...~ ".. Introduction. Diffusion Process. Annealing Cold-Worked Metals
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1 Heat Treater's Guide: Practices and Prcedures fr Nnferrus Allys, 06325G Cpyright 1996 ASM nternatinal ntrductin The principles which gvern heat treatment f metals and allys are applicable t bth ferrus and nnferrus allys. Hwever, in practice there are sufficient differences t make it cnvenient t emphasize as separate tpics the peculiarities f the allys f each class in their respnse t heat treatment. Fr example, in nnferrus allys, eutectid transfrmatins, which play such a prminent rle in steels, are seldm encuntered, s there is less cncern with principles assciated with time-temperaturetransfrmatin diagrams and with martensite frmatin. On the ther hand, the principles assciated with chemical hmgenizatin f cast structures are applicable t many allys in bth classes. The diffusin prcess is invlved in nearly all heat treatments fr nnferrus allys. Cmmn treatments include: Annealing after cld wrking Hmgenizatin f castings Precipitatin hardening treatments Develpment f tw-phase structures Diffusin Prcess n the heat treatment fmetals and allys, the rate f structural change usually is cntrlled by the rate at which atms in the lattice change psitins. Fr example, when cld-wrked cpper is annealed and sftens, r an aluminum-base ally is aged, it is imprtant t knw hw the atms mve relative t each ther s as t bring abut the bserved changes in prperties. This mvement f atms is called diffusin. Tw different diffusin mechanisms are shwn in Fig. 1. Fig. 1 Schematic representatin f tw pssible diffusin mechanisms. (a) Tw atms mve simultaneusly t exchange psitins. (b) Fur atms mve cperatively t rtate simultaneusly t mve... t new psitins..."..... W (a) (b) Annealing Cld-Wrked Metals Cld wrking increases hardness, yield strength, and tensile strength, and lwers ductility. Als, electrical resistivity is imprved because increasing density f dislcatins scatters the electrns. The effects f cld wrking n several prperties are shwn in Fig. 2. Rle f Annealing. n shaping metals by cld wrking, there is a limit t the amunt f plastic defrmatin pssible withut fracture. Annealing restres the metal t a structural cnditin similar t that prir t defrmatin, making further cld wrking pssible. Changes in strength that take place during annealing are indicated by the hardness data in Fig. 3(a). n this instance, data are fr a fixed temperature. A similar result is btained by annealing fr a fixed time at increasing temperatures (Fig. 3b). Recvery, recrystallizatin, and grain grwth are stages in annealing. The stage fr shrt times at lw temperatures in which hardness remains cnstant, r increases slightly, is called the recvery regin. Dislcatins underg mvement by thermal activatin, being rearranged int arrays smewhat mre stable and mre difficult t mve than in the cld wrked, unannealed cnditin. A slight increase in hardness results. Sme prperties regain values they had prir t cld wrking. Hence the term recvery. Electrical cnductivity is ne fthe prperties invlved (see. Fig. 4). Recrystallizatin. With lnger times r at higher temperatures, the structure underges a mre radical change. Small crystals appear which cntain a lw dislcatin density (f a magnitude similar t that prir t cld wrking) and are relatively sft. Crystals nucleate in regins f high dislcatin density, and in the micrstructure appear at r near defrmatin bands. With time, the nuclei grw, and mre nuclei frm in the remaining cld-wrked matrix. Eventually, grains cntact each ther (at that time the riginal cld-wrked material has disappeared). The frmatin fgrains is referred t as recrystallizatin. At this time, strength drps drastically (see Fig. 3 and 4). Grwth in grain size. Micrstructural changes that ccur during annealing are illustrated in Fig. 5. During recvery, the density f defrmatin bands drps, but the change is nt marked. When crystallizatin cmmences, small, equiaxed grains begin t appear (see micrgraph 2 in Fig. 5, and a recrystallized nucleus shwn in Fig. 6). Grains cntinue t frm and t grw until the cld-wrked matrix is cnsumed, which marks the end f the recrystallizatin perid and the beginning f grain grwth.
