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Polymers INTRODUCTION POLYMER: Another word for a plastic material: one which has been made from chains of molecules of one or more MONOMERS. Polymers (plastics) are ORGANIC substances of high MOLECULAR WEIGHT, made from hundreds or thousands of molecules linked together in a repeating chain pattern (also known as macromolecules). THERMOPLASTIC: A plastic material which, when softened in a mould under heat and pressure, forms a shape which can be re softened and re moulded, e.g.: polythene, acrylic, PVC, and nylon. THERMOSET: A plastic which under heat and pressure polymerises into a form which cannot be re softened due to CROSSLINKING of the molecules. It is therefore used for components such as light fittings, saucepan handles and ashtrays. ELASTOMERS: More commonly known as rubber, can be defined as any material which after vulcanisation can be extended to several times it’s original length and return to it’s original length when the force is removed. ADDITIVES: Plastics used in moulding processes are normally in powder or small chips known as granules. Before being moulded into shape they need to be mixed with additives. These come in the forms of: Fillers, Stabilisers, Plasticizers, Lubricants, Antioxidants, Flame retardants, Colorants. COMMON PROCESSES USING PLASTICS: MOULDING: The most common method for forming thermosetting resins such as BAKELITE into ashtrays, radios etc. The moulding powder, usually with a filler is placed in the lower ' female ' part of a two part mould. The top part closed on to it, heat and pressure are applied, the plastic flows around the mould and the final moulding is ejected. EXTRUSION: Process similar to making spaghetti for moulding plastics into continuous lengths of pipes, rods and profiles. The softened material is forced through a shaped DIE.
INJECTION MOULDING: The most widely used high speed process for mass producing plastic articles. Granules are heated and forced under pressure into a mould, which can be single cavity for a bucket or chair, or multi cavity for combs and other small objects.
THERMOFORMING/VACCUM FORMING: The shaping of heat softened thermoplastic sheet through heat and/ or vacuum.
v Polymers consist of large molecules that are made up of smaller repeating units, or monomers. v Polymers containing only one type of monomer are known as HOMOPOLYMERS, v Polymers combining more than one type of monomer are known as COPOLYMERS. v Two general methods exist for forming large molecules from small monomers: addition polymerization and condensation polymerization. v In the chemical process called addition polymerization, monomers join together without the loss of atoms from the molecules. v Some examples of addition polymers are polyethylene, polypropylene, polyphenylethene, polyethenyl ethanoate, and polytetrafluoroethylene (Teflon). v A new method of addition polymerization called group transfer polymerization was announced. v An activating group within the molecule initiating the process transfers to the end of the growing polymer chain as individual monomers insert themselves in the group. v The method has been used for acrylic plastics; it should prove applicable to other plastics as well. CONDENSATION POLYMERS:
Ø Thermosetting plastics are plastics that cannot be remelted once they have hardened. Ø Compression moulding forms thermosetting plastic objects in a steel mould. Ø When heat and pressure are applied, the softened plastic squeezes into all parts of the mould to form the desired shape. Ø Laminating binds layers of materials together in a plastic matrix. The layers are fused when heated plates melt the plastic and squeeze the material together Ø This involves the elimination of water molecules during the linking up of the constituent, this usually form thermosetting plastics in most cases organic acids are made to react with alcohol to produce ester and water, the elimination of that water complete the process this is usually cure by heating the resin or treating it with thermosetting agents. Ø In condensation polymerization the repeat unit is related to the two substances forming the polymer
R1 COOH + R2 OH – R1COOR2 + H2O
A-A-A-A The repeat unit is the same through out the chain, the product is known as HOMO-Polymer,
When you have a particular group alternating or combining with the basic monomer e.g. A - B - A - B -alternating copolymers forming alternating co-polymer, if the alternating is such that the first define a next chain of the other is called Block Polymer e.g. A - A - A + B - B - B A chaining of A through out with B branching is term Graft – copolymer. Ø Thermosetting plastics – phenol- formaldehyde first produced in 1856, this is form by condensations phenol and formaldehyde and on curing could be suitable for water closet (WC) seats, electrical fittings, and paints and vanishes, it is dark in colour. Ø Urea formaldehyde – the second form of thermosetting which is white, creamy plastic used for electrical fittings Ø Melamine formaldehyde is almost similar to urea formaldehyde, its about the hardest plastic around, it is used for the manufacture of plates and adhesives-araldite it can also be impregnated with paper together with special effect in printed or colour pattern and cure into a tough surface impervious to heat, this is called Formica. Ø SILICONES – these are chains of alternating silicon and oxygen ion used for waterproofing materials in the construction industry. PROPERTIES OF POLYMERS. 1 Plastics have a specific gravity of 1 – 1.6. 2 They have low thermal conductivity 3 Are resistant to corrosion 4 They have high coefficient of expansion 5 They have high strength/weight ratio.
