactive groups to meet.

98
 CHAPTER 5
CONCLUSIONS

The goal of this research was to synthesize hydrogen bonding additives that can enhance

the mechanical properties of the MY720-DDS resin system. It was hoped that these additives

will fill free volume to antiplasticize the resin (increasing stiffness and strength); the hydrogen

bonds would yield additional attractive forces thereby making the resin more resistant to crack

propagation; and lastly that these additives would not have adverse effect on other important

resin properties such as glass transition temperature and thermal degradation resistance.

Oligomeric amides additives were synthesized by reacting diamine monomers and diacid

chloride via condensation polymerization. The amide (–CONH-) group is capable of hydrogen

bonding. Oligomers with different number average degree of polymerization, Xn (i.e. related to

average chain length) were synthesized. FTIR and NMR studied proved that the additives have

amide functionalities. Intrinsic viscosity experiments and gel permeation chromatography results

proved that there is a control over chain length by adjusting the reacting monomer ratio.

The first part of the research focused on non-aromatic additives. Dog bone-shaped resins

with additives of different Xn and at different additive loadings were prepared via the cure cycle

2 hours at 120 oC and 2 hours at 200 oC. It was noticed that the additives are not very soluble in

the resin. Some resins are very brittle due to the presence of undissolved additives. Some of them

were already broken and discovered upon dismantling of the mould. The good and better

specimens were used for tensile testing. It was noticed out that the performance of the cured

resin was better when the additive has a longer methylene sequence. It was also found that the

resins were only 90% cured using the cure cycle. The cure cycle was then adjusted to 2 hours at

120 oC and 4 hours at 200 oC and it resulted in 97% completion, which exceeds the industry

99
requirement of 95%. All the succeeding resins were then cured using the new cure cycle. The

resins with additives in general, using the new cycle increased the tensile strength and strain to

break but slightly decreased the stiffness with the exception of the resin with 5% Nylon 12,12

Xn=3 where all tensile strength, strain-to-failure and stiffness increased. The additives therefore,

were more of plasticizers than antiplasticizers.

TMA experiment, runs on resins with Nylon 10,12 Xn=3.67 additives and control resin

show that the additive increases the softening temperature. This behavior can be attributed to the

hydrogen bonds introduced by the additives to the resin. The polymer chains do not move as

easily with the additive due to the additional presence of forces of attraction.

Since solubility was an issue, the research went into a new direction and explored

additives that were less crystalline but have bulky groups to introduce some sort of rigidity to

hopefully improve the resins stiffness. Mixed amide oligomers were synthesized. These additives

were more soluble in the resin compared to the non-aromatics. In general, the resins with

moderate additive loading (5%) are better than those that have 3% and 10% loading.

Resins containing 5% and 10% MDA10 Xn=9, 5% PPDA10 Xn=3.67, and 5% and 10%

PPDA10 Xn=5 improved all the three mechanical parameters stiffness, tensile strength and strain

to failure. The best resins were the ones containing 5% MDA10 Xn=9 (1.6% stiffness, 56.6%

tensile strength and 58.3% strain to failure increase). However, resins containing 5% PPDA10

Xn=3.67 has an increase of 4.1% stiffness, 19.0% tensile strength and 17.6% strain–to-failure

has a greater increase in stiffness. However, the variability of the results in general were a little

high. This is because producing a perfect specimen was hard to achieve. Imperfections like

bubbles sometimes cannot be eliminated

100
 Fracture toughness tests show that the additives increase the resins’ resistance to crack

propagation. Resins containing 3% have greater fracture toughness than the resins containing 5%

additive and fracture toughness decreases with Xn. The decrease in toughness can attributed to

the solubility of the additives into the resin since they are not very soluble at higher loading or

when the additive becomes longer.

The additives MDA10 Xn=3.67 at 3% and 5% loading and MPDA10 Xn=3.67 at 3%

loading slightly increase the glass transition temperature indicating that the hydrogen bonds

made the resin polymer chains less mobile. Thermal degradation analysis shows that the

additives do not lead to new degradation processes. Differential scanning calorimetry runs show

that the MDA10 Xn=3.67 additive at 3% loading increases the activation energy of the curing

process. This is most likely by caused hydrogen bonds of the amide groups of the additive. The

hydrogen bonds gave the material more rigidity and more resistance to movement making the

resin more viscous during the curing process and making it more difficult for the reactive groups

to meet.

Additives that improved the performance of MY720 resin were synthesized. These

additives did not compromise the other important properties of the resin such as glass transition

temperature and thermal degradation pattern and do not alter the curing process of the resin.

101
REFERENCES

102
1. Rakow, J. ISASI 2006 Annual Air Safety Seminar, Cancun, Mexico, September 11-14, 2006,
1-27. http://www.docstoc.com/docs/76893179/Failure-Analysis-of-Composite-Structures-in-
Aircraft-Accidents Retrieved on February 18, 2012.
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composites.php
3. Boeing 787 – Dreamliner. Retrieved on February 16, 2012
http://www.boeing.com/commercial/787family/programfacts.html
4. Liu, H. Journal of Polymer Science: Part A: Polymer Chemistry, 2004, 42, 3143-3156.

5. Moulton, R. Composite Structures; Proceeding of the 1st International Conference on

Composite Structures, 1981, 674-89.
6. Durcon Inc. (2006). Epoxy Resin Chemistry.
http://www.durcon.com/EpoxyResinChemistry.aspx. Retrieved on November 12, 2010:
7. Jeenjitkaew, C. Journal of Adhesion. 2011, 87, 4, 291-312.

8. Girard-Reydet, E. Macromolecules, 1995, 28, 7599-7607.

9. Odian, G. Principles of Polymerization. Wiley-Interscience., New Jersey, USA. 2004.

10. Robeson, L. Polymer Letters, 7, 35-40, 1969

11. Jackson. W. J., Caldwell, J.R., Journal of applied Polymer Science 1967, 2, 211-226

12. Stevenson, W.T.K., Journal of Polymer Science: Part B: Polymer Physics, 24, 717-22 1986.

13. Jackson. W. J., Caldwell, J.R., Journal of applied Polymer Science 1967, 2, 211-226

14. Typical Tensile Strength, Elongation and Tensile Modulus of Polymers

http://www.matweb.com/reference/tensilestrength.aspx Retrieved on February 19, 2012.
15. Brown, H. Journal of Materials Science.8, 7, 941-948.

16. Haldnakar, G. Polymeric Materials; science and engineering, proceedings of the ACS
Division of Polymeric Materials, Science and Engineering. 1990, 62, 120-124.
17. McLean, P. Polymer Composites, 1986, 5, Is 5, 330-336.

103
18. Garton. A. The Journal of Adhesion, 1989, 29, 13-26.

19. Zerda, A. S.; Lesser, A. J. Polymeric materials, 2001, 84, 1000-1002.

20. Don, T. Polymer Engineering and Science, 1996, 36, no. 21, 2601-2612.

21. Mann, P. European Polymer Journal, 1990, 26, No.4, 489-491.

22. Russo, P. Intrinsic Viscosity, 2008. http://macro.lsu.edu/howto/IntrinsicVisc.doc . Retrieved

on February 19, 2012.
23. Goosey, M. Plastics for Electronics, 2nd Ed. Kluwer Academic Publishers, The Netherlands,
p. 17, 1999.
24. Munden, B. Journal of Pharmaceutical Sciences, 1964, 53, 4, 395-401.

25. ASTM International, Standard Test Method for Tensile Properties of Plastics, D638-02.

26. Cain, J. Journal of Engineering Materials Technology, 2006, 128, 1, 34-41.

27. Ting, R. Y.; Cottington, R.L.; Journal of Applied Polymer Science, 1980, 25, 1815-1823.

28. Haines, P.J. Principles of Thermal Analysis and Calorimetry, Royal Society of Chemistry,
Manchester,U.K., 2002.
29. Bandrup, J.Polymer Handbook. Vol. 2, Wiley-Interscience, 2003.

