Chapter 1

Introduction

1.1. Introduction

Tribology is the science that deals with the interactions of solid surface in relative motion. It
includes principles of friction, lubrication and wear. It includes interactions of a solid surface's
exposed face with interfacing materials and environment which may result in loss of material
from the surface. The process leading to loss of material is known as "wear". Among the diverse
applications that tribology finds in this contemporary period, Dental Tribology (Bio Tribology)
has been an area of profound opportunities and research. Dental Wear among all is the major
field of interest in Dental Tribology. It refers to loss of tooth substance due to stress lesions
caused by extrinsic forces on the enamel.

Therefore, use of artificial dental material has facilitated to replace natural human enamel with
those prepared manually with enhanced hardness, increased durability and better aesthetics.
Among the numerous materials commercially available resin composites have replaced the
conventional dental amalgam as the restorative material in dentistry. This can be mainly
attributed to their improved aesthetics, resistance to fracture and low cost. Hence we have
carried out assessment of four commercially available resin composites, understand their
mechanical behavior and effect of different lubricants on the wear volume of each composite
resin subjected to simulated oral conditions in wear simulator.

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

1
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 uncertainity 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.

1.3. 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.

1.3.1. 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.

2
 Fig 1.1 The chemical formula of the dental monomer used in dental composites

1.3.2. Filler disperse phase

The most current composites are filled with silicate particles based on oxides of barium,
strontium, Zinc, aluminum or zirconium. The concentration rate of filler is generally 70%-80%
by Weight. The particle filler size is in the range from 0.04 to 85 μm. The primary purpose of
the filler particles is 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.

1.3.3. 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 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.

1.3.4. Classification of dental resin composites

The composite resins have been classified in different ways, depending on their composition.
According to the particle size of inorganic filler, composite resins are divided into three main
groups: macro filled, micro filled, and hybrid composite.

3
 Composite Type Filler

Densified composites

• Midway-filled < 60% by volume Particles

Ultrafine
< 3 μm Particle
Fine
> 3 μm
• Compact-filled >60% by
> 60% by volume Particles
volume
< 3 μm Particles
Ultrafine
> 3 μm
Fine

Microfine composites
- Homogeneous Average particle size = 0.04 μm

- Heterogeneous
Miscellaneous composites Blends of densified and micro fine composites

Equivalent to what are termed macro fill

Traditional composites
composites in other classifications

Fiber-reinforced composites Industrial-use composites

Table 1.1 Classification of composites

Nano-composites are recent development on the market. They contain filler particles with sizes
less than 10 nm (0.01 μm) and are claimed to provide increased aesthetics, strength and
durability Nano composites are available as Nano hybrid types which contain milled glass
fillers and discrete nanoparticles (40–50 nm) and as Nano fill types, containing both Nano-
sized filler particles, called nanomers and agglomerations of these particles described as “Nano
clusters”. The Nano clusters provide a distinct reinforcing mechanism compared with the micro
fill or Nano hybrid systems resulting in significant improvements to the strength and reliability.

4
Composite type Filler size (μm) Filler material

Macrofilled 10-40 Quartz or glass

Microfilled 0.01-0.1 Colloidal silica

Hybrid 15-20 and 0.01-0.05 Glass and colloidal silica

Modern Hybrid 0.5-1 and 0.01-0.05 Glass, Zirconia and colloidal silica

Nanofiller < 0.01 (10 nm) Silica or Zirconia

Table 1.2 Filler sizes and materials in dental composite materials

Composites also can be classified according to their method of activation

(1) Chemically activated composites.

(2) Light activated composites.

(3) Heat-cured composites.

(4) Dual-cured composites.

1.4. 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
5
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.
Removed material results in debris which are likely to agglomerate, producing larger particles.

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.

1.5. 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.

6
1.6. 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,
hardness, flexural modulus, flexural strength, and toughness . Composite restorative materials,
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
between particles. The size and shape of filler particles are also influential factors affecting the
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

7
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.

1.7. Objectives of the Project

In the present study of assessing the mechanical properties and wear analysis of commercially
available artificial dental materials following are the main objectives:-

i. Fabrication of specimens using four different commercially available composite

materials.
ii. Carrying out Dynamic mechanical analysis, Thermo gravimetric analysis and Fourier
transform infrared spectroscopy on the prepared specimen.
iii. Assessment of wear loss and effect of micro hardness and compressive strength of the
specimens on wear behavior.

8
 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. Dental wear

Magdalena A. Osiewicz et al [2] 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. 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.

Eugeniusz Sajewicz [15] surveyed the literature showing that in many studies on the wear
resistance of tooth enamel or dental materials a large scatter of experimental data has been
obtained when wear tests were performed at a fixed load. Despite the steady loading, wear
conditions vary during sliding, since tooth enamel as well as dental materials have
inhomogeneous structure. This leads to changes in contact interactions between sliding
surfaces, and as a result, we get changes in the friction and wear behaviour of tested materials.
This is why at the same loading the wear can be different. In this study, more reliable approach
to evaluation of the wear resistance of human enamel and dental materials is proposed. The
procedure is based on the correlation between the volumetric wear and the friction energy
dissipated during sliding. The model can be useful to compare the wear resistance of different
dental materials tested in different ambient conditions.

9
H.Y. Yu et al [13] investigated friction and wear behavior of dental Feld spathic porcelains
against uniform silicon nitride balls. The variables of load (10–40 N), reciprocating amplitude
(100–500 µm), frequency (1–4 Hz) and use of artificial saliva lubrication were selected. Tests
lasting up to 10,000 cycles were conducted. The bonded-interface technique was introduced
into the wear test for the subsurface damage evaluation. Special attention was paid to the effects
of friction conditions of tests, material properties and wear mechanism of dental porcelains..
Among three parameters of the tests on the friction coefficient and wear depth of dental
porcelains, the load effect is prominent. Artificial saliva plays an important role in lowering
the friction coefficient and wear loss of dental porcelains. Surface brittle cracks are more
dominant in low sliding cycles while subsurface cone or lateral cracks are prominent in high
sliding cycles.