Polymers can be grouped on the basis of their constituent elements. 1) C, H polyolefin 2) C, H, O polyether, esters and alcohols, carbohydrates (e.g., cotton, Rayon) 3) C, H, Cl (F) PVC, chlorinated and fluorinated polyolefin 4) C, H, N polyimide 5) C, H, N, O polyamides and urethanes - synthetic (e.g., Nylon, acryl amides); silk 6) C, H, N, O, S polyamides - natural (e.g., wool, hair) 7) C, H, N, O, S, Cl chlorinated polyamides (e.g., shrink proofed wool)
RUBBER The raw material is a thermoplastic but when treated with sulphur (vulcanizing) it turns into a thermosetting plastic and with addition of excess sulphur the elasticity would be lost and form a rigid material called Ebonite which is used for decorating terrazzo floors, braking joints into moulding.
SYNTHETIC RUBBER Ø Any artificially produced substance that resembles natural rubber in essential chemical and physical properties can be called synthetic rubber. Ø Substances are produced by chemical reactions, known as condensation or polymerization, of certain unsaturated hydrocarbons. Ø The basic units of synthetic rubber are monomers, which are compounds of relatively low molecular weight that form the building units of huge molecules called polymers. Ø The synthetic rubber is cured by vulcanization. DEVELOPMENT OF SYNTHETIC RUBBER Ø The origin of synthetic-rubber technology can be traced to 1860, Ø The British chemist Charles Hanson Greville Williams determined that natural rubber was a polymer of the monomer isoprene, Ø It has the chemical formula CH2: C (CH 3) CH: CH2. Many efforts were made during the next 70 years to synthesize rubber in the laboratory by using isoprene as the monomer. Ø Other monomers were also investigated, and during World War I German chemists polymerized dimethylbutadiene (formula CH2: C (CH3) C (CH 3): CH2) producing a synthetic rubber called methyl rubber, which was of limited usefulness. Ø A breakthrough in synthetic-rubber research did not occur, however, until about 1930 Ø Synthetic-rubber research initiated in the United States during World War II led to the synthesis of a polymer of isoprene identical in chemical composition with natural rubber.
TYPES OF SYNTHETIC RUBBER NEOPRENE
One of the first successful synthetic rubbers resulting from Carothers's research was neoprene, which is the polymer of the monomer chloroprene, chemical formula CH2: C (Cl) CH: CH2. The raw materials of chloroprene are ethyne and hydrochloric acid. Developed in 1931, Neoprene has high resistance to heat and such chemicals as oils and petroleum. Neoprene is used in hose for conveying petroleum and as an insulating material for cables and in machinery. BUNA RUBBERS v In 1935 German chemists developed the first of a group of synthetic rubbers called Buna, which is produced by copolymerization v That is, the polymerization of two monomers, called co monomers v The name Buna is derived from the initial letters of butadiene, used as one of the comonomers, and natrium (sodium), which was used as a catalyst. v One of these products, Buna-N, uses acrylonitrile (CH2: CH (CN)) as the other comonomer. v Acrylonitrile is produced from cyanide. Buna-N is valuable for uses requiring resistance to the action of oils or abrasion.
BUTYL RUBBER ü Butyl rubber, produced initially in 1940, is prepared by the copolymerization of isobutylene with butadiene or isoprene. ü It is plastic and can be compounded like natural rubber, but is difficult to vulcanize. Although butyl rubber is not as resilient as natural rubber and other synthetics, ü It is extremely resistant to oxidation and the action of corrosive chemicals. ü Because of its low permeability to gas, butyl rubber is used widely for inner tubes in car tyres. OTHER SPECIALITY RUBBERS Ø Many other types of synthetic rubber have been developed for purposes requiring specific properties. Ø One such speciality rubber, called Koroseal, is a polymer of vinyl chloride (CH2: CHCl). Vinyl chloride polymers are heat-, electricity-, and corrosion-resistant and are unaffected by exposure to light or by long storage. Ø Koroseal cannot be vulcanized, Ø Not subjected to high temperatures, it is more resistant to abrasion than natural rubber or leather.