30. Wypych, G. Handbook of Solvents. ChemTech Publishing, 2001.

104
APPENDICES

105
 APPENDIX A

Infrared spectra of additives

1.20 Nylon 6,6 Xn=3

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
wavenumber (cm-1 )

1.20 Nylon 6,6 Xn=5

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

106
 APPENDIX A (Continued)

2.50 Nylon 6,6 Xn=6

2.00

absorbance 1.50

1.00

0.50

0.00
4000 3500 3000 2500 2000 1500 1000 500
-1
wavenumber (cm )

1.20 Nylon 8,10 Xn=6

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

1.20 Nylon 6,12 Xn=3

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

107
 APPENDIX A (Continued)

1.20 Nylon 6,12 Xn=5

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

1.20 Nylon 10,12 Xn=3

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

1.20 Nylon 10,12 Xn=3.67

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

108
 APPENDIX A (Continued)

1.20 Nylon 10,12 Xn= 5

1.00

0.80

absorbance
0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

1.20 Nylon 12,12 Xn=3

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

109
 APPENDIX A (Continued)

MDA10 Xn=3.67

1.20

1.00

0.80
Absorbance
0.60

0.40

0.20

0.00
4,000 3,500 3,000 2,500 2,000 1,500 1,000 500
Wavenumber (cm- )

1.20 MDA10 Xn=5

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

110
 APPENDIX A (Continued)

1.20 MDA10 Xn=9

1.00

0.80
absorbance
0.60

0.40

0.20

0.00
3,950 3,450 2,950 2,450 1,950 1,450 950 450
-1
wavenumber (cm )

1.20 MPDA10 Xn=3.67

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
4000 3600 3200 2800 2400 2000 1600 1200 800 400
wavenumber (cm-)

1.20 MPDA10 Xn=5

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
4000 3600 3200 2800 2400 2000 1600 1200 800 400
wavenumber

111
 APPENDIX A (Continued)

1.20 MPDA10 Xn=9

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
4000 3600 3200 2800 2400 2000 1600 1200 800 400
wavenumber

1.20 PPDA10 Xn=3.67

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3950 3450 2950 2450 1950 1450 950 450
wavenumber

1.20 PPDA10 Xn=5

1.00

0.80
absorbance

0.60

0.40

0.20

0.00
3950 3450 2950 2450 1950 1450 950 450
wavenumber

112
 APPENDIX B

NMR SPECTRA

a. 1H NMR

1
H NMR Spectrum of MDA10 Xn=3.67

12 11 10 9 8 7 6 5 4 3 2 1 0
ppm

1
H NMR Spectrum of MDA10 Xn=5

12 11 10 9 8 7 6 5 4 3 2 1 0
ppm

113
 APPENDIX B (Continued)

1
HNMR Spectrum of MDA10 Xn=9

12 11 10 9 8 7 6 5 4 3 2 1 0
ppm

1
H NMR Spectrum of MPDA10 Xn=3.67
1000
900
800
700
600
500
400
300
200
100
0
12 11 10 9 8 7 6 5 4 3 2 1 0
ppm

1
H NMR Spectrum of MPDA10 Xn=5
800

700

600

500

400

300

200

100

0
12 11 10 9 8 7 6 5 4 3 2 1 0
ppm

114
 APPENDIX B (Continued)

1
H NMR Spectrum of MPDA10 Xn=9
1000
900
800
700
600
500
400
300
200
100
0
12 11 10 9 8 7 6 5 4 3 2 1 0
ppm

1
H NMR Spectrum of PPDA10 Xn=3.67

120

100

80

60

40

20

0
12 11 10 9 8 7 6 5 4 3 2 1 0
ppm

1H NMR Spectrum of PPDA10 Xn=9

1000
900
800
700
600
500
400
300
200
100
0
12 11 10 9 8 7 6 5 4 3 2 1 0
ppm

115
 APPENDIX B (Continued)

b. 13C NMR Spectra

13
C NMR Spectrum of MDA10 Xn=3.67

1000000

800000

600000

400000

200000

0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
Expanded C NMR Spectrum of MDA10 Xn=3.67

140000

120000

100000

80000

60000

40000

20000

0
200 180 160 140 120 100 80 60 40 20 0
ppm

116
 APPENDIX B (Continued)

13
C NMR Spectrum of MDA10 Xn=5
1200000

1000000

800000

600000

400000

200000

0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
C NMR Spectrum of MDA10 Xn=9

900000
800000
700000
600000
500000
400000
300000
200000
100000
0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
Expanded CNMR Spectrum of MDA10 Xn=9

250000

200000

150000

100000

50000

0
200 180 160 140 120 100 80 60 40 20 0
ppm

117
 APPENDIX B (Continued)

13
C NMR Spectrum of MPDA10 Xn=3.67

120000

100000

80000

60000

40000

20000

0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
Expanded C NMR Spectrum of MPDA10 Xn=3.67

40000

35000

30000
25000

20000

15000

10000
5000
0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
C NMR Spectrum MPDA10 Xn=5
600000

500000

400000

300000

200000

100000

0
200 180 160 140 120 100 80 60 40 20 0
ppm

118
 APPENDIX B (Continued)

13
Expanded C NMR Spectrum MPDA10 Xn=5
100000
90000
80000
70000
60000
50000
40000
30000
20000
10000
0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
C NMR Spectrum of MPDA10 Xn=9

800000
700000
600000
500000
400000
300000
200000
100000
0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
Expanded C NMR Spectrum of MPDA10 Xn=9

200000
180000
160000
140000
120000
100000
80000
60000
40000
20000
0
200 180 160 140 120 100 80 60 40 20 0
ppm

119
 APPENDIX B (Continued)

13
C NMR Spectrum of PPDA10 Xn=3.67

700000

600000

500000

400000

300000

200000

100000

0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
Expanded C NMR Spectrum of PPDA10 Xn=3.67

200000
180000
160000
140000
120000
100000
80000
60000
40000
20000
0
200 180 160 140 120 100 80 60 40 20 0
ppm

13
C NMR Spectrum of PPDA10 Xn=9

1000000
900000
800000
700000
600000
500000
400000
300000
200000
100000
0
200 180 160 140 120 100 80 60 40 20 0
ppm

120
 APPENDIX B (Continued)

13
Expanded C NMR Spectrum of PPDA10 Xn=9

50000
45000
40000
35000
30000
25000
20000
15000
10000
5000
0
200 180 160 140 120 100 80 60 40 20 0
ppm

121
 APPENDIX C

INTRINSIC VISCOSITY

Nsp/C vs C for Nylon 6,6 Xn=3.67

16
14 y = 686.2x + 2.9283
2
R = 0.946
12
10
Nsp/C

8
6
4
2
0
0 0.005 0.01 0.015 0.02
C (g/ml)

nsp/C vs C Nylon 6,6 Xn=5

16

14
y = 622.2896x + 5.1931
12 2
R = 0.9418
10
nsp/C

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018
C (g/ml)

122
 APPENDIX C (Continued)

Nsp/C vs C for Nylon 6,6 Xn=6

30

25
y = 866.63x + 10.664
2
R = 0.9736
20
nsp/C

15

10

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018
C (g/ml)

Nsp/C vs C for MDA10 Xn=3.67

35

30

25
nsp/C (ml/g)

y = 382.06x + 19.808
20 2
R = 0.9812
15

10

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04

C (g/ml)

Nsp/C vs C for MDA10 Xn=5

45
40 y = 392.07x + 22.112
2
35 R = 0.9989

30
nsp/C

25
20
15
10
5
0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045
C (g/ml)

123
 APPENDIX C (Continued)

Nsp/C vs C for MDA10 Xn=9

45

40
35
30
y = 453.24x + 27.165
nsp/C 25 2
R = 0.9826
20

15
10
5
0
0.000 0.005 0.010 0.015 0.020 0.025 0.030
C (g/ml)

Nsp/C vs C for MPDA10 Xn=3.67

25

y = 182.5x + 14.327
20 2
R = 0.577

15
nsp/C

10

0
0.000 0.010 0.020 0.030 0.040 0.050

C (g/ml)

Nsp/C vs C for MPDA10 Xn=5

26
24
y = 153.82x + 16.482
22
R2 = 0.9824
nsp/C

20
18
16
14
12
10
0.000 0.010 0.020 0.030 0.040 0.050

C (g/ml)

124
 APPENDIX C (Continued)

Nsp/C vs C for MPDA10 Xn=9

25

20 y = 99.824x + 16.844
2
R = 0.9821
nsp/C
15

10

0
0.000 0.010 0.020 0.030 0.040 0.050 0.060

C (g/ml)

GPC for MPDA10

1.0

0.9 MPDA10 Xn=3.67

MPDA10 Xn=5
0.8
MPDA10 Xn=9
0.7

0.6
W(log M)

0.5 t

0.4

0.3

0.2

0.1

0.0
1.00E+02 1.00E+03 1.00E+04 1.00E+05 1.00E+06
Molar Mass (Da)