J.A. Arsecularatne et al [19] reported a transmission electron microscopy (TEM) analysis of

subsurface of enamel specimens following in vitro reciprocating wear tests with an enamel
cusp sliding on a flat enamel specimen under hydrated conditions. The obtained results showed
that crack formation occurred in the wear scar subsurface. The path followed by these cracks
seems to be dictated either by the histological structure of enamel or by the contact stress field.
Moreover, the analysis of a set of enamel wear results obtained from the literature and
application of fracture-based models, originally developed for ceramics, correlate well,
confirming the similar wear processes taking place in these materials. This analysis also reveals
a marked influence of coefficient of friction on the enamel wear rate: for a higher coefficient
of friction value, enamel wear can be severe even under forces generated during normal
operation of teeth.

2.2. Wear behavior of resin composites

Natthavoot Koottathapea et al [3] 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.

10
Zeynep Duymus Yesil et al [4] 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.

R. Karthick et al [14] evaluated the hardness and tribological properties the Poly (Methyl
methacrylate) PMMA based denture composite reinforced with seashell Nano powder. The
PMMA bio composites containing 2%, 4%, 6%, 8%, 12%, 16% and 20% by weight of seashell
Nano powder and an unfilled composite as control specimen were fabricated. The micro
hardness of the composites was found using Vickers hardness tester. The addition of 2%
seashell Nano powder had no significant effect on the micro hardness. But it was found that on
increasing the seashell Nano powder content, the micro hardness value increased till 12% and
substantially decreased beyond 12% seashell Nano powder. The wear test was performed and
frictional force generated during sliding of specimens were evaluated in pin on disc apparatus.
The wear mechanism and dispersion of seashell Nano powder in the specimen were analyzed
in Scanning Electron Microscopy (SEM). The wear resistant property increased on addition of
seashell Nano powder with 12% seashell Nano powder reinforced composite showing least
frictional force developed during the wear test. The 16% and 20% filled composite developed
more frictional force than developed in 12% filled composite. It was concluded that PMMA
bio composite could be successfully reinforced by seashell Nano powder with better properties
at 12% seashell Nano powder content followed by 8% filled composite.

P.V. Antunes et al [10] carried out two- and three-body wear between frequently used direct
and indirect resin composites. The outcome was that the two-body wear rate of the different
composites opposing the Z250 wheel were significantly higher. Furthermore, it was shown
that the three-body wear rate was independent of the antagonist and in general higher than
the two-body wear rate. To reduce abrasion of the opposing resin composite surface the resin
composite fillers should consist of a softer glass, e.g. barium glass or in case of a harder filler
the size should be reduced to Nano-size.

11
Oscar Borrero-Lopez et al [16] studied the friction and wear behaviors of dental ceramics
against the natural tooth enamel. In this study three dental ceramics, namely zirconia with both
polished and rough surfaces, hot-forged lithium disilicate glass ceramics and silicates based
veneer porcelain were involved with two metallic materials, gold–palladium alloy and Nickel–
chromium alloy, as references. The tribological tests were carried out under artificial saliva
lubrication condition by using freshly extracted natural teeth and samples with controlled
surface roughness. The frictional coefficients versus reciprocating cycles were recorded.
Scanning Electron Microscopy was used to observe the topography of worn teeth enamel
surfaces and antagonists. The frictional coefficient of enamel against gold palladium alloy or
Nickel–chromium alloy was the smallest. The frictional coefficient of enamel against polished
zirconia or porcelain was between that of metal and glass-ceramic. Upon surface polishing,
frictional coefficient between zirconia and enamel was radically decreased. Furrows and
granular debris were observed on the worn surfaces of enamel while sliding against the rough
zirconia or glass ceramic, indicating a abrasive wear mechanism. While chipping flake and pit-
like structure after stripping and crack were observed on the enamel surface while sliding
against polished zirconia or Nickel–chromium alloy, indicating a type of fatigue wear. It
appeared that the friction and wear performances of zirconia could be improved significantly
by adequate surface polishing. This observation indicated that attention must be paid to
carefully design proper occlusal surface contours and correctly choose dental materials in
clinical practice.

S.D. Heintze et al [17] developed a wear method was that mainly simulates attrition wear
using a commercially available chewing simulator In this test, a standardized stylus made of
press able ceramic (Empress) hits flat specimens 120,000 times with a 5 kg weight,a descent
speed of 60 mm/s and a lateral movement of 0.7mm with a speed of 40 mm/s under constant
exchange of water at different temperatures(325×5 ◦C/55 ◦C). The volume loss was measured
on plaster replicas with the Laserscan 3D and the Match 3D software. Twenty-four
experimental and commercial composites (n = 8) were tested with a volumetric wear range of
between 5.5 and 147×10−2 mm3. On standardized specimens made of the same composites,
the Vickers hardness (H), elastic modulus (E) and fracture toughness (K1c) were measured.
The mean particle size (d) and volume content (vf) of the inorganic filler were evaluated.
Furthermore, a differentiation was made between the main filler with the largest mean size (d1,
vf,1) and the total filler content (vf,tot).

12
Michael D. Weir et al [20] developed Nano composite containing calcium fluoride
nanoparticles (nCaF2), and to investigate the long-term mechanical durability including wear,
thermal-cycling and long-term water-aging behavior. For this two types of fillers were used:
nCaF2 with a diameter of 53 nm, and glass particles of 1.4 µm. Four composites were fabricated
with fillers of: (1) 0% nCaF2 + 65% glass; (2) 10% nCaF2 + 55% glass; (3) 20% nCaF2 + 45%
glass; (4) 30% nCaF2 + 35% glass. Three commercial materials were also tested. Specimens
were subjected to thermal-cycling between 5 ◦C and 60 ◦C for 105 cycles, three-body wear for
4× 105 cycles, and water-aging for 2 years. Results indicated that the nCaF2 Nano composites
had flexural strengths in the range of 100–150 MPa, five times higher than the 20–30 MPa for
resin-modified glass ionomer (RMGI). The wear scar depth showed an increasing trend with
increasing nCaF2 filler level. Wear of nCaF2 Nano composites was within the range of wear
for commercial controls. Water-aging decreased the strength of all materials. At 2 years,
flexural strength was 94 MPa for Nano composite with 10% nCaF2, 60 MPa with 20% nCaF2,
and 48 MPa with 30% nCaF2.They are 3–6 fold higher than the 15 MPa for RMGI (p < 0.05).
SEM revealed air bubbles and cracks in a RMGI, while composite control and nCaF2 Nano
composites appeared dense and solid.

