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    Biomaterial CHAPTER Degradation Main Objective ‘To understand the molecolst mechanisms bebad envzonmentaldepeadation of ‘metals, ceramics, and polymecsin the human body. Specific Objectives 1, To dtngush eeween controled and uncontrolled material degradation, 2. To understand how redox reactions case coroson. 3, To compare and contrast pes of cotosion 4 To understand the cotibtion ofthe location ofthe implant ots coreson 5. To compareand conta e degradation of metals, ceramics, and polymers, 6 Todtnguh brween polymer chain cision by hydrolysis and by oxidation, 7. To undestand the factors est iflunce conteolleé polymer and ceramic degradation, 8 To diingish between bulk and surface erosion of biodegradable polymer sem 5.1. Introduction: Degradation in the Biological Environment Ince previous chapters, we hare explained how te physical and mechanical prop- erties of ferent classes of bimaecls are dependent on the atomicimoeclar steotre ofthe materials nts chaps, we wll describe how the degeadstion of material ia the body i also alleced by his structure, and how the degradation proces fet the physical and mechanical properties ofthe overall materi, Biomaterial degradation ca oct in ab aneontrlled manze, which is usually undesirable bcaie ioe lent structural beskdown of the material and pre rmtre file ofthe device. In contas, some materials have been designed to lic implants. Also, specific eacons, such as the actions of inflammatory cells can change he loa chemistry around a device after implantation, As disused further in Chapter 10, spec inammstory els may attach wo the biomaterial surface and ex- | ft i t t 52 ConanDxgaaiton fMeasand Cees 179 through coupling of two reactions oxidation, hich generates eectons, and reduction, which consumes cero. Combinol, these are teed redox reactions. Fora metal M wit valence elton, oxidation canbe represented as MM ne where €° indicates a free election The place where oxidation occurs is elle the anode “The comesponing reduction ration depends on the enviroment in which the (087) “These reduction reactions tke lace atte catode. ‘A simple example of coupled redox reactions isthe formation of an eeto hemiclfrgalvanc) cl aleoclled abate, using a stip of sold rnc immersed ina solason containing snc ios and a stip of copper ina separate contains with 4 solution of copper ions (Fig, 51) The two solutions are connected with salt bridge composed of substance that realy dsociaes into ions, such as KCl The ‘ica is completed by connecting the wo metal strips (electrodes) witha wie so that eketrons can flow from one pice of mex wo the ober. A vokmete is also placed in the ici to record he pteatial ference beemeen the electrodes Teach compartment lle alll reaction occurs. nti example, ine isoxiint tn 2st +26 while, in the other half-cell, copper ions are reduced: ca +27 Sw Ing eZ HOFFA ey Figare 51 ‘An esti (0 vi) 8 stip of sd ne andl oper ai rene incoespuinsl tins cong nin as end ope ins, especie. The te slions are cone veh at edge emp asiboane tht aly ie ‘oso jos has KCL ‘Reonpeed ea formed hy cone the two sal stip (deo) with 2 wre fo tht dowons can fom Fromene icf nent othe tah Arlee i sed co ror he pst diferee Terwaen the erodia thease, LIV. (Adaped wth remisin fom 2) 18 Chapter Sra Dorin Figure 5.2 Inedes rank cen Setar of dilere mes, the paral diference for sch tli mesued wi reset to a standard yee rm suede A. yop Sleawode i fom by bb Wing den cog 2 1 solton of HCl coining 2 Sup of platinum (an ine facie of which the hye to os can be onde ‘ede From spatiale sep te sandd redion potential canbe measured fe ine (a) and copper (b, (Adapeod wih permision ‘row 2) “This ests slow dsolution ofthe sali in anode, with concomitant deposition ‘of copper atthe cathode, The oe ofthe sal bridge iso provide ions that maimain sa neura charge in each hale the concentrations ofthe solutions in each com partmens are 1M and he cll is tested at room temperate (standard conditions), the volneter in the cect should read 1. ‘5.2.1.2Half My Bf (metal Mis educed) Here, the values for BY and Sate thse from the standard reduction poential table fee Table 52), Because M, is oxida, the sgn ofits redocton