This action might not be possible to undo. Are you sure you want to continue?
1 Historical Perspective Materials are so important in the development of civilization that we associate Ages with them. In the origin of human life on Earth, the Stone Age, people used only natural materials, like stone, clay, skins, and wood. When people found copper and how to make it harder y alloying, the !ronze Age started a out "### !$. %he use of iron and steel, a stronger material that gave advantage in wars started at a out &'## !$. %he ne(t ig step was the discovery of a cheap process to make steel around &)*#, which ena led the railroads and the uilding of the modern infrastructure of the industrial world. 1.2 Materials Science and En ineerin +nderstanding of how materials ehave like they do, and why they differ in properties was only possi le with the atomistic understanding allowed y ,uantum mechanics, that first e(plained atoms and then solids starting in the &-"#s. %he com ination of physics, chemistry, and the focus on the relationship etween the properties of a material and its microstructure is the domain of Materials Science. %he development of this science allowed designing materials and provided a knowledge ase for the engineering applications .Materials Engineering/. Str!ct!re0
At the atomic level0 arrangement of atoms in different ways. .1ives different properties for graphite than diamond oth forms of car on./ At the microscopic level0 arrangement of small grains of material that can e identified y microscopy. .1ives different optical properties to transparent vs. frosted glass./
Properties are the way the material responds to the environment. 2or instance, the mechanical, electrical and magnetic properties are the responses to mechanical, electrical and magnetic forces, respectively. 3ther important properties are thermal .transmission of heat, heat capacity/, optical .a sorption, transmission and scattering of light/, and the chemical stability in contact with the environment .like corrosion resistance/. Processin of materials is the application of heat .heat treatment/, mechanical forces, etc. to affect their microstructure and, therefore, their properties. 1." #h$ St!d$ Materials Science and En ineerin %
• • •
%o e a le to select a material for a given use ased on considerations of cost and performance. %o understand the limits of materials and the change of their properties with use. %o e a le to create a new material that will have some desira le properties.
All engineering disciplines need to know a out materials. Even the most 4immaterial4, like software or system engineering depend on the development of new materials, which in turn alter the economics, like software5hardware trade5offs. Increasing applications of system engineering are in materials manufacturing .industrial engineering/ and comple( environmental systems. 1.& Classi'ication o' Materials 6ike many other things, materials are classified in groups, so that our rain can handle the comple(ity. 3ne could classify them according to structure, or properties, or use. %he one that we will use is according to the way the atoms are ound together0 Metals( valence electrons are detached from atoms, and spread in an 7electron sea7 that 4glues4 the ions together. Metals are usually strong, conduct electricity and heat well and are opa,ue to light .shiny if polished/. E(amples0 aluminum, steel, rass, gold. Se)icond!ctors( the onding is covalent .electrons are shared etween atoms/. %heir electrical properties depend e(tremely strongly on minute proportions of contaminants. %hey are opa,ue to visi le light ut transparent to the infrared. E(amples0 Si, 1e, 1aAs.
Cera)ics( atoms ehave mostly like either positive or negative ions, and are ound y $oulom forces etween them. %hey are usually com inations of metals or semiconductors with o(ygen, nitrogen or car on .o(ides, nitrides, and car ides/. E(amples0 glass, porcelain, many minerals. Pol$)ers( are ound y covalent forces and also y weak van der Waals forces, and usually ased on 8, $ and other non5metallic elements. %hey decompose at moderate temperatures .&## 9 :## $/, and are lightweight. 3ther properties vary greatly. E(amples0 plastics .nylon, %eflon, polyester/ and ru er. 3ther categories are not ased on onding. A particular microstructure identifies co)posites* made of different materials in intimate contact .e(ample0 fi erglass, concrete, wood/ to achieve specific properties. +io)aterials can e any type of material that is iocompati le and used, for instance, to replace human ody parts. 1., -dvanced Materials Materials used in 48igh5%ec4 applications, usually designed for ma(imum performance, and normally e(pensive. E(amples are titanium alloys for supersonic airplanes, magnetic alloys for computer disks, special ceramics for the heat shield of the space shuttle, etc. 1.. Modern Material/s Needs
• • • • • •
Engine efficiency increases at high temperatures0 re,uires high temperature structural materials +se of nuclear energy re,uires solving pro lem with residues, or advances in nuclear waste processing. 8ypersonic flight re,uires materials that are light, strong and resist high temperatures. 3ptical communications re,uire optical fi ers that a sor light negligi ly. $ivil construction 9 materials for un reaka le windows. Structures0 materials that are strong like metals and resist corrosion like plastics.
Chapter 2. -TOMIC STRUCTURE -ND +ONDIN0 2.2 1!nda)ental Concepts Atoms are composed of electrons, protons, and neutrons. Electron and protons are negative and positive charges of the same magnitude, &.; < &- $oulom s. %he mass of the electron is negligi le with respect to those of the proton and the neutron, which form the nucleus of the atom. %he unit of mass is an atomic mass unit .amu/ = &.;; < '> kg, and e,uals &?&' the mass of a car on atom. %he $ar on nucleus has @=;, and A=;, where @ is the num er of protons, and A the num er of neutrons. Aeutrons and protons have very similar masses, roughly e,ual to & amu. A neutral atom has the same num er of electrons and protons, @. A mole is the amount of matter that has a mass in grams e,ual to the atomic mass in amu of the atoms. %hus, a mole of car on has a mass of &' grams. %he num er of atoms in a mole is called the Avogadro num er, Aav = ;.#'" < &#'". Aote that Aav = & gram?& amu. $alculating n, the num er of atoms per cm" in a piece of material of density d .g?cm"/. n = Aav < d ? M where M is the atomic mass in amu .grams per mol/. %hus, for graphite .car on/ with a density d = &.) g?cm", M =&', we get ; < &#'" atoms?mol < &.) g?cm" ? &' g?mol/ = - < &#'' $?cm". 2or a molecular solid like ice, one uses the molecular mass, M.8'3/ = &). With a density of & g?cm", one o tains n = "." < &# '' 8'3?cm". Aote that since the water molecule contains " atoms, this is e,uivalent to -.- < &#'' atoms?cm". Most solids have atomic densities around ; < &#'' atoms?cm". %he cu e root of that num er gives the num er of atoms per centimeter, a out "- million. %he mean distance etween atoms is the inverse of that, or #.'* nm. %his is an important num er that gives the scale of atomic structures in solids.
2." Electrons in -to)s %he forces in the atom are repulsions etween electrons and attraction etween electrons and protons. %he neutrons play no significant role. %hus, @ is what characterizes the atom. %he electrons form a cloud around the neutron, of radius of #.#* 9 ' nanometers. Electrons do not move in circular or its, as in popular drawings, ut in 7fuzzy7 or its. We cannot tell how it moves, ut only say what is the pro a ility of finding it at some distance from the nucleus. According to ,uantum mechanics, only certain or its are allowed .thus, the idea of a mini planetary system is not correct/. %he or its are identified y a principal ,uantum num er n, which can e related to the size, n = # is the smallestB n = &, ' .. are larger. .%hey are 4,uantized4 or discrete, eing specified y integers/. %he angular momentum l is ,uantized, and so is the proCection in a specific direction m. %he structure of the atom is determined y the Pauli exclusion principle, only two electrons can e placed in an or it with a given n, l, m – one for each spin. %a le '.& in the te(t ook gives the num er of electrons in each shell .given y n/ and su shells .given y l/. 2.& The Periodic Ta2le Elements are categorized y placing them in the periodic ta le. Elements in a column share similar properties. %he no le gases have closed shells, and so they do not gain or lose electrons near another atom. Alkalis can easily lose an electron and ecome a closed shellB halogens can easily gain one to form a negative ion, again with a closed shell. %he propensity to form closed shells occurs in molecules, when they share electrons to close a molecular shell. E(amples are 8', A', and Aa$l. %he a ility to gain or lose electrons is termed electronegativity or electropositivity, an important factor in ionic onds. 2., +ondin 1orces and Ener ies
%he $oulom forces are simple0 attractive etween electrons and nuclei, repulsive etween electrons and etween nuclei. %he force etween atoms is given y a sum of all the individual forces, and the fact that the electrons are located outside the atom and the nucleus in the center. When two atoms come very close, the force etween them is always repulsive, ecause the electrons stay outside and the nuclei repel each other. +nless oth atoms are ions of the same charge .e.g., oth negative/ the forces etween atoms is always attractive at large internuclear distances r. Since the force is repulsive at small r, and attractive at small r, there is a distance at which the force is zero. %his is the e,uili rium distance at which the atoms prefer to stay. %he interaction energy is the potential energy etween the atoms. It is negative if the atoms are ound and positive if they can move away from each other. %he interaction energy is the integral of the force over the separation distance, so these two ,uantities are directly related. %he interaction energy is a minimum at the e,uili rium position. %his value of the energy is called the bond energy, and is the energy needed to separate completely to infinity .the work that needs to e done to overcome the attractive force./ %he strongest the ond energy, the hardest is to move the atoms, for instance the hardest it is to melt the solid, or to evaporate its atoms. 2.. Pri)ar$ Inter ato)ic +onds Ionic Bonding %his is the ond when one of the atoms is negative .has an e(tra electron/ and another is positive .has lost an electron/. %hen there is a strong, direct $oulom attraction. An e(ample is Aa$l. In the molecule, there are more electrons around $l, forming $l5 and less around Aa, forming AaD. Ionic onds are the strongest onds. In real solids, ionic onding is usually com ined with covalent onding. In this case, the fractional ionic onding is defined as Eionic = &## < F& 9 e(p.5#.'* .GA 9 G!/'H, where GA and G! are the electronegativities of the two atoms, A and !, forming the molecule. Covalent Bonding
In covalent onding, electrons are shared etween the molecules, to saturate the valency. %he simplest e(ample is the 8' molecule, where the electrons spend more time in etween the nuclei than outside, thus producing onding. Metallic Bonding In metals, the atoms are ionized, loosing some electrons from the valence and. %hose electrons form a electron sea, which inds the charged nuclei in place, in a similar way that the electrons in etween the 8 atoms in the 8' molecule ind the protons. 2.3 Secondar$ +ondin 45an der #aals6
Fluctuating Induced Dipole Bonds Since the electrons may e on one side of the atom or the other, a dipole is formed0 the D nucleus at the center, and the electron outside. Since the electron moves, the dipole fluctuates. %his fluctuation in atom A produces a fluctuating electric field that is felt y the electrons of an adCacent atom, !. Atom ! then polarizes so that its outer electrons are on the side of the atom closest to the D side .or opposite to the 9 side/ of the dipole in A. %his ond is called van der Waals onding. Polar Molecule-Induced Dipole Bonds A polar molecule like 8'3 .8s are partially D, 3 is partially 9 /, will induce a dipole in a near y atom, leading to onding. Permanent Dipole Bonds %his is the case of the hydrogen ond in ice. %he 8 end of the molecule is positively charged and can to the negative side of another dipolar molecule, like the 3 side of the 8'3 dipole. 2.7 Molec!les If molecules formed a closed shell due to covalent onding .like 8 ', A'/ then the interaction etween molecules is weak, of the van der Waals type. %hus, molecular solids usually have very low melting points Chapter8"( STRUCTURE O1 CR9ST-:S ".2 1!nda)ental Concepts Atoms self5organize in crystals, most of the time. %he crystalline lattice, is a periodic array of the atoms. When the solid is not crystalline, it is called amorphous. E(amples of crystalline solids are metals, diamond and other precious stones, ice, graphite. E(amples of amorphous solids are glass, amorphous car on .a5$/, amorphous Si, most plastics %o discuss crystalline structures it is useful to consider atoms as eing hard spheres, with well5defined radii. In this scheme, the shortest distance etween two like atoms is one diameter. "." Unit Cells %he unit cell is the smallest structure that repeats itself y translation through the crystal. We construct these symmetrical units with the hard spheres. %he most common types of unit cells are the faced5centered cu ic .2$$/, the ody5centered cu ic .2$$/ and the he(agonal close5packed .8$I/. 3ther types e(ist, particularly among minerals. %he simple cu e .S$/ is often used for didactical purpose, no material has this structure. ".& Metallic Cr$stal Str!ct!res Important properties of the unit cells are ond
Pol$)orphis) and -llotrop$ Some materials may e(ist in more than one crystal structure. An e(ample of allotropy is car on. It is called polycrystalline.• • • • • %he type of atoms and their radii R. Densit$ Co)p!tations %he density of a solid is that of the unit cell.>: %he closest packed direction in a !$$ cell is along the diagonal of the cu eB in a 2$$ cell is along the diagonal of a face of the cu e. which is the fraction of the volume of the cell actually occupied y the hard spheres.. %hen it has a regular geometric structure with flat faces. ".1& -nisotrop$ Lifferent directions in the crystal have a different packing. %hus.1" Pol$cr$stalline Materials A solid can e composed of many crystalline grains. +nit $ell S$ !$$ 2$$ 8$I n & ' : . ". which is the num er of closest neigh ors to which an atom is onded. If the mass of the atom is given in amu . %his causes anisotropy in the properties of crystalsB for instance.>: #.12 Sin le Cr$stals $rystals can e single crystals where the whole solid is one crystal. ABCABC in the 2$$ crystals. then we have to divide it y the Avogadro num er to get Matom. we only count a fraction of the atom. and alternates etween three types of positions. in the hollow sites . n.a" in the case of a cu e/.A/. 2or instance. ABABAB. Cr$stalline and Non8Cr$stalline Materials ". CN .11 Close8Pac.. %he packing is alternate etween two types of sites. not aligned with each other. graphite. o tained y dividing the mass of the atoms . and amorphous car on. ) &' &' a?R ' :K " 'K ' APF #. the formula for the density is0 ".ed Cr$stal Str!ct!res %he 2$$ and 8$I are related. 2or an atom that is shared with m adCacent unit cells. APF = Sum of atomic volumes?Jolume of cell. ". it is called allotropy.. %hey are uilt y packing spheres on top of each other.2ig. ". and have the same APF. in the 8$I structure. . CN. Where they meet is called a grain boundary. which can e(ist as diamond. %he grains can e more or less aligned with respect to each other.) #. atoms along the edge 2$$ crystals are more separated than along the face diagonal.n atoms ( Matom/ and dividing y Vc the volume of the cell .&' of ook/. cell dimensions . &?m. ". side of ase a and height c in 8$I/ in terms of R. the atomic packing factor. the deformation depends on the direction in which a stress is applied. num er of atoms per unit cell. APF. this is called polymorphism. the coordination num er. If the material is an elemental solid..*' #.side a in cu ic cells.
