BONDING IN ATOMS AND MOLECULES ATOMIC STRUCTURE Every atom consists of a very small nucleus composed of protons and

neutrons, which is encircled by moving electrons. Both electrons and protons are electrically charged, the charge magnitude being 1.60 x 10-1 ! that is negative in sign for electrons and positive for protons" neutrons are electrically neutral. #ince the normal atom is electrically neutral, the number of protons in the nucleus must be e$ual to the number of electrons in the surrounding orbital. %he nucleus of an atom accounts for almost all of the mass of that atom, while the diameter of the atom tends to be of the order 10,000 times greater than that of the nucleus. %he &%'()! *+(BE, -./ of an element is given by the number of protons -or electrons/ possessed by a normal atom of that element. &n ion has different number of electrons and protons. %he electrons, particularly those in the outermost orbital -the valence electrons/ determine many engineering properties of materials such as chemical reactivity binding patterns established with other atoms and thus strength characteristics electrical properties and optical characteristics. 0&tomic (ass 1 &tomic *o. 2 *umber of *eutrons3 ELECTRONS IN ATOMS %he number of electrons in a given shell can be obtained from the formula i.e *o. of electrons 1 4n5 where n is the number of shell. %hus for the 1st #hell -6- #hell/, n 11" *o. of electrons 1 4 -1/ 4 1 47 4nd #hell -8- #hell/, n 14" *o. of electrons 1 4 -4/ 4 1 97 :rd #hell -(-#hell/, n 1:" *o. of electrons 1 4 -:/ 4 1 197 ;th #hell -*- #hell/, n 1;" *o. of electrons 1 4 -;/ 4 1 :47 %here are two ways to show how these electrons are arranged in an atom. )n the first method electrons are assumed to revolve around the atomic nucleus in discrete orbitals and the position of any particular electron is more or less well defined in terms of its orbital. <ere too the innermost shell of an atom contains a maximum of two electrons revolving round the nucleus. #uccessive shells contain eight electrons each.

)n the second method electrons are permitted to have only specific values of energy. &n electron may change energy, but in doing so it must ma=e a $uantum >ump either to an allowed higher energy -absorption of energy/ or to a lower energy -emission of energy/. %hese electron energies are being associated with energy levels or states. Electrons are thus said to be arranged in sub-shells-within which no more than two electrons can occupy the same energy levels/ which are for our current purpose s,p,d and f orbitals. <ere too s-orbital ta=es a maximum of two electrons, p-orbital ta=es a maximum of six electrons, d-orbital ta=es a maximum of ten electrons and f-orbital ta=es a maximum of fourteen electrons. *B7 Explain the two ways of arranging electrons in an atom using #odium-11/, !hromium-4;/, !alcium-40/ and #ulphur -16/. BONDING %he arrangements of atoms in any solid material are determined by the character, strength and directionality of the bonding forces, or chemical bonds present within the material. )t should be noted that the bonding exists not only between atoms but also other atomic units such as ions" radicals and molecules if such are present in the material. & completely filled outer electron shell of atoms confers a very high stability to the atoms. Example" *eon and &rgon. &toms of other elements with incomplete outer shells attempt by combination with other atoms to satisfy this condition of stability. #uch atoms achieve this stable configuration by7 i. ,elease of electrons ii. ,eceiving extra electrons ions are formed iii. #haring of electrons

%here are two bond types namely" primary and secondary bonds. & primary bond is formed only if there is a pronounced lowering of the energies of the electrons involved during the formation of the bond. %his lowering of energy of bond electrons ma=es the bond stronger and more stable. %hree limiting types of primary bonds are distinguished on the basis of the positions assumed by the bond electrons during the formation of the bond. %hese are ionic, covalent and metallic bonds.

IONIC BOND %his is really the attractive force existing between a positive and a negative ion when they are brought into close proximity, these ions being formed when the atoms involved lose or gain electrons in order to stabili?e their outer shell. 0Elements are either classified as electro positive or electro negative, depending upon whether they tend to loose or gain electrons in order to achieve this stable outer-shell configuration. )oni?ation energies or potential measure the amount of energy re$uired to remove the successive outer electrons from an atom3. 8ess amount of energy is re$uired to strip one electron from a metal than from a non-metallic atom. %hus, metals are termed electropositive while non-metals are termed electronegative. Example: #odium !hloride, @otassium !hloride, 8ithium Aluoride and (agnesium !hloride. Aor sodium chloride -*acl/ *a -11/7 1s5 4s5 4p6 :sB !l -1C/7 1s5 4s5 4p6 :s5 :pD CHARACTERISTICS OF IONIC COMPOUNDS 1/ 4/ :/ ;/ %hey are electrolytes -explain/ %hey have high melting and boiling points. ,eactions ta=e place by electron transfer. Bonds are non-directional ie. %he magnitude of bond is e$ual in all direction around the ion. D/ !rystal lattice built from ions 6/ !rystals are hard and brittle. COVALENT BOND %his is formed when several atoms share pairs of electrons and have their energies lowered as a result of this. #table covalent bonds are formed between many non-metallic elements since the atoms of these elements

usually possess half filled outer electron shells, which resist the direct electron transfer re$uired for the formation of an ionic bond. Because pairs of electrons are shared in covalent bonds there is some degree of orbital overlap between the bonded atoms. %his overlap is limited by the electrostatic repulsion of the positive charged nuclei, the resultant shapes of the bond orbital determines whether the bond will be directional or non-directional in space with respect to the nuclei. %he greater the degree of orbital overlap the stronger the bond, since extensive overlap means greatly lowered energy levels of the bond electrons. E.g. !l, A, <A, * Aluorine -A/ %hus
F
+

1s5 4s5 4pD " &tomic *o. is

i.e . A - 2 A

*B7 !ovalent bond ma=es the molecule neutral and the two nuclei cannot be separated as ions, as the nuclei share the electrons. CHARACTERISTICS OF COVALENT COMPOUNDS 1/ 4/ :/ ;/ %hey are non-electrolytes %hey have low melting and boiling points (any are volatile li$uids or gases #olid covalent compounds are insoluble in water but soluble in organic solvent. D/ Bonds are directional 6/ !rystal lattice is built from molecules. METALLIC BOND &t the simplest level, this bond may be seen as the result of the individual metallic atoms losing their outer valence electrons, which then exist in the metal as a cloud or electron gas. %he metallic bond is the electrostatic attraction between the fixed positive ion cores of the atoms

and this electrons cloud. & metallic bond thus conceived, can exist only between a large aggregate of metallic atoms and must therefore be nondirectional. E.g.7 )ron, #ilver, Eold, *ic=el, and lead etc. NB7 )f there are FnG atoms in a metal in a given lattice, and the electrovalence of the metal is 21, then FnG electrons will circulate freely throughout the lattice. CHRACTERISTICS OF METALLIC COMPOUNDS 1/ 4/ :/ ;/ D/ %hey are conductors %hey have variable melting and boiling points ,eactions ta=e place by electron transfer Bonds are non-directional !rystal lattice built from positive particles and demorali?ed electrons 6/ !rystals vary in hardness. SECONDARY BONDS %hese are those comparatively wea= intermolecular bonds formed as a result of dipole attractions, the dipole forming as a result of the unbalanced distribution of the electron in asymmetrical molecule. %emporary dipoles attract each other and the bond formed between them is very wea= due to Han der Iaal forces. #econdary bonding exists between virtually all atoms or molecules but its presence may be obscured if any of the three primary bonding type is present. %hey are also evident for inert gases, which have stable electron structures and in addition, between molecules in molecular structures that are covalently bonded. Examples are <ydrogen fluoride, Iater and noble gases. BONDING FORCES AND ENERGIES &toms in solids are =ept at their e$uilibrium positions. %his leaves much space between the atoms. %he spaces between the atoms is attributed to the interatomic repulsive forces which arise due to the mutual repulsion