PET MANUFACTURING METHOD OF CO POLYESTER FOR LOW ACETALDEHYDE CONTENT OF PET BOTTLES,
Ø The present invention provides a manufacturing method of copolyester for low acetaldehyde content of PET bottles. Ø The polyethylene terephthalate (PET) polymer is added with an appropriate modifier in order to decrease the production of acetaldehyde caused by pyrolysis side reaction during the blow molding process of PET bottles. Ø The modifier comprises stabilizer and primary antioxidant, wherein the stabilizer is an inorganic phosphorous compound with an addition quantity of 0.003.about.0.5 weight % based on the weight of the total co polyester copolymer and the primary antioxidant is a hindered phenolic antioxidant containing Ca.sup.+2 with an addition quantity of 0.005.about.5.0 weight % based on the weight of the total co polyester copolymer. Ø The present invention owns an improving effect of decreasing the production of side product--acetaldehyde at least 30% than those without the addition of said modifier. THE MANUFACTURING PROCESS OF THE PET BOTTLE CAN BE SEPARATED TO THREE MAIN STEPS: (1). Melted state polycondensation operation (2). Solid state polycondensation operation (3). Blow moulded manufacturing operation 6
The three main steps of the prior art are described respectively as follows: (1) "Melted State Polycondensation Operation” can be Further Splitted to two Processes (A). Continuous melted state polycondensation operation In the continuous melted state polycondensation operation process, the terephthalic acid (PTA) and the ethylene glycol (EG) are blended to form thick liquid; Ø The isophthalic acid (IPA) 0.about.10 mol % is added thereafter and blended together and then transmitted to esterification tank so as to perform direct esterification. Ø The operation temperature of esterification is between 220.about.265.degree.C. Ø The operation pressure of esterification is between normal pressure and 2.0 kg/cm.sup.2. Ø The produced water and alcohols during said process should be distilled out. Ø While the esterification has completed 95.about.98% of esterification conversion ratio, the esterification has been stopped and the polycondensation is initiated. Ø A catalyst should be added before polycondensation in order to expedite the rate of polycondensation so as to shorten the polycondensation time. Ø Antimony acetate or antimony trioxide or germanium dioxide or titanium, or their mixture can normally be used as catalyst to expedite the completion of polycondensation. Ø In addition, the stabilizer such as phosphoric acid, phosphorous acid, trimethyl phosphate, triphenyl phosphate, triethyl phosphate is added. The polycondensation of PET and its copolymer includes pre-polymerization and mainpolymerization. Ø The operating temperature for pre-polymerization is between 70.about.280.degree.C, The operating vacuum intensity for pre-polymerization between 250.about.15mmHg. The operating temperature for main-polymerization is between 275.about.285.degree.C., Ø The operating pressure for main-polymerization is below 1 mmHg. Ø The intrinsic viscosity of PET polymer is raised to 0.5.about.0.7 dl/g at the end of PET melted state polycondensation.
(B). BATCH MELTED STATE POLYCONDENSATION OPERATION Ø In the batch melted state polycondensation operation process, the dimethyl terephthalate (DMT) and the ethylene glycol (EG) are blended; Ø The transesterification catalyst such as manganese acetate, or zinc acetate, or titanium is added so as to perform transesterification reaction. Ø The operating temperature for transesterification reaction is between 140.about.260.degree.C. Ø The methyl alcohol should be distilled out during the said process. Ø While the transesterification reaction has completed 95.about.98% of esterification conversion ratio, the isophthalic acid (IPA) 0.about.10 mol % is added thereafter and blended together to form copolymer and so as to end the transesterification reaction. A polycondensation type catalyst should be added before melted state
polycondensation in order to expedite the rate of polycondensation so as to shorten the polycondensation reaction time. Ø Antimony acetate or antimony trioxide or germanium dioxide or titanium, or their mixture can be used as catalyst to expedite the completion of polycondensation. Ø In addition, the stabilizer such as phosphoric acid, phosphorous acid, trimethyl phosphate, triphenyl phosphate, triethyl phosphate is added.