potential st be versed (EY), 182 Gs Somes Dagan TABLES Seles sel passive) [ikea boys psi) (30% Ni alloy Copper ‘Alumina bene 38% Zn bass [Nickel base alloys ate) Manganese brome Cotte Zara Ta led 316 wanes eft) 5 50% Sa oder 410 stiles el ci) stron ow carbo sel 2004 auc s 2017 aluinum Cedi Aad 10 alia 5092 slain Gatanzed ae Tie ‘Magpesiumalays Anodic Magpesiom 1 ped wi poss ion IT ‘The ovenll easton ix M+ MS MS My and, adding the standard hall potential, he coresponding electrochemical po- tential fe the ent ellis ‘ABS = (E} ~ BS) (5) Inder to take into account deviations fom the conditions in which the stan dard reduction potentials were measure changes in temperature orion concent tio) the equation becomes ur) MF (52) ae = (et et) - Ta where Rte gas constant (8.314 JK" mol), Tis the absolute temperate (K), Fis Faraday’ constant (96,500 coulombstaol) and, Ef and Fare as previously described This isthe Nernst equation, 52 Conan Degoinon sf end Ces 183 EXAMPLE PROBLEM 5.1 Consider an decker el of inc and copper dsb inn et and asa in Fe SL (a) suming ta the cones ofthe Sluins in ach compartment are 1M ad that thecal tested arom tempest standard eoaicos), how hat the poeta di feeneberwen the cto 5 11V. (b) Conse now hat the comin ote cel have changed lw The cis sted at body temperature (37°C) and the encntatons ofthe zine and copes solos in ch compareene ae pie. scum contains of ese ios (107 pall. ad 15 pg/dL, epic). Casale the petal ifrence betwen the dearodes onder hse contin. (c) Assing the ane on oceans ae ie npr) wat temprtce woul he sem asd obese forthe paceal eres bowen be electrode eg 1.150? Soliton: (a) Ta ths clcwochnial all sess eng ized andthe coppers bing rece as esc in hex. Thus, thefllowing chen acon are oxzig Za ta 4 vote New Zn Ga > Za" + Cu =o Loskicg. up the sandrd cleode potently fom Table 52, we find tht [f= -D768V(Z0) and Bf ~ #04001 Ca). Unde Sandard oodons, te penal ference eeeen the two eto ealtlted by simply abeacing the Sadard eff the anode rom te ated a flows: B= BP BF = OOV-(-0.768)) = 1.1080 In nonstandard conden, he porns diffence Been the eked shuld be caine sng the Nest gen aE BSB nF Her, the emf vals ae as tlre, Ris he gas constant (8314 K mol), Fs Faraday conan (96500 Cali 2, ard the absolute senpeceae T is yen (GPC™ S10). Taeconcentation fic an beeklated tom he given intron ssfolows: (0.90107 gf) eoe/65.39 9 7a)(10 L/L) ~ 0.0164 pM Za Sin theconsatonofnper canbe cleus a (.0015 gfe. g Cay L/L) = 0.0181 yee Paging th vals the sqution ies i eure) ™ con Tse smeCjmal [Tar ya) AB = Lin BE = (0.40¥-(-0765¥))~ 184 capers Borate Dgyactior Figure 53 ‘Av exampe of Pour da ‘gam fr iron, depicting re Bons often and onc 23 fon of cel pial sd pEL The re ns decd in this parr Shr gamle asune tha safae fim of pidecace {anno oxide min fey OOH forme ner rope candions andi Fis pete spit cero sion. The sable of water repre via the digs) ded ies. Aquos co sion, if ecu, wil ake plein evonment fling ferween thee two Ines Sample physilogcl envio ren sock assal ard sic hid ral howe. (Ada with persion om 5) (6) Using the same eqn a in band sving for AY 1.15 yids J sauce) cane -36800(Cfao}) [0781 aM ASV = (0340V + 07689) ~ an sling for T, we ind tha th tenpectice mus be sproximately LOGI forthe psi difeence betwen the decodes teal L.15V! . 5214Gabrani Corsion One ofthe mst common forms of ocsion core sponds well tthe dsipion of pial cletochenzl el and chi is eel falaicorosin. Ia thisaseev deren ype of meals areal coupled when acelin the bed ike the wie connecting the wo code in Fi, 5.1 hysiobi hid becomes the sa bridge completing the cc. In tis swat, thermo ave metal wil dsl tan accelerated pace, For example, file sli sd in onjaneon with aother allo it fen undergoes anodic dsolton owes idle wo pret meal degeadation in sack a syste ley based on th cvs inte inthe plane serie ce Table 5.3} Bese corexon is ver complex proces. One inportant consideration that he oxidation ae duction ates mst be equal so thai locaked ching redace ne reaction, the the cera corxon may be signicanly slowed. An example of his is meal passion, discs inthe next tion, 5.2.2 Pourbaix Diagrams and Passivation In addition tothe parameters discussed above, coerosion activity fora certsin neta