125
 APPENDIX C (Continued)

GPC for MDA10

1.00
0.90 MDA10 Xn=3.67
0.80 MDA10 Xn=5
0.70 MDA10 Xn=9

0.60
W(log M)

0.50
0.40
0.30
0.20
0.10
0.00
1.00E+01 1.00E+02 1.00E+03 1.00E+04 1.00E+05 1.00E+06
Molar Mass (Da)

126
 APPENDIX D

TENSILE TEST RESULTS

a. For Specimens Cured for 2 hours at 140 ºC and 2 hours at 200 ºC

Tensile Testing Curves for Specimens Containing 5% Nylon 6,6 Xn = 3.67

Specimens Containing 5% Nylon 6,6 Xn=3.67

4.50E+07
4.00E+07
3.50E+07
sp 1
3.00E+07
Stress (MPa)

sp 2
2.50E+07
2.00E+07
1.50E+07
1.00E+07
5.00E+06
0.00E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 6,6 Xn = 3.67

Nylon 6,6 Xn = 3.67 5%

specimen stress (MPa) strain (%) modulus (MPa)
sp 1 40.7732 1.351 33.5287
sp 2 32.2679 1.042 33.4529
ave 36.5206 1.197 33.4908
st dev 6.0142 0.218 0.0536
% RSD 16.4679 18.261 0.1600

127
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 6,6 Xn = 5

Specimens Containing 5% Nylon 6,6 Xn=5

2.50E+07

2.00E+07 sp1
sp2
stress (Pa)

1.50E+07
sp3
1.00E+07

5.00E+06

0.00E+00
0 0.2 0.4 0.6 0.8
strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 6,6 Xn = 5

Nylon 6,6 Xn = 5 5%
Specimen stress (MPa) strain (%) modulus (MPa)
sp 1 22.5451 0.702 33.7170
sp 2 20.5422 0.63 33.0620
sp 3 23.2582 0.73 33.1545
ave 22.1152 0.6873 33.3112
st dev 1.4081 0.0516 0.3545
% RSD 6.3672 7.5055 1.0642

128
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 6,8 Xn = 5

Specimens Containing 5% Nylon 6,8 Xn=5

2.50E+07

2.00E+07 sp 1
sp 2
1.50E+07 sp 3
Stress (Pa)

1.00E+07

5.00E+06

0.00E+00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 6,8 Xn = 5

specimen modulus (MPa) strain (%) stress (MPa)

1 33.4971 0.653 21.7459
2 31.2711 0.538 16.8106
3 32.4586 0.632 20.8506
ave 32.4089 0.6077 19.8024
stdev 1.1138 0.0612 2.6293
% RSD 3.4368 10.0779 13.2779

129
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 6,12 Xn = 3.67

Specimens Containing 5% Nylon 6,12 Xn = 3.67

7.00E+07

6.00E+07

5.00E+07 sp 1
stress (Pa)

4.00E+07 sp 2

3.00E+07

2.00E+07

1.00E+07

0.00E+00
0 0.5 1 1.5 2 2.5 3
strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 6,12 Xn = 3.67

Nylon 6,12 Xn = 3.67 5%

Specimen stress (MPa) strain (%) Modulus (MPa)
sp 1 63.8586 2.503 30.5020
sp 2 50.5676 2.152 29.1099
Ave 57.2131 2.3275 29.8060
st dev 9.3981 0.2482 0.9844
% RSD 16.426574 10.66357 3.302661

130
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 6,12 Xn = 5

Specimens Containing 5% Nylon 6,12 Xn=5

8.E+07

7.E+07

6.E+07

5.E+07
sp1
stress (Pa)

4.E+07 sp2

3.E+07

2.E+07

1.E+07

0.E+00
0 0.5 1 1.5 2 2.5 3
strain %

Tensile Testing Summary for Specimens Containing 5% Nylon 6,12 Xn = 5

Containing 5% Nylon 6,12 Xn = 5

sample stress (MPa) strain (%) modulus MPa)
sp 1 68.5274 2.603 35.1186
sp 2 68.9426 2.620 32.7982
ave 68.7350 2.6115 33.9584
st dev 0.2936 0.0120 1.6408
% rsd 0.4271 0.460 4.8318

131
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 10,12 Xn = 3.67

Specimens Containing 5% Nylon 10,12 Xn=3.67

1.00E+08
9.00E+07 sp1
8.00E+07 sp 2
sp 3
7.00E+07
sp 4
Stress (MPa)

6.00E+07
5.00E+07
4.00E+07
3.00E+07
2.00E+07
1.00E+07
0.00E+00
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
Strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 6,12 Xn = 3.67

Nylon 10, 12 Xn = 3.67 5%

sample stress (MPa) strain (%) modulus (MPa)
sp 1 74.3288 2.748 34.4210
sp 2 90.9595 3.840 32.9011
sp 3 65.3933 2.499 32.0302
sp 4 87.7869 3.541 34.0632
ave 79.6171 3.157 33.3539
st dev 11.9119 0.636 1.0953
% RSD 14.9614 20.152 3.2839

132
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 10,12 Xn = 5

Specimens Containing 5% Nylon 10,12 Xn=5

8.00E+07

7.00E+07

6.00E+07
sp 1
5.00E+07
sp 2
Stress (Pa)

4.00E+07 sp 3

3.00E+07

2.00E+07

1.00E+07

0.00E+00
0 0.5 1 1.5 2 2.5 3

Strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 10,12 Xn = 5

nylon 10,12 Xn=5

specimen stress (MPa) strain (%) modulus (MPa)
sp 1 71.4643 2.602 33.2409
sp 2 72.0848 2.691 33.2669
sp 3 57.3356 1.964 33.8758
Ave 66.9616 2.419 33.4612
st dev 8.3421 0.397 0.3593
% RSD 12.4580 16.393 1.0738

133
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 12,12 Xn = 3.67

Specimens Containing 5% Nylon 12,12 Xn=3.67

1.00E+08

8.00E+07 sp 2
sp 3
sp 4
6.00E+07
stress (Pa)

4.00E+07

2.00E+07

0.00E+00
0 1 2 3 4
strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 12,12 Xn = 3.67

nylon 12,12 Xn=3.67 5%

specimen stress (MPa) strain (%) modulus (MPa)
sp 1 64.6362 2.353 32.0030
sp 2 70.4983 2.645 32.0235
sp 3 90.8098 3.787 32.4342
Ave 75.3148 2.928 32.1536
st dev 13.7355 0.758 0.2433
% RSD 18.2374 25.879 0.7566

134
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 12,12 Xn = 5

Specimens Containing 5% Nylon 12,12 Xn=5

8.00E+07
7.00E+07 sp 1
sp 2
6.00E+07
sp 3
Stress (MPa)

5.00E+07
4.00E+07
3.00E+07
2.00E+07
1.00E+07
0.00E+00
0 0.5 1 1.5 2 2.5 3
Strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 12,12 Xn = 5

nylon 12,12 Xn=5 5%

specimen stress (MPa) strain (%) modulus (MPa)
sp 1 69.6994 2.663 32.4721
sp 2 67.7015 2.523 32.0355
sp 3 59.5587 2.159 32.0177
ave 65.6532 2.448 32.1751
st dev 5.3717 0.260 0.2574
% RSD 8.1819 10.626 0.7999

135
 APPENDIX D (Continued)

b. Tensile Test Results for resins cured for 2 hrs at 140 ⁰C and 4 hours at 200 ⁰C

Tensile Testing Curves for Specimens Containing 5% Nylon 10,12 Xn = 3

Specimens Containing 5% Nylon 10,12 Xn=3

8.00E+07

7.00E+07

6.00E+07
sp1
5.00E+07 sp2
stress (Pa)

sp3
4.00E+07

3.00E+07

2.00E+07

1.00E+07

0.00E+00
0 0.5 1 1.5 2 2.5 3
strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 10,12, Xn = 3

nylon 10,12 Xn=3 2h at 140C 4h at 200C

Specimen stress (MPa) strain (%) Modulus (MPa)
sp 1 64.9886 2.391 32.5807
sp 2 69.8105 2.668 31.9496
sp 3 45.1569 1.445 34.5777
Ave 59.9853 2.1680 33.0360
st dev 13.0662 0.6413 1.3719
% RSD 21.7823 29.5789 4.1528

