Part tt. Digesion in Meals Dae Diffusion in Copper and Copper Alloys VB, VIB, and VIB Daniel B. Suirymowier, John X. Manning, and Michael E. Read juan, and erica analy i prenented of dats compiled Grom the acento ites ture concerning dfsinn in copper alloy systems ining element In Groupe 1A, HI, TUB, 1VB, YB, VIB, and VIB. Here the term “copper alloy syste is interpreed in the broadest sence For cxample the review of difasan inthe Cul ate reports all isin stan which vl bath ‘capper and element M, including fusion of Cu io M oF in ony binary, ternary or multicomponent ‘oy cataning M; iusion of Min Co or nay alloy containing Ces and fain of any element in ‘ny aay containing hath Cu and M. Tope include volume difasion, surface difsion, rain boandry Sifsion, tracer difsion, lly interdusin, lecuomigraton, ihermomigraton, disucatwn-pipe ‘iuson, and ifusion in ten ret. An eaensivebibbosraphy i resented long with Rares, labslrprerentatonef dat nd icunsion fel, Key words: Alby dfn: beim: cesium cesoms chromiums tion; curiam; tein boundary differen, Hydrogen spurt dies per: dilfron: electri: iiuid'mea! diferon atu, lates: magnesia anzanese; raybenum: nib: plenum assum, ptesendyrinm, promethiam: thesoms rabid: sodium, cuface disor taal, Terbiomy, terete llc thertogation, hls, nium tngstens uranium, vanadium Contents List of Pablee. sesntnssen 118 3.3. CuCe References List of Figures. . 180 4. Copper-Chromium.... 1. Introdsction. 10 4 Cr Cun 11 Organization of Review According to 42, Cu-Ce Interdiffusion Alloy System... wo 43 Gasca 12. Methods Used to Present and. Com 45 CuGrFe. or W485. Cari 1a § tie CnGrX. Different ypes of Diffusion Coe 47. Molten Metal Studies. cients 18248. CoCr References... 14, Diffusivity. Permeation, and” Sola. 5. Copper-Cesium, bilty of Gases in Metals'and Alloys... 188 6. Copper-Europium 15. Note on References... 18562, But Cosson 1.6. Introduction References SO 18562. CoB References. sonra. 2 CopperDeryli 106%. Copperydrogensenncn 21 Be Cu sn 1% 71. CoH 22. CutsBermnnnnnnnnnmne 187) 72. CuthAw 23, Be Bee eee 18913 CultBe, 24. CuBe Imerdifusion CIID a9 Ta. Gusta 25. AgeHardening. {am 73. Cosi 26. CuBedenn 19376, CoH 27 cubealo : 95 he Cuaben 28, CuBeFe.. 19378 CuHX 9. CuBel. ssnsonneonn 19379, _Electrotransport 210. CuBeOnn nnn 19% 7.20, Molten Metal Studies 2M, GuBeX. nnn 193 711. Cust References 2.12. CuBe References... 193 8, CopperPotassium... 3. Copper-Ceriom: : 19) 81. General Comments. Sh ber Ub 19) 82. Crk References... 32. Cu Ce lectromigration) 195 9, Copper-Lanthanum orth @ Wi eS Samy of Cmte The 9. La» Co sete Manes 92, CulaB ” 4 Phys Chm a. Dete, Yo. 4, No.1 jusion in Systems Involving Elements of the Groups 1A, IA, IIIB, IVB, Contr, Metllarey Dison, Intute for Materials Research, Natio! Bureue of Standards, Washington, D.C 20034 195, 196 196 198 198 198 198 18 198 199 19 199 19 201 201 201 208 208 20 a an cat a 2 213 213 213 213 23 aia178 93. CuLa References. 10. Copper-Lithium YOA. Gut 102. Cui Interdifusion. 10.3. Dislocation Pipe Diffusion 104. ‘Thermotransport 105. CuLi References. 11. Copper-Lutetium Ma. Lat Cu, 112, Gu-Lu Reference. 12. Copper-Magnesium 22.1. General Comments 122. CuMs-Al and CuMs-X, 123. CuMg References... 13. Copper Manganese... 132, Mn*= Ca.scn 132. CuMn Interdiffusion 133. CuMmAl.... 134, CuMnNi 125. GuMnZ, 136. CuMn-X. 18.2. Molten Metals... 138. CuMn References... 14. Copper-Molybdenum 14.1. CuMo Interdiffusion 142. CuMoFe. 163. CuMoX. 1444 Surface Diffusion 145. Grain Boundary Diffusion. 14.6. CuMo References . 15. CopperSodium, 15.1, General Comments 15.2. Cu'Na References, 16. Copper Niobium... 161. Nb" Con 16.2. Cu-Nb Interdifusion 163. CuNhZr 164, CuNb References 11, CopperPromethium 111, Pm*— Cu. 172, Cu-Pm Reference 18, Copper-Praseodymium... 181, Cut Pr OP. GuPr Refercnece 19. Copper-Plutonium...1.. 19.1. Cas loterdifision.. 192, CuPua... 193, CuPu Reference. 20. Copper Rubidium. 21. CopperRhenium, 211. General Comments 21.2. CuRe Reference: 22. Copper-Tantalum.. 22.1. General Comments 22.2. CuTa Reference: 23. Copper-Terbium 23.1. Th? Cu. 232, Curt Reference: 4. Phys Chem Ra. Dat, Vol 4, Ne, 1975 233 233 233 233 233 233 233 233 BUTRYMOWICZ, MANNING, AND READ 24, Copper-Titanium. 24 Cum BT Cu-Ti Interdiffusion.. CoTiAg... CoTeB., CuThH Cutent Cut. CuTiRe. CoTiX ‘Molten Metals Cu-Ti References... 25. Copper-Thulium 25.1 25.2. 26. CopperUranium ... Zot 262. 