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3 Ceramic Biomaterials CERAMIC BIOMATERIALS Lecture Note (October 2013) This lecture note is strictly for Biomedical Engineering Student in STEI – ITB attending EL 3004 and not for commercial purpose. Students are advised to read in advance “Mengenal Sifat Material” by Sudaryatno Sudirham and Ning Utari S. Adopted from: Joseph D. Bronzino, “Biomedical Engineering Fundamentals ”, CRC Press, third edition, 2006, Section V, CHAPTER 39 , by W.C. Billote.] Prepared by Sudaryatno Sudirham (Lecturer) www.darpublic.com CERAMIC BIOMATERIALS [Adopsi dari: Joseph D. Bronzino, “ Biomedical Engineering Fundamentals ”, CRC Press, third edition, 2006, Section V, CHAPTER 39 , by W.C. Billote.] 39.1 INTRODUCTION Ceramics are defined as the art and science of making and using solid articles that have as their essential component, inorganic nonmetallic materials (Kingery et al .. 1976). Ceramics are refractory, polycrystal line compounds, usually inorganic, including silicates, metallic oxides, carbides and various refractory hydrides, sulfides, and selenides. Oxides such as A1203, MgO. Si02, and Zr02 contain metallic and nonmetallic elements and ionic salts, such as NaCl, CsCl, and ZnS (Park and Lakes, 1992). Exceptions to the preceding include covalently bonded ceramics such as diamond and carbonaceous structures like graphite and pyrolized carbons (Park and Lakes. 19921. Ceramics in the form of pottery have been used by humans for thousands of years. Until recently, their use was somewhat limited because of their inherent brittleness, susceptibility to notches or micro-cracks, low tensile strength, and low impact strength. However, within the last 100 years, innovative techniques for fabricating ceramics have led to their use as “high tech” materials. In recent years, humans have realized that ceramics and their composites can also be used to augment or replace various parts of the body, particularly bone. Thus, the ceramics used for the latter purposes are classified as bioceramics . Their relative inertness to the body fluids, high compressive strength, and aesthetically pleasing appearance led to the use of ceramics in dentistry as dental crowns. Some 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 [Park and Lakes, 1992]. Unlike metals and polymers, ceramics are difficult to shear plastically due to the (ionic) nature of the bonding and minimum number of slip systems. These characteristics make the ceramics nonductile and are responsible for almost zero creep at room temperature [Park and Lakes, 1992]. Consequently, ceramics are very susceptible to notches or microcracks because instead of undergoing plastic deformation (or yield) they will fracture elastically on initiation of a crack. At the crack tip the stress could be many times higher than the stress in the material away from the tip, resulting in a stress concentration which weakens the material considerably. The latter makes it difficult to predict the tensile strength of the material (ceramic). This is also the reason ceramics have low tensile strength compared to compressive strength. If a ceramic is flawless, it is very strong even when subjected to tension. Flawless glass fibers have twice the tensile strengths of high strength steel ( ≈7 GPa) [Park and Lakes, 1992]. 1/33 Ceramics are generally hard; in fact, the measurement of hardness is calibrated against ceramic materials. Diamond is the hardest, with a hardness index of 10 on Moh’s scale, and talc (Mg 3Si 3O10 COH) is the softest ceramic (Moh’s hardness 1), while ceramics such as alumina (Al 2O3: hardness 9), quartz (SiO 2: hardness 8), and apatite (Ca 5P3O12 F: hardness 5) are in the middle range. Other characteristics of ceramic materials are (1) their high melting temperatures and (2) low conductivity of electricity and heat. These characteristics are due to the chemical bonding within ceramics. In order to be classified as a bioceramic, the ceramic material must meet or exceed the properties listed in Table 39.1. The number of specific ceramics currently in use or under investigation cannot be accounted for in the space available for bioceramics in this book. Thus, this chapter will focus on a general overview of the relatively bioinert, bioactive or surface reactive ceramics, and biodegradable or resorbable bioceramics. Ceramics used in fabricating implants can be classified as nonabsorbable (relatively inert), bioactive or surface reactive (semi-inert) [Hench, 1991, 1993] and biodegradable or resorbable (non-inert) [Hentrich et al ., 1971; Graves et al. , 1972). Alumina, zirconia, silicone nitrides, and carbons are inert bioceramics. Certain glass ceramics and dense hydroxyapatites are semi-inert (bioreactive) and calcium phosphates and calcium aluminates are resorbable ceramics [Park and Lakes. 1992]. 