136
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 10,12 Xn = 3.67

Specimens Containing 5% Nylon 10,12 Xn=3.67

9.00E+07

8.00E+07

7.00E+07 sp 1
sp 2
6.00E+07
sp 3
stress (Pa)

5.00E+07

4.00E+07

3.00E+07

2.00E+07

1.00E+07

0.00E+00
0 0.5 1 1.5 2 2.5 3 3.5 4
strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 10,12 Xn = 3.67

nylon 10,12 Xn=3.67 2h at 140C 4h at 200C

Specimen stress (MPa) Strain (%) modulus (MPa)
sp 1 68.3478 2.559 32.6462
sp 2 77.4019 3.005 33.9737
sp 3 84.0397 3.614 33.0546
Ave 76.5965 3.059 33.2248
st dev 7.8769 0.530 0.6799
% RSD 10.2836 17.311 2.0464

137
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 10,12 Xn = 5

Specimens Containing 5% Nylon 10,12 Xn=5

8.00E+07
7.00E+07
6.00E+07
5.00E+07
stress (Pa)

4.00E+07
3.00E+07
2.00E+07
1.00E+07
0.00E+00
0 0.5 1 1.5 2 2.5 3
strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 10,12 Xn = 5

nylon 10,12 Xn=5 2h at 140C 4h at 200C

specimen Stress (MPa) strain (%) modulus (MPa)
sp 1 68.3493 2.534 33.9516
sp 2 29.8793 2.691 34.0191

ave 49.1143 2.6125 33.9854

st dev 27.2024 0.1110 0.0477

138
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 12,12 Xn = 3

Specimens Containing 5% Nylon 12,12 X=3

8.00E+07
7.00E+07
6.00E+07
sp 1
Stress (Pa)

5.00E+07
sp 2
4.00E+07
3.00E+07
2.00E+07
1.00E+07
0.00E+00
0 0.5 1 1.5 2 2.5 3
Strain %

Tensile Testing Summary for Specimens Containing 5% Nylon 12,12 Xn = 3

nylon 12,12 Xn=3 2h at 140C 4h at 200C

Specimen stress (MPa) strain (%) modulus (MPa)
sp 1 71.5521 2.552 35.6807
sp 2 73.8450 2.796 33.8127
ave 72.6986 2.6740 34.7467
st dev 1.6213 0.1725 1.3209
% RSD 2.230217192 6.452283269 3.801445543

139
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 12,12 Xn = 3.67

Specimens Containing 5% Nylon12,12 Xn = 3.67

8.00E+07

7.00E+07

6.00E+07 sp 1
sp 2
5.00E+07 sp 3
stress (Pa)

4.00E+07

3.00E+07

2.00E+07

1.00E+07

0.00E+00
0 0.5 1 1.5 2 2.5 3
strain (%)

Tensile Testing Summary for Specimens Containing 5% Nylon 12,12 Xn = 3.67

Nylon 12,12Xn = 3.67 5%

Specimen stress (MPa) strain (%) modulus (MPa)
sp 1 70.8773 2.67 32.0052
sp 2 39.9186 1.36 30.8887
sp 3 59.4882 2.165 31.6549
Ave 56.7614 2.065 31.5163
st dev 15.6585 0.661 0.5710
% RSD 27.5865 31.995 1.8118

140
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% Nylon 12,12 Xn = 5

Specimens Containing 5% Nylon 12,12 Xn=5

9.00E+07
sp 1
8.00E+07
sp 2
7.00E+07 sp3
6.00E+07
stress (Pa)

5.00E+07
4.00E+07
3.00E+07
2.00E+07
1.00E+07
0.00E+00
0 0.5 1 1.5 2 2.5 3 3.5
strain %

Tensile Testing Summary for Specimens Containing 5% Nylon 12,12 Xn = 5

Nylon 12,12 Xn = 5 5%
specimen stress (MPa) strain (%) Modulus (MPa)
sp 1 76.3364 3.056 32.2354
sp 2 63.5238 2.105 32.8278
sp 3 64.5912 2.329 33.5162
Ave 68.1505 2.497 32.8598
st dev 7.1093 0.497 0.6410
% RSD 10.4317 19.914 1.9507

141
 APPENDIX D (Continued)

d. Tensile Testing Results for Specimens Containing MDA10, MPDA10 and PPDA10
Oligomers

Tensile Testing Curves for Specimens Containing 10% MDA10 Xn=3.67

Specimens Containing 3% MDA10 Xn=3.67

6.0E+07

5.0E+07 sp1
sp2
4.0E+07 sp3
sp4
stress (Pa)

sp5
3.0E+07 sp6
sp7

2.0E+07

1.0E+07

0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
strain %

Tensile Testing Summary for Specimens Containing 3% MDA10 Xn=3.67

specimen modulus (MPa) strain (%) stress (MPa)

1 33.8336 1.368 42.8236
2 33.5845 1.269 39.8232
3 34.2566 1.291 40.9951
4 33.9762 1.557 48.5604
5 34.2275 1.362 43.5227
6 35.8359 1.138 38.4628
7 33.0508 1.585 47.8336
ave 34.1093 1.367 43.1459
stdev 0.8666 0.159 3.8543
% RSD 2.5408 11.622 8.9333

142
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% MDA10 Xn=3.67

Specimens with 5% MDA10 Xn=3.67

8.0E+07

7.0E+07

sp1
6.0E+07
sp2
5.0E+07
sp3
stress (Pa)

4.0E+07 sp4

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.5 1 1.5 2 2.5 3
strain %

Tensile Testing Summary for Specimens Containing 5% MDA10 Xn=3.67

Specimen modulus (MPa) strain to failure (%) stress at break (MPa)

1 33.1941 1.922 55.6028
2 32.0142 2.612 69.4020
3 32.7554 1.948 56.6752
4 32.9298 2.028 58.1551
ave 32.7234 2.1275 59.9588
stdev 0.5060 0.326 6.3819
%RSD 1.5464 15.329 10.6437

143
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 10% MDA10 Xn=3.67

Specimens Containing 10% MDA10 Xn=3.67

6.0E+07
sp1
5.0E+07 sp2
sp3
4.0E+07
sp4
stress (Pa)

3.0E+07 sp5

2.0E+07

1.0E+07

0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
strain %

Tensile Testing Summary for Specimens Containing 10% MDA10 Xn=3.67

Specimen Modulus (MPa) strain to failure (%) stress at break (MPa)

1 36.9211 0.98 35.1407
2 36.5445 1.468 49.2595
3 33.1914 1.296 39.7964
4 34.2304 1.173 37.9162
5 32.5800 1.252 38.2985
ave 34.6935 1.234 40.0822
stdev 1.9574 0.178 5.3990
%RSD 5.6421 14.451 13.4698

144
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 3% MDA10 Xn=5

Specimens Containing 3% MDA10 Xn=5

5.0E+07
4.5E+07
4.0E+07 sp1
3.5E+07 sp2
3.0E+07 sp3
stress (Pa)

2.5E+07
2.0E+07
1.5E+07
1.0E+07
5.0E+06
0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
strain %

Tensile Testing Summary for Specimens Containing 3% MDA10 Xn=5

specimen modulus (MPa) strain to failure (%) stress at break (MPa)

1 36.4612 1.390 45.9595
2 35.3390 1.403 45.4694
3 37.5630 1.212 42.5996
ave 36.4544 1.335 44.6762
stdev 1.1120 0.107 1.8150
% RSD 3.0505 7.994 4.0625

145
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% MDA10 Xn=5

Specimens Containing 5% MDA10 Xn=5

4.5E+07

4.0E+07

3.5E+07 sp1
sp2
3.0E+07 sp3
sp4
stress (Pa)

2.5E+07

2.0E+07

1.5E+07

1.0E+07

5.0E+06

0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4
strain %

Tensile Testing Summary for Specimens Containing 5% MDA10 Xn=5

sample modulus (MPa) Strain to failure (%) stress at break (MPa)

1 34.4491 1.310 42.2216
2 34.9568 1.475 47.2632
3 35.0137 1.299 42.2669
4 33.9222 2.037 59.6095
Ave 34.5855 1.530 47.8403
stdev 0.5098 0.347 8.1951
% RSD 1.4741 22.695 17.1302

146
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 3% MDA10 Xn=9

Specimens Containing 3% MDA10 Xn=9

6.0E+07

5.0E+07
sp1
sp2
4.0E+07
sp3
stress (Pa)