alo depends onthe pH of the solution in which it simmered. In order to further efie predictions of corrosion in various environments, « Pourbaix dit ‘gram nay be created. As shown in Fig. 5.3 for iro, a Pourbaix diagram fora 52 Consin/egrdion Mae nd rch 185 gjren metal depicts regions of corosion and now-octoson as a faction of cell potential and pH. Pourbaixdigrams are formed using results from the Nerast Equation and the soluble of gossible degradation produess, as well s other factors. The diagonal dashed line inthe figure cepcesent the stailty of water [Aqueous corrosion, if i occur, wll ake place in environments fling berween these wo ies. “The Pourhax diagram is divided into three main eons coroson, immanity, and passivation. Corosion is arbirarily defined 2 a region in which greater than {17° ofthe meal’ ons are found insouton a equim, les than ths con- entation is measured, the mets may fll io either ofthe other categories i= ‘mane ox pase. Inthe immune region, i isnot energetically favorable for the ‘etal to corrode dissolve) This paesomenon ils called cathodic proection be- ‘use the metal cant act san anode under these conditions, Pasivation occars whe surice oxidation leds tothe formation of a stable sold lm usually an oxide or byoxide) that coats the sufece ofthe metal In this regio, athough it may be enepilly favorable, corosion can be slowed or stopped dc to this thin, insulative bari that eve teanser of ecwons in and ‘ut ofthe metal In patil, mets sacha chromion, ton eke titanium, and alaminum haves tendency to form these coatings “The diagram in Fig, 8.3 als includes ates representing the composition of Ailernt body Eid, so chat ite pose to pedi he eesponse ofa metal in var ‘ows locations inthe body. Te rion found in Pourbaix diagrams ive an idea of which eations ace posible in to, but cannot eect he rate ofthese esctions. This rate, which soften defined ia terms of caren flow pe surface area, is de pendent on othe factors, sch s possible depletion of ions around the cathode. A ‘ealed discussion of coresion ate calculation is beyond the scope ofthis tet. EXAMPLE PROBLEM 5.2 ‘The pl of wounds crested hough he implantation of «materi xn drop ese ably o aii valos ofS oon nape he ypobcal ae of surgeon implanting» bene plat componed of sis se wth anton costing. Asie tat he pt of he ti sue suzounding the implan drops 5 during the wound hang espone and that the ‘argc team dd no oie an alumina sre tat as acienally dropped ino the ‘ect ea the plant, Asam ao tat ap eeosemiacll screed hough ee a teraction betwee the on sluieue and excelled Using the Pours diagram forte genia Bg $3, woud you ape theron coating to code with acl petal ‘of $0.1 Would yo expect the ite outing 0 corrode wth» el poet of 0.402 Sans The dha nes onthe eta gram inate he ange of condons fr whik waters sal, with th coins ling eee ese nes bing conc 1 he Prseres of wate sig he Porbiaigem farwo,at apHf approninacelS, ageous foc tn cr wheat cl ptt is bree approxima #03 nd 30 “Tas at cl oni of 0.10%, ene woud exp the cto Bex cade othe quan envioament pH of 5. Hover ata ce ptt of 040 anda plo one ‘ould or expec aguas cota ete onto csi the condos exe stcity wats (sina bythe dsb ins e their . 5.2.3 Contribution of Processing Parameters Anumbee of adivonal factors bedes metal composition can enhance eoeosion jn von, These inlade metal rocesing and handing techniques, discussed bere, as swell as mechanical loading andthe peseoe of peoens, cells and bacteria which retreated in subsequent sections, Ahi tha causes the presence of diferent mic ‘cosractures within an implant enchange loeaized ion concentrations and hus fet 106 Cupne 5 Srtea Dogar Figure 5.4 An example of crevice cer. Sn onthe ple of bone fixation device. Caton cured inthe nto, dap crak beeen these (not shown) and pit. Arows inde where croion has secured. (Reprinted with pesmisio on 1} Figure 55 Atheorical meshaism of crevie ezrin. Depletion of exgen occurs withthe tree, exusig xidation of the metal in thie lection, while the reminder of te pace beeams th cathode (Adapred with pemision ‘oom (6h) the conesion rate, These canbe the result of tiny aw o racks introduced during fabrication, or overall device design, 5.23.1 Crevice Corosion