Development and Characterization of Self-Healing

Dental Composites
Submitted in partial fulfillment of the requirements for the award of degree of

BACHELOR OF TECHNOLOGY
In
Mechanical Engineering

Guided By: Submitted By:

Dr. Amar Patnaik
Assistant Professor AKHIL SHARMA
Department of Mechanical Engineering (2012UME1529)

CHETAN SHARMA
(2012UME1301)

SAJID ALAM
(2012UME1354)
 DEPARTMENT OF MECHANICAL ENGINEERING
MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY JAIPUR
May 2016
MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY JAIPUR
DEPARTMENT OF MECHANICAL ENGINEERING
Jawahar Lal Nehru Marg, Jaipur-302017(Rajasthan)

CANDIDATES DECLARATION

We hereby certify that following work which is being presented in the Major Project

entitled Development and Characterization of Self-Healing Dental

Composites in the partial fulfillment of requirement for award of the degree of
Bachelors of Technology (B.Tech.) and submitted in Department of Mechanical
Engineering of Malaviya National Institute of Technology Jaipur is an authentic
record of our own work carried out by us during a period from Jan 2016 to May 2016
under the supervision of Dr. Amar Patnaik, Assistant Professor, Department of
Mechanical Engineering, Malaviya National Institute of Technology Jaipur.
The matter presented in this report embodies the result our own work and studies
carried out and has not been submitted anywhere else.

Date: 06/05/2016

AKHIL SHARMA CHETAN SHARMA

(2012UME1529) (2012UME1301)

SAJID ALAM

(2012UME1354)
.

ii
 MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY

DEPARTMENT OF MECHANICAL ENGINEERING JAIPUR 302017 (RAJASTHAN) IN

CERTIFICATE

This is to certify that the project entitled Development and Characterization of Self-Healing
Dental Composites that is being submitted by (AKHIL SHARMA, CHETAN SHARMA,
SAJID ALAM, 2012UME1529, 2012UME1301, 2012UME1354 B.Tech. VIII Semester)
requirement for partial fulfillment of award of the degree of Bachelor of Technology,
(Mechanical Engineering) submitted to the Mechanical Engineering Department
Malaviya National Institute of Technology, Jaipur is found to be satisfactory and is hereby
approved for submission.

Date: 06/05/2016
Dr. Amar Patnaik
Assistant Professor
Department of Mechanical Engineering
Malaviya National Institute of Technology Jaipur, Rajasthan
 Acknowledgement

We take this opportunity to express our profound gratitude and deep regards to our Project
Mentor Dr. Amar Patnaik, Assistant Professor, Department of Mechanical Engineering,
MNIT Jaipur, for his exemplary guidance, monitoring and constant supervision throughout
the complete course of this project.

We also express our sincere regards to Prof. I.K. Bhatt, Director, MNIT Jaipur, for
sanctioning the required sum for executing our project in a successful manner.

We are highly obliged to Mr. Shiv Ranjan Kumar Research Scholar, Department of
Mechanical Engineering, MNIT Jaipur, for providing the necessary guidance and valuable
help regarding for the project.

We are indebted to our project supervisor Dr. Harlal Singh Mali, Assistant Professor,
Department of Mechanical Engineering, MNIT Jaipur for his commendable guidance,
counselling and consistent supervision to encourage us to accomplish each and every aspect
of our project precisely.

In addition, we are also grateful to staff of Tribology Lab, Mechanical Engineering

Department MNIT Jaipur for the valuable information provided by them in their respective
fields. We are grateful for their cooperation during the period of our project.

We also take the opportunity to acknowledge the members and staff of Materials Research
Centre for procuring us with state of the art equipments to carry our research unhindered and
meticulously.

Finally, we would like to express our heartfelt gratitude to one and all who have helped us
directly or indirectly in the completion of the project report.
 Abstract

The value of resin-based dental restorations could be improved by increasing their service lives.

One way to improve longevity is to block micro-cracks that form during or after the composite

hardens in the dental cavity. To date, some bio-compatible Self-Healing Dental Composite

(SHDC) has been proposed but the detailed analysis of physical, mechanical and wear behavior

of dental composite have not been done in a single paper. Along with that, the fillers haven`t

been used in those SHDCs. Toward this end, we propose to fabricate SHDC made with

contemporary dental components, amorphous calcium phosphate fillers, as well as two

additional ingredients: a healing powder (HP, strontium fluoroaluminosilicate particles) and a

healing liquid (HL, aqueous solutions of polyacrylic acids) that is enclosed within silica

microcapsules. As micro-cracks develop, they will break the microcapsules in their propagation

path, thereby releasing HL. This liquid will then react with particles of HP exposed by the crack

formation, forming an insoluble reaction product that fills and seals the cracks.

The key factors to achieve these self-healing of cracks are discussed. The hardness of the SHDC

appeared to be satisfactory. The SHDC was dynamically stable. The wear behavior was also

pleasing. Although, the healing process wasn`t achieved successfully. Importantly, this SHDC

contains only clinically-tested, biocompatible materials, making it readily applicable.

 Plagiarism Status Report

Plagiarism Checker is the software used for this purpose. The Plagiarism level of the report is

17%. The sources used for making of this report are 34 and the amount of data taken from

each source is displayed in the Pie- Chart below.

Contents

Candidates Declaration........................................................................................................ii
Certificate.............................................................................................................................iii
Acknowledgment..................................................................................................................iv
Abstract..................................................................................................................................v
Plagiarism Status Report...........................................................................................................vi
Contents....................................................................................................................................vii
List of tables..............................................................................................................................x
List of figures.............................................................................................................................xi
Abbreviations............................................................................................................................xii
1. Introduction......................................................................................................................1
1.1. Introduction...................................................................................................................1
1.2. Background...................................................................................................................2
1.3. Self-Healing Materials .................................................................................................3
1.3.1. Self-Healing Mechanism....................................................................................3
1.3.2. Microcapsules.....................................................................................................4
1.3.3. Healing Agent and Catalyst................................................................................4
1.4. Glass Ionomer Cement..................................................................................................4
1.5. Resin Composite...........................................................................................................4
1.5.1. Matrix Organic Phase.........................................................................................5
1.5.2. Filler Disperse Phase..........................................................................5
1.5.3. Silane Coupling Agent...6
1.6. Wear Mechanism...........................................................................................................7
1.7. Wear of Dental Resin-based Composite8
1.8. Effect of Parameters on Dental Wear8
1.9. Objective of the Project10
2. Literature review..............................................................................................................11
2.1. Mechanical Properties of Dental Materials.................................................................11
2.2. Characterization Test on the Dental Materials............................................................12
2.3. Dental Wear.13
2.4. Wear Behavior of Resign Composite..........................................................................14
2.5. Research Gap Based on the Literature Survey.15
3. Materials and Methods....................................................................................................16
 3.1. Material.......................................................................................................................15
3.2. Methods.......................................................................................................................16
3.2.1. Micro-Encapsulation Procedure.......................................................................17
3.2.2. Micro Hardness test..........................................................................................17
2.1 Specimen preparation 17
2.2 Testing procedure 18
3.2.3. Compressive Strength Test...............................................................................18
3.2.3.1 Specimen preparation...........................................................................18
3.2.3.2 Testing Procedure.................................................................................19
3.2.4. Fourier Transform Infrared Spectroscopy........................................................19
3.2.4.1 Specimen preparation...........................................................................19
3.2.4.2 Methodology........................................................................................20
3.2.5. Thermo-gravimetric Test..................................................................................21
3.2.5.1 Specimen preparation...........................................................................21
3.2.5.2 Characterization test.............................................................................21
3.2.6. Dynamic Mechnaical Analysis.........................................................................22
3.2.6.1 Specimen preparation...........................................................................22
3.2.6.2 Dynamic Mechanical Analysis Test.....................................................22
3.2.7. Wear Volume....................................................................................................23
3.2.7.1 Specimen preparation...........................................................................23
3.2.7.2 Wear test...............................................................................................24
3.2.8. SEM Analysis...................................................................................................25
3.2.8.1 Specimen Preparation...........................................................................25
3.2.8.2 SEM Test..............................................................................................25
4. Results and Discussion.....................................................................................................26
4.1 Results..........................................................................................................................26
4.1.1 Micro hardness test...........................................................................................26
4.1.2 Compressive Strength Test...............................................................................27
4.1.3 Wear Loss.........................................................................................................28
4.1.4 Characterization Tests......................................................................................29
4.1 Dynamics Mechanical Analysis.................................................................................................29
4.2 Fourier Transform Infrared Spectroscopy..................................................................................31
4.3 Thermo gravimetric Analysis.....................................................................................................32
4.1.5 SEM Analysis...................................................................................................33
 4.2 Discussion....................................................................................................................35
4.2.1 Mechanical Properties......................................................................................35
4.2.2 Characterization Tests......................................................................................36
4.2.3 Wear Analysis...................................................................................................39
4.2.4 SEM Analysis...................................................................................................39
5. Conclusions and Future Scope........................................................................................41
5.1 Conclusions..................................................................................................................41
5.2 Future Scope.................................................................................................................42
References...............................................................................................43