MJ.uired to form a vacancy."## N/ = #. %his means that the forces are not alanced in the same way as for other atoms in the solid.1. and % the temperature in Nelvin . cracks.room temperature/ is much smaller than typical vacancy formation energies. Also.5".1 Introd!ction Materials are often stronger when they have defects.") < '" O?atom5N.zero dimension/ 9 point defects0 vacancies and interstitials. When using eJ as the unit of energy. &L 9 linear defects0 dislocations .uartz/ is still apparent in amorphous Si3' .self interstitial/ or an impurity atom. %here are other ways of making a vacancy. Aote that k%. k is !oltzmann constant./ Chapter8&( IMPER1ECTIONS I)per'ections in Solids &. It is created when the solid is formed.. Point De'ects &. AJ?AA is typically only a out #. since the distance etween atoms cannot e smaller than the size of the hard spheres. Even so.#'* eJ . 2or instance. there is a change in the coordination of atoms around the defect.. %he study of defects is divided according to their dimension0 #L . %hus. k = &. %he num er of vacancies formed y thermal agitation follows the law0 AJ = AA < e(p. Impurities./ = '. surfaces. e the same type In the case of vacancies and interstitials. ut they also occur naturally as a result of thermal vi rations.note. an insignificant num er." < &.eJ?atom. mi(ed/ 'L 9 grain oundaries. .1. there is no long5range order. When MJ is given in Coules. not in o$ or o2/.2 5acancies and Sel'8Interstitials A vacancy is a lattice position that is vacant ecause the atom is missing.5MJ?k%/ where AA is the total num er of atoms in the solid. k = ). in many cases there is some form of short5range order. "L 9 e(tended defects0 pores. An interstitial is an atom that occupies a place outside the normal lattice position. %his means that AJ?AA at room temperature is e(p. It may of atom as the others . MJ is the energy re.edge.. <8Ra$ Di''raction Deter)ination o' Cr$stalline Str!ct!re = not covered ".###& at the melting point. which results in lattice distortion around the defect.$u/ = #.". !ut amorphous does not mean random. 2or instance. screw. a high temperature is needed to have a high thermal concentration of vacancies.' < * eJ?atom5N. Non8Cr$stalline Solids In amorphous solids.silica glass. the tetragonal order of crystalline Si3 ' ..
%he a ility to dissolve is called solubility. Edge dislocations occur when an e(tra plane is inserted.coordination/ decreases. the !urgers vector is perpendicular to the dislocation line.the crystal structure changes/. Solid solutions are0 • • • homogeneous maintain crystal structure contain randomly dispersed impurities .to within &*E/ crystal structure electronegativity . Since energy is re. which is accelerated at high temperatures.& Dislocations>:inear De'ects Lislocations are a rupt changes in the regular ordering of atoms. %his introduces un alanced forces which result in relaxation . in that the num er of neigh ors . %he dislocation line is at the end of the plane.----E pure . Solid solutions are made of a host..uired to form a surface. car on added in small amounts to iron makes steel. 2or instance. Inter'acial De'ects %he environment of an atom at a surface differs from that of an atom in the ulk. the !urgers vector is parallel to the dislocation line. the solvent or matri(/ which dissolves the solute . Impurities are often added to materials to improve the properties. and in atomic percent. !oron impurities added to silicon drastically change its electrical properties. oundary is smaller than the ulk value. %he !urgers vector in metals points in a close packed direction. useful when making the solution. since void Surfaces and interfaces are very reactive and it is usual that impurities segregate there. A very high purity material.minor component/. grains tend to grow in size at the e(pense of smaller grains to minimize energy. useful when trying to understand the material at the atomic level. %his occurs y diffusion.su stitutional or interstitial/ 2actors for high solu ility • • • • Similar Similar Similar Similar atomic size . along a line .dislocation line/ in the solid.the lattice spacing is decreased/ or reconstruction . found y doing a loop around the dislocation line and noticing the e(tra interatomic spacing needed to close the loop.&. %he density of atoms in the region including the grain space occurs in the interface. %hey occur in high density and are very important in mechanical properties of material. In this case. Miscellaneo!s I)per'ections &.called . < &#&. Screw dislocations result when displacing planes relative to each other through shear. say --. %hey are characterized y the !urgers vector.A 9 si( nines/ contains P . %win oundaries0 not co!ered .otherwise a compound is formed/ valence $omposition can e e(pressed in weight percent. ." I)p!rities in Solids All real solids are impure. In an edge dislocation. impurities per cm". which is stronger than iron.
g. In this case..&. atoms?m'5second/ or in terms of mass flu( .. or 5ol!)e De'ects A typical volume defect is porosity. at high temperatures. y the motion of atoms in the solid . %hus.uantum mechanical effect/ and increase in amplitude with temperature..2 Di''!sion Mechanis)s Atom diffusion can occur y the motion of vacancies . there are more atoms moving in regions where their concentration is higher. the effect of diffusion is readily seen y a change in concentration with time.9Md?k%/. %his is more easily achieved when the atoms vi rate strongly." Stead$8State Di''!sion %he flu( of diffusing atoms.. atoms also diffuse ut this motion is hard to detect. . there is a arrier to diffusion created y neigh oring atoms that need to move to let the diffusing atom pass. the effect of temperature in diffusion is given y a !oltzmann factor0 L = L# < e(p. ..e. is e(pressed either in num er of atoms per unit area and per unit time . %he energy arrier is that due to near y atoms which need to move to let the atoms go y.3 -to)ic 5i2rations Atomic vi rations occur. Also. atomic vi rations created y temperature assist diffusion. 2ickQs first law holds that the flu( along direction x is0 J = – D dC/dx Where dC#dx is the gradient of the concentration C.vacancy diffusion/ or impurities . often introduced in the solid during processing. that is. In inhomogeneous materials. +!l. if the temperature is high enough .. although all atoms are moving randomly. Steady state diffusion means that " does not depend on time.a . which means that a type of atoms accumulates in a region or that it is depleted from a region .uation means that diffusion is down the concentration gradient. Ji rations displace transiently atoms from their regular lattice site. .impurity diffusion/.temperature is needed to overcome energy arriers to atomic motion..& Nonstead$8State Di''!sion %his is the case when the diffusion flu( depends on time. ". Chapter8. Similar to the case of vacancy formation.( DI1USSION . %he minus sign in the e.ual num er of atoms moving in one direction than in another. which is highly porous ice. &. which destroys the perfect periodicity we discussed in $hapter ". Aet diffusion occurs ecause. . and $ is the diffusion constant.which may cause them to accumulate in another region/. and diffusion is faster in open lattices or in open directions. %here is a difference etween diffusion and net diffusion. even at zero temperature .g. kg?m'5second/.. 1actors That In'l!ence Di''!sion As stated a ove. In this case there is a net diffusion. ut it is not a force in the mechanistic sense/. In a homogeneous material.transport/. Inhomogeneous materials can ecome homogeneous y diffusion.e. A common e(ample is snow. %his is ecause atoms move randomly and there will e an e..1 Introd!ction Many important reactions and processes in materials occur which happens y diffusion. smaller atoms diffuse more readily than ig ones. . %he concentration gradient is often called the dri!ing %orce in diffusion .
loads/ when they are used. . Introd!ction 3ften materials are su Cect to forces . . irreversi le deformation. L& as a result of a tensile or compressive stress. this is called true stress . Jalid for small strains . In tension and compression tests. . and the way of performing the test. how it is held. the material does not return to its previous dimension ut there is a permanent. e?D @ %he change in dimensions is the reason we use A# to indicate the initial area since it changes during deformation. %hat is why we use common procedures. the area is perpendicular to the a(is of rotation. 2orce divided y area is called stress. %o ena le comparison with specimens of different length. Stress>Strain +ehavior Elastic de'or)ation.2ig. the stress5strain relationship is called 8ooke7s law0 . %here is a change in dimensions.. . Chapter8. Short circuits are often unimportant ecause they constitute a negligi le part of the total area of the material normal to the diffusion flu(. if the deformation is elastic.( Mechanical Properties o' Metals 1. and other conditions.. the material returns to the dimension it had efore the load was applied. also called normalization to the area. or deformation elongation. or standards. this time to the length &.. temperature.. twist/ or reak as a function of applied load. the elongation is also normalized. non permanent Plastic de'or)ation. Leformation is re!ersible. s ? F@AA tensile or compressive stress t ? F@AA shear stress %he unit is the Megapascal = &#. In tensile tests.e(cept the case of ru ers/.>/. compress. Materials scientists learn a out these mechanical properties y testing materials.elongate.see Sec. . which are pu lished y the AS%M. time.specimen/.&/ and the shear strain is given y0 ?t B ". the deformation is the angle of twist. and voids in the material .short circuits like dislocations and grain oundaries/ ecause less atoms need to move to let the diffusing atom pass. In shear or torsion tests. When the stress is removed. the relevant area is that perpendicular to the force. 2or torsional or shear stresses. the load is calculated per unit area. Aewtons?m'. Other Di''!sion Paths Liffusion occurs more easily along surfaces. e. 2. 3ne could divide force y the actual area. When the stress is removed. Mechanical engineers calculate those forces and material scientists how materials deform . Results from the tests depend on the size and shape of material to e tested . Concepts o' Stress and Strain %o compare specimens of different sizes. %his is called strain..
n ? elateral@eaCial %he elastic modulus. of lateral and a(ial strains is called the Poisson)s ratio n. Tensile stren th. shear modulus and Ioisson7s ratio are related y ' = '*. Since the interatomic distances depend on direction in the crystal.##' . ' is large for ceramics . Tensile Properties 9ield point. In practice. 5. %hose su Cect to compression. 2or randomly oriented policrystals. internuclear distance . ' is isotropic.&Dn/ ulge.stronger ionic ond/ and small for polymers . is not that the atomic ond is stretched eyond repair. 4.s%S/ .e.. ' is the slope of the stress5strain curve. called the tensile strength . In some cases. %he point at which this happens is the yield point ecause there the material yields. . !y e(amining these curves we can tell which material has a higher modulus. E is (oung)s modulus or modulus o% elasticity.-./ +he yield stress measures the resistance to plastic de%ormation. the strain deviates from eing proportional to the stress. ... If the stress is too large. When stress continues in the plastic regime. which involves reaking and reforming onds. deforming permanently . and it finally reaks at the %racture point . ut the motion of dislocations. . %he stress at the yield point is called yield stress. or the first derivative of the force vs. Elastic Properties o' Materials Materials su Cect to tension shrink laterally. -nelasticit$ 8ere the ehavior is elastic ut not the stress5strain curve is not immediately reversi le. and then falls as the material starts to develop a nec. . %he ratio 6. %he reason for plastic deformation.plastically/. 8ooke7s law is not valid eyond the yield point. %he effect is normally small for metals ut can e significant for polymers. and is an important measure of the mechanical properties of materials.s?!e %hat is. Lue to thermal vi rations the elastic modulus decreases with temperature.i. the stress5strain passes through a ma(imum../. the relationship is not linear so that E can e defined alternatively as the local slope0 ! = ds@de Shear stresses produce strains according to0 t?" where * is the shear modulus.strain offset. %hey are related to the second derivative of the interatomic potential. ' depends on direction . . Plastic de%ormation is caused by the motion o% dislocations.2ig. 2ig. it is anisotropic/ for single crystals. in normal materials. 9ield stress.2ig.weak covalent ond/.&#/. Elastic moduli measure the sti%%ness of the material. the yield stress is chosen as that causing a permanent strain of #. It takes a while for the strain to return to zero..
ut in the case of compressive stresses there is no ma(imum in the s5e curve.$h. a variation remains in the materials. Hardness Hardness is the resistance to plastic deformation . Co)pressive* Shear* and Torsional De'or)ation $ompressive and shear stresses give similar ehavior to tensile stresses. It is measured y an impact test . %he a ility to deform efore raking. Jickers. . Elastic Recover$ D!rin Plastic De'or)ation If a material is taken eyond the yield point . due to uncontrolled variations during fa rication. %hus. &. is called the actual area . the material again responds elastically at the eginning up to a new yield point that is higher than the original yield point . what we normally do. not stress. so they are well correlated. 5aria2ilit$ o' Material Properties %ests do not produce e(actly the same result ecause of variations in the test e. 10. since no necking occurs. etc. %hey are popular ecause they are easy and non5destructive . For structural applications. even if all those parameters are controlled within strict limits. Luctility can e given either as percent ma(imum elongation ema( or ma(imum area reduction.&#/.g.the increase eyond s%S./. the yield stress is usually a more important property than the tensile strength.it is deformed plastically/ and the stress is then released. )/. procedures. >. non homogenous composition and structure.e. D!ctilit$. Tr!e Stress and Strain When one applies a constant tensile force strength. 8istorically. Resilience. since once the it is passed. etc.uipment. the structure has de%ormed beyond acceptable limits. the material ends up with a permanent strain. !ut. or point is pressed into a material and the size of the dent is measured. where a all. $h.2ig. %he amount of elastic strain that it will take efore reaching the yield point is called elastic strain reco!ery . A ility to a sor energy up to fracture. etc. It is the opposite of 2rittleness. If the stress is reapplied. $apacity to a sor energy elastically. 9. Aow we use standard tests. %he . as is the tensile strength. determined y the a ility of a material to scratch another. !rinell. it was measured on an empirically scale. %he energy per unit volume is the area under the strain-stress cur!e in the elastic region. the material will reak after reaching the tensile transverse area decreases/ ut the stress cannot to the initial area. %he material starts necking . diamond eing the hardest and talc the softer.Aote that it is called strength.that changes with stress/ one 8. operator ias. To! hness.repositioning the two pieces ack together/. If the ratio is to o tains the true stress. DE: ? e)aC C 1AA D D-R ? 4AA 8 A'6@AA %hese are measured after fracture . %here are a few different hardness tests0 Rockwell. specimen fa rication. %he ratio of the force the engineering stress. ut the units are the same... 7. it is a measure of plastic deformation. %he energy per unit volume is the total area under the strain-stress cur!e. 11. MIa.e(cept for the small dent/. a local dent or scratch/.strain hardening.