26.3, 264, 265, 266, 26.7, 21, Copper-Vanadum 21 272. 27a Tm' Can Cu-Tm Reference .. cu U Cu-U Imterdiffusion Cuth0., Pressure Effects... Cul References. CuVGa. Cu GacV References 28. Copper-Tungsten . 28.1. 28.2. 283 2B, 29. CopperZirconium 20.1 292, 29.3, Table 1 ‘Table 2 Table 3 Table Table 5 Table 6. ‘Table 7 Cu-W Interdiffusion Co-W-Ni Surlace Dittusion Cu-W References Cutadr CucZr Interdiffusion CuZrAg, CoZrFe. CuZrNb CuZr0 CuZeUX ve Gods Refercaee list of Tables Impurity Diffusion Coefficients of Bein cree Tracer Uitiusion Coethients of Be. Interdifusion Coeficiente in CurBe. De and Q Valuow for litera CoBe Intrinsic: Ditlusion vflvients of Be and Cu in Carlie (p- Phase Dy and O Vales fo Insinsi Diffie in Custbe fi Phase Grain Bounstary Dillision Caeicients A ie Ca Ie Dad A com 236 186 188 390 v1 191 ae 193,DIFFUSION IN COPPER AND COPPER ALLOYS cue Table & Tracer Diffusion Coefficients of “Ce in Cu, cosy ‘Table ‘Tracer Diffusion Coefficients of set Eu in Cu. ae con ‘Table 10, Diffusion Coefficients of Light Hydro- gen in Cu, Table 11. Dy and Q Values fr Diffusion a Hye gen, Desterivm, and Tritium in Cu Table 12. Permeability Dae fur Hydrogen in Cu Table 18. Diffusion and Permeation Parameters for Hydrogen in Cay... able 14. Ds and O Values for Hydrogen Difla- son in Disordered CuaPA Table 18. Dy and @ Values for Hyrosen Dif sh tu Onde CasP eno ‘Table 16. Diflusion Coefficients of Hy in Co-Pa Alloys at 25°C Conciente of Hy in Cu Pd Fo Table 17 cute Table 18. Activation Energies for Disloca Pipe Diffusion of La in Cu. coi Table 19. Tracer Diffusion Coefficients of *Cuin Li Ou)... Table 20, Tracer Diffusion Coefficients of Cu in Li (Mundy and McFall. cute ‘Table 21. Tracer Dinusion Coemetents of "Lu in Cas. Cums ‘Table 22. Interdiffusion Coefficients of Cu and Ma in ALCoMg and ALCoMg-2n Alloys. : . come ‘Tracer Diffusion Coefficients of Mn I Ce Table 24 Imerdifusion Coeficients in CuMn ‘Table 28. 10 we) Alloys Table 25. Compositions of Materia used bv Ca- ion etal . Table 26. Interdifusion “Coeficients. in’ Cun (28 wet) ‘Table Intcrdiffuston “Coefficients in Con (6-1. at.) a 850 °Coseeoe Table 28. Compositions of Alloys used by Kirk aldy etal . 195, 19 210 210 al 23 as 215, 218 220 20 me 222 Table 29. Vable 3. Table 31, ‘Table 52. ‘Table 83. Table 34, Table 35. Tale 26 ‘Table 87. Table 38. Table 39. Table 40. Fable a1, Table 42. Table 43, ‘Table 44, Table 45. ‘Table 46. Partial Interdiffusion Coefficients in ALCu-Mn at 556.5 °C. Partial Interdiffusion Coethcients. in re Partial Intrinsic Diffusion Coefficients in C2 Mn Comapostions flay Used by Wien berger etal cote Surface Diffusion Coefficients of Cu on Mo. cond ‘Tracer Diffusion Coeficients of Nb in cu Cohn Tracer Diffusion Coefficients of "Pm I Uescsroe uP Tracer Diffusion Coefficients of Cu in Pr cute ‘Tracer Diffusion Cooficients of "Tb fi) Csssssesnnnntnnren cum Impurity Diffusion Coeficiente of Cu in BT... Kirkendall Shifts for CucTi Inerdifu Grain Boundary Diffusion Coefficients of PPAR in Cu-TS (0. WA). oes Dinusion Coemerents of Ti and Bin cots cut ‘Tracer Diffusion Coeficiente of "Tm in Cu. cou ‘Tracer Diffusion Coefficients of *Cuin . cow De and Q Values for Surface Di of Com W. cute Diffusion Coefficients of Oxygen in Zr (Cu (750°C; 1 atm COs pressure). Diffusion Coefficients of Oxygen in Zr Cu (600 and 700 °C; 60 atm CO: pres- se} 170 2 23 08 24 226 28 231 233 g 8 40 2a as 2ar aT 4. Phys. Chem Rel. Dat, Vol, 1, 1975180 Figure 1 Figure 2 Figure 5. Figure 4 Figure 5. Figure 6. Figure 7, Figure 8 Figure 9. igure 10. Figure 1. Figure 12 Figure 13 Figure 1. Figure 15. Figure 16. Figure 17, Figure 18, Figure 19. Figure 20 Figure 21. BUTRYMOWICZ, MANNING, AND READ st of Figures owt Impurity Diflsion Coeficiente of Be in Cu... fone ‘Tracer Diffusion Cocficicate of Cu in Be. ‘Tracer Diffusion Coeficients of Be in Bet ovisnnnnsnnnnnnnnnne Interdifusion Coeficients in’ CuBe vs Beryllium Concentration Activation Energies for Inerdifusion jm Ca Be Alloys. Tnterdifusion Coefficiems in CusBe vs 107... ‘Tracer Diffasion Coefficients of Ce ina cute ‘Tracer Diffusion Coefficients of Cr in Cu. . cuey Tracer Diffusion Coefficients of BEY jn Cinsstnnnee cut Diffusion Coeficients of Hydrogen (amass one) in Cu Diffusion Coefficients of Light Hydro ‘gen, Deuterium, and Tritium in Cu. Permeability of Hydrogen in Cu. Diffusion Coeficients of Hydrogen in CusAu —— Permeability of Hydrogen in Cyan, Diffusion Coefficients of Hydrogen in CuPd aa Permeability of Hydrogen CaP, cuts ‘Tracer Diffusion Coeficients of Cu in ui. se eats ” ‘Tracer Diffusion Coefficients of "Lu in con ‘Tracer Diffusion Coeficients of Ma Fn C0 ss . Interdiffucion Coefficient in Cu-Mn, come Grain Boundary Diffusion | Coet- cients of Cu in Fe and FeMo Alloys 4. Py Chm, el Boe, el Ne, 1995 186 17 188 190 wr 192 wr 200 aa 217 26 Figure 22. Surface Diffusion Coefficients of Cu ‘on Mo. cond, Figure 23. Tracer Diflusion Coeficiente of Nb incu Co-Pm Figure 24. Tracer Difusion Coeficients of “Pm in Cu. vo cue Figure 25, Tracer Diffusion Coefficients of *Cu in Pr. Figure 26. Tracer Diffusion Coefficients of "Tb incu cot Figure 27. Impurity Diffusion Coeficiente of Cu ing : Figure 28. Grain Boundary Diffusion Coefiv of Ag in Cu and Cu-Ti (0.1 W1%) cotm fusion Coeficients of "Tm Figure 29, Tracer in Ca. cou Figure 80. Tracer Diffusion Coeficients of “Cu iny Figuee 81. Layer Thickness af UIC frm Inter diffusion... Figure 32. Effect of Pressure on U-Cu Inter- difllsion orn . cua Figure 83, Inerdifusion Zone Width in Cu/2iee alloy? Figure 84, Osygen Concentration vs Distance for Osidation of « Z-Cu Alloy Figure 85. Weiaht Increase of Zirconium. Coated Copper Exposed to Air 1. Introduction a 29 231 22 24 240 2a mae 28 1.1. Organization of Review According 10 Alley System ‘The present review is the third in a series designed to provide data on difusion in eopper and copper alloys. ‘The first paper [1] in the series covered eapper self fusion. The second paper [2] of the series dealt with diffusion in the coppersilver and copper sold systems, Be Measurements ofthe difusion of radioactive “Cu into herglium has been reported (8) The tracer ditfsion corffcents were determined both perpendicular (D,) tnd parallel (Dj) to the c-axis of the hexagonal close packed structure of borylinm ‘The “Cu was deposited onto the single crystals of “superrefned” beryliom. AMter diffusion, the Grozin method of analysis [5 wes used to determine the o Centration gradient. The calculated values of the di fusion coefients are listed in table 2. A plot ofthe log , and log Dy. (1/7) shown in igure 2 TEMPERATURE (0) vp wo = ™ ee —_ _t 3 25, “Ee 4 8 5 3 we a Aa 4 é od a \ 7 zt me as 98 0s 1OVTIK Ficunt 2. The tracer difsioncaeficen of Ca in pure single ryt of beri se fenton of reciprocal able tepertue 1 Phy Chom Ra. Dot, Vol 4, Na 1, 1975108 BUTRYMOWICZ, MANNING, AND READ HOLE 2. conper-t tracer ai¢feston It is interesting to note thet if the lowest temperature ita escerpted fron fh point is ignored, the two lines could be easily drawn patalicl (and thie ne aniostropy in astivation enersy too aon TTT revealed Assuming the dats at the lowest temperature Texpendscotey raseatel '/ point are correct, the anisotropy of the diffusion of *Cu Sees sical in beryllium can be expressed by the relations Dy 35 exp (—45,900 cal- mo (RT) ems, and 90 exp (49,500 eal-mol4RT) ems. lor Fuuune 8 The weer difeson of bey S0 Ben 0 0 ols feta cf ciprocalabsolteemperture 4. Phy. chem, Ha. Dr, Val Me 1, 1978DIFFUSION IN COPPER AND COPPER ALLOYS There have been no other tracer experiments in this system for comparison with these results, although low: temperature (420-640 °C) results [6] obtained from ion backscattering experiments are consistent with the above-mentioned data. Concurrent with some high temperature creep studies ‘of Be-Cu alloys, Le Hazif and co-workers [7] measured berylium tracer difusion coefficients in ing 10.3 wi% (44.7 at.%) copper. Diffusion rates were measured both parallel (Dj) and perpendicular (D, ) to the © axia in the hexagonal ctructured cingle crys ‘The Gruzin formala [5] was used to calculate the tracer diffusion coefficients in the temperature range 850 to 500 °C. We have obtained the unpublished values of the tracer diffusion coefficients from the above-men tioned authors and plotted them in figure 3 asa function of reciprocal absolute temperature. Our least squares Gi of the data pickle steaig lies which cau be de seribed by the following Archenius expressions: perpendicular to the 0001), _D5{0001}=9.03 exp (46.6 keal-mol-HRT) ems, and parallel othe (0001, #0001) 99 exp(—$7.3 keal -mol-/RT) ems, ‘The abuve values for she pre-exponential factors and activation energies difler slightly from those published by Le Hazif etal Relative to