1.

Structure of matter and principles of adhesion

1.1 Introduction
Recall that solid materials may be divided into two groups: amorphous and crystalline, based on the regularity of their atomic arrangements. The structure of a material is important because it controls the materials physical and mechanical properties. Amorphous materials do not have definite melting points, as their atomic pattern arrangement is irregular and impossible to predict. In general, increasing temperature causes softening of the amorphous material which ultimately melts to liquid form. Thus amorphous materials are often described as frozen or supercooled liquids. Glass and dental polymers are examples of irregularly-arranged amorphous materials. Regularly-arranged crystalline materials are found in dentistry in the form of metal (dental amalgam and wrought metal), and alloys (dental ceramic and cast alloys). Inside matter, the bonds that hold the atoms and molecules together can be divided into primary and secondary bonds. Primary bonds are strong, stable bonds that hold solids together. They include covalent, ionic and metallic bonds. Examples are: Covalent bonding - C-C bonds in denture base polymers, Si-O bonds in porcelain crowns Ionic bonding - NaCl, GIC/polycarboxylate cements-tooth surface (GIC is negatively charged) Metallic bonding - dental amalgam Recall that at the microscopic level, metals have a shared aggregate of free electrons, which contributes to their thermal, electrical, and plastic properties. Secondary bonds are the weak bonds that hold liquids together, or form a weak bond at a liquid-solid or non-chemically-bonded solid-solid interface. They include van der Waals forces and hydrogen bonds, and are formed as a result of forces generated by atomic or molecular dipoles (fluctuating, induced or permanent). Examples of secondary bonding in dentistry are the inter-chain bonds in dental polymers. Bond energy refers to the minimum strength required to break a bond, and is a measure of the strength of that bond.

Materials in dentistry can be classified into three main groups: Ceramics Mainly ionic bonds, some covalent Crystalline or amorphous Inorganic salts Crystalline ceramics Glasses (amorphous) Metals Metallic bonds Crystalline Metallic elements Alloys Intermetallic compounds Polymers Covalent and secondary bonds Amorphous Rigid polymers Waxes Elastomers

Composite materials refer to a combination of two or more of these main material groups. These can be naturally occurring or synthetic. For example, dentine is a naturally-occurring composite material, made of apatite (ceramic) and collagen (polymer). Resin composite is a synthetic composite material, made of quartz fillers (ceramic) and resin (polymer).

1.2 Principles of adhesion

Adhesion is the opposite of cohesion. It describes the attraction between molecules or atoms of two different surfaces brought into contact, whereas cohesion describes attraction between molecules or atoms of the same material. The two different surfaces may be two solids or between a solid surface and a liquid. If between two solids, a thin film of material (liquid) is required for adhesion. This film is called the adhesive; the solid surface is called the adherent, and the point of contact is called the interface. Adhesion can be achieved through chemical or mechanical means, and relies on a number of factors. In relation to the adherent, surface energy and surface roughness have implications for adhesion. In relation to the adhesive, surface tension, contact angle, viscosity and wettability need to be considered.

1.2.1 Factors relating to the adherent

1.2.1.1 Surface energy This is defined as the increase in energy/unit area of solid surface. Surface energy essentially refers to the eagerness with which atoms or molecules on the surface of a solid want to bind with contacting materials (eg. the adhesive). This comes about because the atoms on the solid surface do not have a layer above them to bond with, and thus their bonds are not fully occupied. This surface energy results in surface atoms binding to items in the vicinity, such as dirt, oil, water, or the oral pellicle (in the case of a tooth). Cleaning the surface of the solid clears this debris away and increases the surface energy. 1.2.1.2 Surface roughness A rough surface has a greater surface area than a smooth surface, and therefore a greater prospective bonding area. However, if the adhesive is too viscous, it will sit over cracks and crevices instead of flowing into them, reducing the bonding effectiveness. Therefore, the surface tension of the adhesive must be below the surface energy of the solid for good adhesion.