2.3. Mechanical properties of Dental Materials

Camila D. Mayworm et al [5] compared the wear resistance and hardness of two dental Nano
hybrid composites and evaluated the influence of artificial saliva storage on those properties.
Specimens were made from two commercial Nano hybrid dental composites were subjected to
abrasion tests. Microscopic analysis of the wear surfaces was made using scanning electron
microscopy; hardness was quantified by Vickers hardness test. Those tests were repeated on
specimens stored in artificial saliva. Results show that the wear rate of the studied materials is

within 10−7 mm3/N mm range. After storage in artificial saliva, the wear resistance increases

for both materials. After storage in artificial saliva, the micro hardness of both materials
decreases.

Renan Belli et al [6] studied the fatigue resistance of modern dental ceramic
materials versus dental resin composites for posterior partial restorations. Bar specimens of
five ceramic materials and resin composites were produced according to and stored for 14 days
in distilled water at 37 °C. Specimens were tested in water for initial strength in 4-point
bending. Using the same test set-up, the residual flexural fatigue strength was determined.

13
Results demonstrated dental ceramics and resin composite materials show equivalent fatigue
strength degradation at loads around 0.5σin values. Also, resin composite restorations may be
used as an equivalent alternative to glass-rich-ceramic inlays regarding mechanical
performance.

Adriana Cláudia Lapria Faria et al [18] evaluated microstructure, micro hardness and wear
resistance of experimental titanium alloys containing zirconium and tantalum. Alloys were
melted in arc melting furnace according to the following compositions: Ti–5Zr, Ti–5Ta and
Ti–5Ta–5Zr (%wt). Hemispheres and disks were obtained from wax patterns that were invested
and cast by plasma. Microstructures were evaluated using optical microscopy and X-ray
diffraction (XRD) analysis and also Vickers micro hardness was measured. Hemispherical
samples and disks were used for 2-body wear tests, performed by repeated grinding of the
samples. Wear resistance was assessed as height loss after 40,000 cycles. The data were
compared using ANOVA and post-hoc Tukey test. Ti–5Zr presented structure and the
identified phases were α and α′ while Ti–5Ta and Ti–5Ta–5Zr presented α, β, α′ and α” phases,
but the former presented a lamellar structure, and the other, acicular. The micro hardness of
Ti–5Zr was significantly greater than other materials and cp Ti presented wear resistance
significantly lower than experimental alloys. It was concluded that wear resistance was
improved when adding Ta and Zr to titanium and Zr increased micro hardness of Ti–5Zr alloy.

2.4. Characterization Tests of the Dental materials

Evangelia C. Vouvoudi et al [7] proposed dynamic mechanical analysis (DMA) of

viscoelastic properties that is, the elastic modulus (E′), the loss modulus (E″), the loss
tangent (tanδ) and the glass transition temperature (Tg), of two current commercial light-cured
resin composites, Filtek Supreme Body and Filtek Supreme Translucent, characterized as Nano
filled. The studied dry composites showed comparable values for their properties in spite of
their differences in the filler content and type. Storage of composites in air 37 °C for 1 day
caused a significant post curing which was not continued during storage up to 90 days. Water
and artificial saliva showed the same effect on composites. They caused both post curing and
plasticization. Ethanol/water solution 75% v/v had a more strong effect than water and artificial
saliva due to its organophilic nature. It caused post curing, plasticization and most probably
degradation of the bond filler–silane coupling agent.

14
Irini D. Sideridou et al [8] carried out detailed study of the sorption characteristics of water
or artificial saliva, the determination of flexural strength and the flexural modulus, and the
study of the thermal stability of some current commercial dental light-cured Nano composites
containing Nano-sized filler particles. Three Nano hybrid dental composites and two Nano fill
composites were used in this work. The volumetric shrinkage due to polymerization was
determined. Thermal analysis technique TGA method was used to investigate the thermal
stability of composites. Also the sorption, solubility and volumetric increase were measured
after storage of composites in water or artificial saliva for 30 days. Results showed variation of
flexural strength, flexural modulus order of the chosen composites. The water and artificial
saliva generally showed the same effect on physical properties of the studied composites.
Thermo gravimetric analysis gave good information about the structure and the amount of
organic polymer matrix of composites.

Ruili Wang et al [9] highlighted the use of bimodal silica Nano hybrid composites to be used
as fillers. Experimental composites with various filler compositions were prepared and their
wear behaviors were assessed in this work. The results suggested that composites with
increasing addition of silica nanoparticles in co-fillers possessed lower wear volume and
smoother worn surface. Characterization tests including FTIR analysis, TGA analysis
suggested that the use of bimodal silica nanostructures including silica nanoparticles and Nano
clusters as co-fillers with the appropriate weight ratio is an effective way to improve the wear
behavior of the resin composites.

2.5. Research Gap based on the literature survey

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

 The detailed analysis of mechanical and wear behavior of the have not been compared
in a single paper.
 The study of effect of varying mediums on the wear behavior has not been studied
comprehensively.