of the electronic clouds of the atoms opposing these forces of repulsion are forces of attraction in which the positively charged nucleus of one atom is attracted by the negatively charged electrons of the other atoms. %his is sometimes referred to as the COULOMBIC FORCE. &n e$uilibrium results when the attractive and repulsive forces are e$ual. i.e. when the net force A* is e$ual to ?ero from the e$uation below7 A* 1 A! 2 A, , where A! 1 !oulombic force" A, 1 ,epulsive A! 2 A , 1 0 But A! 1 - 6 -?1 $/ -?4, $/ --------1/ 4 a1 4 a1 4 1 e$uilibrium separation between atoms 6 1 Jo , o 1 permittivity of free space = 1 a x 10 H mKc7 ?1 and ?4 are the valencies of the two ion types. $L 1 electronic charge 1 0.16 x 10-19! &lso, A, 1 - bn an 2 1 ------4/ b, n are empirical constants n 1 9, for ionic solids. !omparing -1/ and -4/, A! x aM5 and A, x aM %his means that the attractive forces predominate at greater distances of atomic separation whereas the repulsive forces predominate at closer atomic spacing. Bond energy E and bond force A, are related by E 1 L Ada En 1 L An da where En is the net energy and An is the net force. En 1 L -A, 2 A!/ da &s atoms are brought together energy is released i.e. Ec is negative -Exothermic, N<1-ve/. &s atoms are separated energy is absorbed i.e. E, is positive -Endothermic N<12ve/.

CRYSTAL STRUCTURE &lmost all metals, some ceramics and some polymers crystalli?e when they solidify i.e. the atoms are arranged in a : O N repeating pattern which extends over a long range of many atomic distances. %here are a number of ways in which the atoms in solids are arranged in : O N. %his arrangement constitutes the SPACE LATTICE (B,&H&)# 8&%%)!E/. & space lattice is therefore defined as a : O N array of discrete points whose arrangement and orientation remain the same irrespective of where the lattice is viewed. #pace lattices are characteri?ed by unit cells which is defined as the fundamental building bloc= with which the lattice is generated along its crystallographic -a1, a4, a:/ direction. #ome examples of space lattices are7 i. ii. iii. iv. v. vi. vii. #imple cubic Body centered cubic Aace centered cubic <exagonal structure (onoclinic str;ucture %riclinic structure ,hombohedral structure

THE SIMPLE CUBIC STRUCTURE

a

FaG is

lattice parameterKsi?e of unit cell

)n this system, eight ad>acent unit cells met at a corner point. %herefore only one eight part of any corner atom is effectively within one unit cell. *umber of atoms in each unit cell 1 1K9 x 9

11 &ll ionic solids are belonging to this class. BODY CENTRED CUBIC (BCC) STRUCTURE

%he unit cell for this structure consists of a sphere at the center of a cube with eight other spheres at the corners of the cube and touching the central sphere. !orner atom 1 9 x 1 9 11 Body centered atom 1 1 %otal *umber of atoms per unit cell 1 4 E.g. Hanadium, (olybdenum, )ron -P/, chromium

FACE CENTRED CUBIC (FCC) STRUCTURE %he unit cell of this structure is made of a sphere in the center of each of the six faces of the cube.
a

!orner atoms 1 1 Aace centered atom 1 Q x 6 1:

 %otal number of atomsKunit cell 1 ; E.g. &luminium, *ic=el, !opper, #ilver, Eold, 8ead, @latinum, )ron -R/ CLOSE PAC!ED HE"AGONAL STRUCTURE (CPH)

!orner atom 1 1 x 14 6 14 Base centered atom 1 Q x 4 11 !entered atom 1 : %otal number atomsKunit cell 1 6 E.g. Beryllium, (agnesium, .inc, !admium

PAC!ING FRACTIONS#ATOMIC PAC!ING FACTOR %his is the fraction of the unit cell that is occupied by atoms or the fraction of solid sphere -assuming atoms to be solid spheres/ volume in a unit cell. i.e. &@A 1 Holume of atoms in a unit cell %otal unit volume *umber of atoms per unit cell x volume of sphere %otal volume of unit cell

F$% BCC
, & a , B a 4 , , A

, , , B ,

&

)n B!! atoms bonds along body diagonal which goes right throughKinto the body of the atom. , is the radius of the atom. -;,/4 1 a4 2 4a4 -from @ythagoras theorem/ 16,4 1 :a4 and raising to a power of :K4 16,:K4 x ,4x:K4 1 ::K4 x a4x:K4. a: 1 -16/ :K4 ,: -------1/ : &lso, number of atoms per unit cell is 4. Holume of sphere 1 ;K:,: Holume of unit cell 1 a: &@A 1 4 x ;K:,: 1 -16/ :K4 ,: : Aurther simplification gives

&@A 1 0.69 %his means that atoms occupy 69S volume of the unit cell. INFLUENCE OF STRUCTURE AND BONDING ON PROPERTIES OF CRYSTALLINE FORMS #%,E*E<%7 this is the measure of the externally applied forces, which are necessary to overcome interval forces of attraction between fundamental particles within the material. )'*)! B'*N tends to be wea= and once it is bro=en complete cleavage ta=es place since, as soon as the position of any ion is disturbed e$uilibrium is upset. %he structure of metal responds internally to the applied load by trying to counteract the magnitude of the applied load and therefore tries to =eep the constituent atoms in their ordered positions. )f, however the load is high enough then the force which holds the atoms in place -i.e. metallic bond/ becomes ineffective and the atoms are then forced into new positions. %he movement of atoms is called #8)@. Ihen performing a forging operation the material only deforms because movement or slip of atoms has occurred on a large scale. Eenerally, the greater the density of atoms within a certain close-pac=ed plane, the greater the spacing between ad>acent layers. A!! has four -;/ sets of close-pac=ed planes per unit cell. %he further apart the layers are, the wea=er is the bond between these layers. <ence bonds between close-pac=ed planes are relatively wea= and such a geometric arrangement leads to ease of slip or deformation. <.!.@ contains one set of close-pac=ed plane per each unit cell, therefore the ability to deform by atomic slip is more restricted than in A.!.!. %his closepac=ed arrangement occurs in the top and base of each hexagonal formation. #tructures with a B.!.! arrangement possess no close-pac=ed planes and therefore the distance between ad>acent layers is small, resulting in greater atomic attraction. )n such an atomic arrangement greater force is re$uired to initiate atomic slip. <ence B.!.! structures are stronger than A.!.! or <.!.@ structures.

POLYMERISATION %he term polymeri?ation means Tmany mersU, where mer is the building bloc= of the long-chain or networ= molecule. & covalent bonding holds mers together. E.g. @olymers are therefore substances whose molecules are composed of great number of repeating groups called ('*'(E,#. @olymeri?ation is simply the process by which monomer units are >oined over and over, to generate each of the constituent giant molecules to give large, complex molecular forms with very high molecular weight. (ost generally the raw materials for synthetic polymers are derived from coal and petroleum products, which are composed of molecules having low molecules weights. %he reactions by which polymeri?ation occurs are grouped into two general classifications O addition and condensation. ADDITION POLYMERISATION &s chain reaction, polymeri?ation is a process by which bi-functional monomer units are attached one at a time in chain li=e fashion to form a linear macro molecule" the composition of the resultant product molecule is an exact multiple for that of the original reactant monomer. %hree distinct stages O initiation, propagation, and termination - are involved in addition to polymeri?ation. Nuring the initiation step an active center capable of propagation is formed by a reaction between an initiator -or catalyst/ species and the monomer unit. @ropagation involves the linear growth of the molecule as monomer units become attached to one another in succession to produce the chain molecule. NB. !hain growth is relatively rapid. %he period VV to grow a molecule consisting of say 1000 over units is on the over of 10VVVVV.