self-diffusion rates in pure beryllium, the copper alloying additions reduce the mobility of the beryllium, A Coke intenitiecion ‘The most important of the early interdiffusion studies was the now “classic” investigation of the rates of Aiffucion of « number of solutes (including Be) ir dre ‘-solid solutions of copper by Rhines and Mehl (3). Their results are often referred to, although their experiments were fraught with difficulties; most notably, those of reerystallization and grain growth in the diffusion zone. The data are presented here, although ite reliability is open to question. ‘Tircis polycrystlliae difuslon eouples were composed of copper electrodeposited onto Cu-Be alloys 9.52-10,05, aL1.AT-1.56 w1% Be). The diffusion temperatures ranged from 701 ta 8S1 °C, The time of diffnsion varied from 8.82 to 34.71 days. A Matano anslysis [8] of the beryliium penetration data allowed for the evaluation of the interdiffusion coefficient. These calculated values are plotted in figure 4 with small extrapolations. at either end of the curves. The log D ve, (1/T) was plotted for a series of concentrations, and the activation eneray. 0. was determined from the clones ‘The rele: 189 tionships between Q and the solute concentrations are ‘summarized in figure 5. Data contained in the diffusion ‘concentration plots were extrapolated to zero herylivin ‘concentration to give an estimate of the impurity diff sion coefficients and are compared to the data of Fogel’son [1] in figure 1 'Nowick (9] was one ofthe first to question the data of Rhines and Mehl. Since the validity of the Rhines-Mehl data above is questionable its use should be with caution. A muliplase, interdifision study in the copper: beryllium system has been reported (10), Diffusion data were obtained for all phases (a, 8, ¥, 6, €) existing in the binary phase diasrams (as displayed in Hansen, Elliott, and Shunk (11). ‘The diffusion couples were composed of pure copper (cathode Cu of 99.95 wi% Cu, containing less than OUI wiv U) bonded to relauvely pure beryllium (which contained 0.13 wi% Fe, 0.07 wt% Cu, 0.08 wi Si, 0.03 wide Mg, 0.08 wr% Ca, 0.011 wi% Al, 002 wie Cand an indatormined amount af ©) Addivianal i fusion couples were made of pure copper-and CuBe alloys of 12.0 wi% (49 at.%) beryllium for diffusion studies pertaining to the 7-phase, and CurBe alloys of (04 wie 82 a6) berylium for diffusion studies relative to the B-phase. The diffusion snneals took place at £650, 750, and 840 °C for 5 to 2000 hours. ‘The concenteation gradiente brought about by inter diffusion were determined, unfortunately, only from microhardness readings. The phases in the diffusion zone were examined metallographically. The growth of the phases was proportional to the square root of the time at temperature. Interdiffusion coefficients were cal Matano method and are listed in table 3. ‘The Arrhenius plot of log D vs. (1/7) for these data is shown in figure 6. ‘The straight-line temperature-dependence of the interdiflusion coefficient allows the calculation of an activation energy, Q, and a pre-exponential, D, in the Arrhenius equation. These ar listed in table 4. ‘The iuttineis iffusion wvefficnis wese caloulated according to Darken (12] for copper and beryllium for the B-phase only and are listed in table 5. Values for the pre-exponential and the activation energy as obtained only from the pure-copper/pure- berylium configuration are listed in table 6. ‘The motion of the weldinterface for a number of ‘aimusion couple confguratlons was recorded by he authors, ‘The results of this multiphase interdiffusion study of Reinhack and Krietech elo not agree with those of Rhines and Mebl (3] in the a-phase. although they are in agree: ment with Nowick’s [9] ealeulations (who made use of the data of Rhines and Meh, This agreement must be considered to be strictly fortuitous in View of the experi= mental difieulties experienced by Rhines and Mebl and the rather imprecise microhardness method of concen lwation analyeie wead by Reinhech and Kvinterh lated via the 4. Phy Chm: Doto, Ve. 4, No, 1975190 BUTRYMOWICZ, MANNING, AND READ BERYLLIUM CONCENTRATION (wt. %) ozs ozs ls us ol t ia i i INTERDIFFUSIN COEFFICIENT ( 10~"em 2/6 z + $ = © @ BERYLLIUM CONCENTRATION (at, % ) 0,800 and 850°C for varying Tents of TABLE 5. Ingerdttuston coeffictente tm the copper-bery2ttum Systen Abate ekeracted