15
 Chapter 3

MATERIALS AND METHODS

3.1. MATERIALS

Four commercially available Nano hybrid composites were used for our study. The details of
the materials used for the study are listed in Table 3.1

Filtek Z250 (3M ESPE, USA, shade A3, batch no. N570303), Brilliant NG – Coltene( Shade
A3 , Batch no. F52563), Prime-Dent (Shade A3, Batch no. RD11N), Valux Plus ((3M ESPE,
USA, shade A3, batch no. N610207)

Materials Type Shade Manufacturer Filler Composition

content

Wt%/vol%

Filtek Z250 Nano hybrid A3 3M ESPE 75/60 Matrix: Bis-EMA, UDMA,

Bis-GMA

Filler: Zirconia, Silica

Brilliant NG Nano hybrid A3 Coltene 80/65 Matrix: Methacrylate

Filler: Amorphous Silica,

Dental Glass

Prime-Dent Nano hybrid A3 Prime Dental 76/60 Matrix: Bis-GMA

Filler: Silica

Valux Plus Nano hybrid A3 3M ESPE 85/66 Matrix: Bis-GMA, TEGDMA

Filler:Zirconia, Silica

16
 Table 3.1 List and information of the composites tested

3.1.1. Artificial Saliva

Artificial Saliva was used as one of the slurries for wear volume analysis. The method of its
preparation has been outlined below:-

1. Dissolving 2g of methyl –p- hydroxybenzoate in 800 ml of distilled water (solubility:

methyl –p- hydroxybenzoate 1g in 400ml of water). 20ml of the solution was storing
for other chemical agent solvent. The remaining solution was storing in refrigerator.
2. Boiling 200ml of distilled water then sprinkled 10 g of sodium carboxymethyl cellulose
into boiling water and stirring until total of sodium carboxymethyl cellulose was
dissolved.
3. Pouring cold methyl –p- hydroxybenzoate solution (from item 1) into sodium
carboxymethyl cellulose solution (from item 2) then mixing them together until they
are in gel form.
4. Dissolving .625gm of KCl in methyl –p- hydroxybenzoate solution (from item 1) then
pouring the solution into the solution in item 3 and mixing them together.
5. Dissolving .059gm of MgCl2.6H2O in methyl –p- hydroxybenzoate solution (from item
1) then pouring the solution into the solution in item 4 and mixing them together.
6. Dissolving 0.166gm of CaCl2.2H2O in methyl –p- hydroxybenzoate solution (from
item 1) then pouring the solution into the solution in item 5 and mixing them together.
7. Dissolving 0.814gm of K2HPO4in methyl –p- hydroxybenzoate solution (from item 1)
then pouring the solution into the solution in item 6 and mixing them together.
8. Dissolving 0.326gm of K2HPO4 in methyl –p- hydroxybenzoate solution (from item 1)
then pouring the solution into the solution in item 7 and mixing them together.
9. Adjusting the pH of artificial saliva to 6.75 with KOH

3.2 METHODS

3.2.1 Micro-Hardness Test

3.2.1.1. Specimen Preparation

Four different composite resins were tested for micro hardness as seen in Table 3.1. Four
samples were prepared from each composite resins by using glass moulds .The

17
composite resins were cured by means of a curing light with high-intensity light at 395–480nm
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.
3.2.1.2. 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 133o± 0.5o between the opposite faces
was used as an indenter. Force used for micro hardness testing was 0.025 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:
𝟏𝟑𝟑°
𝒔𝒊𝒏( )
𝟐
HV= 𝟐𝑭
𝒅𝟐
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.

3.2.2. Compressive Strength Test

3.2.2.1. 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
the test tube was rotated at a uniform speed for homogeneous curing of the sample. The ends
were cured separately. The curing time were 50s, 90s, 112s, 40s for Filtek Z250, Brilliant NG,
Prime-Dent and Valux Plus respectively. 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 37oC for seven days before being the tested.

3.2.2.2. 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

18
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

3.2.3. Fourier Transform Infrared Spectroscopy

3.2.3.1. 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 were 50s, 90s, 112s, 40s for Filtek Z250, Brilliant NG, Prime-Dent
and Valux Plus respectively. The test tubes were broken to obtain the specimen.

3.2.3.2. Testing Procedure

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.
19
 Fig 3.2 Principle of Fourier Transform Infrared Spectroscopy

Fig 3.3 Fourier Transform Infrared Spectroscopy Apparatus

3.2.4. Thermo gravimetric Analysis

3.2.4.1 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 were
50s, 90s, 112s, 40s for Filtek Z250, Brilliant NG, Prime-Dent and Valux Plus respectively. The
test tubes were broken to acquire the specimen.

20
3.2.4.2. Testing Procedure

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 10oC/ min and then decreased to 30oC at 20oC/min.

Fig 3.4 Thermo gravimetric Apparatus

3.2.5. Dynamic Mechanical Analysis

3.2.5.1. 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 were 50s, 90s, 112s, 40s for Filtek
Z250, Brilliant NG, Prime-Dent and Valux Plus respectively. The test tubes were broken to
obtain the specimen. The specimens were rubbed against the silicon carbide paper to make the
ends flat and also to make it of the required length.

3.2.5.2. Testing Procedure

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 tanδ (ratio of loss to storage modulus). DMA tests were performed
on a DMA 8000 (Perkin–Elmer) in compression mode. A frequency of 1 Hz was applied
21
(approximated to average chewing rate) and amplitude of 10 μm. A temperature range of 30–
350 °C and a heating rate of 5°C/min were selected. Storage modulus (E′), loss modulus (E″)
and tangent delta (tanδ) 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

3.2.6. Wear Volume

3.2.6.1 Specimen Preparation

In wear volume test the cylindrical samples of length 15mm 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 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 were 50s, 90s, 112s, 40s
for Filtek Z250, Brilliant NG, Prime-Dent and Valux Plus respectively. 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
37oC 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

22
3.2.6.2 Testing Procedure
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.