List of tables
Sr. No Title Table. No. Page No.

1 List of materials used for the composite 3.1 16

2 Details of composition of different components of dental composite 3.2 16

3 Dental Wear Simulator Parameters 3.1 24

4 Vickers Hardness Value and Standard Deviation for the composites 3.2 27

5 Compressive strength and Standard Deviation for the composites 4.1 28

 List of figures

S. No Title Fig. No Page No.

1. Schematic representation of self-healing concept using embedded 1.1 04

microcapsules.
2. The chemical formula of the dental monomer used in dental composites 1.2 05

3. Methacryloxypropyltrimethoxysilane 1.3 06

4. Compressive Stress Test 3.1 19

5. Principle of Fourier Transform Infrared Spectroscopy 3.2 20

6. Fourier Transform Infrared Spectroscopy Apparatus 3.3 20

7. Thermo gravimetric Apparatus 3.4 21

8. Dynamic Mechanical Analysis Apparatus 3.5 23

9. Prepared Specimen for Wear Test 3.6 23

10. Dental Wear Simulator 3.7 24

11. Comparison of Hardness Values of the composite materials 4.1 26

12. Comparison of Compressive Strength of the composite materials 4.2 27

13. Mass Loss in Saliva 4.3 28

14. Tangent delta as a function of temperature 4.4 29

15. Storage Modulus as a function of temperature 4.5 30

16. Comparison of the mass loss in different mediums 4.6 31

17. Tangent delta as a function of temperature 4.7 33

Abbreviations

SEM Scanning Electron Microscopy

TGA Thermo Gravimetric Analysis

DMA Dynamic Mechanical Analysis

FTIR Fourier Transform Infrared Spectroscopy

BisGMA Bisphenyl glycidyl Dimethacrylate

BisEMA Bisphenol A Ethoxylated Bisphenol Glycol Dimethacrylate

UDMA Urethane Dimethacrylate

TEGDMA Tri-ethylene glycol Dimethacrylate

PMMA Poly Methyl Methacrylate

USA United States Of America

Kgf Kilo Gram Force

HV Hardness Value

UTM Universal Testing Machine

IR Infra Red

cm Centi Meter

PH Power Of Hydrogen

MPA Mega Pascal

SHDC Self Healing Microcapsule Dental Composite

 Chapter 1

Introduction

1.1. Introduction

Self-healing composites are the class of materials which possesses the ability to heal itself

from mechanical damage caused by its usage over time. The concept originated by bio-

mimicking the mechanism of autonomous healing in living beings, for instance repairing of

bones after a crack. Self-healing has become one of the most preferred properties in material

development since the first autonomous crack-repair material was synthesized by groups at

the University of Illinois at Urbana-Champaign (UIUC). Self-healing composites have

revealed the noteworthy improvements in increasing the service life of polymer materials.

Dental resin composites are used significantly in restorative materials, cements for single or

multiple tooth prostheses and orthodontic devices, inlays, onlays, cores and buildups, root

canal posts, and provisional restorations. Degradation of dental resin composites by micro-

cracking generated by thermal and mechanical fatigue is an enduring issue. Additionally,

these failures are hard to detect and impossible to repair. These complications can lead to

decline in service life and disastrous failure of restorations if left untouched. Progress has

been made in healing these micro cracks autonomously by using fracture-release-heal process

13
using Glass Ionomer Cements(GIC) but issues were raised regarding its toughness and

healing efficiency. Hence, we have carried out assessment of four different variants of self-

healing dental composite, understand their mechanical as well as physical behavior and effect

of lubricants on the wear weight of each composite subjected to simulated oral conditions in

wear simulator.

14
1.2. Background

Over the last few decades the use of dental amalgam is continuously decreasing due to poor

aesthetics of amalgam especially for anterior restoration, mercury toxicity, and environmental

considerations. Resin composites have emerged as a viable treatment option for all types of

restorations in dentistry. They are used as adhesives or restorative material in dentistry and

now represent general alternation to dental amalgam The reason for their feasibility as

restorative is their evolution as materials which are insoluble, aesthetic, insensitive to

dehydration, easy to manipulate and reasonably inexpensive. However, like all dental

materials, composites have their own limitations, such as the gap formation caused by

polymerization contraction during setting, leading to marginal discoloration and leakage. In

addition, they are subjected to higher wear rates than ceramics, and although some composites

have wear rates similar to amalgam, many have higher wear rates.

Improvements of mechanical properties of the composite have permitted its use in posterior

teeth with greater reliability. This improvement included; development of smaller particle sizes

of filler, better bonding systems, curing refinements and sealing systems. Composite resin

materials have progressed from macro fills to micro fills and from hybrids to micro hybrids,

and new materials such as packable and Nano filled composites have been introduced to the

dental market. These Nano filled composites have reduced interstitial spacing of the filler

particles and, therefore, provides increased filler loading, better physical properties, and

improved polish retention Hence, even with the improved aesthetics, versatility and quick

reparability, these composite resins tend to wear out raising uncertainty on the durability of the

restorations used. With regard to this aspect, study of wear, its causes and effect of different

restorative materials has been carried out so that composite materials may yield insufficient

wear behavior.