%here is compression near the e(tra plane . &. Variability o% material properties Chapter 3. in a plane they are measured per unit area.$h.uential ond reaking and ond reforming . %hus.ith tensile strength. %he num er of dislocations per unit volume is the dislocation density. ecause eing close increases the potential energy . +asic Concepts Lislocations can e edge dislocations. 12. >. details o% the di%%erent types o% hardness tests.&/. Characteristics o' Dislocations %here is strain around a dislocation which influences how they interact with other dislocations.:/ Lislocations interact among themselves . %hus. 3.:/. a working value for the tensile strength would e sW = s%S ? N. ut in preferred crystallographic directions . Aot tested0 true stress-true stain relationships.leaving ehind a perfect crystal/. the pro a ility that the yield strength is a ove the minimum value tolera le. ell5shaped/.We did not discuss direction and plane nomenclature for slip systems. which is often distri uted in a 1aussian curve . instead of an average value of. %he motion is called slip.*/. etc.slip planes/. %he num er of dislocations increases dramatically during plastic deformation. dislocations and e(ist in com ination of the two . >.slip direction/. that hardness %or a gi!en material correlates . 8ow do we e(plain thisT Since the distance etween atoms is shorter than the average.width/.typ.' 5 :/. say.8$I crystals are more rittle/./ !$$ and 2$$ crystals have more slip systems. the atoms can move more easily with respect to the atoms of the adCacent plane. . %he set of slip planes and directions constitute slip systems. %his leads to the use of a sa%ety %actor N S & . %heir motion . In general. but should . designers use. Slip S$ste)s In single crystals there are preferred planes where dislocations move . %here they do not move in any direction.2ig. and from defects. 2. :.resistance to deformation/ can e improved y putting o stacles to slip. . Introd!ction %he key idea of the chapter is that plastic deformation is due to the motion of a large num er of dislocations. !eing relatively far apart. >. DIS:OC-TIONS -ND STREN0THENIN0 MECH-NISM 1. they repel. the tensile strength. that is more ways for dislocation to propagate.higher atomic density/ and tension following the dislocation line . when dislocations are close and their strain fields add to a larger value. impurities.slip/ occurs y se.2ig. the strength . Lislocations spawn from e(isting dislocations. scre. When they are in the same plane. %he slip planes are those of highest packing density. %hus. Desi n@Sa'et$ 1actors %o take into account varia ility of properties. grain oundaries and surface irregularities.no.measured mechanical properties will show scatter. that is characterized y the mean value and the standard deviation . they repel if they have the same sign and annihilate if they have opposite signs .2ig. &. the distance perpendicular to the plane has to e longer than average. those crystals are more ductile than 8$I crystals .it takes energy to strain a region of the material/.
solid5solution alloying and strain hardening. A ility to deform plastically depends on a ility of dislocations to move.2igs. >.which is like a potential well/. %hese components are resol!ed shear stresses. Slip in Sin le Cr$stals A tensile stress s will have components in any plane that is not perpendicular to the stress. +he %iner the grains. %heir magnitude depends on orientation . >.see 2ig. 2or high5angle grain oundaries.the e(ception is the perfect single crystal.2igs. the larger the area o% grain boundaries that impedes dislocation motion. 9. Leformation y %winning %his topic is not included. tR ? s cos # cos l If the shear stress reaches the critical resol!ed shear stress t$RSS. We discuss the methods of grain5size reduction. %he stress needed is0 s$ ? tCRSS @ 4cos # cos l6)aC at the angles at which t$RSS is a ma(imum. %hus. We discuss others when treating alloys. the yield strength varies with grain size d according to0 s$ ? sA F &$ / d1@2 1rain size can e controlled y the rate of solidification and y plastic deformation.>/. Atomic disorder at the oundary causes discontinuity in slip planes.plastic deformation/ can start.-/. thus achieving a state of low potential energy. It costs strain energy for the dislocation to move away from this state . . strengthening reduces ductility. Solid8Sol!tion Stren thenin Adding another element that goes into interstitial or su stitutional positions in a solution increases strength. especially if it is very misaligned. Small angle grain oundaries are not effective in locking dislocations. 1rain5size reduction usually improves toughness as well. As a result.5. >. %hese are for single5phase metals. polycrystalline metals are stronger than single crystals .&)/ which can 4anchor4 dislocations./ >. %he scarcity of energy at low temperatures is why slip is hindered. When plastic deformation occurs in a grain. as in whiskers. Mec$anisms o# %trengt$ening in Metals 1eneral principles. 8. stress at end of slip plane may trigger new dislocations in adCacent grains.&> and >. dislocations will occur first at slip planes oriented close to this angle with respect to the applied stress . +sually. 3rdinarily. %he impurity atoms cause lattice strain . Strengthening consists in hindering dislocation motion. 6.) and >. %he minimum stress needed for yielding is when % = l = :* degrees0 s$ ? 2tCRSS. it will e constrained y its neigh ors which may e less favora ly oriented. %his occurs when the strain caused y the alloying element compensates that of the dislocation. slip . Stren thenin 2$ 0rain SiEe Red!ction %his is ased on the fact that it is difficult for a dislocation to pass into another grain. Plastic De'or)ation o' Pol$cr$stalline Materials Slip directions vary from crystal to crystal.
It is typically &?" to &?' of the melting temperature. which is proportional to the total area. %his occurs through short5range diffusion ena led y the high temperature. Recover$ 8eating U increased diffusion U enhanced dislocation motion U relieves internal strain energy and reduces the num er of dislocation. %he measure of strain hardening is the percent cold work . 11. %he reason for strain hardening is that the dislocation density increases with plastic deformation . the melting point . 0rain 0roGth %he growth of grain size with temperature can occur in all polycrystalline materials. . the improper design of components. the important parameters are oth temperature and time. "/ increase in the dislocation density. thus grain growth is faster at higher temperatures. .work hardening/ is the reason for the elastic recovery discussed in $h. It occurs y migration of atoms at grain oundaries y diffusion. '/ strain hardening.2ig. weaker. >. 12.cold work/ due to multiplication. %he electrical and thermal conductivity are restored to the values e(isting efore cold working./ Strain hardening . upon heating. ut more ductile . and improper use.ell belo. %he 4driving force4 is the reduction of energy. !elow a 4critical deformation4. recrystallization does not occur. given reduction of the original area.in 6. 1".). Strain Hardenin $uctile metals become stronger . Since recrystallization occurs y diffusion. %hese may e followed y grain growth. Introd!ction 2ailure of materials may have huge costs..cold Gor. 1-I:URE 1. 10. . %he material ecomes softer.E$W/.Iure metals are almost always softer than their alloys. %he average distance etween dislocations then decreases and dislocations start locking the motion of each one. It falls as the E$W is increased.%his is different from hot working is the shaping of materials at high temperatures where large deformation is possi le. Restoration to the state efore cold5work is done y heating through two processes0 recovery and recrystallization.hen they are de%ormed plastically at temperatures . $auses included improper materials selection or processing.''/. y the relative Chapter 7. y more regularly5spaced grains. A# to the final value Ad 0 DC# ? 1AA 4AA=Ad6@AA 'ecover() recr(stalli*ation and "rain "ro+t$ Ilastic deformation causes &/ change in grain size. !ig grains grow at the e(pense of the small ones. Recr$stalliEation Strained grains of cold5worked metal are replaced. Recr$stalliEation te)perat!re0 is that at which the process is complete in one hour.
crack propagation . 5.or faceted te(ture/ when cleavage direction changes from grain to grain.2. y ond reaking/ is along specific crystallographic planes . voids.elipsoid/ y coalescence into a crack fast crack propagation around neck. In most rittle materials. %his type of fracture is transgranular . rittle fracture D!ctile de'or)ation trac. at temperatures elow the melting point. Principles o' 1ract!re Mechanics 2racture occurs due to stress concentration at flaws. ice. 1!nda)entals o' 1ract!re 2racture is a form of failure where the material separates in pieces due to stress. Steps in fracture .in e(tensive slow.microvoids/ void growth . Shear strain at :*o final shear fracture . the enhanced stress near the flaw is0 . cold metals none lower smoother no • Stages of ductile fracture • • • • • Initial necking small cavity formation . etc. which signify plastic deformation. If a is the length of the void and r the radius of curvature.not too cold/ permanent elongation higher rough yes D!ctile 1ract!re +rittle little fast ceramics. cleavage planes/. needs stress most metals . %he fracture is termed ductile or rittle depending on whether the elongation is large or small. propa ation t$pe o' )aterials Garnin strain ener $ 'ract!red s!r'ace nec.through grains/ producing grainy te(ture . like surface scratches. In some materials. irregular.cup and cone/ %he interior surface is fi rous.response to stress/0 • • track formation track propagation Luctile vs. and crack propagation is very fast. • +rittle 1ract!re %here is no apprecia le deformation. fracture is intergranular.
g. etc. At high loads . ).''.t = sm?s# V ' . Initiation and Propa ation Stages is fatigue failure0 I. re.stress5num er of cycles to failure/ are o tained using apparatus like the one shown in 2ig. propagation .&-.2ig. ).N W &#: 5 &#* cycles/./ C!rve /0N curves . %he energy is measured y the change in potential energy . I)pact 1ract!re Testin Aormalized tests. 2ailure y fatigue shows su stantial !ariability . %he characteristics are0 ridges. non5ferrous/ the /0N curve continues to fall with N.plastic regime/. • C$clic Stresses %hese are characterized y maximum. 1ati !e li)it .the fatigue limit/ elow which the material never fails.like some ferrous and %i allows/.'#/.a?r/&?' !ecause of this enhancement. 2or other materials . %his means that there is a ma(imum stress amplitude . 6. crack initiation at high stress points . the /0N curve ecomes horizontal at large N . %his energy is called notc$ toug$nessD!ctile to 2rittle transition occurs in materials when the temperature is dropped elow a transition temperature.2ig. with little plastic deformation it occurs in stages involving the initiation and propagation of cracks.. Alloying usually increases the ductile5 rittle transition temperature . one has low5cycle fatigue . this type of transition occurs at much higher temperatures than for metals.typ.e.-#E/ of metallic failures . not the full length for an internal flaw. flaws with small radius of curvature are called stress raisers.2ig.endurance limit/ occurs for some materials . • Crac. like the $harpy and Izod tests measure the impact energy re. Fatigue 2atigue is the catastrophic failure due to dynamic .s) H 2 sA 4a@r61@2 where s# is the applied macroscopic stress. the stress amplitude.height/ of the pendulum. • • • • long period of cyclic strain the most usual . ).fluctuating/ stresses.stress raisers/ II. and the stress ratio .uired to fracture a notched specimen with a hammer mounted on a pendulum. minimum and mean stress.uires a large num er of cycles . Lifferent types of /0N curves are shown in 2ig. • The %. %he stress concentration factor is0 . no matter how large the num er of cycles is.incremental in each cycle/ . ut the full length for a surface flaw. ).happens also in ceramics and polymers/ is rittle5like even in ductile metals.'&. ).'"/. In this case. &#: to &#*/. 2ailure at low loads is in the elastic strain regime. Aote that a is &?' the length of the flaw. airplanes./ 2or ceramics. It can happen in machine components.
2ig.">/. %he ehavior can e characterized constants for a given material0 de?dt = 1 sn e(p. add residual compressive stresses. Environ)ental E''ects %hermal cycling causes e(pansion and contraction. the strain increases initially fast with time . if possi le. Solutions0 decrease corrosiveness of medium. • . 1actors That -''ect 1ati !e :i'e Mean stress . E(amples0 tur ine lades. Solution0 polish to remove machining flaws add residual compressi!e stress . add protective surface coating. then increases more slowly in the secondary region at a steady rate . • . sharp transitions and edges/. $orrosion also enhances crack propagation. Neys are the time dependence of the strain and the high temperature. Solution0 eliminate restraint y design use materials with low thermal e(pansion coefficients. y car urizing. 2inally the strain increases fast and leads to failure in the tertiary region. 0eneraliEed Creep +ehavior At a constant stress./ case harden. $hemical reactions induced pits which act as stress raisers.e(posing to appropriate gas at high temperature/ • ./ . Surface defects . $orrosion fatigue.III. nitriding . if component is restrained. ).not covered/ .2ig. n and 2c are .lower fatigue life with increasing smean/. • • • • • • o o • o o o Creep • • $reep is the time5varying plastic deformation of a material stressed at high temperatures.52c?R+/ y the following e(pression. %here is essentially no creep at temperatures elow :#E of the melting point. final failure y fracture Nfinal = Ninitiation D Npropagation Stage I 5 propagation • • • slow along crystallographic planes of high shear stress flat and featureless fatigue surface Stage II 5 propagation crack propagates y repetive plastic lunting and sharpening of the crack tip. Stress and Te)perat!re E''ects $reep ecomes more pronounced at higher temperatures . where 1. ).g.. $reep increases at higher applied stresses.scratches. $haracteristics0 • • Creep rate0 de?dt +ime to %ailure. $rack Iropagation Rate .e.primary or transient deformation/. steam generators. hence thermal stress. . y shot peening.'*.creep rate/.
essentially pure components. etc. Solute0 dissolved. Mo.g. W. -llo$s 'or Hi h8Te)perat!re Use %hese are needed for tur ines in Cet engines. Ma(imum content0 saturation. minor component in solution.e. E(ceeding ma(imum content . Ai. %he important factors are a high melting temperature. System0 set of possi le alloys from same component .like when cooling/ leads to precipitation. the microstructure is specified y the num er of phases.• • . %he way to tell is to cut the material. water.the latter is opposite to what is desira le in low5temperature materials/./ Chapter8I( PH-SE DI-0R-MS I. hypersonic airplanes. their proportions.1 Introd!ction $e%initions $omponent0 pure metal or compound . Some creep resistant materials are stainless steels. polish it to a mirror finish.e. b. ased on $o. Systems with two or more phases are heterogeneous. nuclear reactors. ternary. @n in $u5@n alloy. a single solid solution two separated. 3ne with three components./ Solu ility 6imit0 Ma(imum solute concentration that can e dissolved at a given temperature. and superalloys . in a syrup.& Microstr!ct!re %he properties of an alloy do not depend only on concentration of the phases ut how they are arranged structurally at the microscopy level./ Solvent0 host or maCor component in solution.g. d./ . iron5car on system. Lata E(trapolation Methods . %hus. I.2 Sol!2ilit$ :i)it Effect of temperature on solu ility limit. A two5component alloy is called inary.containing elements of high melting point. refractory metal alloys .. %a/. 2e. Ihase0 part with homogeneous physical and chemical characteristics I. ut also happens in ceramics and polymers.not covered. A inary alloy may e a." Phases 3ne5phase systems are homogeneous. and their arrangement in space. a chemical compound. like A . or mi(tures. %his is the case of most metallic alloys. $u.components etch at a different rate/ and o serve the surface under a microscope. a high elastic modulus and large grain size . together with a solid solution. two separated solid solutions. etch it a weak acid . sugar.. I. c. .
