BIOACTIVE GLASS: A REVIEW.

INTRODUCTION

A material is said to be bioactive, if it gives an appropriate biological response and results in

the formation of a bond between material and the tissue. Bioactive glasses are composed of
calcium and phosphate which are present in a proportion that is similar to the bone
hydroxyapatite. These glasses bond to the tissue and are biocompatible. They have a wide
range of medical and dental applications and are currently used as bone grafts, scaffolds and
coating material for dental implants. Hench was the first to develop bioactive glasses (1969)
and these glasses were able to bond to tissues. Safety of these bioactive glasses was a
concern, so various studies were performed to ensure that bioactive glasses are safe for
clinical applications. Wilson et al (1981) reviewed these studies and proposed that bioactive
glasses are safe for clinical use. In addition to remineralization, bioactive glasses have
antibacterial effects. These glasses bond with the bone through formation of a hydroxyapatite
(HAp) layer. The same HAp layer is formed on the surfaces of these materials after soaking
in the simulated body fluid (SBF) which has ion concentrations similar to the human blood
plasma. This discovery was the introduction of the field of bioactive ceramics and the
beginning of the formation of many new materials such as synthetic hydroxyapatite (HAp)
and other calcium phosphates.

COMPOSITION

Bioactive glasses are silicate-based materials, containing calcium and phosphate. Bioactive
glasses have different families and each family has a different composition.

a. Bioglass™ (45S5)- 45S5 bioactive glass is composed of SiO2 (46.1 mol%), CaO (26.9 mol
%), Na2O (24.4 mol%) and P2O5 (2.6 mol%). 45S5 is able to form HCAP (hydroxy
carbonated apatite) in less than 2 hours and binds to tissues and are now being used
intraorally as bone grafting material after gaining FDA approval.

b. HX-BGC - The Materials Laboratory at the State Key Laboratory of Oral Diseases, West
China Hospital of Stomatology, Sichuan University recently developed a novel bioactive
glass-ceramic (SiO2-P2O5- CaO-Na2O-SrO) called HX-BGC, which contains sodium
calcium phosphate (NaCaPO4) and hydroxyapatite as its ceramic phase.

c. Sol gel derived silver bioactive glass (Ag-BG)- The incorporation of Ag as ion within the
glass allows simultaneously a dual antibacterial and remineralizing activity with a controlled
releasing process. These properties could be of important impact for a dental resin composite
as they could lead to the remineralization of the micro gaps under a bacterial free
environment in the treated area.

PROCESS OF FORMATION

Two common processes of bioactive glass formation used are Melting and Sol-Gel process.
Initially, bioactive glasses were obtained by conventional glass technology via melting at
higher temperature. In Conventional melting, the mixture of oxides or carbonates grains (the
glass components), are melted in a platinum crucible and homogenized at high temperatures
up to 1250-1400°C. Then, the molten glass is cast into steel or graphite mould to produce a
bulk implant. Final grind and polish are often necessary for the required tolerance in
periodontal lesions. In conventional glass technology, to produce small fragments, the molten
glass is poured into water or other liquid medium often subsequent grinding is also necessary.

Disadvantages of conventional glass technology are:

A. Very high purity is necessary for optimal bioactivity which is difficult to maintain
in this method due to the high temperatures of processing, the low silica and high alkali
content of the traditional bioactive glass compositions. Such glasses are very reactive and can
dissolve platinum and take other multiple cations as impurities Gross and Strunz have shown
that M3+, M4+, and M5+ impurity cations in bioactive glasses have considerable effects on
tissue bonding. Greenspan and Hench have revealed how bone bonding is sensitive to a small
amount of A13+ in bioactive glasses. Evaporation of P2O5 at high temperatures may also
result in composition uncertainty in the conventional method.

B. Bioactive powders are exposed to contaminants during the conventional glass

processing which exerts negative effects on bioactivity.

C. Conventional method imposes a compositional limitation on bioactive glasses; this

is because of very high liquidus temperature of SiO2 and very high viscosity of silicate melts
with high SiO2 content.

D. The increased production costs of this method is considerable which is due to high
temperature processing in platinum crucibles, multiple handling steps, capital equipment,
labour, maintenance, quality assurance, and quality control.
During the 1980s, in the field of research as an alternative to Conventional technique, low
temperature (600-700°C) sol gel process was evolved.

