Ceramics - Unit 2

Ceramics and Polymers
CERAMICS
What are Ceramics? Ceramics are refractory , polycrystalline compounds , usually inorganic, including silicates, metallic oxides, carbides and various refractory hydrides, sulfides , and selenides.(2 marks) What are the advantages of using Ceramics in dentistry? Ceramics have been used in dentistry for dental crowns owing to their inertness to the body fluids , high compressive strength and good aesthetic appearance. Good biocompatibilty and ease of fabrication. Carbons have found use as implants especially for blood interfacing applications such as heart valves. Due to their high specific strength as fibers and their biocompatibility. Ceramics are also being used as reinforcing components of composite implant materials and for tensile loading applications such as artificial tendon and ligaments
INTRODUCTION
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Ceramics - V.Mythily,JCE
Desired Properties of Implantable Bioceramics

1. Should be nontoxic. 2. Should be noncarcinogenic. 3. Should be nonallergic. 4. Should be noninflammatory. 5. Should be biocompatible. 6. Should be biofunctional for its lifetime in the host.
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Ceramics and its classification

How the difference in structures exist? Ceramics are classified according to their structural compounds of which AmXn is an example. A,X are metals and non metals respectively. The difference between these structures is due to relative size of ions (min. radius ratio). If positive and negative ions are about the same size the structure become a simple cubic. Face centred cubic structure arises when relative sizes of ions are different since positive ions can be fitted in the tetragonal or octagonal spaces created among larger negative ions.
PROPERTIES OF CERAMICS
What are the properties of ceramics? Unlike metals and polymers ,Ceramics are difficult to shear plastically due to ionic nature of bonding. In order to shear , the planes of atoms should slip past each other. However , for ceramics materials the ions of like electric charge repel each other , moving the plane of atoms is thus difficult. This makes the ceramics non ductile and creep at room temperature is almost zero.
PROPERTIES OF CERAMICS
Ceramics are also sensitive to cracks / notches since instead of undergoing plastic deformation they will fracture elastically once the crack propagates. If the ceramics are flawless they are strong even in tension. Glass fibers have tensile strength twice that of a high strength stainless steel.
CLASSES OF CERAMICS
The types of ceramic materials used in biomedical applications may be divided into three classes according to their chemical reactivity with the environment: completely resorbable (Bio Resorbable) surface reactive(Bio Active) nearly inert (Bio Inert)
THREE CLASSES OF CERAMICS (according to their reactivity) completely resorbable More reactive (Calcium phosphate) over a span of times
Yielding mineralized bone growing from the implant surface
surface reactive Bioglass ceramics ; Intermediate behavior Soft tissues/cell membranes
nearly inert Less reactive (alumina/carbons) even after thousands of hours how minimal interfacial bonds with living tissues.
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Resorbable Ceramics
Resorbable Ceramics (first resorbable implant material-Plaster of Paris). Should not have variable resorption rates Should not have poor mechanical properties. Two types of orthophosphoric acid salt namely -tricalcium phosphate (TCP) and hydroxyapatite (HAP) (classified on the basis of Ca/P ratio). The apatite- [Ca10 (PO4)6 (OH)2] crystallizes into the hexagonal rhombic system. The unit cell has dimensions of a = 0.9432 mm and c = 0.6881 nm. The ideal Ca/P ratio of hydroxyapatite is 10/6 and the calculated density is 3.219 g/ml. The substitution of OH- with F- gives a greater structural stability due to the fact that F- has a closer coordination than the hydroxyl, to the nearest calcium.
Bio inert and active CERAMICS