As th name impli, crevice arrosion ocusin areas ith a narrow, deep crack for example, in beeween the screw and plate ofa bone fxaciondvie (ig, 54). Certain metals commonly wed in orthopedic application, such as sales steel, can exhibit tis tye of corrosion, whl other, ike anim and colut-chromium alloys are ess susceptible. Akhough the exact mechanism of crevice corrosion is ot fully understood, its thought to begin withthe depletion of ‘oxygen within the cece. Ac this pin, ony the anode ection i possible in the crevice, which resus in oxidation ofthe metal inthis te, while the reminder of the pie: becomes the cathode. Outside the crevice, oxygen cedaton ress in an erase in pH. A digram ofthis proces is found in Fig, 5S In tae presence of sodium chloride solution as found in the body, crevice cor rosion is further accelerated by the dflason of Cio into the crevice to balance the charge ofthe MP ions created. The compound formed can react further to ‘rodce an insoluble hydroxide and liberate Hs MCI, + akkO > MOH), + alr 52 ConoDepoitonf Weta nk Cais 187 “Tis decreases the local pH and ovies« more corrosive environment, thereby ie rifcaly increasing tert of metal dsoluion within the crevice 5.23.2 Piting Corrosion Pig corrosion i caused by the sme mechan as ‘revce corso, As sown nig, sails stk can also undergo this ype foe reson In this case, procesing ot handing may lad to a small faw or are in which the pasion film onthe surface doped lading tthe formation of ela teal anode snd lege cathode, cae o this inequality in surface area and che fact, that teeter ofboth ecto at be equ the andi eons undergo significant isolton Tis ia partly dangerous typeof cvtosion beau ican go unde- teed unl device fire due othe sal overall material los. 5.23.3 Intergranular Corrosion Devices fabvcated by casing (ee Chapter 6) ‘often hve makin prin and dhs are paca sasepible ty nterranlar eoro- sion. As dctsed in Chapter 3, he grin boundaries re aa heghteneesergy state and therefore may represent nove ative (andi) regions ofthe materia. Pricularly inalloy, this can edt intergranular rack by similar mechanism asthat deserted for crence coeason [Fig ./- A comuvon example ofthis coerosion of snes sel atthe grain boundaries so depletion of chromium nthe re, Chromium s equi to form a passivatng yer onthe mera: ifthis is removed he area uly undergoes corosion and, inthe eaceme case, may crumbleinto many ny pices. 5.2.4 Contribution of the Mechanical Environment In addin to fabscation and hiding parameters, the lcation ofan implant bs large fect on the length of in lapsed boc substantial corrosion cecrs. fade vce used in a tase thet undergoes continued movement andisconstanly under load, the corosion este can he gical higher han for similar deve lcaed ing less stressed environmen. The presence of mechanical stress ca potent cor reson by increasing the nimbe of microcracks i ameta, Ao, a material under stress is ina bigher energy states is more susceptible ro the chemical eeatons that produce corrosion, Figure 5.6 Piting cos seo on 2 sanpleof sinks seel Small Celeron the saa of the recat a8 an ano, = sulingin coon at hat sion Reprined wih emis eon (7) 188 capers Bomatal Dayar Figure 5.7 -Avexsmplofinegandlar cooson The same proces ten in crevice orton asus i his isin, wi the pin boundaries ating a te anode (Reprinted wi eso rom 8} 5.24.1 Stress and Galvanic Corrosion Bending a meal rd or plate will cause the teil side o be anodic compared to the side in compression. This encourages ‘alan: corosion in a material that otherwise would have no difference in electro- chemicl potential Between the two sides, This same eflct can be observed neat sires users (see Chapter 4) such as holes or sharp comers. 