39.2 NONABSORBABLE OR RELATIVELY BIOINERT BIOCERAMICS 39.2.1 Relatively Bioinert Ceramics Relatively bioinert ceramics maintain their physical and mechanical properties while in the host. They resist corrosion and wear and have all the properties listed for bioceramics in Table 39.1. Examples of relatively bioinert ceramics are dense and porous aluminum oxides, zirconia ceramics, and single phase calcium aluminates (Table 39.2). Relatively bioinert ceramics are typically used as structural-support implants. Some of these are bone plates, bone screws, and femoral heads (Table 39.3). Examples of nonstructural support uses are ventilation tubes, sterilization devices [Feenstra and de Groot, 1983] and drug delivery devices (see Table 39.3). TABLE 39.1 Desired Properties of Implantable Bioceramics 2/33 Table 39.2 Examples of Relatively Bioinert Bioceramics 3/33 Table 39.3 Uses of Bioinert Bioceramics 39.2.2 Alumina (A1 2O3) The main source of high purity alumina (aluminum oxide, Al2O3) is bauxite and native corundum. The commonly available alumina (alpha, α) can be prepared by calcining alumina trihydrate. The chemical composition and density of commercially available “pure” calcined alumina are given in Table 39.4. Table 39.4 Chemical Composition of Calcined Alumina Source: Park, J.B. and Lake, LS. I 992. Ceramic Implant MateriaL ,. In: 4/33 Biomaterial An Introcuction, 2nd ed., p.121 Plenum Press, NewYork. The American Society for Testing and Materials (ASTM) specifies that alumina for implant use should contain 9.3% pure alumina and less than 0.1% combined SiO2 and alkali oxides (mostly Na 2O) (F603-78). Alpha alumina has a rhombohedral crystal structure ( a = 4.758 Å and c = 12.991 Å). Natural alumina known as sapphire or ruby, depending on the types of impurities which give rise to color. The single crystal form of alumina has been used successfully to make implants [Kawahara, 1989; Park 1991]. Single crystal alumina can be made by feeding fine alumina powders onto the surface of a seed crystal which is slowly withdrawn from an electric arc or oxy-hydrogen flame as the fused powder builds up. Single crystals of alumina up to 10cm in diameter have been grown by this method [Park and Lakes, 1992]. The strength of polycrystalline alumina depends on its grain size and porosity. Generally, the smaller the grains, the lower the porosity and the higher the strength [Park and Lakes, 1992]. The ASTM standards (F603-78) requires a flexural strength greater than 400 MPa and elastic modulus of 380 GPa (Table 39.5). Aluminum oxide has been used in the area of orthopaedics for more than 25 years [Hench, 1991]. Single crystal alumina has been used in orthopaedics and dental surgery for almost 20 years. Alumina is usually a quite hard material, its hardness varies from 20 to 30 GPa. This high hardness permits its use as an abrasive (emery) and as bearings for watch movements [Park and Lakes, 1992). Both polycrystalline and single crystal alumina have been used clinically. 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 [Park and Lakes. 1992]. Aluminum oxide implants in bones of rhesus monkeys have shown no signs of rejection or toxicity for 350 days [Graves et al ., 1972; Hentrich et al .. 197l]. One of the most popular uses for aluminum oxides is in total hip protheses. Aluminum oxide hip prostheses with an ultra-high molecular weight polyethylene (UHMWPE) socket have been claimed to be a better device than a 5/33 metal prostheses with a UHMWPE socket [Oonishi, 1992]. However, the key for success of any implant, besides the correct surgical implantation, is the highest possible quality control during fabrication of the material and the production of the implant [Hench, 1991]. 39.2.3 Zirconia (ZrO 2) Pure zirconia can be obtained from chemical conversion of zircon (ZrSiO 4), which is an abundant mineral deposit [Park and Lakes, 1992]. Zirconia has a high melting temperature ( Tm = 2953 K) and chemical stability with a = 5.145 Å, b = 0.521 Å, c = 5.311 Å, and β = 99 o14 in [Park and Lakes, 1992]. It undergoes a large volume change during phase changes at high temperature in pure form; therefore, a dopant oxide such as Y 2O3 is used to stabilize the high temperature (cubic) phase. We have used 6 mole% Y 2O3 as dopant to make zirconia for implantation in bone [Hentrich et al . 1971]. Zirconia produced in s manner is referred to as partially stabilized zirconia [Drennan and Steele, 1991]. However, the physical properties of zirconia are somewhat inferior to that of alumina (Table 39.5). High density zirconia oxide showed excellent compatibility with autogenous rhesus monkey bone and was completely nonreactive to the body environment for the duration of the 350 day study [Hentrich et a1 ., 1971]. Zirconia has shown excellent biocompatibility and good wear and friction when combined with ultra-high molecular weight polyethylene (Kumar et al ., 1989; Murakami and Ohtsuki, 1989).
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