15
1.3. Self-Healing Materials

1.3.1. Self-Healing Mechanism

There are many the mechanisms for implementing self-healing like hollow glass fiber repair

mechanism, microencapsulated healing agent, micro vascular network, hollow fiber approach,

inclusion of thermoplastic additives. However the most commonly used is microencapsulated

healing agent method. In this method, Healing is accomplished by incorporating a

microencapsulated healing agent and a catalytic chemical trigger within an epoxy matrix. An

approaching crack ruptures embedded microcapsules, releasing healing agent into the crack

plane through capillary action. Polymerization of the healing agent is triggered by contact with

the embedded catalyst, bonding the crack faces. The damage-induced triggering mechanism

provides site-specific autonomic control of repair.

16
Fig 1.1. Schematic representation of self-healing concept using embedded microcapsules.

1.3.2. Microcapsules

It has two parts, namely, the core and the shell. They may have spherical or irregular shapes and

may vary in size ranging from nano- to microscale. The size and shell thickness of

microcapsules affect the mechanical properties and healing efficiency of the composite.

1.3.3. Healing Agent and Catalyst

Healing agents are liquid active agents such as monomers, dyes, catalysts and hardeners which

is encapsulated inside the microcapsules. Generally, dicyclopentadiene (DCPD) is being used

because it is less expensive, has high longevity and low viscosity making it flow easily after the

cracking of microcapsule. This agent reacts with catalyst which dispersed in the matrix and acts

as an internal trigger. When agent comes in contact with the catalyst, the polymerization starts

and the polymerized agent initiates crack healing. Commonly Grubbs catalyst is used. But

17
research shows that the lack of bio-compatibility of DCPD and Grubbs catalyst makes it toxic

for use in dental applications. Further, recent researches have used polyacrylic acid as healing

agent and fluoroaluminosilicate as catalyst because of its bio-compatibility.

1.4. Glass Ionomer Cement

Glass ionomers are the group of materials that uses silicate glass powder and aqueous solution

of polyacrylic acid. The glass ionomer powder is an acid soluble calcium fluoroalumino silicate

glass- ion leachable glass. They are mixed together in a particular proportion to form cement

which turns into a dental restoration material.

1.5. Resin Composites

Dental resin composites are basically derived from three chemical different materials: organic

matrix or organic phase, filler or disperse phase, and an organosilane which is used as a

coupling agent to bond the filler particles to the organic matrix.

1.5.1. Matrix organic phase

The organic matrix is generally dimethacrylate monomer such as BisGMA, glycol

dimethacrylate, urethane dimethacrylate (UDMA), triethyleneglycol dimethacrylate

(TEGDMA), urethane dimethacrylateethoxylated bisphenol-A-dimethacrylate (Bis-EMA),

decanediol dimethacrylate (D3MA). The advantages of using BisGMA over other monomers

are less shrinkage, higher modulus and reduce toxicity due to its lower volatility and

diffusivity into tissue. Although, BisGMA possesses high strength and hardness the drawback

of this monomer is its high viscosity, because of hydrogen bonding interaction that occur

between hydroxyl groups, which limits the incorporation of inorganic fillers and hence a low

degree of conversion.

18
 Fig 1.2 The chemical formula of the dental monomer used in dental composites

1.5.2. Filler disperse phase

The filler particles is mixed with the resin matrix to increase the strength of composite and to

decrease the amount of matrix material, resulting in increased hardness, decrease wear and

reduction in polymerization shrinkage. The most common fillers materials used are silicate

particles based on oxides of barium, strontium, Zinc, aluminum or zirconium. However the

class nano-fillers like amorphous calcium phosphate is catching the trend due to its high

strength, wear properties and most importantly it releases the fluoride which is essential for the

remineralization of composite and hence hindering secondary caries. The particle size of these

nano-fillers is <100 nm.

1.5.3. Silane coupling agents

To obtain good mechanical properties in dental composites, strong covalent

bond between inorganic fillers and the organic matrix is essential. Bonding of

the two phases is achieved by coating the fillers with a silane coupling agent

19
that has functional groups to link the filler and the matrix chemically. A typical

coupling agent is 3-methacryloxypropyltrimethoxysilane (MPTS)(Fig 1.2) One

end of the molecule can be bonded to the hydroxyl groups of silica particles,

and the other end is capable of copolymerizing into the polymer matrix.

Fig 1.3 3-methacryloxypropyltrimethoxysilane

20
 1.6. Wear Mechanisms

Wear has been defined as a consequence of the interaction between surfaces moving in

contact, causing gradual remove of material .Wear of teeth and restorative materials is the

result of different complex processes that depend primarily on the abrasive nature of food, the

properties of the antagonistic material, the thickness and hardness of enamel, the chewing

behavior along with parafunctional habits, and neuromuscular forces.

Generally, we may distinguish four main types of wear process:-

Adhesive wear occurs when surfaces slide one against another. Volume of material

transferred from one surface to another is proportional to real contact area and sliding

distance;

Abrasive wear probably the most widespread type of wear; occurs when hard asperities

(integral part of the surface two-body abrasion or separate particles which are entrapped

between the surfaces three-body abrasion) plough into softer surface. Generally, this type

of wear is proportional to the hardness of materials in contact, the geometry of abrasive

particles, sliding distance and load;

Fatigue wear as the result of repeated stress caused by clearance size particles trapped by

two moving surfaces. The plastic deformation of material causes the zone of tension behind

the motion. The surfaces are dented and cracking is initiated. These cracks propagate as the

result of repeated stress produced by bearing load. Eventually materials that was surrounded

by cracks is lost. This displaced material may itself form wear debris, causing three-body

abrasion.

Corrosive wear occurs as the result of chemical reactions on worn surfaces. If a chemical

reaction layer forms on the surface then it can be removed by contact with the counter face.
21
Removed material results in debris which are likely to agglomerate, producing larger

particles.

22
However, it is difficult to isolate the wear processes occurring in the mouth as defined above.

Different wear mechanisms work simultaneously and symmetrically with one dominating,

causing the ultimate substance loss.

1.7. Wear of dental resin-based composites

In general, resin-composite restorations are diphase with: 1. hard phase silane-coated

inorganic filler particles embedded in 2. Softer matrix dimethacrylate resin (either Bis-

GMA or urethane dimethacrylate UDMA). In some cases, the proportion of lower molecular

weight monomer such as TEGDMA is introduced to decrease overall viscosity of the system.

Friction of the surface with hard asperities makes the response of composites, which depends

on the size of a hard phase region and the scale of deformation. If the size of hard filler

particles and space between them are smaller than deformation caused by asperities, materials

behave like homogeneous solids and their wear resistance is similar to that of a resin base. If

filler particles and the scale of deformation are of approximate size or filler particles are

larger, then the material behaves like a heterogeneous solid and it wear rate decreases.

To sum up, wear of dental resin-based composites is the result of a number of fundamental

processes, especially: erosion, attrition and abrasion, which may occur simultaneously or

sequentially, acting in various combinations. Their mutual interaction is very complex, what

results in the general tendency of wear process hardly to be predicted.

1.8. Effect of parameters on dental wear

A wider clinical acceptance of polymer composite materials is still limited by unanswered

questions related to their behavior during long term exposure in the oral environment;

specifically, in terms of their competence of mechanical properties like wear resistance,

23
hardness, flexural modulus, flexural strength, and toughness . Composite restorative

materials,

24
when placed in the oral environmental, are constantly subjected to challenges of chemical and

thermal nature and, due to the intake of food and fluids at different temperatures. Such

thermal variations, if significant, would affect the mechanical and tribological properties of

the restorative materials. Dental materials are prone to fracture and abrasion during normal

masticatory function; thus, fracture and wear are the two main failure modes which occur in

posterior restorations. Therefore, mechanical characterization is a key element in

understanding the nature of the dependency between temperature and the expected

performance in an intraoral environment.