uili rium values that can e derived from the tie5line method. Note0 the fractions are inversely proportional to the length to the oundary for the particular phase. pressure is assumed to e constant at one atmosphere.uid phase also occurs gradually. Sometimes diagrams are given with pressure as one of the varia les.I. c. where diffusion is fast. %he e(ample is the $u5Ai alloy of 2ig.uidus line.uili rium cooling Solidification in the solid D li.'a. %he composition of the li./ Auclei of the solid phase form and they grow to consume all the li. operational. +inar$ Iso)orpho!s S$ste)s %his very simple case is one complete li.2ig. near the same radii. I.uantities of phases in e. -.&:/ and to the invalidity of the tie5line method to determine the composition of the solid phase . In the phase diagrams we will discuss.uidus line. %he composition of the solid and the li.uid phase evolves y diffusion.uid phase occurs gradually upon cooling from the li. definition of e. It is achieved given sufficient time. %hese diagrams do not indicate the dynamics when one phase transforms into another.uid phases. Phase EB!ili2ria E./ . b./ Interpretation o' phase dia ra)s Concentrations4 +ie-line method a.uid a ove the li. If the point in the diagram is close to the phase line. !ut the time to achieve e.uid and solid solu ility. 8ence.the . %his is called a metastable state.uid phase. electronegativity and valence. diffusion in the solid state is very slow. 8owever..uid phase from solid or solid D li.uili rium is the state of minimum energy. the new layers that solidify on top of the grains have the e.uili rium is that of a system that does not change with time during o servation. Read compositions.uid phase.uili rium cooling Solidification in the solid D li. %he solidus line is that elow which the solution is completely solid . locate composition and temperature in diagram In two phase region draw tie line or isotherm note intersection with phase oundaries.inetics is so slow/ that a state that is not at an energy minimum may have a long life and appear to e sta le.cored/ grains . / Aon5e.as can e determined y the tie5line method.isotherm/ o tain ratios of line segments lengths.uili rium composition at that temperature ut once they are solid their composition does not change.uid at the solidus line.does not contain a li..uili rium may e so long . an isomorphous system.it still works for the li. -. Develop)ent o' )icrostr!ct!re in iso)orpho!s allo$s a/ E. %he complete solu ility occurs ecause oth $u and Ai have the same crystal structure .2$$/.uid change gradually during cooling . A less strict. %he li3uidus line separates the li. following the e. Fractions4 le!er rule a. construct tie line . the fraction of that phase is large. %hat is.uili rium. %his lead to the formation of layered . the solution is li. !0uili1rium P$ase Diagrams 1ive the relationship of composition of a solution as a function of temperatures and the . .
-9-.uid and two solid phases e(ist in e.uid is solidified when cooling further. hipoeutectic/ or to the right .g. Note0 • • • the melting point of the eutectic alloy is lower than that of the components . is called an intermediate phase or solid solution. %he eutectic microstructure is lamellar . 3ne that e(ists in the middle. like allotropic transformations . separated from the e(tremes. eutectoid and proeutectoid microstructures. %o o tain the concentration of the eutectic microstructure in the final solid solution.. It also shows as J on top of a horizontal line in the phase diagram. Single5phase regions are separated y '5phase regions.uid U Solid Ihase ' I. eutectic structure develops when cooling elow the eutectic temperature.1A Con r!ent Phase Trans'or)ations Another classification scheme. I. Solid Ihase & D li. 6i.uili rium within a phase field.uid region. An important phase is the intermetallic compound. %he eutectic structure then adds when the remaining li. a52e to g52e/ or melting transitions in pure solids.eutectic5like/ reaction is similar to the eutectic reaction ut occurs from one solid phase to two ne. figures -./.2ig. %he inverse reaction occurs when heating. Develop)ent o' )icrostr!ct!re in e!tectic allo$s $ase of lead5tin alloys. I. Congruent transformation is one where there is no change in composition. solid phases.uili rium at the eutectic composition and the eutectic temperature.e.layered/ due to the reduced diffusion distances in the solid state. When using the lever rules. that has a precise chemical compositions.uili rium. . while in the solid D li.hypereutectic/ form a proeutectic phase efore reaching the eutectic temperature.I.&:.or temperature/.I E!tectoid and Peritectic Reactions %he eutectoid . intermetallic compounds are treated like any other phase. eutectoid phase. -.E/. %here are associated eutectoid temperature . e(cept they appear not as a wide region ut as a vertical line.uid phase to a di%%erent solid phase when cooling.3 +inar$ E!tectic S$ste)s Interpretation0 3 tain phases present. the transition is from a solid D li. Solid Ihase & U Solid Ihase ' D Solid Ihase " %he peritectic reaction also involves three solid in e. /ol!us line0 limit of solu ility !utectic or invariant point. At most two phases can e in e. one draws a vertical line at the eutectic concentration and applies the lever rule treating the eutectic as a separate phase .&.# and &##E/ of the phase diagram.eutectic = easy to melt in 1reek/.7 EB!ili2ri!) Dia ra)s Havin Inter)ediate Phases or Co)po!nds A terminal phase or terminal solution is one that e(ists in the e(tremes of concentration . concentration of phases and their fraction . Alloys which are to the left of the eutectic concentration . A layered.
a lamellar or layered structure of two phases0 a5ferrite and cementite .. 1A. Chapter81A( Phase Trans'or)ations in Metals 1A.>. see &#.1& Develop)ent o' Microstr!ct!res in Iron>Car2on -llo$s %he eutectoid composition of austenite is #. the e.Mechanical properties also depend on the microstructure. It is not important in practice.2$$/ 2e5$ solution d5ferrite . grain growth. and strain5hardening. it is important to note that0 Ferrite is so#t and ductile Cementite is $ard and 1rittle %hus.iron car ide/ or cementite. how ferrite and cementite are mi(ed. $ementite is in reality metasta le.ly it forms perlite. .I.g.1" The Iron=Iron Car2ide 41e=1e"C6 Phase Dia ra) %his is one of the most important alloys for structural applications.&: wt E. $oncentrations are usually given in weight percent.. %he new microstructures that form are discussed in $h.uili rium is not achieved y usual cooling from austenite. %he diagram 2eX$ is simplified at low car on concentrations y assuming it is the 2eX2e"$ diagram.1. 8ypoeutectoid alloys contain proeutectoid %errite plus the eutectoid perlite. 8ypereutectoid alloys contain proeutectoid cementite plus perlite. d5ferrite is only sta le at high temperatures. eutectoid reactions.g.*# and >># $. wt E. I. It is not sta le elow the eutectic temperature .!$$/ 2e5$ solution g5austenite . decomposing into a52e and $ when heated for several years etween . The In'l!ence o' Other -llo$in Ele)ents As mentioned in section >. solid5solution strengthening.#'' wtE.*/ . the strength of 2e9$ alloys increase with $ content and also with the addition of other elements. recrystallization. alloying strengthens metals y hindering the motion of dislocations. Since reactions elow the eutectoid temperature are in the solid phase. solidification of a pure metal. %hus. allotropic transformation.>'> $/ unless cooled rapidly .e.$hapter &#/. Alteration of phase composition .-. An intermetallic compound. com ining these two phases in solution an alloy can e o tained with intermediate properties.e. 2or their role in mechanical properties of the alloy. %he ma(imum solu ility of $ in a5 ferrite is #.2 +asic Concepts Ihase transformations that involve a change in the microstructure can occur through0 • • • Liffusion Maintaining the type and num er of phases .uid 2e5$ solution 2e"$ . When it cools slo. in addition to grain5size refinement.1 Introd!ction %he goal is to o tain specific microstructures that will improve the mechanical properties of a metal. %he possi le phases are0 • • • • • a5ferrite ./ I. Austenite has a ma(imum $ concentration of '. &#.2e"$/. that is.!$$/ 2e5$ solution li.
Liffusion occurs %aster at high temperatures.uare root of time. Atoms are displaced y random . which re. the nuclei grow in size at the e(pense of the surrounding material.g. /pheroidite is a coarse phase that forms at temperatures close to the eutectoid temperature.2e"$ or iron car ide/. %he S5shaped curves . %his reduced grain growth leads to fine5grained microstructure .>.end of the transformation/B thus one can read from the diagrams when the transformation occurs. *. case of supercooling/. Since diffusion is low at low temperatures. or nuclei . when plotting percent of material transformed vs. 1A..%ime5 %emperature5%ransformation/ diagrams .a/ plus cementite . log. nucleation occurs fast and grain growth is reduced . We then need to know the effect of ti)e on phase transformations.*/ 1A.uires two processes0 nucleation and gro. $ is called a constant ecause it does not depend on time.uickly to a given temperature +o efore the transformation occurs. Luring roGth.e. %he horizontal line that indicates constant temperature +o intercepts the %%% curves on the left .the nucleation period is longer at higher temperatures/ and not y diffusion . this phase has a very fine . d. defects/.:..fraction of pearlite vs. Microstr!ct!ral and Propert$ Chan es in 1e8C -llo$s 1A. At lower temperatures nucleation starts to ecome slower. N!cleation involves the formation of very small particles. the logarithm of time. which is an indication that it is controlled y the rate of nucleation.uires diffusion.g..#.since it occurs y diffusion.which occurs faster at higher temperatures/. in which case it is said to e thermally acti!ated."/ are displaced to longer times at higher temperatures showing that the transformation is dominated y nucleation . &#. %his means that the transformations are delayed . %he relatively high temperatures caused a slow nucleation ut enhances the growth of the nuclei leading to large grains. When cooling proceeds elow the eutectoid temperature . %his is similar to rain happening when water molecules condensed around dust particles. and a new phase is formed.e.g5 phase/ to pearlite. At higher temperatures. due to the tortuous path0 d 5 c. &#.microscopic/ microstructure. thus leading to coarse pearlite. where nothing seems to happen. .uate if the transformation rate is slow compared to the cooling rate.e. %he kinetic ehavior often has the S5shape form of 2ig. At low temperatures. is not linear in time t .>'> o$/ nucleation of pearlite starts. %he nucleation phase is seen as an incu ation period.• • Liffusionless Iroduction of metasta le phases . and metastable states are formed.$t/ &?' where c is a constant and $ the diffusion constant. one needs to cool the material . so that e. &#. and keep it at that temperature over time. &#. time. that contains ferrite . in $h. eginning of the transformation/ and the right . +sually the transformation rate has the form r 5 A e-2#R+ .. wtE $/ from the austenite . %his time5dependence of the rate at which the reaction .%ine pearlite/.: also indicates that the transformation occurs sooner at low temperatures. grain oundaries.g. %he displacement of a given atom. %he formation of pearlite shown in fig. ut it depends on temperature as we have seen Ihase transformation re.similar to the temperature dependence of the diffusion constant/. which is hindered at low temperatures/.as would e for a straight traCectory/ ut is proportional to the s. martensitic transformation." The Jinetics o' Solid8State Reactions $hange in composition implies atomic rearrangement... Isother)al Trans'or)ation Dia ra)s We use as an e(ample the cooling of an eutectoid alloy . %his is usually the case in practice.g.inetics. fig.al. bainite.&. fig. diffusion allows for larger grain growth. %he family of S5shaped curves at different temperatures can e used to construct the %%% ./ 2or these diagrams to apply. see &#.phase transformation/ occurs is what is meant y the term reaction .& M!ltiphase Trans'or)ations %o descri e phase transformations that occur during cooling.e.th.uili rium microstructures are seldom o tained. e3uilibrium phase diagrams are inade.
spheroidite is softest. 1A. %he time at the high temperature . caused y stresses induced y differential contraction due to thermal inhomogeneities. ainite is stronger than pearlite and martensite is the strongest of all. Martensite is a different phase. which forms when cooling austenite very fast .warping/ of the metal piece. Contin!o!s Coolin Trans'or)ation Dia ra)s 8 not covered 1A.3 Mechanical +ehavior o' 1e8C -llo$s %he strength and hardness of the different microstructures is inversely related to the size of the microstructures.. followed y cooling in air.*# o$ for some time .3uenching/ to elow a ma(imum temperature that is re. $ooling is done slowly to avoid the distortion .& -nnealin o' 1erro!s -llo$s Aormalizing . Reverting the effect of cold work y process annealing eases further deformation.1 Introd!ction Annealing is a heat treatment where the material is taken to a high temperature. this is called an athermal trans%ormation.and not noticea le/ at room temperature.soaking time/ is long enough to allow the desired transformation to occur. 11. %hus. In the e(amples. 8eating allows recovery and recrystallization ut is usually limited to avoid e(cessive grain growth and o(idation. Chapter 11. 1A. ductility and toughness produce a specific microstructure 11. 2or hypo5 and hypereutectoid alloys. the analysis is the same. 8igh temperatures allow diffusion processes to occur fast.!$%/ structure with interstitial $ atoms. !enefits of annealing are0 • • • relieve stresses increase softness. such that the effect of cold working and other heat treatments is maintained. Martensite is metastable and decomposes into ferrite and pearlite ut this is e(tremely slow . or even cracking.or austenitizing/ consists in taking the 2e5$ alloy to the austenitic phase which makes the grain size more uniform. ut the proeutectoid phase that forms efore cooling through the eutectoid temperature is also part of the final microstructure. fine pearlite is stronger than coarse pearlite.7 Te)pered Martensite Martensite is so rittle that it needs to e modified in many practical cases. an e(tremely fine5grained and well dispersed cementite grains in a ferrite matri(. %he stronger and harder the phase the more rittle it ecomes.uired for the transformation.uires a lot of energy. It forms nearly instantaneously when the re.A very important structure is martensite. Ther)al Processin -nnealin Processes o' Metal -llo$s 11. we used an eutectoid composition. 11. a ody5centered tetragonal .uired low temperature is reachedB since no thermal activation is needed. kept there for some time and then cooled.2 Process -nnealin Leforming a piece that has een strengthened y cold working re. %his is done y heating it to '*#5. .tempering/ which produces tempered martensite." Stress Relie' Stresses resulting from machining operations of non5uniform cooling can e eliminated y stress relief annealing at moderately low temperatures.