5.24.25tress Corrosion Cracking Stress oroson cracking occurs toa metal that 's bth ander tension and subjected to a corrosive environment. Tis combination re salts in small racks that frm perpendicular to the direction of applied sess ands particu dangerous because ican our at relatively low loads blow theultimate tense eng) andi solitons tat would aac be wel tolerated by the mat ral One formed, the cack propagate and edt rile fractre, eventhough me ais uadkionally exhibit substantial ductility. Alloys, especially sinless sel ae Sscepeble to this pe of degeadstion in the presence of saline soins like tht found ivi, 5243 Fatigue Corrosion In figue corrosion, continued beng, loading o& rosin around the implant may dsp the passivaing film formed onthe mal and expe the undying surface, leading to corrosion ofthis area. As discussed in hopes aie properties are measaed by recording how many ccs ofloating, a dececanunderg ata certain tes without alr tigi) in easion fr tig te maximum tes fir decease contin athe numberof ding exes increases. Therefor ths typeof arson may sical shore the f ‘au ie ofthe implant and rest in peat devi fa. 52 conenDagaaionfMeabandcearis 189 © 5.244 fretting Corrosion. Unie the oser typeof eocosion sedi tis = ting corrasin sat rated to lading bats dependent on motion net plant Trp of corrosion invosreroal of te met’ passiating ayes ‘prveranal mean, This ca be he creation of ick nthe sure that dss not Pr esate, oF ey poe in which che pase aye is formed and then de ‘Fed pet ei hgh ht ing cotosin plays 2 roe in the dead fone aoand connections bewenfation plats an bone sews Fg 5 5.2.5 Contribution of the Biological Environment Besides he effects of mechanical fctrs the implant’ location in the body ean in- flaace cotesionin other ways. Chemical and celle constituents of he biologie riliea may ae the eonesion ate substasaly. Iti important to emer that the loaned ewionment sexy constant, with diffsion of sons, migration of ‘all, and chen reactions taking place continously, which ads yet another level ‘of complexity pedi corrson rate in vo, “The physiological lads and tissues surrounding an implant ae rich in po tens and cells, The erat of inflammatory cell to the are after biomaterial implantation can cause dasse changes inthe chemistry surrounding the implant, including 4 drop in pH and rckase of song oxiiing agents. Although it may sem that bok of these responses would promae corrosica, thas been found fot some metals thatthe oxidizing agents telesed during inflammation actualy con- tribute to the growth ofthe pasive layer on che surface, so te effects of sur rounding cells on coreosion mt be evaluated forthe specific system of intrest before se inthe body. “The atachment of proses the meal surface (see Chapters 7 and for why this occurs) may abo have a nenbe of fects. Poin can alter the naar of the pase layer on the metal by eaig a bacer eat reduces oxygen dfusion co the urface Thi intr, rede the salty of the oxide layer formed on the implant, Electrochem potest can abo be afcted by proteins ha act s eetron cai= rs hereby shifting all paramere so tha they fall ouside the pasive region on the Pourbaix dagram. Finally cetin proteins requite meal ons to feeton, so they havea ataal affinity to scavenge metal, If they consume a poduct ofthe coroson teaction, thee presence may alert equlisium and favor fre dissolution. ‘As discussed further in Chater 14 bacteria may attach tote implant during insertion or a some Inter pin kading o infection ofthe device. The by-products ‘of bacterial metabolism can cage the regional pH near te material which ats the stability ofthe passive layer. Adionall,bacesa ean consune hydsogey at ion often founda the atde. Like met scavenging by pois tis change ine ‘coon squlibium may eecourge anodic dsoluion : 5.2.6 Means of Corrosion Control Although comosiv atack dv tthe ature ofthe boogia envionment cannot a vray be controle, reduce o corrosion is possible via key decisions inthe design and fabrication ofthe implant, For example, ses-induced corrosion can be mit tated by desing dries ith ew ses elses. Silay, galvanic corrosion may be prevented though selection 2f combinations of meals that are close together in the gana series. Healy, the device would be fabricated fom only nonreactive | cathodic) meas ike gold, ler or plain, but in many cases, th mecbanial | mopersof tse ea im ha cies, To 2 conmrai me ls kown to form passive xide coatings ar often employed tier in their pure ot 190 cages ome grain alloyed form, ro create implants with corrosion resistance as well as sufficient me ‘hana suength. Inaddition, extra provewing steps may be included to prevent specific ypes of

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