The food (oral) simulating liquids also effect the dental wear. Some of them exist in the

mouth, others can simulate its conditions (ingredients, pH and viscosity). Their use enables us

to see a fast wear of the materials in short time and furthermore to take in consideration

processes like chemical affinity, elution or bonding. The major influence regards the organic

phase of the composites which can be affected chemically, since pure fillers are rather inert

toward solvents and solutions. There are two main environments than one would like to

imitate: the usual mouth condition (water, saliva) and the presence of foods/drinks (oils,

alcohol, sugar, salt, etc.). Apparently, the received food remains only for a while into the

mouth where it is masticated. Long-time stays result in intensive erosions, something that we

use to reveal the causes of the phenomena.

Wear behavior is also effected by filler particle size and shape. Finer particles for a fixed-

volume-fraction of filler have been suggested to result in decreased interparticle spacing and

reduced wear. With regards to filler geometry, different shapes are very likely to present

distinct surface area, which again affects the amount of matrix resin in the interfacial region

25
between particles. The size and shape of filler particles are also influential factors affecting

the

26
degree of cure of resin composites. Considering that a more fundamental understanding of

factors that drive the performance of resin composites can assist in the further refinement of

the materials, studies of the wear behavior and degree of conversion of composites afforded

by formulations containing different particular sizes and geometries of filler particles, but

having identical monomeric constituents and filler loadings.

1.9. Objectives of the Project

In the present study of Development and Characterization of Self-Healing Dental

Composite, following are the main objectives:-

1. Fabrication of a samples for self-healing dental composite (SHMDC) by varying

weight percentage of microcapsules.

2. Determination of the physical, mechanical and wear behavior under different oral
environments.

3. Estimation of healing efficacy of the self-healing dental composite (SHMDC).

1
0
 Chapter 2

Literature Review

A detailed literature survey has been carried out on the assessment of the mechanical

behavior and wear analysis of artificial dental materials.

2.1. Mechanical properties of Dental Materials

George Huyang et al [1] Mechanical evaluation was carried out through fracture toughness,

which is determined according to ISO6872: 2014. Five bars (25 mm 4 mm 3 mm) of

each composition were made following the SHDC construction method descripted above.

The specimens were notched by sawing with an IsoMet Low Speed Saw (Buehler, Lake

Bluff, IL, USA) fitted with NTI Flex Diamond Discs (NTI-Kahla GmbH, Kahla, Germany),

and the notch was sharpened using a razor blade polished with 3 m diamond paste. Fracture

toughness was assessed using an Instron 5500R Universal Testing Machine (Instron Corp.,

Canton, MA, USA) set with a loading speed of 0.5 mm/min. The specimens were placed on

a 3-point bending test device, which was constructed with 20mm span distance between

supports and ensuring an equally distributed load. The specimen was loaded until critically

fractured, and the load was immediately stopped to recover the specimen. A drop of water

was added into the notch of the specimen, and the specimen was rested for 4 days. The

process was then repeated to measure the peak load of the healed specimen.

28
 2.2. Characterization Tests on the Dental materials

Junling Wu et al [2] An optical microscope (TE2000-S, Nikon, Japan) was used to examine

the microcapsules. The microcapsule diameters were measured using the optical microscope

together with an image analysis software (Nis-Elements BR2.30, Nikon, Japan). In addition,

the surface morphology of TEGDMA-filled microcapsules was examined with scanning

electronic microscopy (SEM, Quanta 200, FEI, Hillsboro, OR). The ability of the

encapsulated TEGDMA to polymerize was quantified by near-infrared (NIR) spectroscopy

(Nicolet 6700, Thermo Scientific, Waltham, MA). A mixture of microcapsules with 0.5% by

mass of benzoyl peroxide (BPO) initiator powder (the catalyst) (SigmaAldrich) were broken

by manual spatulation and placed in a 6 mm3 mm2 mm Teflon mold. NIR spectra were

acquired immediately after resin paste mixing and at 24 h post-cure in an FTIR spectrometer

(Nicolet 6700, Thermo Scientific). The yield of microcapsules was calculated as the ratio of

the dry weight of total microcapsules of each batch divided by the weight of the initial

substances [29], i.e., urea, resorcinol, ammonium chloride, formaldehyde, TEGDMA and

DHEPT. Microcapsules loaded with TEGDMA were dispersed in acetone and sonicated at 40

Hz for 5 min (Branson, Fisher Scientific). This broke the microcapsules, and the TEGDMA

and DHEPT were dissolved in the acetone solvent. After vacuum filtration and drying for 1 d,

the undissolved microcapsule shell fragments were collected and weighed. The TEGDMA-

DHEPT mass was calculated as the initial weight of the microcapsules minus the shell weight.

The TEGDMA-DHEPT mass fraction in the microcapsules was calculated as the TEGDMA-

DHEPT mass divided by the total mass of the microcapsules.

George Huyang et al [3] A Helios NanoLab 650 Dual Beam SEM/FIB (FEI Company,

Hillsboro, Oregon, USA) with an X-Max 80 mm2 SDD-EDS detector (Oxford Instruments,

29
Abingdon, Oxfordshire, UK) was used to analyze the elemental composition of the fractured

and healed surfaces.

Girish Galgali et al [4] Thermo gravimetric analysis (TGA) of silica microcapsules was

performed using a Perkin Elmer TGA and by scanning from 30 to 330 8C with a heating rate

10 8C/min under a nitrogen atmosphere. SEM analysis was performed using a Jeol JEOL-

7500F. Compression tests were performed using nano-indentor MTSG200 employing an

indentor with a flat 100 mm diameter circular tip and equipped with an optical microscope.

The experiments were performed in the controlled displacement mode with a maximum

displacement distance of 30 mm and a maximum load setting of 550 mN. Microcapsules

were spread onto an aluminum substrate coated with a thin film of UV curing resin. Prior to

the experiments, the aluminum surface was coated with a thin layer of UV curing resin and

exposed to the UV light for 30 min. The hardened resin layer prevents lateral slippage of the

capsules during compression. The optical microscope connected to the nano-indentor was

used to the select single, isolated microcapsules suitable for indentation studies. The

breakage of the capsules was confirmed microscopically. The microcapsule size and size

distribution was analyzed with ImageJ software.

2.3. Dental wear

Magdalena A. Osiewicz et al [5] defined wear as a consequence of the interaction between

surfaces moving in contact, causing gradual remove of material .Wear of teeth and

restorative materials is the result of different complex processes that depend primarily on the

abrasive nature of food, the properties of the antagonistic material, the thickness and

hardness of enamel, the chewing behavior along with parafunctional habits, and

neuromuscular forces upon resin composites as a viable treatment option for all types of

restorations.

30
Resin Composites have been proposed as a viable treatment option for wear resistance of the

tooth. Nowadays direct and indirect resin composites are also frequently applied to build up

the occlusion when extensive tooth wear took place.