1.2.2 Factors relating to the adhesive

1.2.2.1 Surface tension Surface tension is surface energy, but for liquids. If the surface tension of a liquid is high, this means its surface molecules hold strongly together. It will take on a spherical shape when placed on a surface, instead of spreading. This is its lowest energy state. In adhesion, we want the adhesive to fill any rough parts of the surface, so the surface tension of the adhesive should be lower than the surface energy of the solid. Surface tension is reduced by the presence of impurities, and also by increases in temperature. It is naturally higher in liquid metals such as mercury than in normal liquids. 1.2.2.2 Contact angle Contact angle refers to the angle a liquid surface makes in contact with a solid surface. It is inversely proportional to an adhesives wettability. As the contact angle of an adhesive on a solid surface approaches zero, its wettability or spreadability increases, reaching complete wetting at zero. Contact angle depends on the surface tension and energy of the adhesive and surface, and is proportional to the viscosity of the liquid. 1.2.2.3 Viscosity Viscosity describes the resistance of a liquid to flow. Too high, and the adhesive will not spread easily; too low, and the adhesive cannot be adequately controlled in a clinical situation. It is directly proportional to an adhesives contact angle, and inversely proportional to an adhesives penetration into cracks and crevices. 1.2.2.4 Wettability Wettability refers to the ability of an adhesive to spread on the surface of a solid with no air or space left between the materials. It is dependent on the contact angle, surface energy of the solid and viscosity of the liquid. Perfect wettability occurs at a contact angle of zero.

2. Adhesion to enamel and dentine

Acid pretreatment of enamel surfaces with phosphoric acid improves the adhesion of acrylic resin twofold. This leads to improved retention of restorations, strengthening of weakened tooth tissue and a reduction in the need for extensive tooth preparation, and thus the conservation of tooth tissue.

2.1 Mechanisms of enamel and dentine adhesion

These include: Micromechanical interlocking via resin bonding Chemical adhesion to surface precipitates, inorganic or organic tooth components by functional monomers in enamel-dentine adhesives, or GI restoratives Wetting, penetration and formation of a hybrid layer

2.1.1 Bonding to enamel

The susceptibility of enamel prisms to acids is related to their orientation. Resin bonding to enamel involves two stages: acid etching and application of the bonding resin. 2.1.1.1 The acid etch technique Application of acid or acidic primers to the enamel surface roughens it microscopically. This results in increased surface area and wettability. The object of acid etching is thus to prime the enamel surface for application of the adhesive. Resin applied to the enamel surface will then penetrate and interlock mechanically upon curing. Prism orientation, aggressiveness of the acid and duration of acid application all determine the extent of acid etching. In dentistry, a solution of 30-40% phosphoric acid is applied for 10-15 seconds and rinsed. Acid etching has made possible the development of techniques such as: directed bonded porcelain and resin composites veneers and inlays orthodontic brackets resin-bonded protheses pit and fissure sealants

2.1.2 Bonding to dentine

Dentine that has been instrumented or operated on is covered by a smear layer. This is a 0.5-5um thick layer of mineralised collagen, inorganic tooth particles, saliva, blood and microorganisms. Resin bonding to dentine involves three stages: dentine conditioning (pretreatment), priming, and resin bonding. The infiltration or interdigitation of resin composite into pretreated dentine is referred to as resin tags. 2.1.2.1 Dentine conditioning Dentine conditioning is essential for the partial or complete removal, or modification of the smear layer. We need to remove the smear layer as it obstructs effective bonding of resin to dentine. Dentine conditioners are acids that can dissolve or solubilise the smear layer. Acids also cause widening of the dentine tubules and exposure of surface collagen fibrils, by demineralisation of the intertubular and peritubular dentine. Dentine conditioners include 10-20% polyacrylic acid, 10% maleic acid, and 15-20% EDTA. 30-40% phosphoric acid can also be used to etch dentine and enamel simultaneously. 2.1.2.2 Dentine priming Dentine is hydrophilic, while the bonding resin is hydrophobic. Dentine primers make the dentine surface more hydrophobic and receptive to the resin bonding agent. They are made of difunctional monomers, with a methacrylate group that has affinity for the adhesive resin, and another reactive group (aa, phosphate or carboxyl) that has affinity for the exposed collagen network. They are usually carried in solvents (volatile liquids, usually ethanol and acetone) that displace water as the primer penetrates the dentine. This promotes monomer infiltration into the exposed collagen network. 2.1.2.3 Resin bonding agent The resin bonding agent is an adhesive that forms a hybrid layer of resin and dentine tissue upon application and curing. This is necessary for effective bonding of resin to the dentine. Resin bonding agents are made up of hydrophobic monomers. Polymerisation is inhibited by oxygen, so after curing there is usually a 15um thick surface layer of uncured resin, known as the oxygen-inhibition layer.