SOLID STATE POLYCONDENSATION OPERATION The intrinsic viscosity of the PET chip made from Step Melted state polycondensation operation" is somewhere between 0.5.about.0.7 dl/g; The molecular weight of the PET chip is too low for Blow moulded manufacturing operation". Its strength is below enough. Moreover, the residual acetaldehyde in the PET chip is too high to manufacture PET bottles. solid state polycondensation is a necessity to raise the intrinsic viscosity of PET chip up to somewhere between 0.72.about.1.2 dl/g so as to obtain enough molecular weight needed by the succeeding blow moulding process and to reduce the residual acetaldehyde in PET chip to below 1 ppm. One of the solid state polycondensation process is the batch process, where the PET chip is heated in a vacuum revolving tank. The other one is the continuous process, where the PET chip is treated by crystallization and dryness, then an inert gas (such as nitrogen gas) is led into the solid state polycondensation tank in order to raise the intrinsic viscosity and to reduce the residual acetaldehyde in PET chip to below 1 ppm. The solid state polycondensation is operated in an inert gas stream or vacuum environment, the operating temperature of which is between 180.about.240.degree.C.; in general, the operating temperature is below the melting point of PET and its copolymer to prevent stocking from taking place. In normal circumstance, the PET chip solid state polycondensation for continuous process is operated at the exist of inert gas stream. The inert gas includes nitrogen, carbon dioxide, helium, argon, krypton, xenon gases or their mixture. The helium gas is commonly used as inert gas. The continuous solid state polycondensation reactor includes fluidized bed and moving bed. In most cases, a column shape polycondensation reactor is better to be utilized, wherein the PET chip is transmitted through the reactor in a speed which fits the needed reaction time. The column shape reactor should be high enough to allow the PET chip be transmitted by gravity from the top to the bottom of the reactor in a speed that fits the needed reaction retention time to obtain the required final intrinsic viscosity.
Ø Ø Ø
Ø Ø Ø Ø Ø
Ø BLOW MOULDER PROCESSES TO PRODUCE PET BOTTLES The PET chip with high intrinsic viscosity, which has been processed by solid state polycondensation, required by blow moulding is further processed by the ejector and blow moulder to produce transparent PET bottles. Ø The operating temperature of the ejector is somewhere between 260.about.285.degree.C., Ø The acetaldehyde content of PET chips is quickly increased by the function of this high temperature and mechanical shear force. CHEMICAL COMPOSITION OF PET RAW MATERIALS (1) Dicarboxyl acid comprises Terephthalic acid (PTA), Isophthalic acid (IPA), Dimethyl terephthalate (DMT), 2,6-naphthalenedicarboxylic acid (NDA), Dimethyl 2,6naphthalenedicarboxylate. (2)Dihydric alcohol comprises Ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol (CHDM ). (3)As said in (1) and (2), the mole ratio of dicarboxyl acid and dihydric alcohol is 1:1. The other said dicarboxyl acid or dihydric alcohol also can be added in order to prepare co polyester copolymer. At least 80 mole % of the component should be terephthalic acid or 2,6-naphthalenedicarboxylic acid or dimethyl terephthalate or dimethyl 2,6naphthalenedicarboxylate.
(4) The catalyst comprises antimony acetate, antimony trioxide, germanium dioxide, titanium, manganese acetate, zinc acetate. Based on the weight of co polyester, the catalyst metal element manganese is between 0.about.300 ppm or titanium is between 0.about.80 ppm or titanium is between 0.about.300 ppm or germanium is between 0.about.200 ppm. (5) The stabilizer comprises phosphoric acid, phosphorous acid, trimethyl phosphate, triphenyl phosphate, triethyl phosphate. Based on the weight of copolyester, the phosphorus element content is between 5.about.100 ppm, preferably 37.6 ppm. (6) The hindered phenolic antioxidant is Irganox-1425 (Ciba merchandise name). Based on the weight of copolyester, the calcium element is between 5.about.100 ppm, preferably 17.3 ppm. (7)The toner comprises tetrahydrated cobaltous acetate, cobaltous chloride, cobaltous nitrate, salicyl cobaltous salicylate. Based on the weight of copolyester, the cobalt element content is between 0.about.100 ppm.
Ø PMMA positive resists based on special grades of POLYMETHYL METHACRYLATE designed to provide high contrast, high resolution for e-beam, deep UV (220-250nm) and X-ray lithographic processes. Ø In addition, PMMA is often used as a protective layer in III-V device wafer thinning applications. Ø Standard products include 495,000 and 950,000 molecular weights (MW) in a wide range of film thicknesses formulated in chlorobenzene, or the safer solvent anisole. Ø In addition 50,000, 100,000, 200,000 and 2.2 million MW are available upon request. Ø Copolymer resists are based on a mixture of PMMA and ~8.5% methacrylic acid. Copolymer MMA (8.5) MAA is commonly used in combination with PMMA in bi-layer lift-off resist processes where independent control of CD size and shape of each resist layer is required. Ø Standard copolymer resists are formulated in the safer solvent ethyl lactate and are available in a wide range of film thicknesses. Ø In addition, MMA (17.5) MAA copolymer resists are available upon request.