@ropagation may end or terminated by either the reactivity between the two ends of active propagating chains or an active chain and may react with an initiator. %his reaction is used in the synthesis of polyethylene, polypropylene, polyvinyl chloride, and polystyrene etc. Eg. Aormation of polyethylene. %he process begins with an initiator ie hydroxyl free radials -& free radical is a reactive action or group of atoms containing an unpaired electron. I&'('a('$&: %his reaction converts the double bond of one monomer into a single bond of one monomer into a single bond and once completed, the one unsatisfied bonding electron is free to react with the nearest ethylene monomer. < < ! < P%$pa)a('$&: 1 ! <

Te%m'&a('$&:

CONDENSATION POLYMERISATION %his sometimes =nown as #%E@ ,E&!%)'* is the formation of polymers by stepwise intermolecular chemical reactions that normally involve more than one monomer species" there is usually a small molecule weight byproduct such as water, which is eliminated. *o reaction species has the chemical formula of the mer repeat unit, and the intermolecular reaction occurs every time a mer repeat unit is formed.

!ondensation reactions often produce trifunctional monomers capable of forming cross-lin=ed and networ= polymers. %he thermosetting polyesters and phenol O formaldehyde, the nylons and the polycarbonates are produced by condensation polymeri?ation. NET*OR! STRUCTURES & networ= polymer is one whose structure is in the form of a large :Nimensional net. %his networ= forms as a result of cross- lin=ing linear or branched chain polymer. *aturally rubber consists mostly of a linear polymer that can be cross O lin=ed to form a loose networ= with 1-:S sulphur.%he same polymer when reacted with ;0-D0S sulphur is a hard rubber or a tight networ= polymer which are used for ma=ing plastic materials. 8ow networ= density results from small numbers of cross-lin=s, which leads to a soft and flexible polymer. )ncreasing the networ= density increases the stiffness of the polymeric material, which ma=es it very hard. THERMOPLASTIC POLYMERS %hese are materials that become soft and deformable upon heating. %his is characteristic of linear polymeric molecules -including those that are branded but not crossOlin=ed/ %he high Otemperature plasticity is due to the ability of the molecules to side past one another as a result of secondary bonding between them. %he ductility of thermoplastic polymers is reduced upon loo=ing.

THERMOSETTING MATERIALS %hese materials become hard and rigid upon heating. +nli=e thermoplastic polymers, this phenomenon is not lost upon cooling. %his is characteristic of networ= molecular structures formed by the step growth mechanism. %he chemical reaction steps are enhanced by higher temperatures and are irreversible. %hermosetting products can be removed from the mould at the fabrication temperature -%ypically 400Wc O :00Wc/.

Eg. Epoxies -&raldite/7 protective coatings" adhesives etc. @olyesters7 helmets" auto body components" chairs" fans. @henolics7 telephones" auto distributors" motor housing etc. RUBBER MATERIALS %hese are made up of natural and artificial rubbers -Elastomers/ Elastomers are lightly cross-lin=ed materials with very low elastic moduli, which can accommodate large amounts of strain but return to their original dimension when the load is removed. %hey are said to possess linear polymer structures with a small number of cross-lin=ed between molecules and in many cases the molecules form into coils behaving as minute helical springs. Ihen a tensile force sufficient to stretch the material is applied, the molecules partially disentangled and straightened out so that they become oriented in the general direction in which stretching occurs. #ince the molecules become more closely aligned along the direction of the stretching, the forces of the attraction between ad>acent molecules also increase so that the material becomes stronger and stiffer. -!'@'8X(E,# 1 better property combinations than homo polymer. (ade by the polymeri?ation at two species of monomer./ Eg. 1. *atural" @oly isoprene -*atural rubber/ O @neumatic tyres and tubes" heels and soles" gas=ets etc. 4. #tyrene Butadiene !opolymer -#B,/ O %his is predominantly used in automobile tyres manufacture reinforced with !arbon blade, also used for footwear, conveyor belt hosepipe etc. :. &erylomitrile butadiene -*,!/ YExpensive and highly resistant to degradationZ - Easoline, chemicals and oil hose" seals and '-rings, heels and soles etc. ;. !hloroprene -*eoprene K!,/ O Iire and cable chemical tan= lining" bects D. @olysiloxane -#ilicon/ O <igh and low temperature insulations, diaphragms.

POLYMER ADDITIVES &ny additive compounded with basic polymer will influence the structure and hence the properties. #uch additives may be used to stabili?e the polymer, to improve the wor=ing properties to change the mechanical or physical properties or introduce colour. %ypical additives include filler materials, plastici?ers, stabili?ers, colorants and flame-retardants.

(+) FILLER7 %hese are materials most often added to polymers to improve tensile and compressive strengths, abrasion resistance toughness, dimensional and thermal stability and other properties. (aterials used as particulate fillers include wood flours, silica flour and sand, glass, clay, talc, limestone etc. @article si?es range all the way from 10mm to macroscopic dimensions because these inexpensive materials replace some volume of the more expensive polymer" the cost of the final product is reduced. Eg. -i/ (ica added to phenolic type resins improve electrical resistance" -ii/ Erapluite also reduces frication -iii/ &sbestos improves temperature resistance. (,) PLASTICI-ERS: %hese improve the flexibility ductility and toughness of polymers. %heir presence in a polymer soften it and produces reduction in hardness and stiffness. @lastici?ers are generally li$uids having low vapour pressures and low molecule weights. %he small plastici?er molecules occupy positions between the large polymer chains effectively increasing the inter-chain distance with a reduction in the secondary inter-molecular bonding. @lastici?ers are commonly used in polymers that are intrinsically brittle at room temperature, such as @H! etc. )n effect, the plastici?er lowers the glass transition temperature, so that at ambient conditions, the polymers may be used in applications re$uiring some degree of pliability and ductility. Eg. @H! can be plasticised by adding 1DS of vinyl acetate during polymeri?ation. (.) STABILI-ERS: %hese are additives used to reduce polymer degradation. (ost often this deterioration is a result of exposure to heat, light -in particular uv radiation/ and also oxidation. +v radiation interacts

with, and causes severance of some of the covalent bonds along molecular chain, which may also result in some cross-lin=ing. 'xidation is a conse$uence of the chemical interaction between oxygen atoms and the polymer molecules. <eat is as a result of exposure to very high temperatures. E.g.7 - @olyisoprene can absorb up to 1DS oxygen at room temperature, with its elastic being destroyed by the first 1S. &t this temperature natural rubber latex can be used to retard this oxidation process, however at elevated temperatures stabili?ers li=e amines, sulphur compounds are introduced -rubber intended for tyre applications/. !arbon blac= is used as ultra-violet stabili?er. 8ead and %in compounds are also used as heat stabili?ers. (/) FLAME RETARDANTS: %hese are added to reduce the inherent combustibility of most polymers. !ombustion is simply the reaction of a hydrocarbon with oxygen accompanied by substantial heat evolution. %hese retardants may function by interfering with the combustion process through the gas phase, or by initiating a chemical reaction that causes a cooling of the combustion region and cessation of burning. <alogens hinder the process of combustion by terminating free-radical chain-reactions. &dditives that provide this function for halogen-free polymers include !hloride-, Bromine-, and @hosphorous-containing reactants. @igment addition produces opa$ue colours and transparent colours are produced by dyes. (0) COLORANTS: %hese import a specific color to a polymer" they may be added in the form of dyes or pigments. %he molecules in a dye actually dissolve and become part of the molecular structure of the polymer. @igments are filler materials that do not dissolve, but remain as separate phase" )norganic pigments such as titanium oxide and aluminum silicate are much superior to organic colorants in weather resistance, in stability to heat and light and in their resistance to bleeding. (1) ANTISTATIC AGENTS (ANTISTATS) Ihen two surfaces that are in intimate contact are rubbed together or pulled apart, static electricity is generated. %his is due to the transfer of electrons from the surface of the donor material, which conse$uently becomes positively charged, to the surface of the acceptor material, which then

becomes negatively charged. Aor materials that are nonconductive -(ost synthetic polymers are good electrical insulators/, these static charges do not [ow easily along the surfaces and therefore remain \xed or static. )n conductors however, these charges easily flow to the ground ma=ing the level of static charge developed difficult to measure .Electrostatic charges can cause problems when textile, \lms, or powders >oin up in automatic machinery. #par=s, and possibility explosions or \res, can occur when static electricity is induced from plastics on nearby conductor. Namage of sensitive semiconductors and similar complex microelectronic devices can also occur by exposure of such devices to the close approach of a staticcharged polymer material. %here are essentially two types of antistats that are commonly used in polymers to get rid of static electricity7 those that are applied topically and those that are incorporated internally into the polymer. Both improve the conductance of polymer surfaces by absorbing and holding a thin, invisible layer of moisture from the surrounding air onto the polymer surface. %opical coatings are usually applied using wipe, spray, dip, or roller coating techni$ues. )nternal antistats are compounded directly into the polymer mix prior to processing. %hey then migrate slowly and continually through the molecular interstices and the bul= polymer to its surface where they absorb the water necessary to prevent accumulation of static charges. (a>or types of organic antistatic agents include $uaternary ammonium compounds, amines and their derivatives, phosphate esters, fatty acid polyglycol esters, and polyhydric alcohol derivatives such as glycerine and sorbitol.