2.4. Wear behavior of resin composites

Natthavoot Koottathapea et al [6] investigated volume loss and worn surfaces'

morphologies of four resin composites. Specimens were fabricated and mounted in a ball-

on-disc wear testing machine and abraded in water or with the third-body media, poppy seed

slurry and polymethyl methacrylate (PMMA) slurry. Volume loss was determined after 10k

sliding cycles. The worn surfaces were examined with SEM. Volume loss and worn surfaces'

morphologies varied with type of composite and third-body media used.

Zeynep Duymus Yesil et al [7] evaluated the relative wear characteristics of 2 recently

introduced Nano filler-based composite resins and compare them to the more traditional

micro hybrid and micro fill materials that have been used for many years. The results

indicated that the composite resin type did not significantly affect the amount of measured

attrition but did significantly affect abrasive wear. The conventional micro fill composite

resin exhibited significantly less abrasive wear than the Nano hybrid material. Results

indicated that the incorporation of Nano fillers in 2 of the composite resin materials tested did

not significantly improve their wear resistance or the amount of opposing cusp wear when

compared to the traditional materials tested.

2.5. Research Gap based on the literature survey

Based on the detailed literature survey carried out on the topic following are the

recommendations:

31
 The detailed analysis of physical, mechanical and wear behavior of dental composite

have not been done in a single paper.

Self-healing dental composites fabricated in previous researches do not contain any

filler.

Chapter 3

MATERIALS AND METHODS

3.1. MATERIALS

Four variants of Self-healing Dental Composites (SHMDC) with different

composition were used for our study. The details of the materials used for the

study are listed in Table 3.1

Table 3.1 List of materials used for the composite

Resin Composition Filler Material Healing Powder Microcapsule
Material Composition

Bis-GMA, TEGDMA, Amorphous Calcium Strontium SPAN 80 surfactant,

CQ, EDMAB Phosphate fluoroaluminosilicate Decalin, Polyacrylic
particles acid (Healing Liquid),
TEOS, Hydrochloric
acid

Table 3.2 Details of composition of different components of dental composite

Filler Content Healing Powder Microcapsule Resin Content

(%) Content (%) Content (%) (%)

SHMDC-0 6 50 0 44

32
 SHMDC-3 6 50 3 41

SHMDC-6 6 50 6 38

SHMDC-9 6 50 9 35

3.2 METHODS

3.2.1 Micro-Encapsulation Procedure

A mixture of 4.0 mL SPAN 80 surfactant, 100 mL decahydronaphthalene, 4.0 mL milli-

Q water, and 4.0 mL polyacrylic HL was prepared as the water/oil emulsion.

A separate silica mix-ture containing 4.0 mL TEOS and 1 mL hydrochloric acid (2 M)

was mixed separately.

After 1 h, the silica mixture was added dropwise into the water/oil emulsion, and the

combined mixture was stirred at400 rpm for 1 h.

After 1 h, initial signs of precipitation was observed, and the stirring was continued with

heating to 60 C for 45 min.

The resulting precipitate was collected by filtration and washed 3 times with ethanol to

remove excess SPAN 80 surfactant.

The precipitate formed was confirmed by SEM to have microcapsule structure.

3.2.2 Micro-Hardness Test

3.2.2.1. Specimen Preparation

Four different composite resins were tested for micro hardness as seen in Table 3.2. Four

samples were prepared from each composite resins by using glass moulds .The

composite resins were cured by means of a curing light with high-intensity light at 395

33
480nm capable of polymerizing all light-cured dental materials. The curing times were

50s, 90s, 112s, 40s for Filtek Z250, Brilliant NG, Prime-Dent and Valux Plus

respectively. They were then stored in distilled water for seven days at ambient

conditions of 37oC before the test. The specimens in the form of rectangular pieces with

dimension 15*12 mm with thickness of 4mm were prepared for the micro hardness test.

3.2.2.2. Testing Procedure

The prepared specimens were checked for micro hardness under Vickers micro hardness

tester. A diamond pyramid with a square base at an angle of 133 o 0.5o between the opposite

faces was used as an indenter. Force used for micro hardness testing was 0.020 kgf. A

diamond shaped indent was formed and observed under microscope. The length of the

diagonal of the indent were measured to find out the Vickers hardness based on the formula:

)
HV= (

F denotes load in kgf

d denotes arithmetic mean of the two diagonals

HV denotes Vickers Hardness Value

Three readings were taken for each specimen. Mean of the three values represents the

hardness of the specimen.

3.2.3. Compressive Strength Test

3.2.3.1 Specimen Preparation

Cylindrical specimens (n=3) of each composite 4mm diameter, 6mm height were prepared

using a glass test tube. The material was inserted in the test tube by holding the test tubes

against the syringes. It was then compressed for uniformity using pins. It was light cured and

34
the test tube was rotated at a uniform speed for homogeneous curing of the sample. The ends

were cured separately. The curing time was 45s for the four dental composites. The test tubes

were broken to acquire the specimen. The ends were made flat by rubbing them against

Silicon carbide grit paper. After this they were stored in distilled water at 37 oC for seven days

before being the tested.

3.2.3.2 Testing Procedure

The exact diameters of each specimen was measured using digital vernier caliper. The

specimen was placed in the UTM with its ends between the plates. The compressive load was

applied along the axis of the specimen as shown in Fig 3.1 at a cross head speed of 1mm/min

up to failure. The compressive strength was then calculated using the peak load and the

diameter of the specimen.

Fig 3.1 Compressive Stress Test

Compressive strength= F/A

F - Force at failure point

A- Cross section area of the specimen

35
3.2.4 Fourier Transform Infrared Spectroscopy

3.2.4.1 Specimen Preparation

In this test the finely powdered form of the specimens were used. It was obtained after

crushing the cylindrical samples in pastel and mortar. The cylindrical specimens were

prepared using a glass test tube. The material was inserted in the test tube by holding the test

tubes against the syringe openings which were compressed using pins. It was then light cured

and the test tube was rotated at a uniform speed for homogeneous curing of the sample, the

ends were cured separately The curing time was 45s for the four dental composites. The test

tubes were broken to obtain the specimen.

3.2.4.2 Methodology

In this method, the Infrared radiation is passed through the specimen. Some of the radiation is

absorbed and some of it is transmitted creating a spectrum which is like a molecular

fingerprint of a substance, different for every chemical composition. The IR rays passed were

of the range 400-4000 cm-1 wavelength and the spectrum was obtained.

Fig 3.2 Principle of Fourier Transform Infrared Spectroscopy

36
 Fig 3.3 Fourier Transform Infrared Spectroscopy Apparatus

3.2.5 Thermo-gravimetric Analysis

3.2.5.1 Specimen preparation

In this test, coarse grains of the specimens were used. It was prepared by crushing down the

cylindrical samples in pastel and mortar. For every test around 0.5 grams of specimen were

used. The cylindrical specimens were prepared using a glass test tube. The material was

inserted in the test tube by holding the test tubes against the opening of syringe later it was

compressed using pins. It was then light cured and the test tube was rotated at a uniform

speed for homogeneous curing of the sample. The ends were cured separately. The curing

time was 45s for the four dental composites. The test tubes were broken to acquire the

specimen.