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
strain %

Tensile Testing Summary for Specimens Containing 3% MDA10 Xn=9

Specimen Modulus (MPa) strain (%) stress at break (MPa)

1 36.2114 1.163 39.5324
2 33.5668 1.523 46.9286
3 35.0296 1.567 49.6253
ave 34.9359 1.418 45.3621
stdev 1.3248 0.222 5.2256
% RSD 3.7920 15.634 11.5198

147
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% MDA10 Xn=9

Specimens Containing 5% MDA10 Xn=9

9.0E+07

8.0E+07
sp1
7.0E+07
sp2
6.0E+07 sp3
stress (Pa)

5.0E+07 sp4

4.0E+07

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.5 1 1.5 2 2.5 3 3.5
strain %

Tensile Testing Summary for Specimens Containing 5% MDA10 Xn=9

Specimen modulus (MPa) strain (%) stress at break (MPa)

1 36.7700 2.466 72.8903
2 36.7993 2.559 75.7899
3 33.1452 3.010 76.2144
4 31.8003 3.240 79.0401
ave 34.6287 2.819 75.9837
stdev 2.5493 0.368 2.5167
% RSD 7.3619 13.050 3.3122

148
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 10% MDA10 Xn=9

Specimens Containing 10% MDA10 Xn=9

8.0E+07

7.0E+07
sp1
6.0E+07 sp2

5.0E+07 sp3
stress (Pa)

sp4
4.0E+07 sp5

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.5 1 1.5 2 2.5
strain %

Tensile Testing Summary for Specimens Containing 10% MDA10 Xn=9

sample modulus (MPa) strain (%) stress at break (MPa)

1 38.0369 1.378 47.4443
2 34.7003 2.328 69.7930
3 34.6780 1.302 42.4859
4 32.4633 2.162 59.6200
5 33.7085 2.192 60.5699
ave 34.7174 1.872 55.9826
stdev 2.0688 0.491 10.9552
% RSD 5.9590 26.210 19.5689

149
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 3% MPDA10 Xn=3.67

Specimens Containing 3% MPDA10 Xn=3.67

7.0E+07

6.0E+07
sp1
5.0E+07 sp2
sp3
sp4
stress (Pa)

4.0E+07

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.5 1 1.5 2 2.5
strain %

Tensile Testing Summary for Specimens Containing 3% MPDA10 Xn=3.67

Specimen modulus (MPa) strain (%) stress at break (MPa)

1 35.6870 1.691 54.0702
2 35.9517 2.020 63.4879
3 33.8357 1.530 48.2066
4 36.0078 1.719 55.1947
Ave 35.3705 1.740 55.2398
stdev 1.0328 0.204 6.2946
% RSD 2.9199 11.747 11.3951

150
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% MPDA10 Xn=3.67

Specimens Containing 5% MPDA10 Xn=3.67

6.0E+07

5.0E+07 sp1
sp2
sp3
4.0E+07
sp4
stress (Pa)

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
strain %

Tensile Testing Summary for Specimens Containing 3% MPDA10 Xn=3.67

Specimen modulus (MPa) Strain (%) stress at break (MPa)

1 34.7244 0.951 31.9386
2 35.6717 1.245 41.5788
3 34.3274 1.693 51.6853
4 36.1150 1.313 43.7212
Ave 35.2096 1.301 42.2310
Stdev 0.8260 0.305 8.1233
% RSD 2.3460 23.468 19.2354

151
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 3% MPDA10 Xn=5

Specimens Containing 3% MPDA10 Xn=5

5.0E+07
4.5E+07
4.0E+07 sp1
sp2
3.5E+07
sp3
3.0E+07
stress (Pa)

2.5E+07
2.0E+07
1.5E+07
1.0E+07
5.0E+06
0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
strain %

Tensile Testing Summary for Specimens Containing 3% MPDA10 Xn=3.67

Specimen strain (%) stress (MPa) modulus (Mpa)

1 1.277 41.7537 34.8148
2 0.757 27.1849 36.5468
3 1.475 45.8956 33.9869
ave 1.170 38.278 35.1162
stdev 0.371 9.8276 1.3063
% RSD 31.705 25.6743 3.7199

152
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 3% PPDA10 Xn=3.67

Specimens Containing 3% PPDA10 Xn=3.67

7.0E+07

6.0E+07
sp1
sp2
5.0E+07
sp3
sp4
stress (Pa)

4.0E+07 sp5

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.5 1 1.5 2 2.5
strain %

Tensile Testing Summary for Specimens Containing 3% PPDA10 Xn=3.67

Specimen modulus (Mpa) strain % Stress (Mpa)

1 35.8097 1.636 52.9495
2 33.2881 1.829 54.0202
3 33.8838 2.051 58.5377
4 32.1790 1.778 51.6643
5 33.6062 2.109 59.1830
ave 33.7534 1.881 55.2709
stdev 1.3193 0.196 3.3889
% RSD 3.9086 10.441 6.1313

153
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% PPDA10 Xn=3.67

Specimens Containing 5% PPDA10 Xn=3.67

8.0E+07

7.0E+07
sp1
6.0E+07 sp2
sp3
5.0E+07
sp4
stress (Pa)

4.0E+07

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.5 1 1.5 2 2.5
strain %

Tensile Testing Summary for Specimens Containing 5% PPDA10 Xn=3.67

Specimen modulus (MPa) strain % stress (MPa)

1 36.1325 1.704 54.5014
2 35.7912 1.541 50.3034
3 34.9861 2.316 68.4302
4 34.9777 1.903 57.7337
ave 35.4719 1.866 57.7422
stdev 0.5827 0.335 7.7475
% RSD 1.6427 17.928 13.4174

154
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 10% PPDA10 Xn=3.67

Specimens Containing 10% PPDA10 Xn=3.67

4.5E+07

4.0E+07

3.5E+07 sp1
sp2
3.0E+07 sp3
stress (Pa)

2.5E+07

2.0E+07

1.5E+07

1.0E+07

5.0E+06

0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4
strain %

Tensile Testing Summary for Specimens Containing 10% PPDA10 Xn=3.67

specimens strain % stress (MPa) modulus (MPa)

1 1.118 37.01552 34.7453
2 1.127 38.75530 35.8071
3 1.151 39.63420 36.1137
ave 1.132 38.46834 35.5554
stdev 0.017 1.3327 0.7181
% RSD 1.507 3.4645 2.0196

155
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 3% PPDA10 Xn=5

Specimens Containing 3% PPDA10 Xn=5

7.0E+07

6.0E+07
sp1
sp2
5.0E+07
sp3
sp4
stress (Pa)

4.0E+07 sp5

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.5 1 1.5 2 2.5 3
strain %

Tensile Testing Summary for Specimens Containing 3% PPDA10 Xn=5

Specimen modulus (MPa) strain % stress (MPa)

1 34.9193 1.242 40.32238
2 35.3081 1.570 50.06721
3 33.6436 1.747 52.61501
4 31.7737 2.173 60.14417
5 32.2561 2.383 65.12327
ave 33.5802 1.823 53.6544
stdev 1.5652 0.459 9.5570
% RSD 4.6611 25.189 17.8121

156
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% PPDA10 Xn=5

Specimens Containing 5% PPDA10 Xn=5

6.0E+07

5.0E+07
sp1
sp2
sp3
4.0E+07
sp4
stress (Pa)

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
strain %

Tensile Testing Summary for Specimens Containing 5% PPDA10 Xn=5

Specimen strain % stress (MPa) modulus (MPa)

1 1.377 44.2704 35.3012
2 1.655 51.9385 35.6315
3 1.456 45.5443 33.9393
4 1.429 45.5165 34.8249
ave 1.479 46.8175 34.9242
stdev 0.122 3.4654 0.7354
% RSD 8.225 7.4018 2.1057

157
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 10% PPDA10 Xn=5

Specimens Containing 10% PPDA10 Xn=5

7.00E+07

6.00E+07 Sp 1
Sp 2
5.00E+07 Sp 3
Sp 4
4.00E+07
Stress (Pa)

3.00E+07

2.00E+07

1.00E+07

0.00E+00
0 0.5 1 1.5 2 2.5
Strain %

Tensile Testing Summary for Specimens Containing 10% PPDA10 Xn=5

specimen strain (%) stress (MPa) modulus (MPa)

1 2.008 58.7975 33.5722
2 1.994 60.6695 35.8558
3 1.102 37.4085 35.6084
4 1.285 41.9867 34.9919
ave 1.597 49.7156 35.0071
stdev 0.472 11.7427 1.0232
% RSD 29.563 23.6197 2.9229