which needs to e removed for cooling. 8ardena ility is measured y the Oominy end5. cooling needs to e fast enough to avoid partial conversion into perlite or ainite. Spheroidizing consists in prolongued heating Cust elow the eutectoid temperature.3 Heat Treat)ents Irecipitation hardening is achieved y0 a/ solution heat treatment where all the solute atoms are dissolved to form a single5phase solution. will drop from a high value at the surface to a lower value in the interior of the piece.2ig. $ooling is fastest using water. Irecipitation hardening is also called age hardening ecause it involves the hardening of the material over a prolonged time.uent forming operations. 8ardena ility is the a ility of the material to e hardened y forming martensite. 8eat conductivity measures how fast this energy is transported to the colder regions of the piece. 8igh hardena ility means that the hardness curve is relatively flat.&/ to soften pieces which have een hardened y plastic deformation. &&.*. overaging.aging/. 8eat capacity is the energy content of a heated mass. and which need to e machined. and the hardness. c/ precipitation heat treatment where the supersaturated solution is heated to an intermediate temperature to induce precipitation and kept there for some time . together with the heat capacity and heat conductivity are important in determining the cooling rate for different parts of the metal piece. Precipitation Hardenin 8ardening can e enhanced y e(tremely small precipitates that hinder dislocation motion... since it is usually accompanied y large thermal gradients.uirements for precipitation hardening are0 %his is called • apprecia le ma(imum solu ility .2ig. the interior may cool too slowly so that full martensitic conversion is not achieved. %he precipitates form when the solu ility limit is e(ceeded. the martensitic content. %he re. &&. / rapid cooling across the solvus line to e(ceed the solu ility limit. eventually the hardness decreases. %his achieves ma(imum softness that minimizes the energy needed in su se. which results in the soft spheroidite structure discussed in Sect.2ull anneal involves taking hypoeutectoid alloys to the austenite phase and hypereutectoid alloys over the eutectoid temperature . If the piece is thick. &#. 8ardena ility is then given as the dependence of hardness on distance from the . %hus. then oil. 2ast cooling rings the danger of warping and formation of cracks. Hardena2ilit$ %o achieve a full conversion of austenite into hard martensite. 11.uench test . which prevent diffusion.'/. %he shape and size of the piece. and then air. 11. If the process is continued for a very long time. %his leads to a supersaturated solid solution that remains sta le .metasta le/ due to the low temperatures.uenched end. In'l!ence o' K!enchin Medi!)* Speci)en SiEe* and 0eo)etr$ %he cooling rate depends on the cooling medium. Heat Treat)ent o' Steels 1.
2rom ta le &".5/. %he ionic character is given y the difference of electronegativity etween the cations . Cera)ics 8 Str!ct!res and Properties 12. r3.= #.D/ and anions . called zones.= #. Chapter 12.e.. with a proportion that depends on the particular ceramics. clays and sand. so r$?rA = #. r$ = rAa = #. %his leads to contact.silicates/ occur in rocks.. rA =r$l. Aging that occurs at room temperature is called natural aging. in the Aa$l structure . the steps in the processing of alloys are usually0 • • • solution heat treat and .#: nm.&)& nm. configurations where anions have the highest num er of cation neigh ors and viceversa. soils. machining. to distinguish from the artificial aging caused y premeditated heating. ut will not e included in the test.' this implies coordination num er = :.. that is tetrahedral coordination . as o served for this rock5salt structure. . r$?rA. %he parameter that is important in determining contact is the ratio of cation to anion radii.&: nm. rittle and composed of more than one element .*.7 Mechanis) o' Hardenin Strengthening involves the formation of a large num er of microscopic nuclei." Silicate Cera)ics 3(ygen and Silicon are the most a undant elements in EarthQs crust. &". uses more energy when the material is hard. It is accelerated at high temperatures.uench do needed cold working efore hardening do precipitation hardening E(posure of precipitation5hardened alloys to high temperatures may lead to loss of strength y overaging. Jery ionic crystals usually involve cations which are alkalis or alkaline5earths . 3ther structures were shown in class.' gives the coordination num er and geometry as a function of r$?rA.2ig.-/. $ovalent onds involve sharing of valence electrons. %he ond is weekly ionic. rSi = #.g.2 Cr$stal Str!ct!res $eramic onds are mi(ed. &". 2rom ta le &". %a le &".&#' nm. %heir com ination .= #. 8ardening occurs ecause the deformation of the lattice around the precipitates hinder slip.2ig. 11.first two columns of the periodic ta le/ and o(ygen or halogens as anions. with Si :D as the cation and 3'5 as the anion.. etc.').• solu ility curve that falls fast with temperature composition of the alloy that is less than the ma(imum solu ility 11.1 Introd!ction $eramics are inorganic and non5metallic materials that are commonly electrical and thermal insulators. 12. so r$?rA. ionic and covalent.I Miscellaneo!s Considerations Since forming.'/. two in Al'3"/ Cera)ic Str!ct!res 12.' this implies coordination num er = . 2or e(ample. %he uilding criteria for the crystal structure are two0 • • • maintain neutrality charge alance dictates chemical formula achieve closest packing the condition for minimum energy implies ma(imum attraction and minimum repulsion.
%his is more likely for similar ionic radii since this minimizes the energy re.like Si.. van der Waals onding etween layers using the fourth electron. 1raphite has a layered structure with very strong he(agonal onding within the planar layers .condition known as stoichiometry/. with high inde( of refraction semiconductor . ottles.placing large anions in an interstitial position re. 12. cheaper production method include hard coatings for metal tools. and microelectronics. also known as fullerene or ucky5 all .uartz/ or amorphous. &".uires the e(penditure of a large amount of energy. Lefects will appear if the charge of the impurities is not alanced. .creation of un alanced charges re. A recently .&-)*/ discovered formed of car on is the $. for instance.y-de%ect is the a pair of near y cation and anion vacancies. • • • • • • • diamond5cu ic structure . A Fren. Applications include furnaces. diamond. Soda glasses melt at lower temperature than amorphous Si3 ' ecause the addition of Aa'3 .g.& Car2on $ar on is not really a ceramic.after the architect !uckminster 2uller who designed the geodesic structure that $.&/. Silica can e crystalline . . 2uture applications are as a structural material and possi ly in microelectronics.uired for lattice distortion. %o minimize energy.# resem les.transforms to car on when heated/ Synthetic diamonds are made y application of high temperatures and pressures or y chemical vapor deposition.Si 3:/:5. %heir formation is strongly affected y the condition of charge neutrality . electrodes in atteries. ut an allotropic form.# molecule.unlike ceramics/ transparent in the visi le and infrared. 1raphite is a good electrical conductor and chemically sta le even at high temperatures. 2uture applications of this latter. %his leads to easy interplanar cleavage and applications as a lu ricant and for writing . every o(ygen atom is shared y adCacent tetrahedra. may Liamond has very interesting and even unusual properties0 e thought as a type of ceramic. ultra5low friction coatings for space applications. 12.Si3'/. Introduction of impurity atoms in the lattice is likely in conditions where the charge is maintained. and atmospheric contaminants/ that result during cooling from the .uires a lot of energy in lattice distortion/. internal pores.%he tetrahedron is charged0 Si:D D : 3'5 Y . 1e/ covalent $5$ onds highest hardness of any material known very high thermal conductivity .pencils/. $harge neutral defects include the 2renkel and Schottky defects.micro5cracks.el-de%ect is a vacancy5 interstitial pair of cations . Silicates differ on how the tetrahedra are arranged. %his is the case of electronegative impurities that su stitute a lattice anions or electropositive su stitutional impurities.soda/ reaks the tetrahedral network.can e doped to make electronic devices/ metasta le . Cera)ic Phase Dia ra)s 4not covered6 12. I)per'ections in Cera)ics Imperfections include point defects and impurities. the effect of non5stoichiometry is a redistri ution of the atomic charges ./ 2ullerenes and related structures like ucky5onions amd nanotu es are e(ceptionally strong. as in glass. rocket nozzles.3 +rittle 1ract!re o' Cera)ics %he rittle fracture of ceramics limits applications. A lower melting point makes it easy to form glass to make. In silica.using " of the " onding electrons/ and weak..2ig. It occurs due to the unavoida le presence of microscopic flaws . A /chott.. due to the unusual properties that result when fullerenes are doped with other atoms. Aon5stoichiometry refers to a change in composition so that the elements in the ceramic are not in the proportion appropriate for the compound . 12.e.
stone locks in the pyramids/.2 H$drocar2on Molec!les Most polymers are organic. $eramics 5 Applications and Irocessing 1". Pol$)er Str!ct!res 1&. Strengthening y glass tempering is done y heating the glass a ove the glass transition temperature ut elow the softening point and then . &:. tries to contract while in a plastic state after the e(terior has ecome rigid. long elongation/.. %he transparency to light of many ceramics leads to optical uses."/. annealing is used at elevated temperatures is used to remove stresses. $hapter &". like common glass deform y viscous flow .:/.perpendicular to the applied stress/ is usually transgranular. along cleavage planes. %he key factor is the very low production cost and useful properties . %he flaws cannot e closely controlled in manufacturingB this leads to a large varia ility . enzymes.e. like those caused y inhomogeneous temperatures during cooling. that is.1 Introd!ction $eramics properties that are different from those of metals lead to different uses. a crack has first to overcome the residual compressive stress. proteins.like very high5density li. etc. through a viscous stage. %o fracture.melt. Aon5crystalline ceramics. %hese molecules can have single. com ination of transparency and fle(i ility. Artificial polymers are made mostly from oil. %he specific volume does not have an a rupt transition at a temperature ut rather shows a change in slope at the glass-transition temperature .2ig. the e(terior tiles of the Shuttle or iter. photographic cameras. or triple car on onds. In structures.electrostatic/ potentials. %heir use has grown e(ponentially. like in windows. telescopes and microscopes. etc.uids/. eyeglass lenses. such as under fle(ure. and formed from hydrocar on molecules. making tempered glass less suscepti le to fracture. A saturated hydrocarbon is one where all onds are single. cellulose. rather than temperature . which is difficult due to the structure and the strong local . %here is very little plastic deformation efore fracture. %his causes residual compressive stresses on the surface and tensile stresses inside.scatter/ in the fracture strength of ceramic materials. Jiscosity decreases strongly with increases temperature. %his improvement leads to use in automo ile windshields. without a clear melting temperature. especially after WW'. Ilastic deformation in crystalline ceramics is y slip.uenched in an air Cet or oil ath. %his makes ceramics good structural materials under compression .& Heat Treatin 0lasses Similar to the case of metals. glass doors. wood.2 0lass Properties A special characteristic of glasses is that solidification is gradual. 1". %he melting point.1 Introd!ction Iolymers are common in nature. leather. ut not in conditions of tensile stress.g. 1&.e.. dou le. 1ood thermal insulation leads to use in ovens. %he flaws need to crack formation. working point. and crack propagation .. 1ood electrical isolation are used to support conductors in electrical and electronic applications. softening point and annealing point are defined in terms of viscosity. ru er.2ig. starches. Chapter 1. silk. &:.. cotton. %he compressive strength is typically ten times the tensile strength. which cools later than the outside. in the form of wood. %he interior. %he good chemical inertness shows in the sta ility of the structures thousands of years old.g. and depend on glass composition. 1". designs must e done for compressive loads. ricks in houses. the .
& The Che)istr$ o' Pol$)er Molec!les E(amples of polymers are polyvinyl chloride .. Iolymers are composed of asic structures called mer units. %he ack one is a string of car on atoms. Molec!lar #ei ht %he mass of a polymer is not fi(ed. polypropylene.IJ$/.>/0 • • • • linear .*/. 1&. macromolecules that have internal covalent onds. zig5zag structure . etc. %he average molecular weight can e o tained y averaging the masses with the fraction of times they appear . fle(i le. 1&.%a le &*.2ig. nylon and polystyrene. In contrast..num er5average/ or with the mass fraction of the molecules . paraffins and resins have intermediate masses. $n8'nD' . are solid/. &*. 1&. Random kings and coils lead to entanglement.end5to5end.2ig.7 Molec!lar Con'i !rations %he regularity and symmetry of the side5groups can affect strongly the properties of polymers.dou le and triple onds are very rigid/ .due to radiation. &*. like IJ$. 1&. 3. ut is distri uted around a mean value. An e(ample is Iolymers of low mass are li.similar to highly cross5linked structures/." Pol$)er Molec!les Iolymer molecules are huge. since polymer molecules have different lengths. nylon/ ranched cross5linked . often single onded. etc. Wa(es.I%2E or %eflon/. &*.uid or gases.& /. and is o tained mass of the polymer y the mass of a mer unit. 1&. called free5radicals. $hains are represented straight ut in practice they have a three5 dimensional. like in the spaghetti structure shown in 2ig.called high5polymers. methyl. Side groups are atoms or molecules with free onds./ network . the configuration is called isostatic .. Molec!lar Shape Iolymers are usually not linearB ending and rotations can occur around single $5$ onds . 1&. the molecule is a copolymer. poly5tetra5chloro5ethylene .&/.num er of atoms is ma(imum . y dividing the average ut in a different arrangement.2ig.or saturated/.3 Molec!lar Str!ct!re %ypical structures are . 2or most polymers. Among this type are the paraffin compounds. these molecules form very long chains.called. &*.. When there is more than one type of mer present. the molecule is called a homopolymer. %he degree o% polymeri7ation is the average num er of mer units. those of very high mass . A molecule with Cust one mer is a monomer. non5saturated hydrocar ons contain some dou le and triple onds. When all the mers are the same. like 8. a weight fraction/. If the radicals are linked in the same order. improperly. 6somers are molecules that contain the same molecules utane and iso utane. vulcanization.