CERAMICS CERAMICS v Ceramics encompass such a vast array of materials that a concise definition is almost impossible. One workable definition of ceramics is a refractory, inorganic, and nonmetallic material. Ceramics can be divided into two classes: Traditional Advanced Ø Traditional ceramics include clay products, silicate glass and cement; Ø Advanced ceramics consist of carbides (SiC), pure oxides (Al2O3), nitrides (Si3N4), non-silicate glasses and many others.
Ceramics offer many advantages compared to other materials. v They are harder and stiffer than steel; v More heat and corrosion resistant than metals or polymers; less dense than most metals and their alloys; and their raw materials are both plentiful and inexpensive. Ceramic materials display a wide range of properties which facilitate their use in many different product areas. Product Area Aerospace Product space shuttle tiles, thermal barriers, high temperature glass windows, fuel cells glassware, windows, pottery, Corning® ware, magnets, dinnerware, ceramic tiles, lenses, home electronics, microwave transducers catalytic converters, ceramic filters, airbag sensors, ceramic rotors, valves, spark plugs, pressure sensors, thermostats, vibration sensors, oxygen sensors, safety glass windshields, piston rings orthopedic joint replacement, prosthesis, dental restoration, bone implants structural components for ground, air and naval vehicles, missiles, sensors insulators, resistors, superconductors, capacitors, ferroelectric components, microelectronic packaging bricks, cement, membranes and filters, lab equipment
fiber optic/laser communications, TV and radio components, microphones
Ceramics have characteristics that enable them to be used in a wide variety of applications including: • • • • • High heat capacity and low heat conductance Corrosion resistance Electrically insulating, semi conducting, or superconducting Nonmagnetic and magnetic Hard and strong, but brittle
The diversity in their properties stems from their bonding and crystal structures. Atomic Bonding: o Two types of bonding mechanisms occur in ceramic materials, ionic and covalent. o These mechanisms co-exist in the same ceramic material. o Each type of bond leads to different characteristics. ü Ionic bonds most often occur between metallic and non-metallic elements that have large differences in their electro negativities. ü Ionically-bonded structures tend to have rather high melting points, since the bonds are strong and non-directional. ü The other major bonding mechanism in ceramic structures is the covalent bond. Unlike ionic bonds where electrons are transferred, atoms bonded covalently share electrons. ü the elements involved are non-metallic and have small electro negativity differences. ü Many ceramic materials contain both ionic and covalent bonding. ü The overall properties of these materials depend on the dominant bonding mechanism. Comparison of % Covalent and Ionic character with several ceramic compounds’ melting points. Ceramic Compound Magnesium Oxide Aluminum Oxide Silicon Dioxide Silicon Nitride Silicon Carbide Melting Point C 2798 2050 1715 1900 2500 % Covalent character 27% 37% 49% 70% 89% % Ionic character 73% 63% 51% 30% 11%
Classification: Ceramic materials can be divided into two classes: § § . In crystalline materials, a lattice point is occupied either by atoms or ions depending on the bonding mechanism. These atoms (or ions) are arranged in a regularly repeating pattern in three dimensions (i.e., they have long-range order). In contrast, in amorphous materials, the atoms exhibit only short-range order. Some ceramic materials, like silicon dioxide (SiO2), can exist in either form. A crystalline form of SiO2 results when this material is slowly cooled from a temperature (T>TMP @1723 C). Rapid cooling favours noncrystalline formation since time is not allowed for ordered arrangements to form. CRYSTALLINE AMORPHOUS (NONCRYSTALLINE)
Crystalline Silicon dioxide (regular pattern)
Amorphous Silicon dioxide (random pattern)
Comparison in the physical structure of both crystalline and amorphous Silicon dioxide
Thermal Properties: The most important thermal properties of ceramic materials are heat capacity, thermal expansion coefficient, and thermal conductivity. Many applications of ceramics, such as their use as insulating materials, are related to these properties. Thermal energy can be either stored or transmitted by a solid. The ability of a material to absorb heat from its surrounding is its heat capacity. In solid materials at T > 0 K, atoms are constantly vibrating. The atomic vibrations are also affected by the vibrations of adjacent atoms through bonding. Vibrations can be transmitted across the solid. The higher the temperature, the higher the frequency of vibration and the shorter the wavelength of the associated elastic deformation. The potential energy between two bonded atoms can be schematically represented by a diagram:
6 4 Potential Energy 2 0 -2 -4 0.5 1 1.5 2 2.5 Separation Distance (A) (Å)
Graph depicting the potential energy between two bonded atoms • • • The distance at which there is minimum energy (potential well) represents what is usually described as the bond length. A good analogy is a sphere attached to a spring, with the equilibrium position of the spring corresponding to the atom at the bond length (potential well). When the spring is either compressed or stretched from its equilibrium position, the force pulling it back to the equilibrium position is directly proportional to the displacement (Hooke's law). 14
• • • • • • •
The frequency of oscillation is greatest when there is a large spring constant and low mass ball. Ceramics generally have strong bonds and light atoms. They can have high frequency vibrations of the atoms with small disturbances in the crystal lattice. The result is that they typically have both high heat capacities and high melting temperatures. As temperature increases, the vibrational amplitude of the bonds increases. The asymmetry of the curve shows that the interatomic distance also increases with temperature, and this is observed as thermal expansion. The conduction of heat through a solid involves the transfer of energy between vibrating atoms.