Fig 3.7 Dental Wear Simulator

Parameters Assigned value

Load 4N

No. Of cycles 10000

Type of profile 8 Shaped

Speed 40%(4mm/s)

Profile size 100%

Ramp rate 5s

23
 Friction force trip 100 N

Temperature trip 65oC

Table 3.2 Dental Wear Simulator Parameters

The slurry was changed for each material to check the effects of three body wear in different
mediums. Distilled water, Fresh artificial saliva and coke were used as slurry.

The mass loss was calculated by using high precision analytical balance (CONTECH CA-413)
of least count .001gm.

3.2.7. SEM Analysis

3.2.7.1 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.

3.2.7.2 Testing Procedure

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.

24
 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 52 HV for brilliant to 96
HV for Valux plus. The results suggest that Brilliant and Prime Dent exhibited similar Hardness.
The mean hardness for Brilliant and Prime dent were significantly lower than Valux Plus.
Comparable to other studies, the glass-fiber reinforced composite Valux plus exhibited highest
hardness. Brilliant containing a high filler fraction volume of 90% (66 wt %) comprised of
porous SiO2 filler (30 wt %) with a particle size of 3–22 mm, Ba–Al–B–F– Si-glass (26 wt %),

VICKERS HARDNESS
120

96
100
VICKERS HARDNESS (HV)

80
60 58
60 52

40

20

0
Filtek Z250 Brilliant NG Prime-Dent Valux Plus

Materials

Fig 4.1 Comparison of Hardness Values of the composite materials

25
 Materials Reading 1 Reading 2 Reading 3 Mean Standard
(HV) (HV) (HV) Hardness
Deviation(HV)
Value(HV)

Filtek Z250 61 57 62 60 2.16

Brilliant NG 52 55 49 52 2.45

Prime-Dent 61 56 57 58 2.16

Valux Plus 101 91 94 96 4.24

Table 4.1 Vickers Hardness Value and Standard Deviation for the composites

The composites were then dipped in citric acid of different pH (pH=5.5 and pH=3) and stored
for 7 days. The results have been tabulated in Table 4.2 and Table 4.3 respectively. The
comparison has been made in Fig 4.2 of the composites’ hardness before dipping them in citric
acid and after dipping them in citric acid of different pH.

Materials Reading 1 Reading 2 Reading 3 Mean Standard

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

Filtek Z250 46 40 46 44 2.83

Brilliant NG 42 37 41 40 2.16

Prime-Dent 43 50 45 46 2.94

Valux Plus 77 80 68 75 5.09

Table 4.2 Hardness Values after dipping in citric acid (pH=5.5)

26
 Materials Reading 1 Reading 2 Reading 3 Mean Standard
(HV) (HV) (HV) Hardness
Deviation(HV)
Value(HV)

Filtek Z250 33 42 36 37 3.74

Brilliant NG 35 28 36 33 3.55

Prime-Dent 43 36 38 39 2.94

Valux Plus 67 52 61 60 6.16

Table 4.3 Hardness Values after dipping in citric acid (pH=3.0)

Effect of Acidity on Hardness

120

100 96
Vickers Hardness (HV)

80 75

60 58 60
60 52
44 46
37 40 39
40 33

20

0
Filtek Z250 Brilliant NG Prime-Dent Valux Plus

Before dipping in acid After dipping in acid for 7 days(pH=5.5)

After dipping in acid for 7 days(pH=3)

Fig 4.2 Comparison of Hardness Value before and after dipping in citric acid

The values of hardness decreased in acidic medium which can be seen from the Fig 4.2. The
values were effected by pH of the acidic medium, lesser the pH greater the decrease in hardness.
The influence of subjecting the composites to citric acid(varying pH), analogous to day-to-day
food constituents has also been studied by dipping the samples in citric acid for seven days in
pH=5.5 and pH=3 correspondingly. Citric acid at pH=3 led to the greater material loss followed
by citric acid at the pH=5.5

27
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 338.5MPa for Valux Plus
to 392.7 HV for Filtek Z250. . 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.

COMPRESSIVE STRENGTH
400 392.7
390
Compressive Strength (MPa)

378.8
380 372.6
370
360
350
338.5
340
330
320
310
Filtek Z250 Brilliant NG Prime-Dent Valux Plus

Materials

Fig 4.3 Comparison of Compressive Strength of the composite materials

Materials Reading 1 Reading 2 Reading 3 Mean Standard

(MPa) Compression deviation
(MPa) (MPa)
Strength (MPa)
MPa)

Filtek Z250 340.5 406.9 430.7 392.7 38.17

Brilliant NG 350.2 375.4 410.8 378.8 24.86

Prime-Dent 407.8 346.7 363.3 372.6 25.79

Valux Plus 280.4 390.7 345.4 338.5 78.33

Table 4.4 Comparison of Compressive Strength of the composite materials

28
4.1.3. Wear Loss

Wear (mass) loss has been studied for each composite subjected to different media (slurry)
under simulated dental conditions. The mass losses has been shown in the following figures.

0.012

0.01

0.008
Mass Loss (gm)

0.006

0.004

0.002

0
Filtek Z250 Brilliant NG Prime-Dent Valux Plus

Distilled water

Fig 4.4 Mass Loss in Distilled Water

0.012

0.01

0.008
Mass Loss (gm)

0.006

0.004

0.002

0
Filtek Z250 Brilliant NG Prime-Dent Valux Plus

Saliva

Fig 4.5 Mass Loss in Saliva

29
 0.008

0.007

0.006
Mass Loss (gm)

0.005

0.004

0.003

0.002

0.001

0
Filtek Z250 Brilliant NG Prime-Dent Valux Plus

Coke

Fig 4.6 Mass Loss in Coke

0.012

0.01

0.008
Mass Loss (gm)

0.006

0.004

0.002

0
Filtek Z250 Brilliant NG Prime-Dent Valux Plus

Distilled Water Saliva Coke

Fig 4.7 Comparison of the mass loss in different mediums

The wear in distilled water is higher as compared to saliva and coke. This can be due to the fact
that the coefficient of friction of distilled water is highest (approx. = .13) which increases the

30
overall friction between the specimen and antagonist and hence more wear. Coefficient of
friction of saliva (approx. = 0.09) and Coke (0.10) are less, hence less wear

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. “ζ’’ is also determined from the storage
modulus vs temperature graph to compare material content of specimens.