CHAIN CHARACTERISTICS & branched chain molecule will have a wea= Hander Iaals forces existing between them and permit elastic flow to ta=e place. %his confers a lower strength on such molecule. %he greater spacing between ad>acent molecular chains will also influence the toughness, such structure having a relatively high value and so display a measure of flexibility.

)n the case of a linear structure with bul=y side atoms or molecules, the structure is similar to that of branched chains. <owever, there are additional very strong forces of attraction in existence between the bul=y side appendages which tend to increase the density and strength but reduce the toughness and flexibility. & linear molecular chain structure is characteri?ed by a less entanglement and is more li=ely to have its molecular chains arranged in a closely pac=ed, folded arrangement giving a high density polymer. Han der Iaal forces are high in this case and this gives it high strength with low flexibility and toughness. EEFECT OF TEMPERATURE ON STRENGHT OF SOME PLASTICS AND RUBBERS )n thermosetting materials, there is the formation of cross-lin=s across chain molecules. %hese cross-lin=s constitute covalent bonds across these chain molecules which have high strength. )ncreasing the temperature of such material does not easily brea= up these covalent bonds and therefore its strength remains high. %hermoplastic materials are however characteri?ed by wea= Han der Iaal forces which brea= up easily by thermal vibration as a result of increase in temperature. ,ubbers exist as long chain molecules which are irregularly coiled, bent and generally entangled when in the unstressed state -i.e. it is amorphous/. %hese amorphous chains flow past each other when temperature rises. %his causes brea=down of the wea= Han der Iaal forces and thus decrease its strength. CREEP OF A POLYMER %his is the gradual extension under a constant force or a continued slow strain with time when sub>ect to a constant load. !reep 0properties of a polymer are very dependent upon temperature. &t temperature well below the glass transition temperature, a polymer tends to be rigid and have a low creep rate for a given stress. &s temperature increases the creep rate and the amount of elongation increases. N.B

Elass transition, %g O %emperature below, which the polymer changes from rubbery state to a rigid one, and vise versa. VULCANISATION

%his is the transformation of a polymer with a linear structure into one with a networ= structure by means of cross-lin=ing i.e. a non reversible chemical reaction involving sulphur or other suitable agent wherein cross-lin=s are formed between molecular chains in rubber materials. CORROSION %his is the deterioration or destruction of a material because of its reaction with the environment. )t may be classified as dry or wet corrosion and #+,A&!E '])N&%)'* and E&8H&*)! EAAE!%# cause the most common forms SURFACE O"IDATION: %his form of corrosion attac=s the surface of metals and alloys and ta=es in dry air at high temperatures. )n this type of reaction an oxide layer or scale forms on the surface of the metal or alloy through which the metal and the environment or both must diffuse in order for reaction to continue i.e ( (42 2 4e -&t (etal- #cale interface/ 2 Q'4 2 4e '4- -&t #cale- Eas interface / ( 2 Q'4 (' -'ver all/

%he resulting thin continuous oxide film is controlled by transfer of electrons from metal to oxide, or in some instances by migration of metal ions in a strong electric field set up negatively charged oxygen adsorbed on the oxide surface. FACTORS NECESSARY TO PRODUCE AN AC2UEOUS CORROSION CELL & corrosion cell is simply an electrolytic cell where the process of electron flow proceeds spontaneously, the driving force behind the electron flow being the electrical potential difference between the cathode and the anode. %o produce such cell7 -i/ %here must be a cell between the anode and cathode. <ence for metals, the anode and cathode must7 -a/ !onsist of different metal -b/ !onsist of different alloys of the same metal and -c/ <ave different concentrations of oxygen or electrolyte around them. -ii/ %here must be an electrolyte present. -iii/ &n electrical connection must exist between the anode and cathode to facilitate electron flow. MECHANISM OF ATTAC! BY GALVANIC CORROSION )n a corrosion cell Y-i/ O -iii/ Z, corrosion of the less resistant metal is usually increased and the attac= of the more resistant material is decreased as compared with their behavior when not galvanically coupled. %he less resistant metal becomes the &*'NE and the more resistant, the !&%<'NE.

<ere hydrogen ions pass through the electrolyte from cathode, react with the metallic ions produced from the anode and further react with free oxygen absorbed by the electrolyte from the air. %his forms the hydrated product of corrosion while the flow of electrons proceeds from the anode to the cathode.

GALVANIC SERIES %his represents the relative reactivityGs of a number of metals and commercial alloy in seawater. %he alloys near the top are cathodic and unreactive, whereas those at the bottom are most anodic. *o voltages are provided. %he more widely spaced in the series, the greater the potential difference between them and so the greater the rate of corrosion. @latinum Eold Eraphite %itanium #ilver Y:16 #. #teel -passive/Z Y:0; #. #teel -passive/Z Y)nconel -90*i O 1:!r O CAe/ -passive/Z Y*ic=el -passive/Z )ncreasingly inert -!athodic/ Y(onel -C00*i O :0 !u/Z Y!opper O *ic=el alloysZ YBron?es -!u O #u alloysZ Y!opper YBrasses -!u O .u alloysZ Y)nconel -active/Z Y*ic=el -active/Z %in 8ead Y:16 #. #teel -active/ -:0; #. #teel -active/

)ncreasingly active -&nodic/

!ast )ron )ron and steel &luminium alloys !admium !ommercially pure aluminium .inc (agnesium and (agnesium alloys *B7 Nifferent metals have different oxidation potentials since the amount of energy re$uired to remove their valence electrons varies from metal to metal. %he ioni?ation process build up electrical potential =nown as E8E!%,'NE @'%E*%)&8 %he greater the negative potential, the greater the tendency of a metal to dissolve i.e the easier it is for a metal to lose electrons the greater its negative potential and vice versa. ELECTROCHEMICAL CONSIDERATIONS Aor metallic materials, the corrosion process is normally electrochemical i.e. a chemical reaction in which there is transfer of electron from one chemical species to another. (etal atoms characteristically lose or give up electrons in what is termed an '])N&%)'* reaction. i.e. ( (n2 2 ne Eg. Ae Ae42 24e &l &l:2 2 :e %he site at which oxidation ta=es place is called the &*'NE. &*'N)! ,E&!%)'* is sometimes used to denote oxidation reaction. %he electrons generated from each metal atom that is oxidi?ed must be transferred to and become a part of another chemical species in what is termed a ,EN+!%)'* reaction, sometimes =nown as !&%<'N)! reaction. Eg. #ome metals undergo corrosion in acid solutions, which have high concentration of hydrogen -<2/ ions" the <2 ions are reduced as follows" 4<2 2 4e- 1 <4 i.e. hydrogen gas is evolved. Aor an acid solution having dissolved oxygen reduction according to '4 2 ;<2 2 ;e- 1 4<4' will probably occur. Aor a neutral or a basic a$ueous solution in which oxygen is also dissolved,