%he stress5strain ehavior can e rittle.fig.elastomeric or ru er5like/.. lock. linear polymers with small side groups.&'/. Mechanical properties change dramatically with temperature.. or polymers with ulky side groups. Chapter 1. $hain disorder or misalignment. decreasing the strain rate has the same influence on the strain5strength characteristics as increasing the temperature0 the material ecomes softer and more ductile.&&/.lamellae/ . .uired in the crystalline state. the radical groups alternative sides in the chain.2 Stress8Strain +ehavior %he description of stress5strain ehavior is similar to that of metals.micelles/ are em edded in an amorphous matri( . In the atactic configuration. &*. 1&.2ig. ut elongation can e up to &### E in some cases.:/ are chain5folded crystallites in an amorphous matri( that grow radially in spherical shape Zgrains[..&#/. see 2ig. which is common. and environmental conditions.. $rystalline polymers are denser than amorphous polymers. polymers with at least two different types of mers can differ in the way the mers are arranged. &*..2ig. atactic polymers. &.modulus/ and tensile strengths are orders of magnitude smaller than those of metals. which are not too long form crystalline regions easier than ranched. leads to amorphous material since twisting.. plastic and highly elastic ..2ig.11 Pol$)er Cr$stals Lifferent models have een proposed to descri e the arrangement of molecules in semicrytalline polymers. 1&. alternating.In a stereoisomer in a syndiotactic configuration. %he tensile strength is defined at the fracture point .shows different arrangements0 random. so the degree of crystallinity can from the measurement of density. &*. with crystalline regions dispersed within amorphous material. %ensile modulus .like in the li.2ig. ut a very important consideration for polymers is that the mechanical properties depend on the strain rate.2ig. &. network. %hus. temperature. &.. 2ig. Spherulites . &. Pol$)ers. random copolymers." De'or)ation o' Se)icr$stalline Pol$)ers Many semicrystalline polymers have the spherulitic structure and deform in the following steps .'/ and can e lower than the yield strength. 1.1A Pol$)er Cr$stallinit$ $rystallinity in polymers is more comple( than in metals . and graft. 1&."/. &*.2ig. Characteristics* -pplications and Processin e o tained 1. Iolymer single crystals grown are shaped in regular platelets . the radical groups are positioned at random. In general.semicrystalline/.1 Introd!ction 1. the crystallites . In the fringed5micelle model. &.I Copol$)ers $opolymers. kinking and coiling prevent strict ordering re. Iolymer molecules are often partially crystalline . going from glass5like rittle ehavior at low temperatures ..&*.:/0 • • elongation of amorphous tie chains tilting of lamellar chain folds towards the tensile direction .uid5nitrogen demonstration/ to a ru er5like ehavior at high temperatures .
shape of side groups size of molecule side ranches. E(amples are cross5linking . 1.& strengthen the polymer. single vs. %hermosets are harder. 1.e. At high temperatures the ehavior is viscous. %he melting temperature increases with the rate of heating. heating increases the tensile modulus and yield strength.. Aucleation ecomes slower at higher temperatures. is termed !iscoelastic. as cross5linking hinder ending and rotations. like li. 3 stacles to the steps mentioned in 1.2ig..2ig. defects cross5linking Rigid chains have higher melting temperatures.g. more dimensionally sta le. Melting involves reaking of the inter5chain onds.*/. the ehavior.uids. 1. 2or undrawn polymers. $rystallinity increases strength as the secondary onding is enhanced when the molecular chains are closely packed and parallel.• • separation of crystalline lock segments orientation of segments and tie chains in the tensile direction %he macroscopic deformation involves an upper and lower yield point and necking.. dou le onds/ size. &.. Ire5deformation y drawing.thermoplasts/ soften reversi ly when heated .aligned chains have more van der Waals inter5chain onds/ and a large mass .* and #....harden when cooled ack/ +hermosetting polymers . At intermediate temperatures. Cr$stalliEation* Meltin * and 0lass Transition Pheno)ena $rystallization rates are governed y the same type of S5curves we saw in the case of metals ..3 5iscoelasticit$ At low temperatures. analogous to strain hardening in metals. &. Jiscoelasticity is characterized y the viscoelastic rela(ation modulus !r ? s4t6@eA. and reduces the ductility 5 opposite of what happens in metals. and more rittle than thermoplasts. %he melting ehavior of semicrystalline polymers is intermediate etween that of crystalline materials .>/. thickness of the lamellae.slight change in slope of density at the glass5transition temperature/. the neck gets stronger since the deformation aligns the chains so increasing the tensile stress leads to the growth of the neck.. like a ru ery solid. %he glass transition temperature is etween #. +nlike the case of metals.longer molecules have more inter5 chain onds/. like glass. increases strength y orienting the molecular chains.. and depends on the temperature at which the polymer was crystallized. so the glass and melting temperatures depend on0 • • • • • chain stiffness .sharp density change at a melting temperature/ and that of a pure amorphous material . . at small elongation. 1. Ther)oplastic and Ther)osettin Pol$)ers +hermoplastic polymers . amorphous polymers deform elastically. .thermosets/ harden permanently when heated.& 1actors that In'l!ence the Mechanical Properties o' Pol$)ers %he tensile modulus decreases with increasing temperature or diminishing strain rate.) of the melting temperature.
. crosslinking of the elastomeric polymer is achieved y an irreversi le chemical reaction usually at high temperatures . 1. %hermoplasts can have oth rittle and ductile fracture at low temperatures and ductile fracture at high of polymers is much lower than that of metals. Elastomers are thermosetting due to the cross5linking. synthetic ru ers are strengthened y adding car on lack. where monomer units are attached one at a time condensation polymerization. y stepwise intermolecular chemical reactions that produce the mer units. 2or automo ile applications.I 1ract!re o' Pol$)ers As other mechanical properties... %o e elastomeric. the fracture strength 2racture also starts with cracks at flaws. a ehavior first o served in natural ru er. .. %he S atoms are the ones that form the ridge cross5links. 1. and a to ductile transition over a narrow temperature range.hence \vulcanQ/. etc. 2atigue is similar to the case of metals heating which leads to softening... the polymer needs to meet several criteria0 • • • • must not crystallize easily have relatively free chain rotations delayed plastic deformation y cross5linking .If the material is strained to a value e #.12 Elasto)ers In !ulcani7ation.Izod or $harpy tests/.&*/. e a ove the glass transition temperature 1.it is found that the stress needs to this constant value of strain .see figs.. It may occur y0 rittle ut at reduced loads and is more sensitive to fre. $razing a sor s energy thus increasing the fracture strength of the polymer. &. Elastic elongation is due to uncoiling. scratches. 1lassy thermosets have rittle temperatures.2ig. and usually involving the addition of sulfur compounds. 1lassy thremoplasts often suffer gra7ing efore rittle fracture.11 Pol$)eriEation Iolymerization is the synthesis of high polymers from raw materials like oil or coal. 1.chain5reaction/ polymerization. 2racture involves reaking of covalent onds in the fracture ehaviors. Ru ers ecome harder and e(tend less with increasing sulfur content.7 De'or)ation and Elasto)ers Elastomers can e deformed to very large strains and the spring ack elastically to the original length. untwisting and straightening of chains in the stress direction. &.&& and &.uency due to • • addition .achieved y vulcanization/.1A Miscellaneo!s Characteristics Iolymers are rittle at low temperatures and have low impact strengths . $razes are associated with regions of highly localized yielding which leads to the formation of interconnected microvoids . %he time5dependent creep modulus is given y !c ? sA@e4t6.&'/.t/ is measured. chains.. the stress is kept constant at s# and the change of deformation with time e. 1. e reduced with time to maintain In viscoelastic creep.
2 :ar e8Particle Co)posites Iroperties are a com ination of those of the components. ductile ferrite to get a superior material. Aew 5 8igh5tech materials. light. Co)posites 1. strong.In silicone ru ers. which act y restraining the movement of the matri(.polymer5polymer/.. fi ers/ Iroperties of composites depend on • • • properties of phases geometry of dispersed phase .. known for S *### years.aligned or random/ structural . %he rule o# mixtures predicts that an upper limit of the elastic modulus of the composite is given in terms of the elastic moduli of the matri( . dispersion5strengthened composites.'m/ and the particulate ..e. %he matri( ears the maCor portion of the applied load and the small particles hinder dislocation motion. containing &## nm particles.. if well onded. 1. limiting plastic deformation. the ack one $ atoms are replaced y a chain of alternating silicon and o(ygen atoms. orientation/ amount of phase $lassification of composites0 three main categories0 • • • particle5reinforced .particulates. +sual composites have Cust two phases0 rittle cementite with • • matri( . paper. corrosion resistant/.large5particle and dispersion5strengthened/ fi er5reinforced .continuous . which com ines hard. %he idea that a etter com ination of properties can e achieved is called the principle of com ined action. Aatural composites0 wood . Chapter 1. soft.aligned/ and short fi ers . ones . %hey fall in two categories depending on the size of the particles0 • • large5particle composites.'p/ phases y0 !c ? !)2) F !p2p where Vm and Vp are the volume fraction of the two phases.g.particle size. A lower ound is given y0 . A type of composite that has een discussed is perlitic steel. similar to what was discussed under precipitation hardening. distri ution.polymer5ceramics/.continuous/ dispersed phase .laminates and sandwich panels/ Particle8rein'orced co)posites %hese are the cheapest and most widely used. engineered to specific applications 3ld 5 rick5straw composites.1 Introd!ction %he idea is that y com ining two or more distinct materials one can engineer a new material with the desired com ination of properties . %hese elastomers are also cross5linked and are sta le to higher temperatures than $5 ased elastomers.
Iroperties depend on how well it is mi(ed. there is a need for high strength per unit weight . clay and lime5 earing minerals fired to &*## o $ . Ire5stressed concrete shapes are usually prefa ricated. 1.stone and sand/ allows etter packing factor than when using particles of similar size. tungsten car ide or titanium car ide ceramics in $o or Ai. 1. and it is very cheap. &>.. 1i2er8rein'orced co)posites In many applications. Rein%orced concrete is o tained y adding steel rods. it hardens at room temperature and even under water. %he use of different size . A common use is in railroad or highway ridges. too much 5 e(cessive porosity. and applying pressure during hardening.gravel and sand. wires. rittle/ in a metal matri( .. It sets into a solid in minutes and hardens slowly .takes : months for full strength/. Iortland cement is a fine powder of chalk.using finer powder.specific strength/." 5 modulus of composite of W$ particles in $u matri( vs. $oncrete is improved y making the pores smaller .strong. Romans made cement y mi(ing lime . It forms a paste when dissolved in water. adding polymeric lu ricants. Steel has the advantage of a similar thermal e(pansion coefficient.& In'l!ence o' 1i2er :en th . like in aircraft parts. Pre-stressed concrete is o tained y applying tensile stress to the steel rods while the cement is setting and hardening. In its general from. so there is reduced danger of cracking due to thermal stresses. made of a cement matri( that onds particles of different size . ductile/ that enhances toughness.soft. W$ concentration. %he strength depends on the fi er length and its orientation with respect to the stress direction. +sed in auto tires. %he disadvantages are that it is weak and rittle. mesh." Dispersion8Stren thened Co)posites +se of very hard.$a3/ with volcanic ice. and that water in the pores can produce crack when it freezes in cold weather. ena ling it to sustain tensile loads without fracturing. and water. cement is a fine mi(ture of lime. 'ein#orced ru11er is o tained y strengthening with '#5*# nm car on5 lack particles. Concrete %he most common large5particle composite is concrete.calcinated/./ $ement was already known to the Egyptians and the 1reek.!c ? !)!p @ 4!p2) F !)2p6 2ig. When the tensile stress is removed. %he advantage of cement is that it can e poured in place.and soft/ matri( reinforced with stiff fi ers. small particles to strengthen metals and metal alloys. %hey are used for cutting tools for hardened steels. %he efficiency of load transfer etween matri( and fi er depends on the interfacial ond. Iarticles like o(ides do not react so the strengthening action is retained at high temperatures. %his can e achieved y composites consisting of a low5density . alumina. %he effect is like precipitation hardening ut not so strong. 2or instance. silica. the concrete is left under compressive stress. $oncrete is cement strengthened y adding particulates. and the amount of water0 too little 5 incomplete onding. Cermets are composites of ceramic particles .
Electrical Properties Electrical Cond!ction &>. %his makes the force on the fi er e minimum at the ends and ma(imum in the middle. at low values of V.. ut not very stiff and cannot e used at high temperatures. &>. which have the highest specific module .. %his occurs at a distance from the fi er. In'l!ence o' 1i2er Orientation %he composite is stronger along the direction of orientation of the fi ers and weakest in a direction perpendicular to the fi er. 2or discontinuous. Nevlar. the current is proportional to V. according to 3hm7s law0 I = 2@' where R is the electrical resistance. 1.$2R$/ use car on fi ers. random fi ers. defined as the minimum length at which the center of the fi er reaches the ultimate . low cost and good properties. %o achieve effective strengthening and stiffening. inert. the properties are isotropic. 1. aircraft components. a current of magnitude 6 flows.12R$/ are strong. the strain is limited y the fi er. rake and clutch linings. ' = rl@A .module divided y weight/. like in the tug5of5 war game. %he pull is uniform over the area of the fi er. allow high temperature use.. Applications include fishing rods.tensile/ strength sf. Right ne(t to the fi er. a more unified condition for effective strengthening is that the aspect ratio of the fi er is l#d 8 sf ?' tm. %hus. Chapter 13.length l and area A through which the current passes/. It is a composite of strong and fle(i le cellulose fi ers . golf clu s. when the matri( achieves the ma(imum shear strength tm0 lc = s' d @2 t) Since it is proportional to the diameter of the fi er d. Applications include auto and oat odies. Applications include ullet5proof vests.linear polymer/ surrounded and held together y a matri( of lignin and other polymers. Pol$)er MatriC Co)posites 6argest and most diverse use of composites due to ease of fa rication.' 3hmQs 6aw When an electric potential V is applied across a material. aircraft components. a shear stress appears in the matri( that pulls from the fi er. the fi ers must e larger than a critical length lc. Wood is ten times stronger in the a(ial direction than in the radial or tangential directions. tires. %he properties are anisotropic and vary widely among types of wood.2ig. $2R$ are strong. 1lass5fi er reinforced composites . corrosion resistant and lightweight.. R depends on the intrinsic resisti!ity r of the material and on the geometry . $ar on5fi er reinforced composites .Aormally the matri( has a much lower modulus than the fi er so it strains more. Wood0 %his is one of the oldest and the most widely used structural material. In most metals. and aremid5fi er composite . for a composite under tension.-/ can e used as te(tile fi ers.