0.18

0.16

0.14

0.12
Tangent Delta

0.1

0.08

0.06

0.04

0.02

0
0 50 100 150 200 250 300 350 400

Filtek z250 Briliant Prime Dent Valux

Fig 4.8 Tangent delta as a function of temperature

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

Valux Plus >Filtek Z250 > Brilliant Coltene >Prime Dent

31
The values of Filtek Z250, Brilliant Coltene and Prime Dent are quite close to each other but
Valux plus’s glass transition temperature is very high. Prime Dent shows highest value of tan
delta at a particular temperature and Filtek exhibits the lowest value.

The width at half the peak value is highest in the case of Valux plus which shows that it is most
heterogeneous among the four composites indicating it has more filler particles.

4.000E+08

3.500E+08

3.000E+08

2.500E+08
Storage Modulus

2.000E+08

1.500E+08

1.000E+08

5.000E+07

0.000E+00
0 50 100 150 200 250 300 350 400

Filtek Z250 Brilliant Prime-Dent Valux Plus

Fig 4.9 Storage Modulus as a function of temperature

We can clearly see values of “ζ’’ parameter in the graph. Valux plus has least value. It is the
ratio of temperature and storage modulus at a point where the modulus becomes constant with
increase in temperature. Prime dent shows highest value of “ζ’’ parameter indicating that it has
less filler material and Valux plus has the highest filler content.

32
 3.500E+07

3.000E+07

2.500E+07
LOss Modulus

2.000E+07

1.500E+07

1.000E+07

5.000E+06

0.000E+00
0 50 100 150 200 250 300 350 400

Filtek Z250 Brilliant Prime-Dent Valux Plus

Fig 4.10 Loss Modulus as a function of temperature

4.1.4.2 Fourier Transform Infrared Spectroscopy

The solid phase (KBr disk) infrared spectroscopy was used in the spectral range of 400 to 4000
wave numbers (cm-1) to prepare basic reference system for the comparison between artificial
composite dental materials commercially available.

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 composite materials are presented in the
following Fig. 4.11

33
 Fig 4.11 FTIR spectra of the resin composites

4.1.4.3 Thermo gravimetric Analysis

Fig 4.12 TGA analysis of the resin 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 Filtek Z250, Brilliant, Prime Dent and
Valux Plus are 220oC, 260oC, 175oC, 225oC respectively. The above thermo gravimetric

34
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, Brilliant having the highest onset
temperature has the highest thermal stability and Valux Plus having the lowest onset
temperature has the least thermal stability. The thermal stability of Valux Plus and Filtek Z250
have intermittent values.

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. Prime-dent
shows maximum worn surface as expected. The surfaces of Filtek Z250, Brilliant and Valux
plus are rather uniformly abraded. The surface morphology in case of wear in coke shows that
black areas are supposedly compressed zones of pre- polymer particles, whereas the bright
zones show typical fracture patterns in the fine filler .The worning out of surfaces is lesser as
compared to previous case showing minor cracks and indentation. The surface morphologies
of materials showed minimum wear in case of saliva, Brilliant showing fewer minor parallel
cracks on the surface.

(a) Filtek250 (b) Brilliant NG

35
 (c) Prime-Dent (d) Valux Plus

Fig 4.13 The Morphology of wear scars on flat specimens following wear testing with
distilled water as medium

(a) Filtek Z250 (b) Brilliant NG

(c) Prime-Dent (d) Valux Plus

Fig 4.14 The morphology of wear scars on flat specimens following wear testing with
saliva as medium

36
 (a) Filtek Z250 (b) Brilliant

(c) Prime- Dent (d) Valux Plus

Fig 4.15 The Morphology of wear scars on flat specimens following wear testing with
Coke as medium

37
4.2 DISCUSSION

Considering the long-term clinical performance of resin materials, wear resistance is an

essential aspect unanimously, especially for posterior restorations in occlusal stress-bearing
areas. The composition, size, and loading content of inorganic fillers have the potential to
influence the wear performance. Besides, finer particles have been proved to result in enhanced
polish ability and wear resistance of resin composites attributed to the decreased interparticle
spacing, compared with micro- fillers .Recently, with the development of Resin Based
Composites, Nano clusters have been launched into the market for achieving outstanding
physical–mechanical properties, in particular the excellent wear-resistance and esthetic
appearance. In this present work, the as-prepared silica Nano clusters are composed of silica
nanoparticles and their agglomerated particles, using Nano-size silica particles as building
blocks, and served as inorganic fillers. The addition of extra silica nanoparticles in co-fillers is
actually a shortcut to reduce interparticle filler spacing and enhance wear resistance of resin
materials. In view of the matrix composition keeping fixed, wear behavior of experimental
resin composites was explored from the constituent and filler loading of inorganic fillers in our
work.

4.2.1 Mechanical Properties

In our present study, we have evaluated the effect of filler content on hardness of dental
composite used. The results suggest that Brilliant and Prime Dent exhibited similar Hardness.
The mean hardness for Brilliant and Prime dent were significantly lower than Valux Plus.
Comparable to other studies, the glass-fiber reinforced composite Valux plus exhibited highest
hardness. Brilliant containing a high filler fraction volume of 90% (66 wt %) comprised of
porous SiO2 filler (30 wt %) with a particle size of 3–22 mm, Ba–Al–B–F– Si-glass (26 wt %),
Al–F– Si-glass (5 wt %), and Sr–F (5 wt.%), demonstrated lowest mechanical hardness. A
superior mechanical hardness for a lower (45%) rather than a higher (55%) filler-volume
fraction was deduced from the results. This negative effect is assumed to be related to inherent
flaws, especially air porosities included in the composite material. 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 filler–matrix-interactions have a greater influence on
fracture parameter of dental composites than the structure of the organic matrix.
The influence of subjecting the composites to citric acid(varying pH), analogous to day-to-day
food constituents has also been studied by dipping the samples in citric acid for seven days in

