Chapter 3

Materials

3.1 Introduction

A composite has two or more classes of engineering materials combined in such a way that the

advantages of each class of material may be realized and the disadvantages minimized, thereby

yielding a unique final product that is superior to either of its principle components alone

(Callister, 1997). It is often more common to be composed of just two phases: the matrix,

which is continuous and surrounds the second phase, the reinforcement. Depending on the

form of reinforcement (Figure 3.1), composite materials can be classified as (1) fiber-

reinforced, (2) particle-reinforced or (3) structural composite.

COMPOSITES

Particle-reinforced Fiber-reinforced Structural

Large- Dispersion- Continuous Discontinuous Laminates Sandwich

particle strengthened (aligned) (short) panels

Aligned Randomly
orientated

Figure 3.1: Composite classification

Source: Callister, 1997: p512

Particles are used to increase the modulus and decrease the permeability and ductility of the

matrix. Fibers also increase the modulus of the matrix materials. The strong covalent bonds

along the fiber’s length give them very high modulus in this direction because to break or

extend the fiber, the bonds must also be broken or moved. Hence, taking the loading

conditions of an archwire into consideration, fiber-reinforced composites are most suitable.

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3.2 Fiber-reinforced composite

For fiber-reinforced composites, the dispersed phase has the geometry of a fiber, i.e. a large

length-to-diameter (aspect) ratio. The mechanical characteristics of the composite depend not

only on the properties of the fiber, but also the degree to which an applied load is transmitted

to the fibers by the matrix phase. These materials can exhibit a wide range of properties,

depending on the choice of matrix, fiber, fiber orientation and fiber volume fraction and also

the strength of the fiber-matrix interfacial bond.

Although there are several kinds of reinforcement configurations such as, chopped short and

long fibers, unidirectional fiber, woven fabric, knitted fabric and braided fabric, the strength of

the composite is significantly higher when the fibers are continuously aligned (Table 3.1). For

the fabrication of composite archwires, unidirectional composite is most suitable to meet the

required mechanical properties.

Table 3.1: Reinforcement efficiency of fiber-reinforced composites for several orientations

and at various directions of stress application
Reinforcement
Fiber Orientation Stress Direction
Efficiency
Parallel to fibers 1
All fibers parallel
Perpendicular to fibers 0
Fibers randomly and uniformly distributed Any direction in the plane of the
3/8
within a specific plane fibers
Fibers randomly and uniformly distributed
within three dimensions in space Any direction 1/5

Source: Krenchel, 1964

3.3 Selection Parameter

The archwire is placed within the oral cavity for a substantial period of time. As mentioned in

Chapter 2, it should be biocompatible and biostable, which means the archwire, should not

disintegrate nor produce an adverse reaction in the oral environment. The stresses of oral

functions must also be endured. Furthermore, to meet the primary objectives of this project, the

wire has to be aesthetic. Hence the selected material should be translucent, transmitting the

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color of the teeth, or tooth-colored. It is also critical that the materials selected for the archwire

possess the required properties for clinical use.

To meet the required aesthetic properties of the archwire, polymer-matrix composites are most

suitable. Ceramic-matrix composites can be aesthetic but unfortunately their porous structure,

low fracture toughness (brittleness) and abrasion make it difficult to supply a stable

mechanical property. In the following sections, the three important constituents of a composite

- the reinforcement, matrix and the fiber-matrix interface - are considered for the fabrication of

a composite archwire.

3.4 Matrix

For fiber-reinforced composites, the matrix phase serves several functions. First, it binds the

fibers together and acts as the medium by which an externally applied stress is transmitted and

distributed to the fibers. The second function of the matrix is to protect the individual fibers

from surface damage as a result of mechanical abrasion or chemical reactions with the

environment. Finally the matrix separates the fibers and by virtue of its relative softness and

plasticity, prevents the propagation of brittle cracks from fiber to fiber, which could result in

catastrophic failure; in other words, the matrix phase serves as a barrier to crack propagation

(Callister, 1997). In addition to these, it is important that the matrix has an aesthetically

pleasing color. In this study two different aesthetically pleasing matrix systems were used; an

epoxy resin and a MMA-based dental resin.

3.4.1 Epoxy resins

Epoxy-matrix composites generally have the best mechanical properties. Epoxy, a thermoset,

is one of the most versatile materials frequently used in composite manufacturing and come in

various grades.

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The medical and dental fields also use epoxy adhesives (Goodman, 1998). Furthermore, it has

the desired aesthetic properties that are required for this project. The transparent resin (CHEMI

R-50/CHEMI H-64 – Appendix A.1) used in this study was obtained from Chemicrete

Enterprises Pte. Ltd (Singapore). Though this epoxy resin is not a FDA-approved grade, it was

chosen due to its availability and to study the feasibility of the fabrication methodology.

3.4.2 Dental resins

Dental resins are MMA based resins, widely used in restorative dentistry. The advantages of

these resins are that they are tooth-shade and come in various viscosities. In this study, a

suitable resin, Metafil Flo (Sun Medical, Japan) was used. This resin is commonly used in

dentistry (Appendix A.2), hence has proven biocompatibility in the oral environment.

Furthermore, it has an aesthetically pleasing appearance.

3.5 Reinforcement

A variety of fibers are used in composite materials. The three most commonly used fibers are

aramid, carbon and glass (Table 3.2). Aramid fibers are made from a high strength

hydrocarbon such as Kevlar. Carbon fibers have very high strength and stiffness but are also

rather expensive due to the processing involved. However, glass fibers are the most common

of all reinforcing fibers due to their low cost.