Nearly inert ceramics e.g., alumina and carbons show little chemical reactivity even after thousands of hours or exposure to the physiological pH and therefore show minimal interfacial bonds with living tissues.
Surface reactive bioglass ceramics exhibit an intermediate behaviour. In these ceramics, surface provides bonding sites for the proteinaceous constituents of soft tissues and cell membranes, producing tissue adherence.
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CERAMICS
The more reactive materials like calcium phosphate, release ions from the surface over a period of time as well as provide protein bond sites. The ions released, aid in promoting hydroxyapatite nucleation, yielding mineralized bone, growing from the implant surface. We will now see about the different classes of ceramic materials
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BIO INERT CERAMICS
Uses of Bioinert Bioceramics

1. In reconstruction of acetabular cavities. 2. As bone plates and screws. 3. In the form of ceramic-ceramic composites. 4. In the form of ceramic-polymer composites. 5. As drug delivery devices. 6. As femoral heads. 7. As middle ear ossicles. 8. In the reconstruction of orbital rims. 9. As components of total and partial hips. 10. In the form of sterilization tubes. 11. As ventilation tubes. 12. In the repair of the cardiovascular area.
Bioinert PYROLYTIC CARBON

The carbons are inert ceramic materials.
Carbon materials are widely used because it has good biocompatibility with bone and other tissues
high strength and an elastic modulus close to that of bone Unlike metals, polymers and some other ceramics carbonaceous materials do not suffer from fatigue.
Carbons can be made in many allotropic forms: crystalline diamond, graphite, noncrystalline glassy carbon, and quasicrystalline pyrolitic carbon. Among these, only pyrolitic carbon is widely utilized for implant fabrication; it is normally used as a surface coating.
CARBON
Pyrolytic carbons are formed by deposition of the isotropic structure on a while in a fluidized bed, at controlled temperature between 1000 to 24000C. Pyrolysis of a hydrocarbon gas at temperature of less than 15000C has been most useful for applications in implants. They are called as low-temperature isotropic (LTI) Carbons. The increased mechanical properties are directly related to increased density, which indicates that the properties of pyrolitic carbon depend mainly on the aggregate structure of the material.
CARBON
These thin films of LTI carbon have good bonding strength to a number of metals with value ranging from (10Mpa to 35MPa) with the ultimate value being dependent upon conditions of deposition. The anisotropy, density, crystalline, size and structure of the deposited carbon can be controlled by temperature, composition of fluidizing gas, bed geometry and residence time of the gas molecules in the bed.
The inclusion of silicon with pyrolytic carbon makes it very hard, so that its wear resistance increases.
CARBON
Vitreous carbon is a polycrystalline solid with a very small grain size, formed by the controlled pyrolysis of a polymer such as phenol formaldehyde resin, rayon and polyacrylonitrile.
A carbon residue remains after volatile residues are driven off.The resulting volume shrinkage is about 50%.
As with the LTI carbons, the structure is isotropic and the density is close to 1.5g/cm3.
Wear resistance and strength, however, are not as good as the pyrolytic LTI carbons.
Carbons exhibit excellent compatibility with tissue. Compatibility of pyrolitic carbon-coated devices with blood have resulted in extensive use of these devices for repairing diseased heart valves and blood vessels
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CARBON
The third type of turbostratic carbon is vapor deposited at a low temperature. These carbons are called ultra low temperature isotropic carbons (ULTI). Carbon atoms are evaporated from heated carbon source and condensed into a cool substrate of ceramic, metal or polymer. The thickness of the coating is usually less than 1m . An advantage of this process is that the coating does not change the mechanical properties of the substrate while biocompatibility of carbon is conferred on the surface.
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CARBON
Pyrolytic LTI carbon is used because it is highly biocompatible, especially when used as a blood interface. Carbon coatings find wide applications in heart values, blood vessel grafts, percutaneous devices because of exceptional compatibility with soft tissues and blood. Carbon does not provoke an inflammatory response in adjacent tissues and no foreign body reactions to the materials have been observed. Bone and soft tissues are much more tolerant to carbon than other materials.
DIFFERENT VARIETIES OF CARBON (NEARLY INERT CERAMICS)