2.2 Classification of enamel-dentine adhesives

2.2.1 Resin-based adhesives
Total etch adhesives: this involves the simultaneous phosphoric acid etching of enamel and dentine, and a subsequent rinse and dry. Although convenient, a disadvantage of total etch adhesives is that they tend to overetch and/or overdry the dentine. This results in collapse of collagen fibrils, poor resin infiltration and compromises resin bonding. Self-etch adhesives: acidic monomers are used as the conditioning and priming agent. It involves simultaneous demineralisation of dentine and infiltration of resin primer into the exposed collagen fibrils. Without a rinse/dry step, the risk of collapse of the collagen fibrils is eliminated. The self-etch approach is less technique-sensitive as fewer steps are involved. 2.2.1.1 Historical development of adhesives Skipping this for now. Fifth-generation adhesives (used today): these adhesives were developed with the aim of ensuring fewer bottles/application steps and therefore reducing time of use. This was done by combining conditioner and primer (self-etching primer) or primer and adhesive (self-etching adhesive).

2.2.2 Glass ionomer restoratives

These are comprised of a reactive, ion-releasing glass and an aqueous solution of polyalkenoic acid. Adhesion using the GI approach is by micromechanical and chemical mechanisms. Pretreatment of enamel or dentine with a polyalkenoic acid conditioner allows for micromechanical interlocking of the cement with the enamel/dentine surface. GI chemically adheres to hydroxyapatite by ionic bonding between the calcium of hydroxyapatite and the carboxylate groups of the polyalkenoic acid.

2.3 Evaluation of enamel-dentine adhesive effectiveness

Evaluation of effectiveness is best carried out by clinical trials. In the absence of these, the most common laboratory tests of bonding effectiveness are: bond strength tests (tensile or shear bond strength) leakage tests (microleakage or nanoleakage tests)

3. Properties of dental materials

A basic knowledge of the science of dental materials, their clinical applications and laboratory usage is essential to the dentist. The characteristics of the ideal dental material are that it should be: biocompatible mechanically stable and durable resistant to corrosion or chemicals aesthetically pleasing minimally thermally and electrically conductive tasteless and odourless cleanable and repairable dimensionally stable adherent to tissues easy to manipulate cost-effective

The properties of dental materials can be further classified into physical, chemical/electrochemical and biological.

3.1 Physical properties of dental materials

These are based on the fundamentals of physics as relate to mass, energy, force, electricity, heat, light, atomic structure and other physical phenomena. We can therefore divide physical properties into: optical (eg. discolouration) thermal mechanical (eg. setting time, water absorption, shelf life) electrical (eg. in the case of dental amalgams or metal alloys) But based on usage, physical properties generally fall into three categories: properties of unmixed materials, of materials during storage, and of set materials.

3.1.1 Time-dependent physical properties

3.1.1.1 Viscosity Viscosity is a measure of a materials resistance to flow, and of a fluids consistency. It is influenced by time and temperature, especially for setting liquids. Many dental materials involve the mixing of two components, which may set from one state to another (liquid to solid, as in dental cements, or vice versa, as in dental waxes). This time-dependent property introduces the concepts of working time and setting time, which are used to evaluate the materials, and optimisation of which determines a materials physical success. 3.1.1.2 Creep Creep is the dimensional change that occurs when a material undergoes continuous compression. It is a property of viscoelastic materials only (ie. solids and amorphous materials, not fluids), and implies a relatively small deformation under a relatively large and constant stress over a certain period of time. Examples are long-term use of amalgam restorations. 3.1.1.3 Flow Flow is a measure of material deformation under static load. It is the opposite of creep in that deformation of the material is large while the load is static and small. It is used in the context of solids and amorphous materials only - like creep - and not fluids, like viscosity. Examples of materials that can be tested for flow are amorphous materials (eg. waxes) and elastomeric impression materials (eg. polysulfides, silicones and polyethers).