'4 2 4<4' 2 ;e - 1 ;-'<-/ & metal may be totally reduced from an ionic to a neutral metallic state as (n2 2 ne 1 ( )n an electrochemical reaction, the individual oxidation and reduction reactions are termed <&8A O ,E&!%)'*# and the total rate of oxidation must e$ual the total rate of reduction, or all electrons generated through oxidation must be consumed by reduction. E.g. !onsider a ?inc metal immersed in an acid solution containing <2 ions. &t some regions on the metal surface, ?inc will experience oxidation or corrosion. i.e. .n .n42 2 4e- VVVVVVV. -1/ #ince ?inc is a metal and therefore a good electrical conductor, these electrons may be transferred to an ad>acent region at which the <2 ions are reduced, thus 4<2 2 4e- 1 <4. VVVVVV -4/ )f no other oxidation or reduction occur, the total electrochemical reaction is >ust the sum of the two reactions above or .n .n42 2 4e4<2 2 4e<4 -gas/ 2 .n 2 4< .n42 2 <4 -gas/ ELECTRODE POTENTIALS *ot all metallic materials oxidi?e to form ions with the same degree of ease. !onsider the electrochemical cell shown below.

%he cell halves are separated by a membrane, which limits the mixing of the two solutions. )f the iron copper electrodes are connected electrically,

reduction will occur for copper at the expense of the oxidation of iron as follows7 !u42 2 Ae 1 !u 2 Ae42 %his means !u42 ions will deposit as metallic copper on the electrode, while iron dissolves -corrodes/ on the other side of the cell and goes into solution as Ae42 ions. %hus, the two half-cell reactions are represented by the reactions7 Ae Ae42 24e!u42 2 4e!u &s a result of the movement of electrons and ions, an electric potential or voltage will develop between the two cell halves. !onsider the generali?ed reactions involving the oxidation of metal (1 and the reduction of metal (4 as (1 (1n2 2 ne-H1W n2 (4 2 ne(4 2H4 W Ihere HWGs are standard electrode potential. #ince (1 is oxidi?ed, the sign of H1W is opposite in sign to that as it appears in the standard emf series. %herefore adding the two e$uations above we have (1 2 (4 n2 (1 n2 2 (4 VVVVVV. -^/ %he overall cell potential _HW 1 H4W O H1W. Aor such a reaction to occur spontaneously _HW must be positive. INFLUENCE OF CONCENTRATION AND TEMPERATURE ON CELL POTENTIAL %he emf series applies to pure metals in )( solutions of their ions, at 4DW!. &ltering temperature or solution concentration or using alloy electrode instead of pure metals change the cell potential, and in some cases, the spontaneous reactions direction may be reversed. )f (1 and (4 electrodes are pure metals 0from -^/3, the cell potential depends on the absolute temperature % and the molar ion concentration. Y(12nZ and Y(4n2Z according to the *erst e$uation. _H1 -H4W - H1W/ O ,% )n Y(12nZ *A Y(42nZ

, is gas constant, n is the number of electrons participating in either of the half Ocell reactions and A is the faraday constant - 6,D00 !K (ol/. &t 4DWc -about room temperature/ _H 1 -H4W - H1W/ O 0.D 4 log 0(12n3 n 0(42n3 _H is in Holts. Aor reaction spontaneity, _H must be positive.

&lternatively it can be stated as _H 1 -H4W - H1W/ O 0.D 4 log = n where = 1 0!3c0N3d 0&3a0B3b Ihere 0&3a etc represents activity of the given chemical species. Aor ionic solutions, the activity is the molar concentrations. Aor gases the activity is the pressure in atmospheres. %he activity of pure solid metal is ta=en as 1.0. &lso note that @< 1 Olog10 0<23 E.g !alculate the cell voltage at 4DW! for a .nKAe galvanic cell when 0.n423 1 0.D( and 0Ae423 1 0.1( SOLUTION )n the standard emf series, .n is anodic to Ae i.e .n .n42 2 4e H1 1 O 0.CD:H 42 3 Ae 2 4e Ae H4 1 O 0.;;0H 42 42 Ae 2 .n .n 2 Ae H4` - H1` 1 O 0.;;0H O -O 0.C6:H/ Arom *erst e$uation 1 0.:4:H

_H 1 -H4W - H1W/ O 0.D 4 log 0.n423 0Ae 03 n 0Ae423 0.n 03 _H 1 0.:4: O 0.D 4 log 00.D(3 013 , 00.1(3 013 _H 1 0.:04H

FACTORS AFFECTING CORROSION (+) METAL COMPOSITION #MICROSTRUCTURE (ost metals comprise a solid solution which contain inter metallic particles. #ince these two live together in the same metal, there exists a potential difference between them, the solid solution having a lower potential difference and hence corroding. E.g. Aerrous metals O Aerrite -#olid solution/ )ron !arbideKgraphite -)nter -metallic compound/ )ntermetallic compounds are carbon O based and cathodic to )ron. %his means when ferrons metal is in the presence of electrolyte, the ferrite will corrode preferentially. )f the carbon based compound is more finely dispersed, as a result of heat treatment, the corrosion resistance improves considerably. )f impurities exist in the metal then the metal will corrode in close proximity to the impurity. (,) TEMPERATURE: )t is however to be noted that the effects of temperature on metal or alloy cannot generali?e. But under normal conditions, increase in temperature increases the rate of chemical reactions and therefore the corrosion rate and vice versa. (.) STRUCTURAL DESIGN7 %he design of structures should be such that there is no permanent contact of the metal surface with water. Nesigns where water could be trapped without being able to evaporate readily are very prone to corrosion, even if the metal is well covered by surface coating at these positions. &lso threaded >oints, small area anode next to large area cathode should be avoided in galvanic couples.

REDUCTION OF CORROSION ATTAC! (+) CHOICE OF METAL#ALLOY !orrosion effect is reduced or minimi?ed by selecting a material which is corrosion resistant in that particular medium it is going to wor= in. MATERIAL -a/ #tainless steelK@%AE -b/ #teel -:/ 8ead -;/ *ic=el and its alloys SUITABLE ENVIRONMENT *itric acid !oncentrated <4#'; Nilute <4#'; &l=aline #olution

Aor reducing environments such as air Ofree acids and a$ueous solution, *i, !opper and their alloys are fre$uently employed. Aor oxidi?ing environments, chromium-containing alloys are used. !eramics posses excellent corrosion resistance but are brittle and have lower tensile strengths. @olymers are more resistant to chloride ions and hydrochloric acid. (,) CHEMICAL INHIBITORS &n inhibitor is a substance that when added in small concentrations to an environment decreases the corrosion rate. )n a sense, an inhibitor can be considered as a reducing catalyst. Me(al &luminium &luminum #teel E&4'%$&me&( *acl, :.DS #ea water Iater I&5'6'($% 1S #odium !hloride 0.CDS #econdary &my Ben?oic acid

(.) PROTECTIVE COATINGS %hese are made up of7

(') Me(all'78: (ethods used in applying metallic coatings are electroplating, hot dipping, flame spraying, cladding etc. ('') N$& Me(all'7 #I&$%)a&'7: (ethods used are spraying, diffusion coating, chemical conversion etc. ('4) O%)a&'7 C$a('&): %his is mainly applied by paining or spraying using paints, vanishes and lac$uers. %o apply a coat on any surface -a/ F'%8( p%epa%e (5e 89%:a7e7- %his is roughening the surface to obtain mechanical bond as well as to remove dirt, rust, mill scale, oil, grease and other impurities. -b/ P%'me (5e 89%:a7e: @riming of the surface is done by adding a primer such as tin chromate, ?inc dust, red lead oxide, red iron oxide etc which acts as barrier by filling crevices and other surface defects. %hey also contain rust inhibitive pigments. -c/ &dd the actual coating material. ELECTROPLATING <ere the metal to be coated is immersed in a solution of the metal to be plated and passing direct current between the part and another electrode. %he electroplate can be a single metal, layers of several metals, or even an alloy. <ere, the actual metal to be plated is made the cathode with non-reactive anode li=e stainless steel, lead or carbon in a solution of the metal to be used in plating or electroplating metal in its solution. E.g. Aor an automobile bumper, its inner layer of nic=el -for corrosion protection/ and a tin top layer chromium -primarily for appearance/. DIFFUSION COATING <ere, oxides, phosphates, and chromates are used. %he coating involves heat treatment to cause alloy formation by diffusion of one metal into the other. <ence parts to be coated are pac=ed into solid materials and exposed to gaseous environments containing the metal that forms the coating. E.g !olori?ing in which steel components are treated in a heated rotating cylinder containing a mixture of &luminium and &luminium oxide powders.