Pyrolitic carbon; Pyrolysis of hyrdocarbon gas (methane) 15000 degrees Low temperature isotropic (LTI) phase Good bonding strength to metals (10 Mpa 35 Mpa) Inclusion of Si with C, wear resistance increases drastically Vitreous carbon (glassy carbon); controlled pyrolysis of a polymer such as phenol formaldehyde resin, rayon and polyacrylonitrile Low temperature isotropic phase Good biocompatibility, but strength and wear resistance are not good as LTI carbons Turbostratic carbon (Ultra low temperature isotropic carbons (ULTI)) Carbon atoms are evaporated from heated carbon source and condensed into a cool substrate of ceramic, metal or polymer. Good biocompatibility
Bio Inert -ALUMINA

Alumina is Aluminium oxide.
Prepared by calcining aluminium trihydide . ASTM specification for alumina: Al2O3 - 99.6%, SiO2 0.12%, Fe2O3- 0.03% and Na2O -0.04%. The main attraction for high purity alumina to orthopedic surgeons for its use is its high corrosion resistance wear resistance The implant devices are prepared from purified alumina powder by isostatic pressing and subsequent firing at 1500-17000C. The high hardness is accompanied by low friction and wear and inertness to the in vivo environment. These properties make alumina an ideal material for use in joint replacements.
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Chemical Composition of Calcined Alumina

Chemicals Al2O3 SiO2 Fe2O3 Na2O Composition (Weight %) 99.6 0.12 0.03 0.04
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Alumina (Aluminium oxide)

Natural single crystal alumina known as sapphire High-density alumina ; prepared from purified alumina powder by isostatic pressing and subsequent firing at 1500-17000C. -alumina has a hcp crystal structure (a=0.4758 nm and c=1.2999nm)
Alumina ceramic femoral component
load bearing hip prostheses and dental implants, hip and knee joints, tibial plate, femur shaft, shoulders, vertebra, and ankle joint prostheses
Porous network ; SEM images
high corrosion resistance wear resistance Surface finishing small grain size biomechanically correct design exact implantation technique
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ALUMINA
Natural single crystal alumina known as sapphire has been successfully used to make implants. High-density alumina is used in load bearing hip prostheses and dental implants because of its combination of excellent corrosion resistance, good biocompatibility, high wear resistance and reasonable strength. Hardness varies from 2000 Kg/ mm2 to 3000Kg/mm2.High hardness accompanied by low friction and wear makes it a good candidate for joint replacements inspite of its brittleness. Strength, fatigue resistance and fracture toughness of polycrystalline alumina are function of grain size and purity. The strength of alumina depends on the porosity also.
One of the most popular uses for aluminum oxide is in total hip protheses. Aluminum oxide hip protheses with an ultra-high molecular weight polyethylene (UHMWPE) socket have been claimed to be a better device than a metal prostheses with a UHMWPE 9/2/2012 Ceramics - V.Mythily,JCE 26 socket
ALUMINA
Orthopedic uses of alumina consist of hip and knee joints, tibial plate, femur shaft, shoulders, vertebra, and ankle joint prostheses.
Alumina ceramic femoral component (Kyocera Inc.; Japan)
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ALUMINA
The hip prostheses consist of a square or cylindrical shaped alumina socket, the latter with an outer screw profile, for cement free anchorage to the bone. An alumina ball is attached to a metal femoral stem by aid of self locking tapers. The stem itself is implanted with PMMA cement, though recently cement free prostheses have also been developed. Different combinations of sockets, screws and balls made of alumina are used.
ALUMINA
Alumina finds applications in dentistry as well as in a reconstructive maxillofacial surgery to cover bone defects. Alumina is not cytotoxic and there is no activation of bodys immune response. Alumina implants do not show inflammatory or progressive fibrotic reactions.
However, worn out alumina particles are observed in the interstitium of the lung, in reticuloendothelial cells of liver, spleen and bone marrow after phagocytosis.
ALUMINA
The important prerequisites for success of alumina implants are,
Surface finishing
small grain size
biomechanically correct design