3.2.5.2. Characterization Test

37
In TGA, the change in weight of a specimen is measured as a function of temperature in the

atmosphere of nitrogen/ helium/ air/ other gas or vacuum. In our study, it was performed on

Perkin Elmer TGA 4000 in atmosphere of nitrogen. The temperature was increased from

30oC to 350oC at the rate of 5oC/ min.

Fig 3.4 Thermo gravimetric Apparatus

3.2.6.Dynamic Mechanical Analysis

3.2.6.1 Specimen preparation

In DMA the cylindrical samples of length 6mm and diameter 5mm were used. The cylindrical

specimens were prepared using a glass test tube. The material was inserted in the test tube by

holding the test tubes against the opening of syringe later it was compressed using pins. It

was then light cured and the test tube was rotated at a uniform speed for homogeneous curing

of the sample, the ends were cured separately. The curing time was 45s for the four dental

composites. The test tubes were broken to obtain the specimen. The specimens were rubbed

38
against the silicon carbide paper to make the ends flat and also to make it of the required

length.

3.2.6.2 Dynamic Mechanical Analysis Test

DMA is a powerful technique where a sinusoidal stress is applied and the resultant strain is

measured. The properties measured under this oscillating loading are storage modulus (E)

loss or viscous modulus (E) and tan (ratio of loss to storage modulus). DMA tests were

performed on a DMA 8000 (PerkinElmer) in compression mode. A frequency of 1 Hz was

applied (approximated to average chewing rate) and amplitude of 10 m. A temperature range

of 30 350 C and a heating rate of 5C/min were selected. Storage modulus (E ), loss

modulus (E) and tangent delta (tan) were plotted against temperature over this period. After

the DMA cycle, the sample was allowed to cool naturally to room temperature

Fig 3.5 Dynamic Mechanical Analysis Apparatus

3.2.7 Wear Volume

3.2.7.1 Specimen Preparation

In wear volume test the cylindrical samples of length 13mm and diameter 5mm were used.

The cylindrical specimens were prepared using a glass test tube. The material was then

inserted in the test tube by holding the test tubes against the opening of the syringe and

39
compressed using pins. It was then light cured and the test tube rotated at a uniform speed

for homogeneous curing of the sample. The ends were cured separately. The curing time was

45s for the four dental composites. The test tubes were broken to separate the specimen. The

specimens were rubbed against silicon carbide paper to make the ends flat and make it of

exact length. After this they were stored in distilled water at 37 oC for seven days before being

tested. The samples were heated in furnace at around 90 oC for an hour to remove excess

moisture.

Fig 3.6 Prepared Specimen for Wear Test

3.2.7.2 Wear Test

The test was performed on DUCOM dental wear simulator. The simulator

has four stations in which four specimens can be mounted simultaneously.

It is pneumatically controlled. The specimens were mounted in the fixtures

and circular antagonist disks (material SS304) were fixed below the

fixtures. Simulations of the machine were studied on WINDUCOM software

available with the machine. Parameters like load, no. of cycles, type of

profile, speed, and profile size can be varied. The slurry between the

specimen and antagonist can also be varied.

40
 Fig 3.7 Dental Wear Simulator

Table3.3 Dental Wear Simulator Parameters

Parameters Assigned value

Load 4N

No. Of cycles 10000

Type of profile 8 Shaped

Speed 40% (4mm/s)

Profile size 100%

Ramp rate 5s

Friction force trip 100 N

Temperature trip 65oC

Fresh artificial saliva was used as the slurry medium. The mass loss was calculated by using

high precision analytical balance (CONTECH CA-413) of least count .001gm.

41
3.2.8 SEM Analysis

3.2.8.1 Specimen preparation

The worn out samples from dental simulator were used in this test the length of the sample

were reduced to 10mm to mount it on the machine. The conductive coating was done over the

sample for the test.

3.2.8.2 SEM Test

In this test a focused beam of high energy electrons is used to generate a variety of signals at

a surface of solid specimen. The signals are derived from electron sample interaction that

reveal information about the sample including external morphology, chemical composition

and crystalline structure and orientation of the material making up the sample.

42
 Chapter 4

RESULTS AND DISCUSSION

4.1 RESULTS

4.1.1. Micro Hardness Test

Mean values and the standard deviation of the Vickers hardness of the

material tested are shown in Fig 4.1 and tabulated in Table 4.1. The values

varied from 42 HV for SHMDC-0 to 78 HV for SHMDC-9.

Micro Hardness

Fig 4.1 Comparison of Hardness Values of the composite materials

 Table 4.1 Vickers Hardness Value and Standard Deviation for the composites

Materials Reading 1 Reading 2 Reading 3 Mean Standard

(HV) (HV) (HV) Hardness
Deviation(HV)
Value(HV)

SHMDC-0 46 37 43 42 4.58

SHMDC-3 69 54 51 58 9.64

SHMDC-6 73 60 65 66 6.55

SHMDC-9 77 83 74 78 4.58

4.1.2. Compressive Strength Test

Mean values and the standard deviation of the compressive

test of the material tested are shown in Fig 4.3 and tabulated in
Table 4.4. The values varied from 206.63 MPa for SHMDC-0 to
105.28 MPa for SHMDC-6.

Compression Test

Fig 4.2 Comparison of Compressive Strength of the composite

materials

44
Materials Sample 1 Sample 2 Sample 3 Mean Standard
(MPa) (MPa) (MPa) Compression deviation
Strength (MPa)
(MPa)

SHMDC-0 223.08 158.20 238.60 206.63 42.65

SHMDC-3 123.97 135.19 142.30 133.82 9.23

SHMDC-6 142.96 79.38 86.50 105.28 34.84

SHMDC-9 107.93 98.70 135.66 114.09 19.23

Table 4.2 Compressive strength and Standard Deviation for the

composites

4.1.3 Wear Loss

Wear (mass) loss has been studied for each composite subjected to saliva as

medium under simulated dental conditions. The mass losses has been shown in

the following figures for different number of cycles.

Wear Test

SHMDC-0 SHMDC-3 SHMDC-6 SHMDC-9

Fig 4.3 Mass Loss in Saliva

45
4.1.4 Characterization Tests

4.1.4.1 Dynamics Mechanical Analysis

Dynamics Mechanical Analysis of four specimens were done under compression mode.

Storage modulus, loss modulus and tangent delta were plotted against temperature. Tg

(Glass Transition temperature) of the specimens were obtained from the graph. It is the

temperature indicated by the peak of tangent delta. Width at the half of the tangent delta is

also determined to compare the filler particle content in materials. is also determined

from the storage modulus vs temperature graph to compare material content of specimens.

Tangent Delta vs Temperature

SHMDC-0 SHMDC-3 SHMDC-3

SHMDC-6 SHMDC-9

46
 Fig 4.4 Tangent delta as a function of temperature

The values of Tg can be compared for different materials, Tg of specimens are in the order:

SHMDC-0>SHMDC-9>SHMDC-6>SHMDC-3

The values of SHMDC-9, SHMDC-6 and SHMDC-3 are quite close to each other but glass

transition temperature of SHMDC-0 is very high. SHMDC-0 shows highest value of tan delta

at a particular temperature and SHMDC-0 exhibits the lowest value. The width at half the peak

value is highest in the case of SHMDC-3 which shows that it is most heterogeneous among the

four composites.