3.1.1.4 Stress relaxation Stress relaxation refers to the reduction in stress, or force, over time in a material that is under a constant load. This is a slow and gradual phenomenon. An example is the decrease in force in orthodontic plastic and latex bands with use, which creates the need to regularly change the bands. 3.1.1.5 Colour Colour is important for aesthetics, and its appreciation and reproduction are being increasingly promoted in the context of general, not just cosmetic, dentistry.

3.1.2 Thermal properties

3.1.2.1 Thermal conductivity Thermal conductivity describes the rate at which heat flows through a material, and is measured by heat flow/unit temperature gradient. Materials with high thermal conductivity have a high ability to transmit heat and are termed conductors (eg. gold and base metals). Materials with low thermal conductivity are termed insulators (eg. enamel and dentine). Restorative materials directly in contact with the pulp or other oral tissues should have low thermal conductivity. 3.1.2.2 Thermal diffusivity Thermal diffusivity is a measure of the rate at which a body with a non-uniform temperature approaches equilibrium. In short, it is an indication of the amount of heat absorbed by a material. Even more important than thermal conductivity, thermal diffusivity of dental materials should be similar to that of organic teeth, as a variable state of heat transfer occurs in the mouth during periods of ingestion of hot/cold foods and drinks. 3.1.2.3 Coefficient of thermal expansion This is a fractional measure of the change in length of a material per 1K rise in temperature. An ideal restorative material should have similar values of thermal conductivity, diffusivity and coefficient of thermal expansion similar to that of the tooth. Otherwise, marginal gaps may form between tooth and restoration, leading to breakdown of adhesive bonds.

Thermal conductivity (Wm-1C-1) Enamel Dentine Acrylic resin Dental amalgam Composite resin GIC Gold Water 291.7 0.55 0.92 0.63 0.21 23.02

Thermal diffusivity (mm2s-1) 0.47 0.18 0.12 9.6 0.68 0.20 119

Coefficient of thermal expansion 11.4 9.0 90 25 25-60 11 14

3.1.3 Mechanical properties

The mechanical properties of a material describe the elastic and plastic resistance of a material to deformation or fracture. This is more in relation to static (solid) than dynamic (fluid) bodies. Mechanical properties are characterised by the stress-strain curve.

3.1.3.1 Stress Stress is defined as force applied per unit area. It is an internal resistance created within the material equal and opposite in direction to the applied external force. Applied forces may be axial (tensile or compressive), or shear, bending, or torsional. The resulting internal forces are one or a combination of axial or shear. In relation to dental materials, we are concerned with: Tensile stress: expansive stress, the stress created when a body is subjected to forces pulling in opposite directions in a straight line. It is accompanied by a tensile strain (fractional change in length). Compressive stress: the stress created when a body is subjected to forces pushing towards each other in a straight line. It is accompanied by a compressive strain, and is more useful for comparing brittle materials that are tensionally weak. Shear stress: the stress created when a body is subjected to forces directed parallel to each other but not on a straight line (a sliding or twisting motion). 3.1.3.2 Strain Strain is a measure of the fractional change in length of a material when subjected to an applied force. Strain may be recoverable (elastic), non-recoverable (plastic), or time-dependent. The extent of recovery thus depends on the elastic properties of the material.

Change in dimensions of a material for a given application of stress can be plotted on a stress-strain curve. Differences in elastic properties of materials are mirrored in their stress-strain curve relationships. From this we can typify classes of materials. 3.1.3.3 Proportional limit The proportional limit describes the maximum stress at which a material will not depart from linear proportionality of stress to strain. Above the proportional limit - evidently - stress is no longer proportional to strain. The elastic region is the region before the proportional limit. The plastic region is the region after it. 3.1.3.4 Elastic limit The elastic limit describes the maximum stress a material is able to sustain before permanent deformation. If a material is linearly elastic, proportional limit often equals elastic limit. In superelastic materials, a non-linear elastic behaviour is observed, but when force is removed, strain returns to zero. 3.1.3.5 Permanent deformation Permanent deformation describes the property of a material beyond the proportional limit. With removal of force on the material, stress returns to zero, but strain (the materials original dimension) does not. Thus permanent deformation refers to irreversible bending, stretching, compression or other deformation of a material. Permanent deformation may also be referred to as plastic deformation. 3.1.3.6 Yield strength Yield strength describes the strength required by a material to produce a given amount of plastic strain. It may be used in materials that have irregular or non-linear stress-strain curves, in which determination of the proportional limit is difficult. 3.1.3.7 Ultimate strength Ultimate strength is the maximum stress (tensile, compressive and/or shear) a material can withstand before fracture. In brittle materials, US often equals the fracture strength. In dentistry, ultimate strength is used to estimate the cross-sectional area or dimensions of an alloy necessary for a particular restoration. The compressive strength of enamel is higher than dentine, however its tensile strength is lower.