158
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 3% PPDA10 Xn=9

Specimens Containing 3% PPDA10 Xn=9

6.0E+07

5.0E+07
sp1
sp2
4.0E+07 sp3
sp4
stress (Pa)

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
strain %

Tensile Testing Summary for Specimens Containing 3% PPDA10 Xn=9

Specimen modulus (MPa) Strain ( %) stress (MPa)

1 33.7138 1.860 55.1534
2 34.7895 1.774 55.2160
3 35.5154 1.022 35.1204
4 36.2434 1.175 40.2908
ave 35.0655 1.458 46.4452
stdev 1.0791 0.421 10.3100
% RSD 3.0773 28.878 22.1982

159
 APPENDIX D (Continued)

Tensile Testing Curves for Specimens Containing 5% PPDA10 Xn=9

Specimens Containing 5% MDA10 Xn=9

8.0E+07

7.0E+07

sp1
6.0E+07 sp2
sp3
5.0E+07 sp4
stress (Pa)

4.0E+07

3.0E+07

2.0E+07

1.0E+07

0.0E+00
0 0.5 1 1.5 2 2.5 3
strain %

Tensile Testing Summary for Specimens Containing 5% PPDA10 Xn=9

Specimen strain (%) stress (MPa) Modulus (MPa)

1 1.588 47.5440 33.7188
2 1.424 44.2970 34.3718
3 2.693 71.7302 32.9774
4 2.384 64.3618 33.2683
ave 2.022 56.9832 33.5841
stdev 0.613 13.1904 0.6073
% RSD 30.312 23.1478 1.8083

160
 APPENDIX E

FRACTURE TOUGHNESS

Stress-Strain Curves of Control Resins

Control Resin Specimen 2

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

Control Resin Specimen 3

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04
Crosshead Displacement (cm)

161
 APPENDIX E (Continued)

Control Resin Specimen 4

250

Load (N) 200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

Control Resin Specimen 5

250

200
Load (N)

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02
Crosshead Displacement (cm)

Control Resin Specimen 6

250

200
Load (N)

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014
Crosshead Displacement (cm)

162
 APPENDIX E (Continued)

Stress-Strain Curves for Resins Containing 3% MDA10 Xn=3.67

Fracture Toughness Test for MDA10 Xn=3.67 3% Specimen 1

250

200

150
Load (N)

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03
Crosshead Displacement (cm)

Fracture Toughness Test for MDA10 Xn=3.67 3% Specimen 2

2.5E+02

2.0E+02

1.5E+02
Load (N)

1.0E+02

5.0E+01

0.0E+00
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

Fracture Toughness Test for MDA10 Xn=3.67 3% Specimen 4

3.0E+02

2.5E+02

2.0E+02
Load (N)

1.5E+02

1.0E+02

5.0E+01

0.0E+00
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

163
 APPENDIX E (Continued)

Summary of Fracture Toughness Test on Resins Containing 3% MDA10 Xn=3.67

MDA10 hole to
Xn=3.67 fracture crack elastic edge fracture Fracture
3% geometrical load (N) length a modulus E dist W thickness energy toughness
Specimen factor P (m) (Pa) (m) b (m) (J/m2) (MPa*m1/2)
1 23.146148 224.45 0.00331 34109276.87 0.025 0.0064 102308.36 1.8681
2 23.146148 243.84 0.00349 34109276.87 0.025 0.0064 127318.49 2.0839
3 23.146148 318.79 0.00235 34109276.87 0.025 0.0064 146523.94 2.2356
4 23.146148 269.17 0.00277 34109276.87 0.025 0.0064 123132.56 2.0494
average 2.0592
std dev 0.15
% RSD 7.33

Stress-Strain Curves for Resins Containing 5% MDA10 Xn=3.67

Fracture Tougness Test for MDA10 Xn=3.67 5% Specimen 1

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

Fracture Tougness Test for MDA10 Xn=3.67 5% Specimen 2

400

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045
Crosshead Displacement (cm)

164
 APPENDIX E (Continued)

Fracture Tougness Test for MDA10 Xn=3.67 5% Specimen 3

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

Fracture Tougness Test for MDA10 Xn=3.67 5% Specimen 4

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03
Crosshead Displacement (cm)

Summary of Fracture Toughness Test for Resins Containing 5% MDA10 Xn=3.67

MDA10 hole to
Xn=3.67 fracture crack elastic edge fracture Fracture
5% geometrical load (N) length a modulus E dist W thickness toughness Toughness
Specimen factor P (m) (Pa) (m) b (m) (J/m2) (MPa*m1/2)
1 23.14614784 272.93 0.00270 32723385.49 0.025 0.0064 128623.20 2.0516
2 23.14614784 385.96 0.00153 32723385.49 0.025 0.0064 145758.65 2.1840
3 23.14614784 278.13 0.00259 32723385.49 0.025 0.0064 127888.10 2.0457
4 23.14614784 238.70 0.00305 32723385.49 0.025 0.0064 111141.36 1.9071
average 128352.83 2.0471
std dev 14136.08 0.11
% RSD 11.01 5.52

165
 APPENDIX E (Continued)

Stress-Strain Curves for Resin Containing 3% MDA10 Xn=5

Fracture Toughness for MDA10 Xn=5 3% Specimen 1

400

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03
Crosshead Displacement (cm)

Fracture Toughness for MDA10 Xn=5 3% Specimen 2

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Dispalcement (cm)

Fracture Toughness for MDA10 Xn=5 3% Specimen 3

300

250

200
Load (N)

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018
Crosshead Dispalcement (cm)

166
 APPENDIX E (Continued)

Summary of Fracture Toughness Test for Resins Containing 3% MDA10 Xn=5

MDA10
Xn=3.67 fracture crack elastic hole to fracture Fracture
3% geometrical load length modulus E edge dist thickness energy Toughness
Specimen factor (Pa) P a (m) (Pa) W (m) b (m) (J/m2) (MPa*m1/2)
1 23.14615 360.53 0.0014 36454413.14 0.025 0.0064 105957.58 1.965355
2 23.14615 327.46 0.0015 36454413.14 0.025 0.0064 92954.43 1.840815
3 23.14615 267.78 0.0030 36454413.14 0.025 0.0064 124316.49 2.128822
average 1.9783
std dev 0.14
% RSD 7.30

Stress-Strain Curves for Resins Containing 5% MDA10 Xn=5

Fracture Toughness Test for MDA10 Xn=5 5% Specimen 1

70

60

50
Load (N)

40

30

20

10

0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08
Crosshead Displacement (cm)

Fracture Toughness Test for MDA10 Xn=5 5% Specimen 2

140

120

100
Load (N)

80

60

40

20

0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
Crosshead Displacement (cm)

167
 APPENDIX E (Continued)

Fracture Toughness Test for MDA10 Xn=5 5% Specimen 3

100
90
80
70
Load (N)

60
50
40
30
20
10
0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05
Crosshead Displacement (cm)

Fracture Toughness Test for MDA10 Xn=5 5% Specimen 4

300

250

200
Load (N)

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02
Crosshead Displacement (cm)

Summary of Fracture Toughness Test for Resins Containing 5% MDA10 Xn=5

MDA10 fracture crack elastic hole to fracture fracture

Xn=5 geometrical load (N) length a modulus E edge dist thickness toughness toughness
5% factor, Y P (m) (Pa) W (m) b (m) (J/m2) (MPa*m1/2)
1 23.14615 77.33 0.0320 34585453.93 0.025 0.0064 115777.48 2.001054
2 23.14615 321.27 0.00180 34585453.93 0.025 0.0064 112418.64 1.971814
3 23.14615 98.79 0.0120 34585453.93 0.025 0.0064 70683.86 1.563532
4 23.14615 277.01 0.00219 34585453.93 0.025 0.0064 101686.51 1.875333
average 1.8529
std dev 0.20
% RSD 10.81

168
 APPENDIX E (Continued)

Stress-Strain Curves for Resins Containing 5% MDA10 Xn=9

Fracture Toughness for MDA10 Xn=9 5% Specimen 1

400

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

Fracture Toughness for MDA10 Xn=9 5% Specimen 2

400
350
300
250
Load (N)

200
150
100
50
0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05
Crosshead Displacement (cm)