3hm7s law can then e e(pressed in terms of the current density : 5 6#A as0 3=s! %he conductivity is one of the properties of materials that varies most widely. there is an energy gap etween the valence and conduction ands.: Electronic and Ionic $onduction In metals. like light of sufficiently small wavelength. %he electric field in the material is '5V?l. . In metals there are empty states Cust a ove the 2ermi levels. At room temperature.uires 'g?'. In metals. and they also feel the electric field produced y their own nucleus and that of the other atoms.g.oles are vacant states in the valence and that are created when an electron is removed. the distance etween atoms in the solid.see Sect. car on vs.uires that electrons e a le to gain energy in an electric fieldB this is not possi le in these materials ecause that would imply that the electrons are promoted into the for idden and gap. &>.+ S **. their valence electrons interact due to $oulom forces. say. If this pro a ility is.W5m/ for good electrical insulators.&*/. to &#: . 2irst. or from energetic radiation. thus the name ionic conduction .+ has the usual meaning. Si vs. %he second effect. %he precise location of the ands and and gaps depends on the type of atom . the current is carried y electrons. $onduction in insulators is y electrons in the conduction and and y holes in the valence and. and the atomic arrangement . the valence electrons of atoms form wide valence ands when they form a solid. Al/. so energy is needed to promote an electron to the conduction and.&>.5'g?'. As a result of all these effects. %he num er of electrons participating in electrical conduction is e(tremely small. %he pro a ility that an electron reaches the conduction and is a out e(p.+/ where 'g is the and gap and . due to the Iauli e(clusion principle. from &#> .e. the valence and is filled. &>. $onduction in %erms of !and and Atomic !onding Models $onduction in metals is y electrons in the conduction and. diamond/. and no more electrons can e added. the electrons occupy states up to the Fermi le!el. %he ands are separated y gaps. $onduction occurs y promoting electrons into the conduction band. that starts at the 2ermi level..e. %he promotion energy is negligi ly small so that at any temperature electrons can e found in the conduction and. %his re. constraining the electrons to a small volume raises their energy.+ = #. Semiconductors have conductivities in the range &# 5. .) eJ can e used as the condition for an insulator.g. and hence the name electronic conduction. A working definition for the difference etween semiconductors and insulators is that in semiconductors.* Energy !and Structures in Solids When atoms come together to form a solid.. electrons can reach the conduction and at ordinary temperatures. the charge carriers are ions. In ionic crystals.which include the energy/. y 8eisen erg7s uncertainty principle. %his energy may come from heat. this is called promotion.. '. where in insulators they cannot. where electrons can e promoted." Electrical $onductivity %he electrical conducti!ity is the inverse of the resistivity0 s 5 9#r. In insulators. &-.W5m/. separated y the valence and y an infinitesimal amount.W5m/ typical of metals to '# . limits the num er of electrons that can have the same property . &>. W &# 5': one would not find a single electron in the conduction and in a solid of & cu ic centimeter. where electrons cannot e(ist. In addition. following Iauli7s principle. In semiconductors and insulators. Electrical conduction re.uantum mechanical effects happen. two specific .#* eJB thus 'g S '.
.in vacuum. as a sum of resistivities due to thermal vi rations. grain oundaries impurities 3ne can e(press the total resistivity rtot y the Matthiessen rule. thus intrinsic means pure. When high resistivity materials are needed. Intrinsic means that electrical conductivity does not depend on impurities. for applications where mechanical strength is important. the alloy $u!e is used.> Electron Mo ility ond. and with alloying. %he electrical conductivity is0 s ? n L eL m e where n is the concentration of electrons . semiconductors have covalent partially ionic onded. 2ig. vd? = me ! which means that there is a friction force proportional to velocity. like in electrical heaters. in the opposite direction to the field ecause of their negative charge. which can e0 o o o o atoms displaced y lattice vi rations vacancies and interstitials dislocations.lower resistivity/ is silver. which has a nearly as good r. especially those that operate at high temperature. which is half as good as $u. nichrome . %hus electrons move randomly ut with a net drift in the direction opposite to the electric field. In an electric field. Since it is very e(pensive. in the a sence of o stacles . &>. %he electrons scatter y collisions with atoms and vacancies that change drastically their direction of motion. %he conductivity of an intrinsic semiconductor is0 . impurities and dislocations. %he drift velocity is constant. $opper is soft so.Electrical $haracteristics of $ommercial Alloys %he est material for electrical conduction . %o achieve low r it is necessary to remove gases occluded in the metal during fa rication.n is used to indicate that the carriers of electricity are negative particles/. the situation is different.) illustrates how the resistivity increases with temperature. $onduction is y electrons and holes. whereas insulators usually are Electrons are accelerated in an electric field '. where e is the electric charge. 3ne of the effects of this is that electrons do not scatter from a perfect lattice. &>. &-.) Electrical Resistivity of Metals %he resistivity then depends on collisions.!esides having relatively small 'g. like inside a %J tu e/ the electron speeds up continuously in an electric field. %hey scatter y defects. In e(trinsic semiconductors the conductivity depends on the concentration of impurities. &>. with deformation. copper is preferred.ual to the electric field times a constant called the mobility m. e. at an only modest increase in r. %his force produces a constant acceleration so that. %he force acting on the electron is 5e'.Ai$r/ or graphite are used.&# Intrinsic Semiconduction Semiconductors can e intrinsic or extrinsic. In a solid. %his friction translates into energy that goes into the lattice as heat. &>. %his is the way that electric heaters work. electrons and holes move in opposite direction ecause they have opposite charges. Al is also more resistant to corrosion. Muantum mechanics tells us that electrons ehave like waves. When weight is important one uses Al.
eventually the ehavior is dominated y the intrinsic type of conductivity. %hey are made y doping. Since this hole is unlike a hole in the matri(. %he dependence of conductivity on temperature is like other thermally activated processes0 s ? A eCp4=! @2&56 where A is a constant . oth the impurity levels and valence electrons are ionized.me D mh/ .only for intrinsic semiconductors/. one due to the thermal promotion of electrons from donor levels or holes from acceptor levels. a hole is produced %hus0 n?p %hus. &>. It is called p-type if pSn and n-type if nSp. in addition to this dependence. s = ' n ]e] . %he energy level of the donor state is close to the conduction and. At high temperatures. %his means that conduction occurs mainly y the holes .s ? n LeL me F p LeL mh where p is the hole concentration and mh the hole mo ility. 3ne finds that electrons move much faster than holes0 me 4 mh In an intrinsic semiconductor. elements in columns J and JI of the periodic ta le are donors for semiconductors in the IJ column. %his means that the conduction occurs mainly y the donated electrons .ard bias. from which the and gap energy can e determined. If the positive side of a attery is connected to the p-side. %wo common methods of doping are diffusion and ion implantation. %he ond with the neigh ors is incomplete and so they can capture or accept electrons from adCacent silicon atoms. Si and 1e. it does not move easily y capturing electrons from adCacent atoms.&: Semiconductor Levices A semiconductor diode is made y the intimate Cunction of a p-type and an n5type semiconductor . an e(trinsic semiconductor may have different concentrations of holes and electrons. &>.ionized/ easily at room temperature. %he dependence on temperature is also e(ponential ut it eventually saturates at high temperatures where all the donors are emptied or all the acceptors are filled.the mo ility varies much more slowly with temperature/. the addition of a very small concentration of impurity atoms. . a situation called %or. &?+ produces a straight line of slope 'g?'. like ! in Si. the intensity of the electrical current that passes through the material depends on the polarity of the applied voltage.the ionized donor/ ehind. %he energy level of the acceptor is close to the valence and. with * valence electrons. is an electron donor in Si since only : electrons are used to ond to the Si lattice when it su stitutes for a Si atom. 2or instance phosphorous. E(cess holes are produced y su stitutional impurities that have fewer valence electrons per atom than the matri(.&& E(trinsic Semiconduction +nlike intrinsic semiconductors. %his means that at low temperatures. where they recom ine .annihilate/. E(trinsic semiconductors have.&' %he %emperature Jariation of $onductivity and $arrier $oncentration %emperature causes electrons to e promoted to the conduction and and from donor levels. E(cess electron carriers are produced y su stitutional impurities that have more valence electron per atom than the semiconductor matri(. &>. so that the electron is promoted .thus n-type/. the diode y the promotion of each electron to the conduction and. %hey are called acceptors. %his is the case of elements of group II and III in column IJ semiconductors.an n-p :unction<. %hus. a large amount of current can flow since holes and electrons are pushed into the Cunction region. e(trinsic semiconductors have larger conductivity than intrinsic semiconductors. leaving a hole . Ilotting ln s vs. so that an electron may easily hop from the valence and to complete the ond leaving a hole ehind. +nlike a metal. If the polarity of the voltage is flipped.thus p-type/. or holes to acceptor levels. ut since the impurities are very low in num er and they are e(hausted.
A small voltage applied to the ase has a large effect on the current passing through the transistor. Another common device is the M3S2E% transistor where a gate serves the function of the ase in a Cunction transistor.D3 and 93/ separated at a distance d is p 5 3d.'#/ is used to convert alternating current into direct current.&. At low temperatures.&) 2ield Jectors and Iolarization %he dipole moment of a pair of positive and negative charges .displace the negative and positive charge so that their center of gravity is different/. A p-n-p :unction transistor contains two diodes ack5to5 ack. &>. 8igh temperatures produce more vacancies and higher ionic conductivity.2ig. &>. In terms of the voltage etween the plates. due to the deposition of moisture that contains impurity ions. &>. separated y a small distance l. are charged develops etween the plates ! ? D@eeA where $ 5 2?A.''/. &-.operates under re!erse bias. this is referred to as ionic conduction. e# is called the vacuum permittivity and e the relative permittivity. 8oles and electrons are removed from the region of the Cunction. the dipole tends to align so that the positive charge points in the field direction.e = & for vacuum/. $ation vacancies allow ionic motion in the direction of an applied electric field. 92. electrical conduction in insulators is usually along the surface. %he central region is very thin and is called the base. or dielectric constant . 2or a given applied voltage V. 6onic polari7ation0 cations and anions in an ionic crystal are displaced with respect to each other. %his is called rectification. %eflon is an e(ceptionally good • • 'lectronic polari7ation0 the electrons in atoms are displaced relative to the nucleus. an electric field ut can e made to conduct y doping. the charge density ecomes $ 5 $# ' = P. .&. where 2# is the charge of a vacuum capacitor with the same V. $ontrol of the current through the transistor is y means of the electric field induced y the gate. With 2) 5 PA. there will e an increase in the charge in the plates y an amount 2) so that the total charge ecomes 2 5 2) = 2#. &-. which is isolated electrically y an o(ide layer. If an electric field is applied. 2or this reason. the current is very small under reverse ias. Electrical Iroperties of Iolymers Iolymers are usually good insulators insulator. which therefore ecomes depleted of carriers and ehaves like an insulator. V 5 $l#ee# = 2 l#Aee# = 2 # C %he constant C= Aee#?l is called the capacitance of the plates. &>. and this can e used to amplify electrical signals . the and gap is too large for thermal electron promotion. &-. %he asymmetric current5voltage characteristics of diodes .&> $apacitance When two parallel plates of area A. Dielectric +ehavior A dielectric is an electrical insulator that can e made to e(hi it an electric dipole structure .2ig.%ypes of Iolarization %hree types of polarization can e caused y an electric field0 y D2.&* $onduction in Ionic Materials In ionic materials. Lipoles etween the plates of a capacitor will produce an electric field that opposes the applied field.e9&/ ' . where the polari7ation P = e# . V 5 ' l.
uire dielectrics of high e that can function at high fre. normal glass does form su 5microscopic flaws when e(posed to moisture.see elow/. so they respond more rapidly to a changing electric field. Lue to its rittleness.small rela(ation times/. in an avalanche process . &>.'# 2re.uire the rotation of a molecule can occur only if the oscillation is relatively slow . Iolymers usually have lower e.2ig. CORROSION Corrosion is deterioration of essential properties in a material due to reactions with its surroundings. ut the process can e strongly affected y e(posure to certain su stances . where the %i:D is in the center of the unit cell and four 3'5 in the central plane can e displaced to one side or the other of this central ion . %wo possi le arrangements of this asymmetry results in two distinct polarizations.n.'" 2erroelectricity Ferroelectric materials are ceramics that e(hi it permanent polarization in the a sence of an electric field. $orrosion can e concentrated locally to form a pit or crack. &>.such as light/ only electronic polarization can occur.uencies .or electrical discharge/.uencies .': Iiezoelectricity In a pie7olectric material.M8z range or slower/. free other electrons.do. and porcelain/. At smaller fre. When corrosion does occur. which re.uartz.""/.uency Lependence of the Lielectric $onstant Electrons have much smaller mass than ions. %he time needed y the specific polarization to occur is called the relaxation time. Corrosion in non)etals Most ceramic materials are almost entirely immune to corrosion. %his is called dielectric brea. A common e(ample of corrosion protection in ceramics is the lime added to soda5lime glass to reduce its solu ility in waterB though it is not nearly as solu le as pure sodium silicate. 2or electric field that oscillates at very high fre. rather than an electrochemical process. in turn. an applied mechanical stress causes electric polarization relative displacement of anions and cations. While some efforts to reduce corrosion merely redirect the damage into less visi le. &>. !a%i3".s/ and?or salt. 3rientation of permanent dipoles. and accelerate them to such high energies that they can. or it can e(tend across a wide area to produce general deterioration. Most structural alloys corrode merely from e(posure to moisture in the air. and typically produces o(ide. controlled corrosion treatments such as passivation and chromate5conversion will increase a material7s corrosion resistance. y the . and the field necessary to start the is called the dielectric strength or reakdown strength. In the most common use of the word. which can e used to code 4#4 and 4&4 in ferroelectric memories. %his is due to the asymmetric location of positive and negative charges within the unit cell.• >rientation polari7ation0 permanent dipoles . &-. the relative displacement of positive and negative ions can occur.s/ of the original metal. %his is commonly known as rust. like . such flaws cause a dramatic reduction in the strength of a glass o Cect during its first few hours at room temperature. glass. this means a loss of an electron of metals reacting with water and o(ygen. %he strong ionic and?or covalent onds that hold them together leave very little free chemical energy in the structureB they can e thought of as already corroded. $orrosion also includes the dissolution of ceramic materials and can refer to discoloration and weakening of polymers y the sun7s ultraviolet light.'' Lielectric Materials $apacitors re. it is almost always a simple dissolution of the material or chemical reaction. A typical ferroelectric is arium titanate. &>. like mica.'& Lielectric Strength Jery high electric fields . Many of the ceramics have these properties.like 8'3/ are aligned. Weakening of iron due to o(idation of the iron atoms is a well5known e(ample of electrochemical corrosion. less predicta le forms.uencies. &>.S&#) J?m/ can free electrons from atoms. %his type of damage usually affects metallic materials.