UCS (MPa) Enamel Dentine 384 297

UTS (MPa) 10.3 51.7

Elastic Modulus (GPa) 50 15

3.1.3.8 Fracture strength

Refers to the maximum stress needed to fracture a material, and is used to characterise the strength of a material. In elastic materials that undergo elongation, fracture strength may be less than the ultimate strength, because their cross-sectional area decreases before fracture, and stress is calculated from the original cross-sectional area of the material. 3.1.3.9 Diametral tensile strength This is a measure of the tensile strength of brittle materials. It may also be referred to as the diametral compressive strength. We have done this in lab: it involves subjecting a specimen in the form of a disc to compression on two opposing sides. A tensile stress develops within the material perpendicular to the plane of the applied force. The force at which it fractures is the DTS. 3.1.3.10 Flexure strength Flexure strength is the maximum stress can withstand under fracture under a bending force. It is important in evaluating denture base resins, which are often subjected to similar stresses under masticatory load. 3.1.3.11 Fatigue strength Fatigue strength describes the strength at which a material fails following repeated dynamic loading. Factors influencing fatigue strength may include material surface roughness, and the presence and size of internal flaws. Knowing the fatigue strength of dental materials is important as dental materials will typically undergo many repeated low to moderate stresses while in service. 3.1.3.12 Impact strength Impact strength is the total energy absorbed by a material before fracture, when subjected to a sudden blow or impact. Materials with low elastic moduli and high tensile strength exhibit the greatest impact strength. 3.1.3.13 Elastic modulus Elastic modulus, or Youngs modulus of elasticity, refers to the relative stiffness or rigidity of a material within its elastic range. It is the slope of the linear segment of a stress-strain curve, and can be measured by means of a compressive or tensile test. The elastic modulus is an inherent property of a material and unaffected by elastic stress within the material. Knowing the elastic modulus is critical as dental materials have different requirements for rigidity and flexibility depending on their intended use. 3.1.3.14 Dynamic Youngs modulus This measures the stiffness of a material at a high rate of load application and high rate of strain. It is important in the assessment of materials such as athletic mouth protectors. 3.1.3.15 Resilience Resilience describes the resistance of a material to permanent deformation. It is a measure of the amount of energy necessary to deform a material up to its proportional limit. It can be measured by the area below the elastic region of a stress-strain curve. In dentistry, knowing the resilience of orthodontic wires lets us know how much force can be exerted on a tooth before the wire loses its elasticity, and hence how much the tooth can move before the wire essentially becomes afunctional. 3.1.3.16 Hardness Hardness is defined as a materials ability to resist a) permanent surface indentation or penetration, and/ or b) plastic deformation. It is measured as force/unit area of indentation. Scratches and food lodgement

of dental materials can limit fatigue strength and the lifetime of the restoration. Measurement of hardness is carried out using the Knoop, Vickers, Brinell and Rockwell tests. Enamel is almost five times harder than dentine with a hardness strength of 343KHN (to dentines 68KHN). Cementum is correspondingly softer with a hardness strength of 40KHN. Within dentine, peritubular material is the hardest (250KHN) while intertubular material near the pulp is softest (15KHN).

3.2 Chemical properties of dental materials These relate to the setting reactions of materials and their degradation during function. As the oral environment comprises oral fluids such as water, saliva, and acids, dental materials must be chemically stable and not dissolve, absorb or leach out substances which may adversely affect their stability and durability. 3.3 Biological properties of dental materials These relate to the effects dental materials have on surrounding living tissue. An ideal dental material should not be irritant, toxic, allergenic or carcinogenic to surrounding tissue, or the manufacturers or dental personnel.