Comparison of thermal properties of different ceramic materials. Material Melting Temp.(oC) Heat Capacity (J/kg.K) 900 Coefficient of Linear Expansion 1/oCx10-6 23.6 Thermal Conductivity (W/m.K) 247
Aluminum metal Copper metal Alumina Fused silica Soda-lime glass
2050 1650 700
775 740 840
8.8 0.5 9.0
30.1 2.0 1.7
Polyethylene 120 Polystyrene 65-75
Ø One of the most interesting high-temperature applications of ceramic materials is their use on the space shuttle. Ø Almost the entire exterior of the shuttle is covered with ceramic tiles made from high purity amorphous silica fibers. Ø Those exposed to the highest temperatures have an added layer of high-emittance glass. These tiles can tolerate temperatures up to 1480 C for a limited amount of time. 15
The high temperatures experienced by the shuttle during entry and ascent are shown in Figure 955
315 650 1465
Temperatures are in Celsius degrees. Temps marked with an * signify ascent temperatures.
*1175 *425 *430 980
* 420 *405 Diagram of space shuttle's ascent and descent temperatures v The melting point of aluminium is 660 C. v The tiles keep the temperature of the aluminium shell of the shuttle at or below 175 C while the exterior temperatures can exceed 1400 C. v The tiles cool off rapidly, so that after exposure to such high temperatures they are cool enough to be held in the bare hand in about 10 seconds. v The thickness of these ceramic tiles varies from only 0.5 inches to 3.5 inches.
maximum exposure temperature
Temp ( C)
660 T 175 0.0 mp
Tile Thickness (in)
Graph of inner temperature of tile versus tile thickness. The shuttle also uses ceramic applications in fabrics for gap fillers and thermal barriers, reinforced carbon-carbon composites for the nose cone and wing leading edges, and high temperature glass windows.
Tensile Strength Brittle fracture Breaking Elastic Strength Strain (a) Strain (b)
Tensile Bending Compressive
Electrical Properties: • • • • • • • The electrical properties of ceramic materials vary greatly, with characteristic measures spanning over many orders of magnitude. Ceramics are probably best known as electrical insulators. Ceramic insulators (such as BaTiO3) can be polarized and used as capacitors. Other ceramics conduct electrons when a threshold energy is reached, and are thus called semiconductors. In 1986, a new class of ceramics was discovered, the high Tc superconductors. These materials conduct electricity with essentially zero resistance. ceramics known as piezoelectric can generate an electrical response to a mechanical force or vice versa. Electrical Resistivity of different materials. Type Material Metallic conductors: Copper CuO2 Semiconductors: SiC Germanium Insulators: Fire-clay brick Si3N4 Polystyrene Superconductors: YBa2Cu3O7-x Resistivity ( -cm) 1.7 x 10-6 3 x 10-5 10 40 108 >1014 1018 <10-22 (below Tc) 17
Anyone who has used a portable cassette player, personal computer, or other electronic device is taking advantage of ceramic dielectric materials. . The structure of a capacitor is shown in the diagram.