Fracture Toughness for MDA10 Xn=9 5% Specimen 3

400

350

300

250
Load (N)

200

150

100

50

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Crosshead Dispalcement (cm)

169
 APPENDIX E (Continued)

Fracture Toughness for MDA10 Xn=9 5% Specimen 4

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045
Crosshead Displacement (cm)

Fracture Toughness for MDA10 Xn=9 3% Specimen 5

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05
Crosshead Displacement (cm)

Fracture Toughness for MDA10 Xn=9 3% Specimen 6

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement(cm)

170
 APPENDIX E (Continued)

Summary of Fracture Toughness Test on Resins Containing 5% MDA10 Xn=9

MDA10 fracture crack elastic hole to fracture fracture
Xn=9 geometrical load (N) length a modulus E edge dist thickness energy toughness
5% factor, Y P (m) (Pa) W (m) b (m) (J/m2) (Pa*m1/2)
1 23.14615 360.04 0.0011 34628706.08 0.025 0.0064 86172.14 1.7274
2 23.14615 353.33 0.0013 34628706.08 0.025 0.0064 95064.26 1.8144
3 23.14615 361.15 0.0013 34628706.08 0.025 0.0064 99319.94 1.8545
4 23.14615 283.75 0.0024 34628706.08 0.025 0.0064 115317.00 1.9983
5 23.14615 260.77 0.0028 34628706.08 0.025 0.0064 114247.71 1.9890
6 23.14615 313.17 0.0013 34628706.08 0.025 0.0064 77050.43 1.6334
average 1.8362
std dev 0.14
% RSD 7.83

Stress-Strain Curves for Resins Containing 3% MPDA10 Xn=3.67

Fracture Toughness for MPDA10 Xn = 3.67 3% Specimen 1

250

200

150
Load (N)

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

171
 APPENDIX E (Continued)

Fracture Toughness for MPDA10 Xn = 3.67 3% Specimen 2

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

Fracture Toughness for MPDA10 Xn = 3.67 3% Specimen 3

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

Fracture Toughness for MPDA10 Xn = 3.67 3% Specimen 4

350

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshoead Displacement (cm)

172
 APPENDIX E (Continued)

Fracture Toughness for MPDA10 Xn = 3.67 3% Specimen 5

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

Summary of Fracture Toughness Test on Resins Containing 3% MPDA10 Xn=3.67

hole to
MPDA10 fracture crack elastic edge fracture fracture
Xn=3.67 geometrical load (N) length a modulus E dist W thickness energy toughness
3% factor, Y P (m) (Pa) (m) b (m) (J/m2) (Pa*m1/2)
1 23.14614784 217.48 0.00348 35370539.97 0.025 0.0064 97388.93 1.8560
2 23.14614784 244.15 0.00299 35370539.97 0.025 0.0064 105449.91 1.9313
3 23.14614784 238.16 0.00289 35370539.97 0.025 0.0064 96988.07 1.8522
4 23.14614784 305.71 0.00261 35370539.97 0.025 0.0064 144322.90 2.2594
5 23.14614784 267.02 0.00238 35370539.97 0.025 0.0064 100403.25 1.8845
average 1.9567
std dev 0.17
% RSD 8.80

Stress-Strain Curves for Resins Containing 3% MPDA10 Xn=9

173
 APPENDIX E (Continued)

Fracture Toughness For MPDA10 Xn = 3.67 5% Specimen 1

400

350

300

250
Load (N)

200

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02
Crosshead Displacement (cm)

Fracture Toughness For MPDA10 Xn = 3.67 5% Specimen 2

350

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

Fracture Toughness For MPDA10 Xn = 3.67 5% Specimen 3

400

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

174
 APPENDIX E (Continued)

Fracture Toughness For MPDA10 Xn = 3.67 5% Specimen 4

300

250

200
Load (N)

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012
Crosshead Displacement (cm)

Fracture Toughness For MPDA10 Xn = 3.67 5% Specimen 5

350

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

Fracture Toughness For MPDA10 Xn = 3.67 5% Specimen 6

450

400

350

300
Load (N)

250

200

150

100

50

0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
Crosshead Displacement (cm)

175
 APPENDIX E (Continued)

Summary of Fracture Toughness Test on Resins Containing 5% MPDA10 Xn=3.67

hole to
MPDA10 fracture crack elastic edge fracture Fracture
Xn=3.67 geometrical load length a modulus E dist W thickness energy toughness
5% factor, Y (N) P (m) (Pa) (m) b (m) (J/m2) (Pa*m1/2)
1 23.14615 352.13 0.0015 35209621.42 0.025 0.0064 110549.16 1.9729
2 23.14615 299.68 0.0019 35209621.42 0.025 0.0064 101423.12 1.8897
3 23.14615 363.42 0.0012 35209621.42 0.025 0.0064 94200.97 1.8212
4 23.14615 253.30 0.0027 35209621.42 0.025 0.0064 102969.09 1.9041
5 23.14615 323.87 0.00194 35209621.42 0.025 0.0064 120948.90 2.0636
6 23.14615 324.45 0.0013 35209621.42 0.025 0.0064 81335.96 1.6923
average 101904.53 1.8906
std dev 13573.46 0.13
% RSD 13.32 6.73

Stress-Strain Curves for Resins Containing 3% PPDA10 Xn=3.67

Fracture Toughness for PPDA10 Xn=3.67 3% Specimen 1

250

200

150
Load (N)

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=3.67 3% Specimen 2

400

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

176
 APPENDIX E (Continued)

Fracture Toughness for PPDA10 Xn=3.67 3% Specimen 3

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=3.67 3% Specimen 4

600

500

400
Load (N)

300

200

100

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

Summary of Fracture Toughness Test for Resins Containing 3% PPDA10 Xn=3.67

PPDA10 fracture crack elastic hole to fracture fracture

Xn=3.67 geometrical load length a modulus E edge dist thickness toughness toughness
3% factor, Y (N) P (m) (Pa) W (m) b (m) (J/m2) (Pa*m1/2)
1 23.14615 207.782 0.00465 33753364.41 0.025 0.0064 124471.35 2.0497
2 23.14615 354.48 0.00155 33753364.41 0.025 0.0064 120758.32 2.0189
3 23.14615 319.25 0.0023 33753364.41 0.025 0.0064 145346.17 2.2149
4 23.14615 480.69 0.00122 33753364.41 0.025 0.0064 174778.87 2.4289
average 2.1781
std dev 0.19
% RSD 8.63

177
 APPENDIX E (Continued)

Stress- Strain Curves for Resins Containing 5% PPDA10 Xn=3.67

Fracture Toughness for PPDA10 Xn=3.67 5% Specimen 1

250

Load (N) 200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=3.67 5% Specimen 2

400
350
300
250
Load (N)

200
150
100
50
0
0 0.01 0.02 0.03 0.04 0.05 0.06
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=3.67 5% Specimen 3

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05
Crosshead Displacement (cm)

178
 APPENDIX E (Continued)

Fracture Toughness for PPDA10 Xn=3.67 5% Specimen 4

350

300

Load (N) 250

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045
Crosshead Displacement (cm)

Summary of Fracture Toughness Test for Resins Containing 5% PPDA10 Xn=3.67

PPDA10 fracture crack elastic hole to fracture fracture

Xn=3.67 geometrical load (N) length a modulus E edge dist thickness toughness toughness
5% factor, Y P (m) (Pa) W (m) b (m) (J/m2) (Pa*m1/2)
1 23.14615 217.33 0.0036 35471875.43 0.025 0.0064 99478.72 1.8785
2 23.14615 347.19 0.0015 35471875.43 0.025 0.0064 106674.77 1.9452
3 23.14615 304.30 0.0020 35471875.43 0.025 0.0064 109261.52 1.9687
4 23.14615 312.37 0.0021 35471875.43 0.025 0.0064 120892.39 2.0708
average 1.9658
std dev 0.08
% RSD 4.06

179
 APPENDIX E (Continued)

Stress-Strain Curves for Resins Containing 3% PPDA10 Xn=5

Fracture Toughness for PPDA10 Xn = 5 3% Specimen 1

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04

Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn = 5 3% Specimen 2

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn = 5 3% Specimen 3

300

250

200
Load (N)

150

100

50

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Crosshead Displacement (cm)

180
 APPENDIX E (Continued)

Fracture Toughness for PPDA10 Xn = 5 3% Specimen 4

350

300

250
Load (N)
200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045 0.05
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn = 5 3% Specimen 5