Steps for producing a sol-gel derived glass are:

1. Mixing the metal alkoxides in the solution to synthesize an inorganic network

2. Hydrolysis

3. Gelation

4. low-temperature firing

Rounan Li et al (1991)212was observed that glasses made from the sol-gel process
required lower temperatures as compared to conventional melting methods. Rate of the
surface of HAp formation for the sol-gel based materials is more rapid. Also, it allows the
production of other glass ceramics such as SiO2–CaO–P2O5, SiO2–P2O5– Al2O3–CaO–
Na2O– K2O. On the surface of these glasses, the formation and the rapid increase of the
thickness of HAp layer were observed as a result of contact with Tris buffer and simulated
body fluid (SBF). It has also been suggested by Peltola T et al (1999) that glasses made from
sol-gel processing have increased bioactivity.169

ADVANTAGES:

1. Ease of powder production

2. Better control of bioactivity

3. High homogeneity

4. Good control of particles size and morphology and the easy preparation of thin films and
coatings

MECHANISM OF HAp LAYER FORMATION ON BIOACTIVE GLASSES

Protein adsorption, incorporation of collagen fibrils, attachment of bone progenitor cells, cell
differentiation, the excretion of bone extracellular matrix and its mineralization are involved
in the formation of HAp layer-bone bond. Osteogenesis, due to the dissolution products of the
glass on osteoprogenitor cells, stimulates new bone growth. Different Stages of Hap layer
formation on Bioactive Glasses: When bioactive glass is present in an aqueous solution;
Calcium ions dissolve into the body fluid with a silica-rich interlayer formation on the glass
surfaces. Nucleation of HAp occurs due to supersaturation of surrounding tissue fluid with Ca
ions. Calcium, phosphate, and hydroxide ions react to facilitate the growth and nucleation of
the HAp layer. As well, it is possible that carbonate or fluoride anions incorporate in the
reactions, Different glass compositions Bioactive Glass were used by Kokubo et al(1990)43
to study the growth of apatite in simulated body fluid (SBF) and confirmed that apatite can
form on the surface of Bioglass® in SBF. During immersion in SBF, structural and chemical
changes seen to the surface of bioactive glass simultaneously, with different processes are
leaching, degradation, and precipitation. In the leaching process, through the exchange of the
cations H+ and H3O+, metal ions like Na+ and Ca2+ are released and the pH at the interface
increases up to 7.4. In parallel, hydroxyl ions locally break the silica-oxygen bonding. Then,
silicon as silicic acid, Si (OH)4, is released into the solution. Subsequently, a silicic acid gel
layer form. Simultaneously, the glass releases calcium and phosphorus and an amorphous
calcium phosphate-rich phase is formed on the surface. The CaP phase then crystallizes into a
hydroxyapatite (HAp) structure. The growth of the apatite is therefore based on utilization of
calcium and phosphate ions from SBF.43

PROPERTIES:

GLASS TRANSITION TEMPERATURE OF A BIOACTIVE GLASS

Glass transition temperature (Tg) is a range of transformation when an amorphous

solid is changed into a super cooled liquid on heating. Properties like dissolution rate and
strength of different glasses can be compared with the help of Tg. The most important
properties of a glass are Tg and peak crystallisation temperature. A big processing window
between these two makes sure that the glass sinters without crystallization. If a bioactive
glass crystallizes, it becomes less bioactive.

NETWORK CONNECTIVITY OF A BIOACTIVE GLASS

The number of bridging oxygen atoms are responsible for the network connectivity
(NC) because these bridging oxygen atoms join the two neighbouring polyhedra. .NC can be
utilized to assess the bioactivity, surface reactivity and solubility of a glass.NC is an
important 200JP Imran Farooq et al tool for designing new glasses with different
compositions for different applications. Relationship between Tg and Hardness. A linear
relationship exists between Tg and hardness of a bioactive glass. A decreased Tg of a
bioactive glass predicts that the glass has reduced hardness. A similar relation between
hardness and Tg of a bioactive glass was explained by Baesso et al; (1999) where hardness
was found to be decreasing with a decreasing Tg.

EFFECT OF FLUORIDE ON THE BIOACTIVITY OF THE GLASS

Fluoride prevents demineralization and increases remineralization. For the prevention of

caries, the role of fluoride is very important as it forms FAP (fluorapatite) by replacing
hydroxyl ions in apatite structure. This substitution has a profound effect on solubility of
enamel. Keeping the importance of fluoride in mind, its incorporation in bioactive glasses is
of immense interest. Brauer D et al (2009) performed a study to understand the effect of
addition of fluoride in the properties of bioactive glasses. CaF2 concentration was increased
in SiO2-CaOP2O5- Na2O system while network connectivity was kept constant. It was
observed that incorporation of fluorine in bioactive glass, decreased its Tg which means that
the glass has reduced hardness and is more bioactive. Also, the onset of crystallization and
peak temperatures were decreased when CaF2 was increased.