%hese steels are used in petroleum and chemical industries. Aor organic coatings, follow the procedures above i.e. steps -a/ O -c/ E.g. -i/ &mine O Eood water, acid, al=ali and solvent resistance, hard and good temperature resistance. -ii/ @olyamide O Eood water, al=ali resistance, tough and good temperature resistance. -iii/ !oal tar7 - Excellent resistance to water, #ea water and soil immersion. (/) CATHODIC PROTECTION: <ere metal with lower electrode potential is used as the anode. %his reaction simply involves supplying, from an external source, electrons to the metal to be protected, ma=ing it a cathode" and this suppresses metal dissolution. E.g steel structures will corrode more rapidly if it becomes anodic to its environment. %hus the hull of a ship can be expected to rust more $uic=ly at the stern since it is anodic to the nearby (anganese bron?e propellers in the vicinity of seawater acting as an electrolyte. Ihen slabs of ?inc or magnesium are bolted to the hull near the propellers, it corrodes. %his is because it is more anodic than the steel hull towards the propellers. IRON ; CARBON DIAGRAMS

(') FERRITE (<): %his is the interstitial solid solution of carbon in body centered cubic iron7 -a/ )t is soft and malleable

-b/ )t is stable below 10W! -c/ )t can contain a maximum of 0.04S! -at C4:W!/ ('') AUSTENITE (=): %his is the interstitial solid solution of carbon in face centered cubic irons. -a/ it is non-magnetic -b/ -b/ )t can contain up to 4S carbon -c/ )t is stable between C4:Wc and 1; :Wc (''') CEMENTITE (Fe.C): %his is formed when carbon precipitates from &ustenite. )t is hard and brittle. ('4) PEARLITE: %his is the eutectoid mixture of ferrite and cementite formed by the transformation of austenite during cooling. )t has a lamellar structure. &lso from the diagram the following types of steels could be identified. (4) HYPO EUTECTOID: %his is made up of less than 0.9S!. )ts structure is ferrite and pearlite. (4') EUTECTOID: %his is made up of exactly 0.9S carbon. )ts structure is fully pearlitic. (4'') HYPEREUTECTOID: %his is made up of more than 0.9S carbon. )ts structure is made up of pearlite and cementite. +pper !ritical %emperature -&:/ is the minimum temperature above which only austenite phase will prevail. 8ower !ritical %emperature -&1/ is the temperature, below which, under e$uilibrium conditions, all austenite will have transformed into ferrite and cementite phases. %he solubility line shows the maximum amount of carbon that can dissolve in ferrite -i.e. 0.04S/. (oving down this line brings out -precipitates/ the carbon out of the ferrite solid solution to form pure iron. EFFECTS OF TEMPERATURE ON MICROSTRUCTURE UNDER E2ULIBRIUM CONDITIONS

FOR >.,? CARBON

&t %1 the structure is fully austenitic.

&t %4 : R

P 2R

<ere some austenite phase is transformed into ferrite phase at the grain boundaries of the austenite phase. %he first P- phase is the primary ferrite.

&t %: a % a %4 : <ere more P-phase forms from R-phase.

&t %: : %he last R-phase which remains will transform at the eutectoid point i.e transforms spontaneously into pearlites - a mixture of ferrite and cementite/.

<sec.2 Ae:!

&t %; there is no transformation i.e. normal cooling to room temperature

NON E2ULIBRIUM COOLING )f a hypereutectoid, eutectoid and hypoeutectoid steels are $uenched fro the 9 Ophase, the resulting microstructure cannot be explained using e$uilibrium phase diagram. )n this case we obtain marteusites, which are very hard and brittle. (uch of the hardness and strength in $uince steels is attributed to (artensite. )n its formation, R-phase atoms are not allowed to diffuse to their e$uilibrium positions.

Niagram

TEMPERING OF MARTENSITIC STEELS (artensitic steels are two hard and brittle for meaningful engineering use. Ie need therefore to introduce some toughness in the material by tempering

it. %empering is a heat treatment in the range 400 O 600W!, which permits some of the carbon to precipitate from the super saturated solid solution giving a reduced hardness and improved toughness. )n this process, the steel sample is =ept at the temperature above for a number of hours i.e. -heated to the temperature range above/. %he metal stable view structure transforms into ferrite together with some spheriodised carbide. %he material loses some hardness but gains toughness. N.B: )nternal stresses, which have wea=ening effects on the material, are introduced as a result of this $uenching and tempering the steel at 400Wc can relieve this.

EFFECTS OF TEMPERING TEMPERATURE ON MICRO STRUCTURE AND PROPERTIES %he higher the tempering temperature, the more closely will the original martensitic structure revert to this ferrite O cementite mixture and so strength and hardness fall progressively, whilst toughness and ductility increases i.e. there is formation of spheroidal carbide. &t low tempering temperatures, another form of martensites containing low percentage of carbon together with E-carbides are formed. %his result in a slight increase in hardness with brittleness significantly reduced.

POLYMER DEGRADATION @olymeric materials also experience deterioration by means of environmental interactions. <owever, an undesirable interaction is specified as degradation rather than corrosion because the processes are basically dissimilar. Ihereas most metallic corrosion reactions are electrochemical, by contrast, polymeric degradation is physiochemical" that is, it involves physical as well as chemical phenomena. Aurthermore, a wide variety of reactions and adverse conse$uences are possible for polymer degradation. @olymers may deteriorate by swelling and dissolution. !ovalent bond rupture, as a result of heat energy, chemical reactions, and radiation is also possible, ordinarily with an attendant reduction in mechanical integrity. )t should also be mentioned that because of the chemical complexity of polymers, their degradation mechanisms are not well understood. %o briefly cite a couple of examples of polymer degradation, polyethylene, if exposed to high temperatures in an oxygen atmosphere, suffers an impairment of its mechanical properties by becoming brittle. &lso, the utility of poly-vinyl chloride/may be limited because this material may become colored when exposed to high temperatures, although such environments do not affect its mechanical characteristics. S@ell'&) a&A D'88$l9('$& Ihen polymers are exposed to li$uids, the main forms of degradation are swelling and dissolution. Iith swelling, the li$uid or solute diffuses into and is absorbed within the polymer" the small solute molecules fit into and occupy positions among the polymer molecules. %hus the macromolecules are forced apart such that the specimen expands or swells. Aurthermore, this increase in chain separation results in a reduction of the secondary intermolecular bonding forces" as a conse$uence, the material becomes softer and more ductile. %he li$uid solute also lowers the glass transition temperature and, if depressed below the ambient temperature, will cause a once strong material to become rubbery and wea=. #welling may be considered to be a partial dissolution process in which there is only limited solubility of the polymer in the solvent. Nissolution, which occurs when the polymer is completely soluble, may be thought of as >ust a continuation of swelling. &s a rule of thumb, the greater the similarity of chemical structure between the solvent and polymer, the greater is the li=elihood of