f8on be cucotee at) gE AEE Bg oar culce-secst ast) eB eae Bre 4. Phys Chem Ra. Dat, Va. No.1, 1975DIFFUSION IN COPPER AND COPPER ALLOYS 181 BERYLUUM CONCENTRATION (wt %) » BERYLLIUM CONCENTRATION (ot %) Frccne 6. The vation energy for interdifusion between copper and Cure aloye loephas)as function of Bergiam onenntraion Diffusion couples of zone-refined beryllium and high purity copper foil were used to study the beryllium: rich end of the Be-Cu phase diagram (13, 14), No dif fasion data were reported, nor is enough data presented tocaleulate such Beryllium diffusion into copper has been studied by ‘packing copper specimens in beryllium powder and an nealing at 600 to 800°C [15]. Hardness readings and retallographie examination were used to determine the beryliium penetration into the copper. The results are not very conclusive, other than that maximum diffusion TABLE 4. Diffusion paraneters for interdiffusion in the copper-berylliun system. Data taken from [10] Phase Do Q (om? /s) (keai /no1) a 1.9 x 107? 4s 8 8.4 x 1072 28 gg Sea ae ae 31 $12 «10-8 33 was attained at 800°C in 10 hours; the diffusion depth being 1 mm, Heating copper in @ beryllium chloride atmosphere has been employed in creating diffusion costings [16]. In view of the few experiments devoted to the inter diffusion of copper and beryllium and the results “obtained, itis clear that some additional experimentation is needed to clear up some of the doubts existing in the data 2.5. Age-Hardening Copper berylivm alloys have been used for strain enhanced diffusion investigations [17-19]. The growth ‘of agehardening precipitates in these alloys allows one to observe diffusion at very small values of (Dt), 1g polyerystalline alloy specimens. Ultrasonic ns were found to slightly accelerate the pre- {ABLE S. aeéyl ium and copper sntrinste dgftuston SccHictentg snUhe'a hose of Se erpted from Lo) Diffusion 1 Dtent/3) configuration peep capper culee-tecas att) Ho soviet 4. Phys Chem, Ba. Dat, Va. 4, He 1, 1975192 BUTRYMOWICZ, MANNING, AND READ TEMPERATURE (°C) if i q a PN SR I AY oN ™~ DB ip-paasey wD Gy Phase) 0B fa-Puase) © 5 (e-paase XD te PHASED No wal WoT UK) FLoune 6. The iterdifision oven inthe a, 7.8 and ephase ofthe Coe ‘psten as fenton of reciprocal ascot temperatre TABLE 6. Intrinsic diffusion Parameters in s-phase for the diffusion pair Cu/se. Data a Diffusing Do ated (cm?/s) Be 3.5 x Love cu 4.5 « 1073 4. Phys Chem, a. Dot, Vo. 4, Ne 1, 1975, ‘taken from Q (kcal/mol) cipitation hardening in Cu-Be alloys in the early stages of frvadiation, This small increase in the hardening. rate ean probably be ascribed entirely to the acoustic ‘enhancement of grain boundary precipitation, rather than to the sanie energy setting dislocations in motion fand the consequent production of vacancies. It is not likely that acoustic energy in the kHz frequency range, uused in these experiments, will be absorbed by and produce the to-and-ir0 motion nl dislocations (although this acoustie energy can he absurbed at grain bounda ries) [20]. However, whi slelevts are introduced into @ aystem by strain, Inrducns measurement is not @ jable methuel vf wionitoring siffusion, since other effects, such is enlinerd nucleation oF dislocation production, cwuldl lsu le altering the hardnessDIFFUSION IN COPPER AND COPPER ALLOYS 2.6 Cote-Ag Studies have heen made on the effect of heryllinm additions on the grain boundary diffusion of silver in polyerystalline copper [21, 22]. The results confit, but the earlier results (which claimed that beryllium retards both the volume and grain-boundary diffusion ‘of silver in copper) are believed to be in error because ‘of the rather inaccurate method of analysis (micro structure comparicone). The more recent investigation utilized a radioactive tracer (Ag) vacuum sputtered ‘onto the Cu-Be alloy specimens. After diffusion anneals, the specimens were analyzed using Gruzin's method [23]. Grain boundary diffusion coefficients were calcu lated using Fisher's analysis [24]. The calculations assumed a grain boundary width of approximately 20. can and a volume alfusion cveficlen for Ag in the Cu-Be alloys of approximately 10-* om?