47
 Storage Modulus vs Temperature

SHMDC-0 SHMDC-3 SHMDC-6 SHMDC-9

Fig 4.5 Storage Modulus as a function of temperature

48
We can clearly see values of parameter in the graph. SHMDC-9 has least value. It is the

ratio of temperature and storage modulus at a point where the modulus becomes constant

with increase in temperature. SHMDC-0 shows highest value of parameter indicating

that it has less microcapsules and SHMDC-9 has the highest microcapsules content.

Loss Modulus vs Temperature

SHMDC-0 SHMDC-3 SHMDC-6 SHMDC-9

49
 Fig 4.10 Loss Modulus as a function of temperature

4.1.4.2 Fourier Transform Infrared Spectroscopy of microcapsules

The solid phase (KBr disk) infrared spectroscopy was used in the spectral range of 400 to

4000 wave numbers (cm-1) to confirm the encapsulation of healing liquid (polyacrylic acid)

inside the microcapsules.

The received IR spectra of compounds were reported as percentage transmittance values as a

function of wave number in cm-1 The IR spectra of Healing liquid containing microcapsules

are presented in Fig. 4.11

The FTIR spectra from Healing liquid containing microcapsules indicated the presence of

COOH groups (Fig. 4.11) with an absorbance peak at 1726.51 cm1.

Fig 4.11 FTIR spectra of the microcapsule

4.1.4.3 Thermo gravimetric Analysis

50
 (a) SHMDC-3
(b) SHMDC-6

(a) SHMDC-9

Fig 4.7 TGA analysis of the dental composites

The above graph shows the decrease in weight of sample as a function of increase in external

temperature. The temperature at which the weight loss begins is called onset temperature. It

can be seen from the graph that the onset temperature of SHMDC-3, SHMDC-6 and

SHMDC-9 are 118oC, 120oC, 125oC respectively. The above thermo-gravimetric analysis

graph helps in determining the thermal stability of the samples used for tests. The onset

temperature has a proportional relationship with thermal stability i.e., Greater the onset

temperature, higher the thermal stability of the material. So, SHMDC-9 having the highest
51
onset temperature has the highest thermal stability and SHMDC-3 having the lowest onset

temperature has the least thermal stability.

4.1.5 SEM Analysis

The microscopic images of the worn surfaces have been observed under Scanning Electron

Microscopy subjected to three different medium. After wear testing the morphology of wear

scar is investigated using FESEM. Following figures illustrate the morphologies of the wear

scars in water. The surfaces are highly abraded showing distinct long cracks along the sliding

path in addition to some pin pointed holes due to the removal of filler particles. SHMDC-9

shows maximum worn surface as expected. The urfaces of SHMDC-0, SHMDC-6 and

SHMDC-9 are rather uniformly abraded. The surface of SHMDC-9 is showing distinct wear

lines. The surface morphologies of materials showed minimum wear in case of saliva,

SHMDC-9 showing fewer minor parallel cracks on the surface.

(a) SHMDC-0 (b) SHMDC-3

52
 (c) SHMDC-6 (d)
SHMDC-9

Fig 4.8 The Morphology of wear scars on

flat specimens following wear testing with
saliva as medium

53
4.2 DISCUSSION

Considering the long-term clinical performance

of resin materials, self-healing efficacy and

wear resistance is an essential aspect

unanimously, especially for posterior

restorations in occlusal stress-bearing areas.

The composition, size, and loading content of

microcapsules have the potential to influence the healing efficacy and wear performance.

Besides, there is no generalized pattern observed in the effect of loading content on the self-healing

efficacy and wear performance. This is due to the fact that although microcapsules acts as fillers because of

silica coating on it but increase in microcapsules loading content may hinders the chain formation,

increases the inter-particle microcapsule spacing and thus bonding between the constituents of composite

resin. This will result in the lack of wear performance of the composite resin. Silica microcapsules were

used because they had the elastic modulus matching the fillers in the dental composites, which prevented

premature fracture during composite preparation. In addition, the acidic and hydrophilic nature of the HL

required an identical medium during encapsulation process. Further, the loading content of healing powder

effects the healing efficacy. As compared to previous researches, we have taken considerably lesser

amount of healing powder content which resulted in hampering the self-healing of composite resin after

crack. However, we have supplemented the constituents of composite resin with amorphous calcium

phosphate nano-fillers, which resulted in improvement in wear performance and other mechanical

properties. Moreover in view of the matrix composition keeping fixed, wear behavior and other

mechanical properties of experimental resin composites was explored from the constituent

and loading of microcapsules in our work.

4.2.1 Mechanical Properties

54
 In our present study, we have evaluated the effect of filler content on mechanical properties

like Micro Hardness, Compressive Strength and wear loss of the four dental composites used.

effect of filler content on hardness of dental composite used. The results of Micro Hardness

suggest that Brilliant and Prime Dent exhibited similar Hardness. The mean hardness for

SHMDC-0, SHMDC-3 and SHMDC-6 were significantly lower than SHMDC-9. Comparable

to other studies, SHMDC-9 exhibited the highest hardness. SHMDC-0 containing a filler

fraction volume of 6% (66 wt %) and 0% Healing liquid containing microcapsules,

demonstrated lowest mechanical hardness. A superior mechanical hardness for a higher (9%)

rather than a lower (0%) microcapsule fraction was deduced from the results. This positive

effect is assumed to be related to presence of Silica microcapsules. The hardness of the

composite resins was also influenced by monomer structures of the resin matrix besides the

filler system. The filler load level and the fillermatrix-interactions have a greater influence

on fracture parameter of dental composites than the structure of the organic matrix.

Compressive strength is an important property for dental posteriors. It has been evaluated in

our study that SHMDC-0 shows the highest value of compressive strength (206.63 MPa) and

SHMDC-9 shows the lowest value of compressive strength (114.09 MPa). This shows that

microcapsule percentage is a significant factor in the contribution to compressive strength. So

there is variation in the compressive strength with the increase in the Zirconia volume

percentage evident in the compressive strength values with SHMDC-0 exhibiting highest

compressive strength as well as highest microcapsule weight fraction compared to other three

dental composites. Further, we can find out the exact volume percentage of microcapsule

which will give maximum compressive strength. This can be done by using optimization

procedures. Variation in the compressive strength with variation in filler is probably quite

complex, because of multiple factors associated with the compressive strength of the resin

matrix i.e. the filler particles, including particle size and distribution.
55
4.2.2 Characterization Tests

The Thermo gravimetric analysis of the dental composites used to determine the thermal

stability of the material displayed weight losses due to chemical reaction(decomposition, loss

of water of crystallization, combustion) and physical transition (vaporization, evaporation,

sublimation).Occasionally a gain in weight is observed due to chemical reactions(reaction

with gaseous substances in the purge gas like O2 , CO2 and physical transitions(absorption of

gaseous substances on samples). Thermal degradation of SHMDC-9 shows a single step of

decomposition at 125. The decomposition is due to the evaporation of water. Similarly the

thermo gravimetric analysis of SHMDC-6 and SHMDC-3 show a single step of

decomposition at 118 and 120 respectively due to loss of water by evaporation. There

are two stages of decomposition in the TGA of SHMDC-3. The first step of decomposition

which occur at 175 is due is due to loss of water molecules and the second step of

decomposition which occurs at 210 is due to decomposition of small molecules such as

CO,CO2 and NH3 on increasing the temperature.