swelling andKor dissolution. Aor example, many hydrocarbon rubbers readily absorb hydrocarbon li$uids such as gasoline. #welling and dissolution traits also are affected by temperature as well as characteristics of the molecular structure. )n general, increasing molecular weight, increasing degree of crosslin=ing and crystallinity, and decreasing temperature result in a reduction of these deteriorative processes. !ondensation polymers li=e nylons, polyesters, and polycarbonates are susceptible to hydrolysis -degradation due to exposure to water/. #tructural alteration of some polymers may occur as a result of exposure to different chemical environments. (ost thermoplastics in contact with organic li$uids and vapors, which ordinarily may not be considered solvents for the polymers, can undergo environmental stress crac=ing and cra?ing. %his may result in a loss of lifetime performance or mechanical stability and ultimately contribute to premature mechanical failure of the polymer under stress. C5em'7al Rea7('$& E::e7(8 'xygen, o?one, and other substances can cause or accelerate chain scission as a result of chemical reaction. %his effect is especially prevalent in vulcani?ed rubbers that have doubly bonded carbon atoms along the bac=bone molecular chains, and that are exposed to o?one -':/, an atmospheric pollutant. 'ne such scission reaction may be represented by

where the chain is severed at the point of the double bond" , and represent groups of atoms that are unaffected during the reaction. 'rdinarily, if the rubber is in an unstressed state, a film will form on the surface, protecting the bul= material from any further reaction. <owever, when these materials are sub>ected to tensile stresses, crac=s and crevices form and grow in a direction perpendicular to the stress" eventually, rupture of the material may occur. %his is why the sidewalls on rubber bicycle tires develop crac=s as they age. &pparently these crac=s result from large numbers of o?one-induced scissions. !hemical degradation is a particular problem for polymers used in areas with high levels of air pollutants such as smog and o?one. (any of these chain scission reactions involve reactive groups termed free radicals. #tabili?ers may be

added to protect polymers from oxidation. %he stabili?ers either sacrificially react with the o?one to consume it, or they react with and eliminate the free radicals before they -the free radicals/ can inflict more damage. *B7 #cission is the severence or rupture of molecular chain bonds. E::e7( $: UV RaA'a('$& $& P$lBme%8 Ul(%a4'$le( -+H/ light is electromagnetic radiation with a wavelength shorter than that of visible light, but longer than ]-rays, that is, in the range 10 nm to ;00 nm, corresponding to photon energies from : eH to 14; eH. )t is so-named because the spectrum consists of electromagnetic waves with fre$uencies higher than those that humans identify as the colour violet. %hese fre$uencies are invisible to humans, but visible to a number of insects and birds. +H light is found in sunlight -where it constitutes about 10S of the energy in vacuum/ and is emitted by electric arcs and speciali?ed lights such as mercury lamps etc. )t can cause chemical reactions, and causes many substances to glow or fluoresce. (ost ultraviolet is classified as non-ioni?ing radiation. %he higher energies of the ultraviolet spectrum from wavelengths about 10 nm to 140 nm -bextremeb ultraviolet/ are ioni?ing, but these wavelengths are absorbed by dioxygen and other gases in the air, and thus have an extremely short path length through air. <owever, the entire spectrum of ultraviolet radiation has some of the biological features of ioni?ing radiation, in doing far more damage to many molecules in biological systems than is accounted for by simple heating effects -an example is sunburn/. %hese properties derive from the ultraviolet photonbs power to alter chemical bonds in molecules, even without having enough energy to ioni?e atoms. )n addition to short wave +H bloc=ed by oxygen, a great deal -c CS/ of mid-range ultraviolet -almost all +H above 490 nm and most up to :1D nm/ is bloc=ed by the o?one layer, and li=e ioni?ing short wave +H, would cause much damage to living organisms if it penetrated the atmosphere. )ndeed, the existence of the o?one layer is what allows life to exist on land, outside of the deep oceans. +H energy absorbed by plastics can excite photons, which then create free radicals. Ihile many pure plastics cannot absorb +H radiation, the presence of catalyst residues and other impurities will often act as free radical receptors, and degradation occurs. )t only ta=es a very small amount of impurity for the degradation to occur, e.g. trace parts per billion values of sodium in polycarbonate -@!/ will initiate color instability. )n the presence of oxygen, the free radicals form oxygen

hydroperoxides that can brea= the double bonds of the bac=bone chain leading to a brittle structure and this process is often called photooxidation. (any polymers used in consumer products are also degraded by +H light , and need addition of +H absorbers to inhibit attac=, especially if the products are exposed to sunlight. %he problem appears as discoloration or fading, crac=ing, and, sometimes, total product disintegration if crac=ing has proceeded sufficiently. %he rate of attac= increases with exposure time and sunlight intensity. #ensitive polymers include thermoplastics, such as polypropylene, polyethylene, and poly-methyl methacrylate/ as well as speciality fibers li=e aramids. +H absorption leads to chain degradation and loss of strength at sensitive points in the chain structure. )n addition, many pigments and dyes absorb +H and change colour, so paintings and textiles may need extra protection both from sunlight and fluorescent bulbs, two common sources of +H radiation. 'ld and anti$ue paintings such as watercolour paintings, for example, usually must be placed away from direct sunlight. !ommon window glass provides some protection by absorbing some of the harmful +H, but valuable artifacts need extra shielding. (any museums place blac= curtains over watercolour paintings and ancient textiles, for example. #ince watercolours can have very low pigment levels, they need extra protection from +H light. %inted glasses, such as sunglasses also provide protection from +H rays. POLYMER ADDITIVES &ny additive compounded with basic polymer will influence the structure and hence the properties. #uch additives may be used to stabili?e the polymer, to improve the wor=ing properties to change the mechanical or physical properties or introduce colour. %ypical additives include filler materials, plastici?ers, stabili?ers, colorants and flame-retardants. (+) FILLER7 %hese are materials most often added to polymers to improve tensile and compressive strengths, abrasion resistance toughness, dimensional and thermal stability and other properties. (aterials used as particulate fillers include wood flours, silica flour and sand, glass, clay, talc, limestone etc. @article si?es range all the way from 10mm to macroscopic dimensions because these inexpensive materials replace some volume of the more expensive polymer" the cost of the final product is reduced. Eg.

-i/ (ica added to phenolic type resins improve electrical resistance" -ii/ Erapluite also reduces frication -iii/ &sbestos improves temperature resistance. (,) PLASTICI-ERS: %hese improve the flexibility ductility and toughness of polymers. %heir presence in a polymer soften it and produces reduction in hardness and stiffness. @lastici?ers are generally li$uids having low vapour pressures and low molecule weights. %he small plastici?er molecules occupy positions between the large polymer chains effectively increasing the inter-chain distance with a reduction in the secondary inter-molecular bonding. @lastici?ers are commonly used in polymers that are intrinsically brittle at room temperature, such as @H! etc. )n effect, the plastici?er lowers the glass transition temperature, so that at ambient conditions, the polymers may be used in applications re$uiring some degree of pliability and ductility. Eg. @H! can be plasticised by adding 1DS of vinyl acetate during polymeri?ation. (.) STABILI-ERS: %hese are additives used to reduce polymer degradation. (ost often this deterioration is a result of exposure to heat, light -in particular uv radiation/ and also oxidation. +v radiation interacts with, and causes severance of some of the covalent bonds along molecular chain, which may also result in some cross-lin=ing. 'xidation is a conse$uence of the chemical interaction between oxygen atoms and the polymer molecules. <eat is as a result of exposure to very high temperatures. E.g.7 - @olyisoprene can absorb up to 1DS oxygen at room temperature, with its elastic being destroyed by the first 1S. &t this temperature natural rubber latex can be used to retard this oxidation process, however at elevated temperatures stabili?ers li=e amines, sulphur compounds are introduced -rubber intended for tyre applications/. !arbon blac= is used as ultra-violet stabili?er. 8ead and %in compounds are also used as heat stabili?ers. (/) FLAME RETARDANTS: %hese are added to reduce the inherent combustibility of most polymers. !ombustion is simply the reaction of a hydrocarbon with oxygen accompanied by substantial heat evolution. %hese retardants may function by interfering with the combustion process through the gas phase, or by initiating a chemical reaction that causes a cooling of the combustion region and cessation of burning. <alogens hinder the process of combustion by terminating free-radical chain-reactions. &dditives that provide this function for halogen-free polymers include !hloride-, Bromine-, and @hosphorous-containing