exact implantation technique
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Zirconia (ZrO2)
Pure zirconia can be obtained from chemical conversion of zircon (ZrSiO4 ), which is an abundant mineral deposit .Zirconia has a high melting temperature (Tm = 2953 K) and chemical stability with a = 5.145 , b= 0.521 ,C = 5.311 , and = 9914. It undergoes a large volume change during phase changes at high temperature in pure form; therefore, a dopant oxide such as Y2O3 is used to stabilize the high temperature (cubic) phase. Zirconia has shown excellent biocompatibility and good wear and friction when combined with ultrahigh molecular weight polyethylene.
BIOACTIVE CERAMICS
GLASS CERAMICS
The main for the invention of this type of implant material is to achieve a controlled surface reactivity that will induce a direct chemical bond between the implant and the surrounding tissues. Glass ceramics are polycrystalline ceramics. The glass ceramics serves this purpose. Bioglass and Ceravital are two glass ceramics, having fine-grained structure with excellent mechanical and thermal properties, which are used in implants. The composition of Ceravital is similar to bioglass in Sio2 content but differ in CaO,MgO,Na2O.
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Glass ceramics are polycrystalline ceramics made by controlled crystallization of glasses ( photosensitive glasses), in which small amounts of copper, silver, and gold are precipitated by ultraviolet light irradiation. These metallic precipitates help to nucleate and crystallize the glass into a fine grained ceramic which possesses excellent mechanical and thermal properties. Both Bioglass and Ceravital glass ceramics have been used as implants
The formation of glass ceramics is influenced by the nucleation and growth of small (<1 m diameter) crystals as well as the size distribution of these crystals. It is estimated that about 1012 to 1015 nuclei per cubic centimeter are required to achieve such small crystals. In addition to the metallic agents already mentioned, Pt groups, TiO2, ZrO2, and P2O5 are widely used for nucleation and crystallization. The nucleation of glass is carried out at temperatures much lower than the melting temperature. During processing the melt viscosity is kept in the range of 1011 and 1012 Poise for 1 to 2 h. In order to obtain a larger fraction of the microcrystalline phase, the material is further heated to an appropriate temperature for maximum crystal growth. Deformation of the product, phase transformation within the crystalline phases, or redissolution of some of the phases should be avoided. The crystallization is usually more than 90% complete with grain sizes 0.1 to 1 m. These grains are much smaller than those of conventional ceramics. The glass ceramics developed for implantation are SiO2-CaO-Na2O-P2O5 and Li2OZnO-SiO2 systems. Two major groups are experimenting with the SiO2-CaO-Na2O-P2O5 glass ceramic.
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Glass Ceramics To achieve a controlled surface reactivity that will induce a direct chemical bond between the implant and the surrounding tissues. Also known as 45S5 glass. It is composed of SiO2, Na2O, CaO and P2O5.
Bioglass
45 wt.% of SiO2 and 5:1 ratio of CaO to P2O5. Lower Ca/P ratios do not bond to bone.
Bioglass and Ceravital; fine-grained structure with excellent mechanical and thermal properties The composition of Ceravital is similar to bioglass in Sio2 content but differ in CaO,MgO,Na2O. Bioglass implants have several advantages like high mechanical properties surface biocompatible properties. Ceravital
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GLASS CERAMICS
Bioglass implants have several advantages like high mechanical properties surface biocompatible properties. The surface-reactive implants respond to the local pH changes by releasing divalent ions.
The surface reactivity can be controlled by the composition of the implant.
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Temperature-time cycle for a glassceramic
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GLASS CERAMICS
The bioglass ceramics containing less reactive fluoride acquire a fibrous capsule when implanted in rat femurs. The major drawback of glass ceramic is its brittleness.
Therefore, they cannot be used for major load-bearing implants such as joint implants.
However glass ceramics can be used as fillers for bone cement, dental restorative composite and as coating material.
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Ceravital
The composition of Ceravital is similar to that of Bioglass in SiO2 content but differs somewhat in other components. In order to control the dissolution rate, Al2O3, TiO2, and Ta2O5 are added in Ceravital glass ceramic. The mixtures, after melting in a platinum crucible at 1500C for three h, are annealed and cooled. The nucleation and crystallization emperatures are 680C and 750C, respectively, each for 24 h. When the size of crystallites reaches pproximately 4 and the characteristic needle structure is not formed, the process is stopped to obtain a fine grain structured glass ceramic
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Desirable properties OF Glass ceramics