/s at 590 °C. The volume diffusion coefficient assumption was bated on similar work in Cu-Sh allovs (25. Al the diffusion studies were performed at 590 °C for 100 hours, although prediffusion heat treatments were different for each specimen. The results are given Im table 7 and seem to jndicate that minor additions of beryllium (of the order of 0.1 wi%/07 at.) accelerate the grain boundary diffusion of silver in copper. Special note shonld he taken thet results are hated spon a “ess-than rigorous” calculation. 27. CuBe-Al Copper-aluminum alloys have been heated in beryl lium powders at 600-800 °C for 2 to 10 hours, and the depth of the beryllium diffusion determined from hardness mearurements and micrographic observations {15}. The authors report that maximum diffusion oc ‘curred at 800 °C (and 10 hours of annealing), and the depth of diffusion was 8 mm. 28. Cu-be-Fe Copper containing 19.15 at.% (8.25 w19) beryllium has been interdifiused with iron in the temperature range TABLE 7. Grain boundary diffusion coefticients of silver in a Cu-Be (0.1 wts) alloy at 590°C. Data extracted from [21,221 Pre- diffusion Dyp(em?/s) Heat Treatment gb None 3.7 «1078 100 h @ 863 °C 24 x oe 100 h @ 863 °C and = 5.5 « 1078 50h 6 500 8c, 199 1000 to 1100 °C [26, 27}. The beryliium alloying addition reduced the iron grain boundary penetration of eopper. 29. Cu-beH ‘The addition of 2 at.% (0.8 wt%) berylium 10 copper ‘eauses he Iydioyen perimesbillty w dectewe by a factor of three (relative to pure Cu) in the temperature range 700-500 °C [28]. 210. Cu ‘The high temperature oxidation characteristic of CucBe alloys has been reported [29-32] Although no diffusion coeficients were measured, the quantitative data taken did allow the authors to speculate on the rela tive rates of diffusion of copper and beryllium through the oxide layers of diet specimens 2.1, CuBex The wires has been qualitatively investigated [35] diffusion coeficients were reported ‘The very high affinity of beryllium for oxygen and rogen has made the fusion welding of beryllium end berylium-alloys difficult and complicated. As a conse quence, much study has been directed towards the solid pase welding of dhese materials and a great deal of Titereture generated. The bulk of these investigations were concerned with obtaining a reasonably sound bond between the metals. rather than a study of the di fusion processes which took place. In view of the fact thot most of this Ltersture is not “diffusion studies per se,” we will not go into the details of the results presented In this literature, but rather refer the reader to the review literature which already exists in this area [4-37] for the extraction of any data he might need. 2.12. Cu. 1D} Fogeson, RL "Dison of Brym and Sco i {in Rosia) Fit. Mel Metalloved. 35,6}, 1907-109 (973), (ay rogersons RL Ugs . h FonoEseALYrane Akins Re “XeRey Difracton Investigation of ul Difeion Poly crystalline Mateidls" Gin Karsan) Fi. Tverd. Tela 1 1028-108 971 So. Phy. So State 18, 856-058 (19 (6) hoes FN, wl Meh, Ry “Rater of Diflein inthe Alpe ‘Sold Salton of Copper,” Trans. Ar, lt. Mi, Metall Ene 128, 185-222 (1938) [also puhliched as AIME Tech. Pb Not (6) Deyowy Me Mae a bites ares 1 Cu6¢ in Be.” Con Inter. sar a Meare do Bey, Sd, Grenoble, 1965 [Presses Univ. de France, Grenoble, 1968) pp 189-161 for Studying Dison and SeiDifosion in Alle, Sef Di fasion of Cabo" (in Rusin) Dob. Akad. Neuk SSSR 86, 209-292 (1952 anltion salable from NTIS ae TT 7 sa) [6] Myers §.M.,Pieron &T., and Prevendes, TS. "Study of Co Dilfenion in Be Using an Bachscatering.” Phys. Rev. BS, 851-3964 0978) HL Le Hani Ro Alin, ama Disicaon Climb ip Berlbum sed Bee Single Cet sicrdftasion of yramalley-costed Cu Be alley and no References wie 4. Pye hom. Rel: ote, Va. 4, Ne, 1975194 BUTRYMOWICZ, MANNING, AND READ Meta Trans. dy 1275-1281 978s Eran, Metal. Tom 5. 974117) {0) Maran, 6. "On sh Rlaon Breen the Bix Cocient ‘and Concentration of Said Mets (The Nickel Capper Sy tem" Jap. 1 Phy. B, 108-18 (933). (9) Novick, AS, “A Rebterpreation of Experiments on ner Dio." ppl Phos 2, 182186 (1560), 100) Renbach, Re and Kriteey Fy “Dison in the Copper Ber Tor Shalem” tn German) 2. Met 84, T7819 1963) Ieonltionavalable from NTIS ax TT 7259054, [DM Hiacen, Me Conatitton of Binary Alloy MoU Bosk ‘Corin, New York, 15M 2n cio Elion, RP Con tution of Binary Alley, First Supplement (Mctrv-Hl Book Gn ne, New York, 145}: Shunk FA Contin of Bi Nox Yor, 1, 112} Daren, 5, "Dison, Moby and Thi Iran tough Free Encrey in Binary Metalic Ses,” Tran ATs Min. Tech Pb No 291) hem (28) Hanmond ML, Davinwy. AT Sebaon M1: Laced Mises & Space Co Plo Akt Cali, Borie ich End of Fite Binary Stems. Tech, Regt APMLATRe6=228 (A. 1965), 1p asa rm NTIS ge AD 40989 (04) acobon, Mad Hammond M.L, "The Sot Sli ‘Siher. Alison, Chroma Copper, and lon in Zone Refined Beri” Tron AME 242586199 196 1] Pi No As and Shulman, MeL "Diu of Beye a rpper snd Ie bys” tn Rasian) Metaog. 