reactants. @igment addition produces opa$ue colours and transparent colours are produced by dyes. (0) COLORANTS: %hese import a specific color to a polymer" they may be added in the form of dyes or pigments. %he molecules in a dye actually dissolve and become part of the molecular structure of the polymer. @igments are filler materials that do not dissolve, but remain as separate phase" )norganic pigments such as titanium oxide and aluminum silicate are much superior to organic colorants in weather resistance, in stability to heat and light and in their resistance to bleeding. (1) ANTISTATIC AGENTS (ANTISTATS) Ihen two surfaces that are in intimate contact are rubbed together or pulled apart, static electricity is generated. %his is due to the transfer of electrons from the surface of the donor material, which conse$uently becomes positively charged, to the surface of the acceptor material, which then becomes negatively charged. Aor materials that are nonconductive -(ost synthetic polymers are good electrical insulators/, these static charges do not [ow easily along the surfaces and therefore remain \xed or static. )n conductors however, these charges easily flow to the ground ma=ing the level of static charge developed difficult to measure .Electrostatic charges can cause problems when textile, \lms, or powders >oin up in automatic machinery. #par=s, and possibility explosions or \res, can occur when static electricity is induced from plastics on nearby conductor. Namage of sensitive semiconductors and similar complex microelectronic devices can also occur by exposure of such devices to the close approach of a static-charged polymer material. %here are essentially two types of antistats that are commonly used in polymers to get rid of static electricity7 those that are applied topically and those that are incorporated internally into the polymer. Both improve the conductance of polymer surfaces by absorbing and holding a thin, invisible layer of moisture from the surrounding air onto the polymer surface. %opical coatings are usually applied using wipe, spray, dip, or roller coating techni$ues. )nternal antistats are compounded directly into the polymer mix prior to processing. %hey then migrate slowly and continually through the molecular interstices and the bul= polymer to its surface where they absorb the water necessary to prevent accumulation of static charges. (a>or types of organic antistatic agents include $uaternary ammonium compounds, amines and their derivatives, phosphate esters, fatty acid polyglycol esters, and polyhydric alcohol derivatives such as glycerine and sorbitol.

C$p$lBme%'8a('$& (acromolecular design and architecture through copolymeri?ation of monomers has led to a number of commercially important polymers. !opolymer composition can be varied over wide limits, resulting in a wide range of propertyKprocess performance. & copolymer may be composed of comparable amounts of the constituent monomers. %he properties of the resulting copolymer will be substantially different from those of the parent homopolymers. 'n the other hand, the copolymer may contain only a very small amount of one of the monomers. )n this case, the gross physical characteristics of the copolymer probably approximate those of the homopolymer of the ma>or constituent, while the minor constituent confers speci\c chemical properties on the copolymer. Ie now illustrate these principles by discussing some examples. #%X,E*EOB+%&N)E*E !'@'8X(E,# @olybutadiene is an elastomeric material with good elastic properties and outstanding toughness and resilience. <owever, it has relatively poor resistance to oils, solvents, oxidation, and abrasion. @olystyrene, on the other hand, is relatively chemically inert and is $uite resistant to al=alis, halide acids, and oxidi?ing and reducing agents. )t is also very easy to process. But then, polystyrene is $uite brittle with a low heat-de[ection temperature -94 to 99`!/. #tyrene and butadiene copolymers provide a good illustration of the considerable latitude in the variation of polymer properties that can be achieved by a careful manipulation of the composition of the copolymer and the distribution of these components. #tyrene and butadiene can be copolymeri?ed to produce either random, graft, or bloc= copolymers. #tyreneObutadiene random copolymer exhibits a homogeneous single phase and has properties intermediate to those of the parent homopolymer. 'n the other hand, bloc= or graft copolymers of styrene and butadiene form heterogeneous multiphase systems whose properties are not simply characteristic of each homopolymer, but are dictated by the multiphase character of the copolymer. (ost of the defects of polybutadiene homopolymer can be overcome by the incorporation of 49S styrene into the copolymer. %his is due essentially to the great rigidity and other bene\cial properties of the styrene molecule. %he enhanced properties of #B, and its ease of processability ma=es #B, the preferred material over natural rubber in such applications as belting, hose, and molded goods and in vulcani?ed

sheet and [ooring. ,ubber shoe soles are made almost exclusively from #B,. !opolymers containing about 4DS styrene are also useful adhesives, especially in the form of a$ueous dispersion or in solution. )f the ratio of styrene to butadiene is in the range 607;0 and higher, the copolymer is nontac=y and is used in hot-melt adhesives and latex paints. Aor example, emulsion copolymers composed of C;S styrene and 4DS butadiene -by weight/ \nd wide applications in paints. )n those applications, the hardness of polystyrene is partially retained, but its brittleness is modi\ed by the presence of butadiene. &!,X8'*)%,)8E-B+%&N)E*E-#%X,E*E -&B#/ &B# is the generic name of a family of engineering thermoplastics produced by a combination of three monomers7 acrylonitrile, butadiene, and styrene. %he overall property balance of the terpolymer is a result of the contribution of the uni$ue characteristics of each monomer. @olymer chemical resistance and heat and aging stability depend on acrylonitrile, while its toughness, impact resistance, and property retention at low temperature are developed through butadiene. !opolymer rigidity, glossy surface appearance, and ease of processability are contributions from styrene. %he terpolymer properties are controlled by manipulation of the ratio and distribution of the three components. &B# resins consist essentially of two phases7 a rubbery phase dispersed in a continuous glassy matrix of styreneOacrylonitrile copolymer -#&*/ through a boundary layer of #&* graft. %he dispersed rubbery phase is rubber polymeri?ed from butadiene. #tyrene and acrylonitrile are graftpolymeri?ed to the rubber thus forming the boundary layer between the dispersed rubber phase and the continuous glassy matrix. )ncreased molecular weight of #&* improves product strength and ease of processability, while the concentration, si?e, and distribution of the rubber particles in[uence product toughness and impact strength. By a careful variation of the parameters controlling the phases, a family of &B# with a broad range of properties has been developed. E%<X8E*E !'@'8X(E,# 8ow-density polyethylene -8N@E/ is produced under high pressures and temperatures. )t \nds applications in \lm and sheeting uses and in in>ection-molded products such as insulated wires and cables. )ts physical properties are dictated by three structural variables7 density, molecular weight, and molecular weight distribution. &s density increases, barrier properties, hardness, abrasion, heat, and chemical resistance, strength, and surface gloss increase. 'n the other hand, decreasing density results in enhanced toughness, stress-crac= resistance, clarity, [exibility, and

elongation and in reduced creep and mold shrin=age. (elt index -()/ is a measure of molecular weight" it decreases with increasing molecular weight. )ncreasing () improves clarity, surface gloss, and mold shrin=age. Necreasing () leads to improved creep and heat resistance, toughness, melt strength, and stress-crac=ing. *arrower molecular weight distribution gives better impact strength, but reduced resin processability. & broader molecular weight distribution is more shear sensitive and, conse$uently, leads to shear viscosity at high shear rates and is thus easier to process. By copolymeri?ing ethylene with polar P-ole\ns, it is possible to produce a variety of materials ranging from rubbery to low melting products d suitable for hot-melt adhesives d to those that demonstrate unusual toughness and [exibility. %his class of copolymers can be represented by the general formula

where , is a polar group li=e Ethylene O ethyl acrylate, Ethylene O vinyl acetate etc. %he introduction of comonomers with a polar pendant group, ,, produces a highly branched random copolymer but with increased interchain interaction. %hus, relative to the homopolymer, these copolymers have enhanced [exibility, toughness, stress-crac=ing resistance, oil and grease resistance, clarity, and weatherability. )n general, the range of properties of the copolymer can be varied by varying the proportion and molecular weight of the comonomer.