charge +q + + + + + + + + + + capacitor plates - - - - - - - - - charge -q external battery
The charge of the capacitor is stored between its two plates. The amount of charge (q) that it can hold depends on its voltage (V) and its capacitance (C). q = CV The dielectric is inserted between the plates of a capacitor, raising the capacitance of the system by a factor equal to its dielectric constant, k. q = (kC)V o Using materials that have large dielectric constants allows large amounts of charge to be stored on extremely small capacitors. o This is a significant contribution to the continuing miniaturization of electronics (e.g., lap top computers, portable CD players, cellular phones, even hearing aids!). ü The dielectric strength of a material is its ability to continuously hold electrons at a high voltage. ü When a capacitor is fully charged, there is virtually no current passing through it. ü The magnetic field strength necessary to produce breakdown of a material is its dielectric strength. ü Some ceramic materials have extremely high dielectric strengths. Electrical property constants of different ceramic materials. Material Air Polystyrene Glass (Pyrex) Dielectric constant at 1 MHz 1.00059 2.54 - 2.56 5.6 Dielectric strength (kV/cm) 30 240 142 18
Alumina Porcelain Titanium dioxide
4.5 - 8.4 6.0 - 8.0 14 - 110
16 - 63 16 - 157 39 - 83
v Electrical current in solids is most often the result of the flow of electrons (electronic conduction). v In metals, mobile, conducting electrons are scattered by thermal vibrations (phonons), and this scattering is observed as resistance. v Thus, in metals, resistivity increases as temperature increases. v In contrast, valence electrons in ceramic materials are usually not in the conduction band, thus most ceramics are considered insulators. v Conductivity can be increased by doping the material with impurities. v Thermal energy will also promote electrons into the conduction band, so that in ceramics, conductivity increases (and resistivity decreases) as temperature increases. v A superconductor can transmit electrical current with no resistance or power loss. v For most materials, resistivity gradually decreases as temperature decreases. Superconductors have a critical temperature, Tc, at which the resistivity drops sharply to virtually zero.
nonsuperconductors Electrical Resistivity
superconductors Tc Temperature (K)
Ø Pure metals and metal alloys were the first known superconductors. Ø All had critical temperatures at or below 30K and required cooling with liquid helium. The new ceramic superconductors usually contain copper oxide planes such as YBa2Cu3O7 discovered in 1987 with Tc = 93 K. 19
Ø They have critical temperatures above the boiling point of liquid nitrogen (77.4 K), which makes many potential applications of superconductors much more practical. Ø This is due to the lower cost of liquid nitrogen and the easier design of cryogenic devices.
Copper Oxygen Barium Yttrium
In addition to their critical temperature, two other parameters define the region where a ceramic material is superconducting: ü The critical current and ü The critical magnetic field. As long as the conditions are within the critical parameters of temperature, current, and magnetic field, the material behaves as a superconductor. Any of these values is exceeded, superconductivity is destroyed. Applications of superconductors which rely on their current carrying ability include electrical power generation, storage and distribution. SQUIDS (Superconducting Quantum Interference Devices) are electronic devices that use superconductors as sensitive detectors of electromagnetic radiation. Possible applications in the field of medicine include the development of advanced MRI (Magnetic Resonance Imaging) units based on magnets made of superconducting coils. The magnetic applications of superconductors are also of major importance. Superconductors are perfect diamagnets, meaning that they will repel magnetic fields. This exclusion of an applied magnetic field is called the Meissner effect and is the basis for the proposed use of superconductors to magnetically levitate trains. .
Ceramic Processing: Processing of ceramic materials describes the way in which ceramic objects (e.g., glass windows, turbocharger rotor blades, optical fibres, and capacitors) are produced. Processing begins with the raw materials needed to produce the finished components, and includes many individual steps that differ significantly depending on the type of ceramic material, crystalline versus glass. Processing of Crystalline Ceramics Raw Material Selection Preparation Consolidation Sintering Glass Processing Raw Material Selection Melting Pouring Annealing
ü Raw material selection involves obtaining and preparing the right materials for the final product. ü Traditional ceramics use various forms of clay. ü Glass makers start with primarily silica. ü Advanced ceramics use several different raw materials depending on the applications (i.e., properties needed). Material Al2O3 (aluminum oxide) MgO (magnesium oxide) SiO2 (Silicon dioxide) ZrO2 (zirconium oxide) SiC (silicon carbide) Si3N4 (silicon nitride) Uses Spark-plug insulating bodies, substrates for microelectronic packaging electrical insulators, refractory brick cookware, optical fibers cubic zirconia, oxygen sensors kiln parts, heating elements, abrasives turbocharger rotors, piston valves
Ø For crystalline ceramics, the characteristics of the raw materials (powders) such as their particle size and purity are very important as they affect the structure (e.g., grain size) and properties (e.g., strength) of the final component. Ø Strength increases with decreasing grain size, most starting powders are milled (or ground) to produce a fine powder (diameter < 1 µm). Ø Dry powders are difficult to shape, processing additives like water; polymers, etc. are added to improve their plasticity. Ø Consolidation involves forming the ceramic mixture into the specified shape.