18, 90-96 {U6} Pashverwa, LS. “Reactive Dison Duting Thermodieson Beis af Capper Hydrogen and Bey Care Atmosphere" tn Resse) Fi, Svea Tella 214-216 (190. (00| Hagens 1 Asan She J.C, “The Infene of Ulead on the Kiowics of Precipitation Hlardenion In 4 Ci-Be Aly, Meu So 2,816 1B Faia. H.V., Efecto Insonton ding the Precipitation Hardening Aly” Sound 135-99 980. 19} Okada Mt Shin 5. Miva Mand Mato "On the Joint Mechanisms Weld” tin pants) Nippon Ki zou Gabo 26, 585-5911. 120 rn AF "Difonion Under Mechs Sr." n Difision recesses oth Thomas rake Near Sy, W.Mi. Mirand.L- Swinton Condon and Brech, New York 191, Vl i Section 35, pp. 219-20 (2) Arthas Voy loon, S.A sad Times A Ny "On ‘sialic Materia” Gy Russian) Fe Met. Metelbned (6) 2 255-260 1960) (Phy, Met. Metall 6,2), 71 1956) tes alte take 8 yn the Ec of Conan Died Adare on the Frnt i sion of Siher ito Polersaline Copper” Gn Rosin) ‘Trad, Int Fit Metal. Urls Fil Akad Nak SSSR, ese 1 (23) Grain, P-L tn Rsaan) Ph Metlloved. Fi, Metal 31.210 on (24) Fisher, J. C.,“Colealation of Difason Pence rash, (25) Adar, VL late, $M, Timnfeye, A. Natl Haan 1.1." Study of Intergeauler Dison Metals ed Aly, Sn laledoaniva Po Zhraorch cited by TP Bain Kal Akai Nauk SSSR, Mosc 19) Val. ye sin avaliable from NTIS ns Iveta of Heat Bessn Aloe AD a81551 [26 Sites, Fe "Toone of Apia te ‘he Dion 4. Phys Chom. el ete, Vol 4, No.1, 1975 of Copper to Gamma Ion. Past" Gin Slovenian) Ru Met Zh 4, 817-387 1196) fearlaton aah fom NTIS se TT 70 Seo} [at Sires, F.“InBuence of Alphe Forming Bement oF Copper in Game $37, 899-807 980, (29) Bayan, Yr a and ced, Yu y “Tener ‘of Hydrogen Permeability through Copper aad ie ly (Gn Rosson) Uc Zap. Lenngr. Gos. Uni. No 45, 4-99 0905, on} Ps and Praca, A “Vigh Temp Characeries ‘of « Group of Oxkation Reisen Copper Base Alloy," I-lat Met 81, 229-236 0952-1959, [90] Mask. F, “Tovesgaon of the Osdatin of Copper Beryllium 52,58-544006), [31] Han, W. Ke, “The Difsion of Hydrogen though OxyzenFee Copper," Chem. Phys. 7, 908-807 1998. [90] Kiera, and Watante, ¥-n Tapanon), Nip Kinga abla 29, 85 565. [88] Knadson, CL, and Kench, JR, “Anmestng fects Plated ‘Wire Mesiory Elemente. Parti Interdifunion of Caper and ermal.” IEEE Trane, Macn, 7. 82-858 107, (34) Goldman. By Locked Mies & Space Co. Sumnyale, Calif, Joining of Beyliom and ts Aloe by Welding andor Brasng? dn Annoated Biblgraphy, Special Bibra Ste 19, 3 oa alae om NTS a [35] Pane, H. “The Jing of Diesinar Metal No 51611968. pp. (a6) Tyee, RF. The Solid Phase Weng of Metts St. Marin’ Pres, New Var. 1968, [st] Moffman, Jr A, Base, G- Ry Beraasa, R, Cy and Catrall 3B. K. “Difosign Bonding Berlium Copper fr Ulva High Strength Jina” Weld 41, 160s-To6e 196 3. Copper-Cerium 3.1. Cet > C0 er diflusion coethcient of the rare earth metal isotope "Ce in copper has been studied in the tempera ture interval 752 t0 970 °C {I}. The values of the tracer Aifusion cosfficiente were obtained by two. different experimental methods, the residual activity method (Grozin’s technique [2) and seriaksectioning with analyses of the sections removed (as described by Makin et al. [3D In these experiments, the cerium isotope was distolved in water, then 1 polished surface of the polyerystalline copper specimens Wehere It is allwed ley. Dusing eve vacua dif sion anneals, the hydrated rare carth chloride de- composed to an oxide from which the cerium isotopes diffused into the conper. All but the measurements at 950 C (which used the serial-sectioning technique) utilized the residual activity method. The plots of the residual activity versus the correspon distance showed steep slopes near the specimen surface (up to a penetration distance of 0.2 to 0.3 um) alier which there was a more gradual decline. It was assumed, ‘was maintained at a position, xo, near the surface (this resulted in a small deviation of 10% in the diffu: sion coefficients). The concentration-penetration plots ‘could he fitted to ertur function curves, and tracer dif he Difsion Gn Frenchy Mem, So Rev Me DIE Re. iasferred to theDIFFUSION IN COPPER AND COPPER ALLOYS. 