38
pH=5.5 and pH=3 correspondingly. Citric acid at pH=3 led to the greater material loss followed
by citric acid at the pH=5.5.Conversely substantial material loss was obtained under distilled
water. This order is further confirmed by the observed morphology of the enamel surfaces
exposed to the above solutions in the SEM images. Additionally, the high corrosive potential
solutions also penetrated along the organic sheaths into the relatively sound enamel below the
surface, forming deeper and longer subsurface cracks. This material loss has been related to
the hardness of the composites used. The materials having higher hardness were less effected
by the decrease in pH. They had a greater corrosion resistance resulting in lesser material loss.
This can be attributed to diffusion of H+ ions leading to greater material loss due to
undissociated acid molecules.
Compressive strength is an important property for dental posteriors. It has been evaluated in
our study based on Si/Zr composition. The contribution of Zirconia volume percentage in the
compressive strength is 33.29, whereas for silica volume percentage the contribution is 36.89
& for glass volume percentage contribution is 29.82 towards compressive strength. This shows
that Zirconia volume 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 Filtek Z250 exhibiting
highest compressive strength as well as highest zirconia volume fraction compared to other
three resin composites. This shows that Zirconia is a major contributing factor in the
compressive strength of dental composite and with increase in the volume percentage of
Zirconia the compressive strength definitely increases. Further, we can find out the exact
volume percentage of Zirconia, silica and glass 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.

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 Filtek Z250 shows a single step of
39
decomposition at 225℃. The decomposition is due to the evaporation of water. Similarly the
thermo gravimetric analysis of Brilliant and valux plus shows a single step of decomposition
at 260℃ and 225℃ respectively due to loss of water by evaporation. There are two stages of
decomposition in the TGA of Valux plus. 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 275℃ 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 four commercially available Nano Hybrid resin
composites that have been studied. The silanized inorganic particles were identified by FTIR
spectrometer (Perkin Elmer Spectrum Two, USA) equipped with 4000–400 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 1720 cm-1 due
to ester (-COOCH3) and aldehyde (R(C=O)H ) in the prepared specimens . These bands are
assigned to organic matrix i.e. Bis-GMA, Bis-EMA, UDMA, TEGDMA. Intense transmitting
bands near 1100 cm-1, 800 cm-1 and 470 cm-1 were characteristic for the Si-O-Si group. The
characteristic C-O stretching vibration appears at 1087 cm -1 for all the composites and the C-
N stretching vibration at 1485 cm-1 were obtained. Small peaks around 2956 cm-1 indicating
presence of carboxylic groups in the composites.

In the dynamical mechanical analysis, the studied Nano hybrid 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 Valux plus with the highest filler content (87.0 wt %) also
showed the highest elastic modulus and other showed lesser values for elastic modulus. The
values of tangent delta of Valux plus at low temperatures are very low indicating it is less
flexible at lower temperatures. Even the peak value which is attained at a temp of around 225℃
is lower than other material. Glass transition temperature of Valux plus was highest among
specimens. The width at half the peak value of tan delta shows the heterogeneity of composite.

40
Valux plus 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
material’s 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. Valux plus showed lower value than
others due probably to the slight higher filler content and different filler type. On the other
hand, the ζ 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 ζ
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 ζ parameter was used to study the
crosslinking density. This parameter is generally considered to be inversely correlated to the
crosslinking density of the polymer network, with lower ζ values corresponding to higher
crosslinking density and heterogeneity. Valux 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 and coke is taken as another medium
because the increasing consumption of carbonated drinks puts teeth at a high
risk of chemical attack. Moreover, the wear in distilled water is higher as compared to saliva
and coke. This can be due to the fact that the coefficient of friction of distilled water is highest
(approx. = .13) which increases the overall friction between the specimen and antagonist and
hence more wear. Coefficient of friction of saliva (approx. = 0.09) and

41
Coke (0.10) are less, hence less wear. 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:
𝑉 = 𝐾𝑃𝐿/𝐻
In the present study, the normal load and sliding distance are both constant for different medium
(slurry) during wear testing, hence Eq. (1) can be simplified as:
𝑉 = 𝑘/𝐻
Where k is constant and k=KPL. The wear and hardness showed relationship in coke as a
medium, but not in the case of water and saliva. In coke, Valux plus showed least wear,
probably because of its highest hardness. So, we propose that wear is inversely proportional to
hardness of material as shown by the simplified archard equation. The wear and hardness
doesn’t show any relationship in case of water and saliva being used as medium (slurry) for
wear.

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 Nano-hybrid resin composites
coated with platinum. The fabrication, particle and filler size, curing time, 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 decreasing the filler size and increasing the filler content. Filtek Z250, Brilliant,
Prime dent and Valux Plus are all Nano hybrid resin composites. All samples have same filler
size of about 10 nm. Microscopic images shows Valux Plus has lesser wear than remaining all
material in artificial saliva and coke. Prime dent shows highest wear as well as lowest filler
content. This shows that higher the filler 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 Nano-hybrids. 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.
42
 Chapter 5

Conclusions and Future Scope

5.1 Conclusions

Based on hardness test it can be concluded that Valux Plus is the hardest material and it is
hardness is significantly more than other composites. The other three have hardness values
comparable to each other. Presence of acidic medium has a significant effect on hardness. There
is a significant reduction in hardness values of all the four materials. More acidic the medium
greater is the effect on hardness values.

Compressive strength of Filtek Z250 was highest among the four composites compared. Valux
Plus showed a low compressive strength but the compressive strength values for materials were
in very close proximity to one another owing to the presence of zirconia in all of them. Filtek
has the highest zirconia volume fraction and hence, highest compressive strength.