There are many techniques available for this step:
P liquid powder Rubber mold pestle P powder
P injection P powder Extrusion molding powder Injection molding
slurry product plaster Slip casting Die pressing
Ceramic processing aides. Ø Sintering is the final step in the process. Ø Sintering at high temperatures (800 to 1800 C) causes densification that gives the ceramic product its strength and other properties. Ø The individual ceramic particles coalesce to form a continuous solid network and pores are eliminated. Ø The microstructure of the sintered product contains dense grains, where an individual grain is composed of many starting particles.
forming Raw powder Formed product
sintering Sintered product
Microstructure of raw, formed, and sintered ceramic products
GLASS PROCESSING v Glass processing is different from crystalline processing. v One of the considerations that must be examined is the solidifying behaviour of glass. Glasses are most commonly made by rapidly quenching a melt. v This means that the elements making up the glass material are unable to move into positions that allow them to form the crystalline regularity. v The result is that the glass structure is disordered or amorphous. v One of the most notable characteristics of glasses is the way they change between solid and liquid states. v Crystals, which transform abruptly at a precise temperature (i.e., their melting point) glasses, undergo a gradual transition. v The melting temperature (Tm) of a substance and the so-called glass transition temperature (Tg), v The substance is considered a supercooled liquid. v When glass is worked between Tg and Tm, one can achieve virtually any shape. v The glass blowing technique is a fascinating demonstration of the incredible ability to deform a glass.
SuperCooled liquid specific volume Glass
Tg temperature Specific Volume vs. Temperature graph for a typical ceramic material
In the area between Tg and Tm, the crystalline material remains solid. The amorphous (glass) material however, shrinkage passes through a phase due to known as a freezing super-cooled liquid. This is when the glass crystalline can be easily deformed solid if the applied stresses are sufficiently high. Tm
Ø Glass processing does not require an optimum size particle (although smaller pieces melt faster). Ø The selections of glass raw materials and chemical additives (which, for example, can alter the color of the glass) are heated up (700 - 1600 C), Ø Melted and finally poured onto or into a quick-cool form or plate. There are four different forming techniques used to fabricate glass. Technique Application Pressing Table ware Blowing Jars Drawing Windows Fiber forming Fiber optics
During the glass formation, there may be stresses that have been introduced by rapid cooling or special treatments that the glass needs (such as layering or strengthening). Additional heat treatment is needed to “heal” the glass. Annealing, in which the glass is heated to the annealing point (a temperature just below the softening point where the viscosity is approximately 108 Poise) and then slowly cooled to room temperature, is one such process.
ALUMINA GENERAL PROPERTIES Specific Gravity: 3.90 Crystal Size: Range 2-50 Micron, Avg 15-30 Surface Finish, As Fired: 26 Surface Finish, Ground: 17 Water Absorption: None Permeability: Gas Tight Flexural Strength, Typical 25 oC: 331 MPa (48 kpsi) Flexural Strength, Typical 1000 oC: 193 MPa (28 kpsi) Compressive Strength: 2071 MPa (>300 kpsi) Modulus of Elasticity Typical 25 oC: 345 GPa (50 x 106 psi) Color: Ivory Specific Heat @ 100 oC: 880 J/Kg-oK, 0.21 Cal/g/oC Maximum Temperature (for no load conditions): 1750 oC, 3180 oF Thermal Conductivity, 25 oC: 29.4 W/mK Thermal Conductivity, 100 oC: 23.0 W/mK THERMAL COEFFICIENT OF EXPANSION: 25 - 200 oC: 6.7 x 10-6/oC 25 - 500 oC: 7.3 x 10-6/oC 25 - 800 oC: 7.8 x 10-6/oC 25 - 1000 oC: 8.0 x 10-6/oC
DIELECTRIC STRENGTH 6.35 mm: 8.7 kv/mm 3.18 mm: 11.6 kv/mm Spec. 1.27 mm: 16.5 kv/mm
BORON NITRIDE GENERAL PROPERTIES Compressive Strength 25 oC (ACMA-1) lg/in2: 15 x 10.3 Modulus of Elasticity 25 oC (sonic): 11.4 x 10.6 Modulus of Rupture lb/in2 @ 25 oC: 6350 @ 1000 oC: 6760 @ 1350 oC: 3495 Density (ASTM C20), g/cm2: 1.90 Hardness: 205 Water absorption, % weight gain: % weight gain in 168 hours @ 25oC and 80%-100% relative humidity: 0.16 Thermal Expansion Degrees (C-1 x 10-6): 75oC - 5000C: 0.0 75oC - 1000oC: 0.0 75oC - 1500oC: 0.09 75oC - 2000oC: 1.30 Thermal Conductivity, (W/moC): @ 100oC: 39.7 @ 350oC: 31.2 @ 700oC: 28.8 Maximum Use Temperature in Inert or reducing atmosphere (oC): 2000 Oxidizing Atmosphere (oC): 1200