195 fusion coeficients were calculated using values of ce vbiained by extrapolating the residual activity curves. ‘To check the validity ofthis residual activity analysis, serial-sectioning experiments also were performed. High activity was found at the surface. The remaining points fia plot uf log specie eal tance could be fitted by two straight lines. The first straight line segment extended from near the surface tw a depth of ~20 am. Ia Gaussian penetration profile was assumed (rather than the error function assumed for the residual activity measurement) and the dif: fusion coefficient then ealeulated from the slope of frst line, results in agreement with the residual activity measurements were obtained. These values are also given in table 8. TABLE 8. Cerium-141 tracer diffusion coefficients in copper [1]. 7(°C) D8 (m?/s) 950 84.35 x 10012 950 84.02 = 10732 930 Sigh x aunt? 947 3i91 x 100}? 947 3i71 x 10013 sno 2176 x 103 861 ila7 x 100}? 861 Les x 100}? 800 7187 x 10014 800 7.51 * ort 760 5.86 x 1072 760 5.73 x 107} ‘These values were determined from serial sectioning of the specimens whereas the remaining values were determined from residual activity measurements. ‘The second straight line segment in the log concen- tration versus square of penetration plot from the serial: sectioning experiments covered the remaining points fn the profile eid sliwed saaller slope an le fest segment, Diffusion coefficients calculated from this segment varied greatly from one specimen to another and were larger than those quoted in the table, perhaps reflecting diffosion slong short-eireuiting paths, such a= dislocations. iflusion coefficients from the table are plotted in hhgure 7. Our least squares analysis of these values yields the following expression, D_= 2.38 10-* exp (~26.7 keal - mol-1/RT) ems, represented by the solid line on figure 7, It should be noted that the Dy and Q contained in the above expres- ‘ion differ somewhat from the authors’ published values, tis apparent from these results that, even at tempera tures close to the melting point, the diffusion of cerium us copper takes place only very slowly. Also, the De value of 2.38 X 10-* cm/s is unusually low. Neverthe: less, similar results (with D* actually a factor of 10 lower) were found hy the same authors for teacer if sion of other rare earths (Lu, Pm, ‘Tb, and Tm) in copper. Qualitatively, similar results were also found previously by Williams and Slifkin [4] for difusion of rare earths in silver and lead. The author of these papers propose that the large size of the rare earth atoms, which makes solubility dificult, also impedes atoms on dislocations or other structural defects more Tikely 3.2. Cu— Ceo (Electromigration) ‘The solid-state electromigration of copper in > cerium has been observed in purification studies (5, 6 ‘The cerium specimens were cut from sheet rolled from ingots obtained from molten saltmetal equilibrations during which radioactive copper tracers were intr duced: Epecimens were clectralyted butween nickel electrodes containing resistance heaters and no gradient in temperature exceeding 10°C was observed. Speci- men temperatures were controlled to within 3°C ‘or 4°C. Although the electromigration chamber was evacuated, a slight amount of surface oxidation was observed. After 242 hours of electromigration at 600°C, the concentration profile of copper was determined from spectrographic analysis. The data show very slight diffusion of copper to the anode. The authors speculated thar the anodedirected diffusion af capper is primarily due to the potential field effect and that any contribu tion from electron momentum transfer forces, if present, is minimal. More recent experiments [7 utilising electromigration to purify cerium, have found copper being transported to the cathode. It is not clear why the disagreement 3.8, CuCe References HB “Impurity Diesen of Rare Ea Metal i Copper Inian J. Pate Appl. Phys. 8, 324-330 1970 [2] Crazin, PL, "Applicaton of Arial Radioactive Indicators for ‘Stusing Gituston and’ SeltDituson tn Aloy, Season ‘God Proc. Phys Soe: Lond B10, 348-952 (991). [8] Wiliams Je G. Py and Slik, L, “Trager Inlbiity and the ‘Anoraloas Dison of Rare Earths in Silver and Lead" Acta Metal. 11,319-322(056, (9) stores RE) Seta Fy and Moe, JR Soe eto: “ifosion ia Gamme-Cetum, Gamma reso, end. Epon