Glass ceramics have several desirable properties compared to glasses and ceramics. The thermal coefficient of expansion is very low, typically 107 to 105C1, and in some cases it can even be made negative. Due to the controlled grain size and improved resistance to surface damage, the tensile strength of these materials can be increased by at least a factor of two, from about 100 to 200 MPa. The resistance to scratching and abrasion of glass ceramics is similar to that of sapphire .The mechanical strength of the interfacial bond between bone and Bioglass ceramic is on the same order of magnitude as the strength of the bulk glass ceramic (850 kg/cm2 or 83.3 MPa), which is about three-fourths that of the host bone strength A negative characteristic of the glass ceramic is its brittleness.
BIORESORBABLE CERAMICS
RESORBABLE CERAMICS
One of the first resorbable implant substance uses was Plaster of Paris. The reasons why Plaster of Paris is not widely used are
variable resorption rates

poor mechanical properties.
Two types of orthophosphoric acid salt namely tricalcium phosphate (TCP) and hydroxyapatite (HAP) find widespread use as resorbable Ceramics
Uses of Biodegradable Bioceramics

1. As drug delivery devices. 2. For repairing damaged bone due to disease or trauma. 3. For filling space vacated by bone screws, donor bone, excised tumors, and diseased bone loss. 4. For repairing and fusion of spinal and lumbosacral vertebrae 5. For repairing herniated discs. 6. For repairing maxillofacial and dental defects 7. Hydroxyapatite Ocular Implants.
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RESORBABLE CERAMICS - APATITE

The apatite- [Ca10 (PO4)6 (OH)2] crystallizes into the hexagonal rhombic prism. The unit cell has dimensions of a = 0.9432 mm and c = 0.6881 nm. The ideal Ca/P ratio of hydroxyapatite is 10/6 and the calculated density is 3.219 g/ml.
The substitution of OH- with F- gives a greater structural stability due to the fact that F- has a closer coordination than the hydroxyl, to the nearest calcium.
RESORBABLE CERAMICS
HYDROXYAPATITE The synthetic hydroxyapatite Ca10(PO4)6(OH)2 is prepared by the reaction of Ca(OH)2 and H3PO4 in an aqueous solution.
The addition of fluorine to form fluoro-apatites may be beneficial for the surrounding bone.
Fluoride treatments have been shown to cause a marked increase in bone formation and comprehensive strength of osteoporetic tissues. It has a high modulus of elasticity (40-117 GPa). The Poisson s ratio is 0.27 which is close to natural bone (0.3)
RESORBABLE CERAMICS
The Key properties of hydroxyapatite are, The ability to integrate in bone structures and support bone ingrowth, without breaking down or dissolving
Hydroxyapatite is a thermally unstable compound, decomposing at temperature from about 800-1200C depending on its stoichiometry.
The wide variations in properties of polycrystalline calcium phosphates are due to the variations in the structure and manufacturing processes. Depending on the final firing conditions, the calcium phosphate can be calcium hydroxyapatite or -whitlockite.
In many instances, both types of structures exist in the same final product Polycrystalline hydroxyapatite has a high elastic modulus (40 to 117 GPa). Hard tissue such as bone, dentin, and dental enamel are natural composites which contain hydroxyapatite (or a similar mineral), as well as protein, other organic materials, and water. Enamel is the stiffest hard tissue, with an elastic modulus of 74 GPa, and contains the most mineral. Dentin ( E = 21 GPa) and compact bone ( E = 12 to 18 GPa) contain comparatively less mineral. The Poissons ratio for the mineral or synthetic hydroxyapatite is about 0.27 which is close to that of bone ( 0.3)
Manufacturing of HAP
Ca (NO3)2 and NaH2PO4 precipitates Filteringdrying to fine particle powder. Calcination /3 hours at 900oC (to promote crystallization) Pressing and sintering at 1050-1200oC for 3 hours. Grain boundary formation.
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RESORBABLE CERAMICS
Can be crystallized into salts, hydroxy apatite and B- whitlockite depending on the Ca/P ratio, presence of impurities , water and temperature. At low temperature (< 900oC ) hydroxy apatite form and at high temperature the bwhitlockite will be formed. The apatite form of calcium phosphate closely mimics the mineral phase of bone and teeth.
Hydroxyapatite Synthesis Method