one standard medium is aerated. however. room5temperature seawater/.e. %he remainder of this article is a out electrochemical corrosion. %wo metals in electrical contact share the same electron gas. %he . $oulom ic attraction holds these oppositely5charged particles together. ased on how strongly its ions are ound to the surface. and the num er of electrons present at the metal7s surface. one metal will e either more noble or more acti!e than the ne(t. so that the tug5of5war at each surface is translated into a competition for free electrons etween the two materials. and chlorine. Additives can slow these process very effectively. If a more suscepti le material is used. %he overall interaction etween electrons and ions tends to produce a state of local thermodynamic e. ut the positively5charged ions are attracted to negatively charged particles outside the metal as well. meaning that they strongly affect all of these varia les. where small molecules infiltrate the structure. . either due to the fundamental nature of the electrochemical processes involved or due to the details of how reaction products form. In turn. there is a certain amount of energy to e gained or lost y dissolving into the electrolyte or ecoming a part of the metal. many techni. Electroche)ical theor$ ?ain article4 'lectrochemistry 3ne way to understand the structure of metals on the asis of particles is to imagine an array of positively5 charged ions sitting in a negatively5charged 4gas4 of free electrons. even though their corrosion is thermodynamically favora le. and can e a very useful in predicting and understanding corrosion. magnesium.i. very little entropy can e gained y mi(ing a given mass of polymer with another su stance. 0alvanic series ?ain article4 *al!anic series In a given environment . it happens at an accepta ly slow rate. causing rittleness or other undesira le changes. Mechanisms which reak polymer chains are familiar to iologists ecause of their effect on LAA0 ionizing radiation . and so the term 4corrosion4 is only applied to them in a loose sense of the word. titanium dio(ide or car on lack/.%he degradation of polymeric materials is due to a wide array of comple( and often poorly5understood physiochemical processes. corrosion processes cause electrochemical changes. More common 4 ase4 metals can only e protected y more temporary means. %he most common form of degradation. is a decrease in polymer chain length.uantity of energy then strongly depends on a host of varia les. A more common and related pro lem is s. making them generally . and o(idizers such as o(ygen. reducing strength and stiffness and causing a volume change.. $onversely.uite difficult to dissolve. Some metals have naturally slow reaction kinetics. see galvanic series.nota ly fle(i le vinyl/ are intentionally swelled with plasticizers. and is a large part of their intrinsic value. ut has such slow kinetics that it is effectively immune to electrochemical corrosion under normal conditions. 1old nuggets do not corrode. %he no le metal will tend to take electrons from the active one.most commonly ultraviolet light/. %his hierarchy is called a *al!anic series. which can e leached out of the structure. While corrosion of these metals is continuous and ongoing. 2or a given ion at the surface of a metal. including the types of ions in a solution and their concentrations. Any corrosion products of gold or platinum tend to decompose spontaneously into pure metal.elling. Resistance to corrosion Some metals are more intrinsically resistant to corrosion than others. !ecause of their large molecular weight. ozone.uili rium that can often e descri ed using asic chemistry and a knowledge of initial conditions. %hese are strikingly different from the other processes discussed here. which reflects an atom5scale tug5of5war etween the electron gas and dissolved anions. Ilastic shopping ags often do not include these additives so that they reak down more easily as litter.ues can e applied during an item7s manufacture and use to protect its materials from damage. While dissolution is a pro lem in some polymer applications. such as the negative ions . 2or some e(amples. An e(treme e(ample is graphite. even on a geological time scale. free radicals. %hese include such metals as zinc. which is why these elements can e found in metallic form on Earth. and cadmium. it is relatively simple to design against. many polymers . and can e as simple as a +J5a sor ing pigment . %he materials most resistant to corrosion are those for which corrosion is thermodynamically unfavora le. which releases large amounts of energy upon o(idation.anions/ in an electrolyte. %he resulting mass flow or electrical current can e measured to esta lish a hierarchy of materials in the medium of interest. while the electrolyte hosts a flow of ions in the same direction.
Such methods o viously make the system less sensitive to scratches or defects in the coating. At the end of the treatment. 2or this reason. and the application of enamel are the most common anti5corrosion treatments. ECpos!re to a liB!id )etal s!ch as )erc!r$ or hot solder can o'ten circ!)vent passivation )echanis)s. #hen this la$er stops roGin at less than a )icro)etre thic. and fuel pipelines and tanksB steel pier piles. With a uniform potential. there are tradeoffs in mechanical fle(i ility versus resistance to a rasion and high temperature. the pores are allowed to seal. #hile this e''ect is in so)e sense a propert$ o' the )aterial* it serves as an indirect . forming a harder5than5usual surface layer. So)e conditions that inhi2it passivation incl!de( hi h pH 'or al!)in!)* loG pH or the presence o' chloride ions 'or stainless steel* hi h te)perat!re 'or titani!) 4in Ghich case the oCide dissolves into the )etal* rather than the electrol$te6 and 'l!oride ions 'or silicon. .Passivation ?ain article4 Passi!ation 0iven the ri ht conditions* a thin 'il) o' corrosion prod!cts can 'or) on a )etal/s s!r'ace spontaneo!sl$* actin as a 2arrier to '!rther oCidation. The e''ect o' pH is recorded !sin Po!r2aiC dia ra)s* 2!t )an$ other 'actors are in'l!ential.pushed/ more negative until the metal surface has a uniform potential.ue to control the corrosion of a metal surface y making that surface the cathode of an electrochemical cell. ships. chromium on steel/. and?or easier5to5process/ structural material. and if the plating is more no le than the su strate . and offshore oil platforms.often cheaper. 2or effective $I. S!r'ace treat)ents *al!ani7ation Ilating. normal passivation processes take over to protect the damaged area. driven y the difference in electrochemical potential etween the anode and the cathode.especially in recirculating systems/. and a wide range of specially5designed chemicals that resem le surfactants . water. Electrochemical conditions in the ath are carefully adCusted so that uniform pores several nanometers wide appear in the metal7s o(ide film.inetic 2arrier( the reaction is o'ten B!ite rapid !nless and !ntil an i)per)ea2le la$er 'or)s. the potential of the steel surface is polarized . the driving force for the corrosion reaction is halted. phosphates.$I/ is a techni. It is a method used to protect metal structures from corrosion. corrosion inhi itors can often e added to it. painting.noGn as passivation 4r!st* 'or eCa)ple* !s!all$ roGs to 2e )!ch thic. the anode material corrodes under the influence of the steel. -nodiEation ?ain article4 Anodising Aluminium alloys often undergo a surface treatment. !nder the conditions that a )aterial Gill 2e !sed in* the pheno)enon is .for e(ample.er* and so is not considered passivation* 2eca!se this )iCed oCidiEed la$er is not protective6. Reactive coatings If the environment is controlled .i. These conditions reB!ired 'or passivation are speci'ic to the )aterial. chromates. Passivation in air and Gater at )oderate pH is seen in s!ch )aterials as al!)ini!)* stainless steel* titani!)* and silicon. Cathodic protection ?ain article4 Cathodic protection $athodic protection . long5chain organic molecules with ionic end groups/. %he polarization is caused y the current flow from the anode to the cathode. Ilatings usually fail only in small sections. $athodic protection systems are most commonly used to protect steel. If this coating is scratched. to suppress electrochemical reactions. it is often wise to plate with a more active metal such as zinc or cadmium.aline environ)ent o' concrete does 'or steel re2ar. Aside from cosmetic and manufacturing issues. a galvanic couple will cause any e(posed area to corrode much more rapidly than an unplated surface would. tougher. %hey work y providing a arrier of corrosion5resistant material etween the damaging environment and the . 2or galvanic $I systems. On the other hand* so)eti)es !n!s!al conditions can 2rin on passivation in )aterials that are nor)all$ !nprotected* as the al. since e(tra inhi itors can e made availa le wherever metal ecomes e(posed.Roman water systems are famous for their mineral deposits/. %hese form an electrically insulating and?or chemically impermea le coating on e(posed metal surfaces. $hemicals that inhi it corrosion include some of the salts in hard water .e. %hese pores allow the o(ide to grow much thicker than passivating conditions would allow. and eventually it must e replaced.
0alvanic corrosion ?ain article4 *al!anic corrosion 1alvanic corrosion occurs when two different metals electrically contact each other and are immersed in an electrolyte. ut care must e taken not to trust it too thoroughly. since the interior of a pit is naturally deprived of o(ygen. making those areas much less resistant to corrosion. they can continue to grow even when conditions return to normal. 2or e(ample.usually via a wire or direct contact/. %hese include high silicon cast iron. zinc is often used as a sacrificial anode for steel structures. types of metal. this is limited to a small zone. neither metal would normally corrode as . 1alvanic corrosion is often utilised in sacrificial anodes. #eld deca$ and . an electrically conductive path and an ionically conductive path are necessary.in types "'& and ":>. ut tiny local fluctuations will degrade the o(ide film in a few critical points. they often escape notice and cause pro lems among those who are not familiar with them. salinity. Corrosion in passivated )aterials Iassivation is e(tremely useful in alleviating corrosion damage.smaller is generally less desira le/. Pittin corrosion ?ain article4 Pitting corrosion $ertain conditions. Impressed $urrent $athodic Irotection . respectively/. galvanic anodes cannot economically deliver enough current to provide complete protection..uickly without the electrically conductive connection . or a thin film pierced y an invisi ly small hole can hide a thum sized pit from view.temperature.e. typically only &)E/. What type of metal.ni'eline attac.uire special heat treatment after welding to prevent the similar phenomenon of . such as low concentrations of o(ygen or high concentrations of species such as chloride which compete as anions. mi(ed metal o(ide or platinum coated titanium or nio ium coated rod and wires. While the corrosion pits only nucleate under fairly e(treme circumstances. and operating conditions . Micro2ial corrosion . %he surface area ratio of the anode and cathode will directly affect the corrosion rates of the materials.uality alloy will corrode if its a ility to form a passivating film is hindered.$hromium. Anodes for I$$I systems are tu ular and solid rod shapes of various specialized materials. chromium car ides can form in the grain oundaries of stainless alloys. ut it can e prevented y control of the alloy7s environment. eliminating crevices/. graphite. often only a few micrometres across.i.I$$I/ systems use anodes connected to a L$ power source . Lue to the elevated temperatures of welding or during improper heat treatment. almost all of the surface will remain protected. Special alloys. the sharp tips of e(tremely long and narrow can cause stress concentration to the point that otherwise tough alloys can shatter. can interfere with a given alloy7s a ility to re5form a passivating film. 1alvanic corrosion is of maCor interest to the marine industry and also anywhere water can contact pipes or metal structures.. %his creates a galvanic couple with the well5protected alloy near y. %his effects a galvanic couple where the more active metal corrodes at an accelerated rate and the more no le metal corrodes at a retarded rate.s/ to use is readily determined y following the galvanic series. In the worst case. Iitting remains among the most common and damaging forms of corrosion in passivated alloys. since its passivating ehavior relies on the presence of a minor alloying component . depending upon conditions. ?ain article4 6ntergranular corrosion Stainless steel can pose special corrosion challenges. either with low car on content or with added car on 4getters4 such as titanium and nio ium . which often includes ensuring that the material is e(posed to o(ygen uniformly . 2actors such as relative size of anode . %his chemical reaction ro s the material of chromium in the zone near the grain oundary.corrosion of the grain oundaries near welds/ in highly corrosive environments. In order for galvanic corrosion to occur. In e(treme cases. @c. which causes it to proceed more rapidly.2or larger structures. As its name applies. %hese pro lems are especially dangerous ecause they are difficult to detect efore a part or structure fails. Even a high5. can prevent this effect.ni%eline attac. which leads to ./ will affect galvanic corrosion.a cathodic protection rectifier/. humidity. $orrosion at these points will e greatly amplified. When immersed. such as pipelines or docked naval ships.eld decay . and can cause corrosion pits of several types. %his zone is very near the weld. ut the latter re. !ecause the resulting modes of corrosion are more e(otic and their immediate results are less visi le than rust and other ulk corrosion. making it even less noticea le&.
$oncentration cells can form in the deposits of corrosion products.typically a metal/ under very high temperature conditions. other acteria o(idize sulfur and produce sulfuric acid causing iogenic sulfide corrosion. is a corrosion caused or promoted y microorganisms. Such high temperature corrosion products in the form of compacted o(ide layer glazes have also een shown to prevent or reduce wear during high temperature sliding contact of metallic . %he formation of o(ides on stainless steels. 2or e(ample.?ain article4 ?icrobial corrosion Micro ial corrosion. sulphur or other compounds capa le of o(idising . %he products of high temperature corrosion can potentially e turned to the advantage of the engineer. causing and enhancing galvanic corrosion. causing sulfide stress cracking. usually chemoautotrophs.or assisting the o(idation of/ the material concerned. %his non5galvanic form of corrosion can occur when a metal is su Cect to a high temperature atmosphere containing o(ygen. in oth the presence and lack of o(ygen. power generation and even in car engines have to resist sustained periods at high temperature in which they may e e(posed to an atmosphere containing potentially highly corrosive products of com ustion.or metallic and ceramic/ surfaces. some acteria directly o(idize iron to iron o(ides and hydro(ides. can provide a protective layer preventing further atmospheric attack. materials used in aerospace. . for e(ample. Hi h te)perat!re corrosion 8igh temperature corrosion is chemical deterioration of a material . In presence of o(ygen. Sulfate5reducing acteria are common in lack of o(ygenB they produce hydrogen sulfide. It can apply to oth metals and non5metallic materials. allowing for a material to e used for sustained periods at oth room and high temperature in hostile conditions. or acterial corrosion.