Infrared spectroscopy was conducted as a useful and available method for quick identification

of chemical compounds. The IR spectroscopy is used to identify some fragments of solid

substances to obtain authenticated information about the vibration origin of the ester,

carboxylic and alcoholic groups in the microcapsules that have been studied. The COOH

groups were identified by FTIR spectrometer (Perkin Elmer Spectrum Two, USA) equipped

with 4000400 cm-1 wave range, 32 scans, and 4 cm-1 resolution. A blank KBr pellet was used

for the collection of the background spectrum. FTIR spectrum of the composites shows a

peak around 1726.51 cm-1 due to ester (-COOCH3) in the prepared specimens.

56
In the dynamical mechanical analysis, the studied dental composites show differences in the

composition and the content of organic matrix. Presently, there is no consensus on the

positive effect of a certain particle size and shape of filler on the mechanical properties. Even

the comparison of experimental composite formulations has resulted in unclear findings

suggesting that the filler load was the main factor for determining elastic modulus properties,

while filler size and shape should be considered as secondary fine-tuning factors for

altering material properties. In our work SHMDC-0 with the lowest microcapsule content (0

wt %) also showed the highest elastic modulus and other showed lesser values for elastic

modulus. The values of tangent delta of SHMDC-0 at low temperatures are high indicating

it is more flexible at lower temperatures. The width at half the peak value of tan delta shows

the heterogeneity of composite. SHMDC-3 has highest among the four composites. Glass

transition temperature (Tg) is an important physical property of the cured matrix of dental

composites. The dental composites must have a Tg higher than the maximum temperature in

the oral cavity to preserve the materials physical and mechanical properties. Inadequate

polymerization determines a low final Tg in material. Intraoral temperatures that exceed the

Tg may result in material softening and consequently in failure of the clinical procedure. The

loss modulus represents the viscous nature of the composite. Higher value suggests greater

ability to relieve excess energy built up through moderate viscous flow during tooth function.

SHMDC-0 showed higher value than others due probably to the slight lower filler content.

On the other hand, the parameter is also a good tool for presenting the heterogeneity of a

polydimethacrylate network. When the storage modulus curve reaches a plateau, the

corresponding absolute temperature divided by the corresponding modulus, known as the

parameter, is calculated as shown in Fig. 2. The modulus of the plateau (rubber modulus) and

the temperature at which this plateau is reached, increases not only with the crosslinking

density but also with the heterogeneity of the material. The parameter was used to study the
57
crosslinking density. This parameter is generally considered to be inversely correlated to the

crosslinking density of the polymer network, with lower values corresponding to higher

crosslinking density and heterogeneity. SHMDC-0 showed higher values than the other three.

4.2.3 Wear Analysis

Teeth wear is the main reason for the need of teeth replacement. So, it is a much needed

requirement for a high wear resistive and low cost material for artificial tooth. Types of teeth

wear are attrition (enamel on enamel contact), abrasion (wear due to abrasive particles in

toothpaste or food), abfraction (cracking in enamel and subsequent material loss), and erosion

(chemical decomposition of the tooth).Attrition is simulated by two body wear in the test,

here distilled water is used as medium similarly abrasion is simulated by three body wear in

which coke and saliva are taken as mediums. We have chosen saliva as our medium for wear

to simulate the actual conditions of wear in a human mouth.

As a model for abrasive wear, we consider the Archard equation for sliding wear of material

with acidic lubricants. In this model, the wear volume (V) is related to the normal load, P,

sliding distance, L, and hardness of flat surface, H, as:

=/

In the present study, the normal load and sliding distance are both constant for different

medium (slurry) during wear testing, hence above can be simplified as:

= /

Where k is constant and k=KPL. The wear and hardness showed relationship in saliva as a

medium. In saliva, SHMDC-9 showed least wear, probably because of its highest hardness.

58
So, we propose that wear is inversely proportional to hardness of material as shown by the

simplified archard equation.

4.2.4 SEM Analysis

Surface roughness is the most frequently used parameter in assessing the surface quality of

different restorative materials. Due to the limitations of the quantitative measurement

methods, the results are often verified qualitatively with scanning electron microscopy (SEM)

to demonstrate shape and contour changes that may not be shown by the profilometer. This

study aimed to investigate the surface roughness and morphology of the four dental

composites. The fabrication, particle and filler size, applied force, liquid medium of the wear

affect the results. In addition to the finishing and polishing treatments, the surface roughness

of the composites is also influenced by several material factors such as the type, shape, size

and distribution of the inorganic fillers. The surface roughness has been decreased by

increasing the microcapsule content. All samples have same microcapsule size of about 10

nm. Microscopic images shows SHMDC-9 has lesser wear than remaining all material in

artificial saliva. SHMDC-0 shows highest wear as well as lowest microcapsule content. This

shows that higher the microcapsule content, lower will be wear. Higher filler content is

expected to protect the resin matrix from excessive abrasion, resulting in smoother surfaces;

however, fillers that are much harder than the resin matrix may cause prominent matrix

abrasion during polishing, which was also observed with the other dental composites. The

abrasion of the softer resin matrix may result in a lack of support of the fillers, leading to

further filler roughening of the surface.

59
 Chapter 5

Conclusions and Future Scope

5.1 Conclusions

Based on hardness test it can be concluded that SHMDC-9 is the hardest material and it is

hardness is significantly more than other composites. The other three have hardness values

comparable to each other. There is a significant reduction in hardness values of all the four

materials.

Compressive strength of SHMDC-0 was highest among the four composites compared.

SHMDC-9 showed a low compressive strength but the compressive strength values for

SHMDC-3, SHMDC-6 and SHMDC-9 were in very close proximity to one another.

Dynamic Mechanical analysis suggested SHMDC-0 is the most dynamically stable material

even in high temperature ranges. Its glass transition temperature was very high as compared

to other three whose glass transition temperatures were very close to each other. SHMDC-0

also showed highest values of storage modulus and parameter indicating high filler

fraction rate.

Thermo-gravimetric analysis of the composites showed that SHMDC-9 is the most thermally

stable material among the four compared. Fourier transform Infrared spectroscopy performed

at 400-4000cm-1 showed the constituent functional groups present in the microcapsules. At

around 1726 cm-1 the microcapsules showed a peak depicting presence of ester group.
Wear analysis of the materials subjected to varying medium showed that wear pattern was

dependent on mediums. In saliva, SHMDC-0 showed minimum wear whereas SHMDC-9

showed minimum wear. The correlation between hardness and wear was deduced from the

tests in case of saliva as a medium.

The FESEM of the worn out samples showed a direct relationship with the mass reduction.

FESEM images of more worn samples with respect to mass reduction out had rougher

surface.

5.2 Future Scope

We have compared the four dental composites on the basis of their mechanical properties and

wear behavior. All the materials have some advantages and disadvantage and we cannot make

a clear demarcation of which is the best, probably a good mechanical property comes with the

cost of other. We were unable to establish relationship in some tests of the results with the

chemical properties of the composites, which might require detailed research work.

Atomic force microscopy could have been done of the worn out samples to get a better idea

of the surface morphology of the specimens. Further research could be done to establish a

relationship between the chemical composition and mechanical and behavior of the

composites.
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