Prepare the following solutions: Solution 1: Dissolve 157.6 g calcium nitrate tetrahydrate [Ca(NO3)24H2O] in 500 ml DI water. Bring the solution to a pH of 11 by adding 70 ml ammonium hydroxide *NH4OH+. Bring the solution to 800 ml with DI water. Solution 2: Dissolve 52.8 g ammonium phosphate dibasic [(NH4)2HPO4] in 500 ml DI water. Bring the solution to a pH of 11 by adding 150 ml ammonium hydroxide *NH4OH+. Add DI water until the precipitate is completely dissolved, 250350 ml. 1. Add one-half of Solution 1 to a 2 L separatory funnel. 2. Add one-half of Solution 2 to a 2 L separatory funnel. 3. Titrate both solutions into a 4 L beaker with heat and constant stirring. 4. Boil gently for 30 min. 5. Repeat steps 14 for the rest of Solutions 1 and 2. 6. Let cool completely allowing precipitate to settle to bottom of beaker. 7. Pour contents of beaker into 250 ml polypropylene bottles. 8. Centrifuge bottles for 10 min at (10,000 rpm) 16,000 g. 9. Collect precipitate from the six bottles into two and resuspend with DI water. 10. Fill the four empty bottles with the reaction mixture and centrifuge all six as before. 11. Collect precipitant from the two bottles that were resuspended with DI water. 12. Combine remaining four bottles into two bottles and resuspend with DI water. 13. Repeat steps 1012 as necessary. 14. Dry precipitate for 2448 h at 70C. 15. Calcine the precipitate for one hour at 1140C. 16. Grind and sieve product as desired.
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Ceramics - Unit 2

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Ceramics - Unit 2

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Ceramics and Polymers

Desired Properties of Implantable Bioceramics

Ceramics and its classification

Yielding mineralized bone growing from the implant surface

surface reactive Bioglass ceramics ; Intermediate behavior Soft tissues/cell membranes

Bio inert and active CERAMICS

BIO INERT CERAMICS

Uses of Bioinert Bioceramics

Bioinert PYROLYTIC CARBON

DIFFERENT VARIETIES OF CARBON (NEARLY INERT CERAMICS)

Bio Inert -ALUMINA

Chemical Composition of Calcined Alumina

Alumina (Aluminium oxide)

Porous network ; SEM images

Alumina ceramic femoral component (Kyocera Inc.; Japan)

biomechanically correct design

The surface reactivity can be controlled by the composition of the implant.

Temperature-time cycle for a glassceramic

Desirable properties OF Glass ceramics

variable resorption rates

Uses of Biodegradable Bioceramics

RESORBABLE CERAMICS - APATITE

Hydroxyapatite Synthesis Method

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