EFFECT OF SODIUM ON THE BIOACTIVITY OF THE GLASS:

The content of sodium oxide can affect the properties of a glass. Wallace KE et al (1999)
explained the relationship between sodium oxide content and different properties of bioactive
glasses, like hardness and bioactivity. SiO2-CaOP2O5- Na2O glass system was used to
study. Network connectivity was kept constant by removing one mole percent of CaO and
adding one mole percent of Na2O. It was observed that by increasing Na2O content, the Tg
and peak crystallization temperature declined linearly. NC of a glass is not affected when
Na2O is replaced with CaO in a glass. However, this replacement has an influence on the
packing of atoms. Glass network expands when Na2O is increased and this results in a
decrease in density of the glass. Because of this property, Na2O is referred to as network
disrupter. The addition of Na2O has an effect on Tg because Tg is an expression of network
disruption of a glass; therefore, Tg is reduced when Na2O content is increased.

INDICATIONS OF BIOACTIVE GLASS AND ITS USES.

 In dentistry, Different forms of bioactive glasses including particles, porous

scaffolds, or dense constructs have been used in clinical applications.

 In 1988, in tooth extraction, a simple cone of Bioglass®, termed the End osseous
Ridge Maintenance Implant (ERMI®) (monolithic shape), was used to preserve the height of
the alveolar ridge.
  In 1993, Perio-Glas® (NovaBone Products LLC, Alachua, Florida) as the first
particulate bioactive glass with the particle sizes of 90–710 μm was introduced for the repair
of bony defects of the jaw and bone loss arising from periodontal disease also it is used in
―guided tissue regeneration‖. In addition to its bioactive properties as a Perio-Glas® used to
produce bioactive glass slurry with applications in root canal sterilization tools prior to
insertion of implants.

 Bioactive Glass for Treatment of Hypersensitivity: A very fine Bioglass®

particulate called NovaMin® (NovaMin Technology, GlaxoSmithKline, Florida, UK), with a
particle size of ~18 μm is used as an active repair agent in toothpaste. Bioglass® particles
adhere to the dentine and form a HAp layer: by blocking of the tubules relieves the pain for
longer periods.

 Remineralization Using Bioactive Glass: Demineralization and remineralization are

natural processes which continuously occur for teeth. For strong enamel, natural
remineralization is not enough, so bioactive glasses are used to augment the process.
Bioactive glasses have unique remineralizing properties and are generally introduced into
various dentifrices as very fine particles to provide calcium and phosphorus to the tooth
surface. In 2014, Mehta et al. showed that bioactive glass (Novamin®) and casein
phosphopeptide amorphous calcium phosphate (CPP-ACP) successfully remineralized early
enamel caries.63

 Bioactive Glass Coatings: As metals are bioinert, the metallic implants are
encapsulated with fibrous tissue after implantation. The hydroxyapatite layer forms on
bioactive glass Bioactive Glass 134 coatings and improves the bonding of implants to the
host bone. Dental field is the best for application of bioactive glass Coatings. Here,
Coefficient thermal expansion of the glass and the metal must match to prevent the glass
pulling away from the metal during the processing. e.g. on titanium implants with screw
threads, coating with the following composition (by weight): 53% SiO2, 6% Na2O, 22%
CaO, 11% K2O, 5% MgO, 2% P2O5, and 1% B2O3 on titanium implants, which were first
tested in rabbit femurs. Compared to noncoated implants, more bone grew on the coated
implants. S53P4, as one kind of bioactive glass, can kill pathogens connected with enamel
caries (Streptococcus mutans), root caries (Actinomyces naeslundii, S. mutans) and
periodontitis (e.g. Actinobacillus actinomycetemcomitas) .Less than 1 mg ml1 of SOL-GEL
DERIVED glass in culture is needed to kill bacteria such as Escherichia coli, Pseudomonas
aeruginosa and Staphylococcus aureus, compared to 50 mg ml-1 of silver-free glasses to be
bactericidal.

 Bioactive glasses when used for air polishing, yielded better results in terms of stain
removal and patient comfort as compared to traditional sodium bicarbonate powder.

 Bioactive glass can also be utilized for cutting cavities in teeth by air abrasion175 .