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045
Crosshead Displacement (cm)

Summary of Fracture Toughness Test for Resins Containing 3% PPDA10 Xn=5

PPDA10 fracture crack elastic hole to fracture fracture

Xn=5 geometrical load P length modulus E edge dist thickness toughness toughness
3% factor, Y (N) a (m) (Pa) W (m) b (m) (J/m2) (MPa*m1/2)
1 23.14615 245.03 0.0027 33580167.25 0.025 0.0064 101029.92 1.8419
2 23.14615 281.99 0.0019 33580167.25 0.025 0.0064 94159.58 1.7782
3 23.14615 255.75 0.0024 33580167.25 0.025 0.0064 97830.09 1.8125
4 23.14615 326.06 0.0018 33580167.25 0.025 0.0064 119265.00 2.0012
5 23.14615 272.19 0.0024 33580167.25 0.025 0.0064 110810.06 1.9290
average 1.8726
std dev 0.09
% RSD 4.87

181
 APPENDIX E (Continued)

Stress-Strain Curves for Resins Containing 5% PPDA10 Xn=5

Fracture Toughness for PPDA10 Xn=5 5% Specimen 1

400

350

300

250
Load (N))

200

150

100

50

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=5 5% Specimen 2

250

200

150
Load (N)

100

50

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=5 5% Specimen 3

400

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04 0.045
Crosshead Displacement (cm)

182
 APPENDIX E (Continued)

Fracture Toughness for PPDA10 Xn=5 5% Specimen 4

300

250

200
Load (N)

150

100

50

0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=5 5% Specimen 5

250

200

150
Load (N)

100

50

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Crosshead Displacement (cm)

Summary of Fracture Toughness Test on Resins Containing 5% PPDA10 Xn=5

PPDA10 fracture crack elastic hole to fracture fracture

Xn=5 geometrical load length a modulus E edge dist thickness energy toughness
5% factor, Y (N) P (m) (Pa) W (m) b (m) (J/m2) (MPa*m1/2)
1 23.14615 354.96 0.0017 34924215.12 0.025 0.0064 128351.51 2.1172
2 23.14615 230.50 0.0036 34924215.12 0.025 0.0064 114609.84 2.0007
3 23.14615 337.21 0.0022 34924215.12 0.025 0.0064 149901.91 2.2881
4 23.14615 241.40 0.0035 34924215.12 0.025 0.0064 122216.86 2.0660
5 23.14615 234.27 0.0038 34924215.12 0.025 0.0064 124966.85 2.0891
average 128009.39 2.1122
std dev 13245.36 0.11
% RSD 10.35 5.08

183
 APPENDIX E (Continued)

Stress-Strain Curves for Resins Containing 3% PPDA10 Xn=9

Fracture Toughness for PPDA10 Xn=9 3% Specimen 1

300

250

200
Load (N)

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=9 3% Specimen 2

400
350
300
250
Load (N)

200
150
100
50
0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035

Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=9 3% Specimen 3

300

250

200
Load (N)

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02
Crosshead Displacement (cm)

184
 APPENDIX E (Continued)

Fracture Toughness for PPDA10 Xn=9 3% Specimen 4

400

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=9 3% Specimen 5

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=9 3% Specimen 6

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03
Crosshead Displacement (cm)

185
 APPENDIX E (Continued)

Summary of Fracture Toughness Test for Resins Containing 3% PPDA10 Xn=9

PPDA10 fracture crack elastic hole to fracture fracture

Xn=9 geometrical load (N) length a modulus E edge dist thickness toughness toughness
3% factor, Y P (m) (Pa) W (m) b (m) (J/m2) (MPa*m1/2)
1 23.14615 266.17 0.00215 35065514.88 0.025 0.0064 90907.06 1.7854
2 23.14615 351.65 0.00148 35065514.88 0.025 0.0064 109224.80 1.9570
3 23.14615 247.82 0.00235 35065514.88 0.025 0.0064 86136.07 1.7379
4 23.14615 339.11 0.00170 35065514.88 0.025 0.0064 116670.76 2.0227
5 23.14615 274.28 0.00181 35065514.88 0.025 0.0064 81262.26 1.6880
6 23.14615 332.89 0.00133 35065514.88 0.025 0.0064 87963.19 1.7563
average 1.8246
std dev 0.13
% RSD 7.32

Stress Strain Curves for Resins Containing 5% PPDA10 Xn=9

Fracture Toughness for PPDA10 Xn=9 5% Specimen 1

400

350

300

250
Load (N)

200

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=9 5% Specimen 2

300

250

200
Load (N)

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025
Crosshead Displacement (cm)

186
 APPENDIX E (Continued)

Fracture Toughness for PPDA10 Xn=9 5% Specimen 3

300

250

200
Load (N)

150

100

50

0
0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=9 5% Specimen 4

400

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035
Crosshead Displacement (cm)

Fracture Toughness for PPDA10 Xn=9 5% Specimen 5

400

350

300

250
Load (N)

200

150

100

50

0
0 0.005 0.01 0.015 0.02 0.025 0.03
Crosshead Displacement (cm)

187
 APPENDIX E (Continued)

Summary of Fracture Toughness Test of Resins Containing 5% PPDA10 Xn=9

hole to
PPDA10 fracture crack elastic edge fracture Fracture
Xn=9 geometrical load P length a modulus E dist W thickness toughness toughness
5% factor, Y (N) (m) (Pa) (m) b (m) (J/m2) (MPa*m1/2)
1 23.14615 335.28 0.00125 2114713.10 0.025 0.0064 1390524.99 1.7148
2 23.14615 279.71 0.00205 1674548.75 0.025 0.0064 2004363.63 1.8320
3 23.14615 252.77 0.0024 1894792.73 0.025 0.0064 1693658.10 1.7914
4 23.14615 377.89 0.00111 1772602.21 0.025 0.0064 1871417.84 1.8213
5 23.14615 348.71 0.00125 2106793.70 0.025 0.0064 1509811.92 1.7835
average 1.7886
std dev 0.05
% RSD 2.57

188
 APPENDIX F

DIFFERENTIAL CALORIMETRY PLOTS

Degree of cure vs Temperature of Control Resin and

Resin Containing 3% MDA10 Xn=3.67 at 1 ºC/min
1.2

1
Degree of Cure

0.8

0.6 control
with additive
0.4

0.2

0
100 120 140 160 180 200 220 240 260 280
Temperature (ºC)

Degree of cure vs Temperature of Control Resin and Resin

Containing 3% MDA10 Xn=3.67 at 2 ºC/min
1.2

1
Degree of Cure

0.8

0.6 control
with additive

0.4

0.2

0
100 120 140 160 180 200 220 240 260
Temperature (ºC)

189
 APPENDIX F (Continued)

Degree of cure vs Temperature of Control Resin and

Resin Containing 3% MDA10 Xn=3.67 at 3 ºC/min
1.2

1
Degree of Cure

0.8

0.6

0.4 control
with additive
0.2

0
100 120 140 160 180 200 220 240 260 280
Temperature (ºC)

Degree of Cure vs Temperature of Control Resin and

Resin Containing 3% MDA10 Xn=3.67 at 4 ºC/min
1.2

1
Degree of Cure

0.8

0.6
control
with additive
0.4

0.2

0
100 150 200 250 300
Temperature (ºC)

190
 APPENDIX F (Continued)

Degree of Cure vs Temperature of Control Resin and

1.2 Resin Containing 3% MDA10 Xn=3.67 at 7 @5 ºC/min

1
Degree of Cure

0.8

0.6
control
0.4 with additive

0.2

0
100 150 200 250 300
Temperature (ºC)

Degree of cure vs Temperature of Control Resin and

1.2
Resin with MDA10 Xn=3.67 @10 ºC/min

1
Degree of Cure

0.8

0.6

0.4
control
0.2 with additive

0
100 150 200 250 300
Temperature (ºC)

191
 APPENDIX F (Continued)

Degree of cure vs Temperature of Control Resin and

1.2 Resin with MDA10 Xn=3.67 @15 ºC/min

0.8
Degree of Cure

0.6
control
0.4 with additive

0.2

0
100 150 200 250 300
-0.2
Temperature (ºC)

Degree of cure vs Temperature of Control Resin

and Resin with MDA10 Xn=3.67 @ 20 ºC/min
1.2

1
control
Degree of Cure

0.8
with additive
0.6

0.4

0.2

0
100 150 200 250 300 350
Temperature (ºC)

192