Table 3.2: Tensile strength and tensile modulus of carbon, aramid and glass fibers
Type of Fiber Tensile Strength (GPa) Tensile Modulus (GPa)

Carbon 2 – 5.3 160 – 440

Aramid 3.1 – 3.6 60 - 180

Glass 2.4 – 3.7 69 - 86

Source: http://www.netcomposites.com/education.asp?sequence=30

Glass fibers tend to be transparent even in the form of a fiber. Glass fiber itself is relatively

strong and when composed with a matrix resin, high specific strength can be achieved. Their

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excellent transparency compared to carbon and aramid fibers is the major advantage that

makes them prime candidate for use as reinforcement in aesthetic dentistry.

3.6 Fiber-Matrix interface

Generally in composite technology, two methods reported to improve the mechanical

properties of composites are

i. Controlling the volume fraction of reinforcement and/or

ii. Strengthening the interface between the matrix and the reinforcement.

The disadvantage in method (i) is that the non-uniform dispersion of the fibers leads to a non-

uniform stress distribution in the wire, while method (ii) has not been investigated with respect

to composite orthodontic wires.

Most of the past studies focused on varying the constituent materials composition and trying

different fiber and matrix combination to achieve the required performance. In addition to the

volume content of fiber and matrix, it must be mentioned that interface between fiber and

matrix has a significant effect on the performance of fibrous composites, especially in moist

environment (Schutte, 1994), like that of the oral environment. In the case of glass fiber

composites, glass fibers are generally treated by silane coupling agent to enhance chemical

bonds between fiber and matrix. Untreated fibers can act as inclusion bodies within matrix

and, instead of strengthening, actually weaken the resin by breaking up the homogeneity of the

matrix (Solnit, 1991). With the application of a silane coupling agent, a chemical bond

between the matrix and the glass fibers is established.

The important treatment parameters such as temperature, reaction time between glass fiber and

coupling agent and, appropriate choice and concentration of coupling agent, influence the

mechanical performance of composite. For dental composites, there are several reports on the

influence of silane coupling agent on mechanical property of composites (Jancar &

Dibenedetto; Jancar et al, 1993; Ferracane, 1998). Although composite researchers have

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looked into composite interface, it must be noted that the effect of silane treatment is greatly

depended upon the loading conditions, specimen geometry (size) as well as the volume

fraction. Thus it is important to study the effect of silane treatment in relation to archwire

bending and select the appropriate coupling agent as well as the right concentration.

3.6.1 Treatment Procedure

In this study, three different silane coupling agents (Figure 3.2) were applied to the reinforcing

fibers. The reinforcement was E-glass fiber yarns, each containing 200 fiber filaments

(filament diameter = 9µm, Unitica Glass Fiber, Japan). Three different groups of treated glass

fibers were prepared,

1. fibers treated with γ-aminopropyltriethoxy silane (amino silane),

2. fibers treated with γ-glycidoxypropyltrimethoxy silane (epoxy silane) and

3. fibers treated with γ-metacryloxypropyltrimethoxy silane (metacrylate silane)

OC2H5

H2N C3H6 Si OC2H5 γ-aminopropyltriethoxy silane

(amino silane)
OC2H5

OCH3

H2C CH CH2 O C3H6 Si OCH3 γ-glycidoxypropyltrimethoxy silane

(epoxy silane)
O
OCH3

CH3 OCH3

H2C C C O C3H6 Si OCH3 γ-metacryloxypropyltrimethoxy silane

(metacrylate silane)
O OCH3

Figure 3.2: Chemical Structure of Coupling agents

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Treatments 1 and 2 are suitable for epoxy-matrix composites whereas treatment 3 is for MMA-

based matrix composites. The silane coupling agents were provided by Shinetsu Chemical,

Japan (Appendix A3). Silane coupling treatment of glass fibers (Figure 3.3) were conducted as

follows.

1. Remove Binder for fibers

a. Place as received fibers in furnace at 400 °C for 40 hrs

2. Prepare acidified coupling agent solution

a. Add required wt% of silane coupling agent to 0.2M acetic acid

b. Immerse fibers (after binder is removed and cooled down) into solution for

10min

3. Remove fibers and dab off excess moisture and then place in the oven at 100 °C

for 20min.

Six different aqueous silane solutions: 1.0wt% and 2.0wt% amino silane, 1.0wt% and 2.0wt%

epoxy silane and 1.0wt% and 2.0wt% metacrylate silane were prepared for treatment. Table

3.2 shows the types of treated fibers used in this study.

(2)
Acidified Silane Coupling Agent
Treatment Immerse GF; 10mins

(3)
(1)
Oven Dry
Remove Binder
@100ºC; 20 min
@400ºC; 40 hrs
Furnace

Oven

Figure 3.3: Silane treatment of glass fibers

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Table 3.3: Types of silane treatment applied to glass fibers

Treatment Silane Coupling Agent Silane Concentration (wt%) Matrix

1.0
1 Amino silane Epoxy
2.0
1.0
2 Epoxy silane Epoxy
2.0
1.0
3 Metacrylate silane Dental resin
2.0

3.7 Conclusion

Based on the loading conditions and functional requirements of the archwire, continuous fiber-

reinforced polymer composite systems were selected. To develop aesthetically pleasing wires,

epoxy resin and dental resin were selected as matrix and glass fibers as reinforcement.

Furthermore, to improve the fiber-matrix interface and hence the archwire performance, silane

treatment of glass fibers was proposed.

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