Dynamic Mechanical analysis suggested Valux plus 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. Valux Plus also
showed highest values of storage modulus and “ζ” parameter indicating high filler fraction rate.
Thermo Gravimetric analysis of the composites showed that Brilliant 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 material. At around
1720cm-1 all the composites showed a peak depicting presence of ester and aldehyde group in
all the composites.

Wear analysis of the materials subjected to varying medium showed that wear pattern was
dependent on mediums. In distilled water, brilliant showed minimum wear whereas in coke
and saliva Valux plus showed minimum wear. The correlation between hardness and wear was
deduced from the tests in case of saliva and coke.

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.

43
Samples worn out in distilled water had rougher surface as compared to saliva and coke as
distilled water has more coefficient of friction as compared to other two.

5.2 Future Scope

We have compared the four Nano hybrid 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.

44
References

[1] Yun-Qi Wu, Joseph A Arsecularatne, Mark Hoffman, Effect of acidity upon attrition–
corrosion of human dental enamel-Journal of the mechanical behavior of biomedical materials
44, January 2015, 23–34.

[2] Magdalena A. Osiewicza, Arie Werner, Jolanta Pytko-Polonczyk, Franciscus J.M. Roeters,
Cornelis J. Kleverlaan, Contact- and contact-free wear between various resin composites-
Dental Materials Volume 31, Issue 2, February 2015, 134–140.

[3] Natthavoot Koottathapea, Hidekazu Takahashia, Naohiko Iwasaki, Masafumi Kanehira,

Werner J. Finger, Two- and three-body wear of composite resins-Dental Materials Volume 28,
Issue 12, December 2012,1261–1270.

[4] Zeynep Duymus Yesil, Satish Alapati, William Johnston, Robert R. Seghi, Evaluation of
the wear resistance of new nanocomposite resin restorative materials-The Journal of Prosthetic
Dentistry Volume 99, Issue 6, June 2008, 435–443.

[5] Camila D. Mayworma, Sérgio S. Camargo Jr., Fernando L. Bastian, Influence of artificial
saliva on abrasive wear and microhardness of dental composites filled with nanoparticles-
Journal of Dentistry Volume 36, Issue 9, September 2008, 703–710.

[6] Renan Belli, Eva Geinzer, Anna Muschweck, Anselm Petschelt, Ulrich Lohbauer,
Mechanical fatigue degradation of ceramics versus resin composites for dental restorations-
Dental Materials Volume 30, Issue 4, April 2014, 424–432.

[7] Evangelia C. Vouvoudi, Irini D. Sideridou, Effect of food/oral-simulating liquids on

dynamic mechanical thermal properties of dental nanohybrid light-cured resin composites-
Dental Materials Volume 29, Issue 8, August 2013, 842–850.

[8] Irini D. Sideridou, , Evangelia C. Vouvoudi, Evanthia A. Adamidou, Dynamic mechanical

thermal properties of the dental light-cured nanohybrid composite Kalore, GC: Effect of
various food/oral simulating liquids-Dental MaterialsVolume 31, Issue 2, February 2015, 154–
161.

[9] Ruili Wang, Shuang Bao, Fengwei Liu, Xiaoze Jiang, Qinghong Zhang, Bin Sun, Meifang
Zhu, Wear behavior of light-cured resin composites with bimodal silica nanostructures as

45
fillers-Materials Science and Engineering: C Volume 33, Issue 8, 1 December 2013,4759–
4766.

[10] P.V. Antunes, A. Ramalho, E.V.P. Carrilho, Mechanical and wear behaviours of nano and
microfilled polymeric composite: Effect of filler fraction and size Materials and Design 61,
March 2014, 50–60.

[11] Lin Wang, Yihong Liu, Wenjie Si, Hailan Feng, Yongqing Tao, Zhizuo Ma, Friction
and wear behaviors of dental ceramics against natural tooth enamel- Journal of the European
Ceramic Society 32, June 2012, 2599–2606.

[12] Nathaniel C. Lawsona, Deniz Cakir, Preston Beck, Mark S. Litaker, John O. Burgess,
Characterization of third-body media particles and their effect on in vitro composite wear
dental materials 28, June 2012, e118–e126.

[13] H.Y. Yu, Z.B. Cai , P.D. Rena, M.H. Zhu, Z.R. Zhou, Friction and wear behavior of dental
feldspathic porcelain, Wear 261, December 2006, 611–621.

[14] R. Karthick, P. Sirisha, M. Ravi Sankar, Mechanical and Tribological Properties of

PMMA-Sea Shell based Biocomposite for Dental application, Procedia Materials Science 6,
December 2014, 1989 – 2000.

[15] Eugeniusz Sajewicz, On evaluation of wear resistance of tooth enamel and dental
materials, Wear 260, August 2006, 1256–1261.

[16] Oscar Borrero-Lopez, Antonia Pajares, Paul J.Constantino, Brian R.Lawn, A model for
predicting wear rates in tooth enamel, journal of the mechanical behavior of biomedical
materials 37 May 2014, 226–234.

[17] S.D. Heintze , G. Zellweger, G. Zappini, The relationship between physical parameters
and wear of dental composites, Wear 263 January 2007, 1138–1146.

[18] Adriana Cláudia Lapria Faria, Renata Cristina Silveira Rodrigues, Ana Paula Rosifini
Alves Claro, Maria da Gloria Chiarello de Mattos, Ricardo Faria Ribeiro, Wear resistance of
experimental titanium alloys for dental applications, Journal of the mechanical behavior of
biomedical materials 4, January 2011, 1873-1879.

[19] J.A. Arsecularatne, M. Hoffman, Ceramic-like wear behaviour of human dental enamel,
Journal of the mechanical behavior of biomedical materials 8, October 2011, 47-57.
46
[20] Michael D. Weir, Jennifer L. Moreau, Eric D. Levine, Howard E. Strassler, Laurence C.
Chow, Hockin H.K. Xu, Nanocomposite containing CaF2 nanoparticles: Thermal cycling,
wear and long-term water-aging, Dental Materials 28, September 2011, 642-652.

47