2 Heat Treater's Guide: Practices and Prcedures fr Nnferrus Allys, 06325G Cpyright 1996 ASM nternatinal 2/ Heat Treater's Guide: Nnferrus Allys , , Fig. 2 Effect f cld wrking (by rlling at 25 C, r 77 F) n the tensile mechanical prperties and hardness f xygen-free, high-cnductivity (OFHC) cpper "0!'" '0.s f----/ s -S Ol t> f----+-yield strength, ksi --+:=---1 "0 '". Hardness, HB g> ,,,L-----Y' Qi "E '" L..- -'-- -'- ---J'--_----' Reductin in area, % a:l '1f-+---f f-----t f-=+_ la) 40 L..-_-'-..L-_---L --'-_----' See Fig 14 fr micrstructures at numbered regins lime, h a, Cl 100 Vi l) Q) lb) 40 <, Cu-5Zn -, r lime, h Fig.3 (a) Effect f annealingtime at fixed temperature (400 C, r 750 OF) n hardness f a Cu-5Zn slid-slutin ally cld wrked %. (b) Effect f annealing temperature at fixed time (15 min) n hardness f a Cu-5Zn slid-slutin ally cld wrked % a:l 100 '>0... > i 's 't; Hardnes a: 40 Vi «i 1 l). Q) tq) Qi '" Q) <, Ol "E 30.s Resistivit;- 1'0-... Annealing temperature, f Fig. 4 Effect f annealing temperature n hardness and electri cal resistivity f nickel. The metal has been cld wrked at 25 C 120 (77 OF) almst t fracture. Annealing time, 1 h '# Annealing temperature, C '0;.c '" u
3 Heat Treater's Guide: Practices and Prcedures fr Nnferrus Allys, 06325G Cpyright 1996 ASM nternatinal ntrductin /3 With further annealing, grain size cntinues t grw (see micrgraphs 3, 4, and 5 in Fig. 5). Because annealing f cld-wrked metals usually is carried ut t sften the material, the temperature and time needed t cmplete recrystallizatin must be knwn t determine the prper heat treatment. The recrystallizatin temperature is cmmnly referred t as an indicatr f the temperature at which metal must be annealed fr sftening. As a rule f thumb, the recrystallizatin temperature is apprximately 0.3 t 0.6 f the abslute melting pint. n the case fcu-zn slid slutin allys, the additin f zinc t cpper lwers the melting pint, and the recrystallizatin temperature will decrease fr high zinc cntents (20 t 30%, fr example), see Fig Rckwell B N recrystallizatin yet; still in recvery 127 Rckwell B Recrystallizatin just beginning Fig. 5 Micrstructure f a CU-5Zn ally, cld rlled t %, then annealed fr different times at 400 C (750 OF). The numbers refer t the different annealing times shwn in Fig.3(a) 100 urn 63 Rckwell B Recrystallizatin essentially cmplete; grain grwth beginning Rckwell B 100 urn llm 58 Rckwell B J.m
4 Heat Treater's Guide: Practices and Prcedures fr Nnferrus Allys, 06325G 4/ Heat Treater's Guide: Nnferrus Allys Cpyright 1996 ASM nternatinal defrmatin bnds recrystallized grain Fig. 6 High-magnificatin scanning electrn micrgraph shwing a small recrystallized nucleus. Cu-5Zn ally, cld wrked by rlling 20 C (68 OF) t a reductin in thickness f %; annealed min at 350 C (6 OF) annealing wins Fractin Cu-20Zn Annealing temperature. f Apprximate f melting recrystallizatin abslute - Ally temperature temperature Pure Cu 220 C (493 K) 0.36 Cu-5Zn 410 C (683 K) t:. Cu-20Zn 320 C (593 K) 0.47 Fig. 7 llustratin f effect f zinc cntent f Cu-Zn slid-slutin allys n the annealing prcess. The allys were riginally cld rlled at 25 C (77 OF) t % reductin in thickness. The recrystallizatin temperatures listed are based n the inflectin pint f each curve 140 :: n, Cl 120 1: :: 100 lr. Cu-5Zn <. E." ( "'- Pure cpper : Annealing temperature, C 0 Hmgenizatin f Castings This treatment is applied prir t the mechanical prcessing f cast ingt and is ften used even when an bject is cast essentially t its final shape. Temperatures and times used in this prcess depend n the diffusin rate and the starting structure. n chemical hmgenizatin annealing, chemical gradients in a dendritically cred structure can be reduced at a sufficiently high temperature fr a sufficient time. The rate f diffusin is given by an apprpriate slutin t Fick's law. As a cnservative apprximatin, the required time is x 2 "" Dt, where x is the distance between regins f lw and f high cncentratin in the dendrite cell, which is ne-halff cell size.
5 Heat Treater's Guide: Practices and Prcedures fr Nnferrus Allys, 06325G Cpyright 1996 ASM nternatinal ntrductin 5 Precipitatin Hardening Treatments n designing allys fr strength, an apprach ften taken is t develp an ally in which the structure cnsists fparticles which impede dislcatin mtin dispersed in a ductile matrix. The fmer the dispersin, fr the same amunt fparticles, the strnger the material. Such a dispersin can be btained by chsing an ally that, at elevated temperature, is single phase, but that n cling will precipitate anther phase in the matrix. A heat treatment is then develped t give the desired distributin f the precipitate in the matrix. f hardening ccurs frm this structure, then the prcess is called precipitatin hardening r age hardening. Hwever, nt all allys in which such a dispersin can be develped will harden. Slutin Heat Treatment. A prerequisite t precipitatin hardening is the ability t heat the ally t a temperature range wherein all f the slute is disslved, s that a single-phase structure is attained. This is shwn schematically in Fig. 8 fr a 10% B ally in a hypthetical system A-B. Heating abve the slvus temperaturet2 fr this ally and hlding in the a range fr sufficient time will frm the single phase a. This is the required slutin heat treatment. The Prcess f Precipitatin. After quenching frm the a regin (Fig. 8), precipitatin is achieved by reheating the ally belw the slvus (T2 in Fig. 8) at a suitable temperature fr a suitable time. Precipitatin Hardening. The high strength is prducedby the fmely dispersed precipitates that frm during precipitatin treatments (which may include either natural rm-temperature aging, r artificial aging at elevated temperatures). The effect f temperature and time n aging is illustrated by the data in Fig. 9. As pinted ut previusly, the higher the precipitatin temperature, the lwer the maximum hardness, because less precipitate frms as the slvus temperature is apprached. Hwever, the higher the temperature, the higher the rate f precipitatin, and hence the maximum hardness is attained in less time. n mst cmmercial precipitatin-hardenable allys, the rate f precipitatin is lw at ambient temperature, althugh sufficiently rapid t bring abut measurable hardness changes in a reasnable time, as shwn in Fig. 9 fr aging at 30 C (85 "F), fhardening ccurs at r near ambient temperature, it is termed age hardening; aging at ther temperatures is called precipitatin hardening. Fig. 8 Hypthetical phase diagram f system A-B. The decreasingslubilityf B ina withdecreasing temperature allwsan ally cntaining 10% B t be single-phase at high temperature (that is, abve 7;) but tw-phase at lwtemperature (1;) %BinA 130, , """"""7---..,.-----, , ,f-/-lC-----" j Fig. 9 Hardness as a functin f aging time fr an A-4Cu ally. The ally was slutin annealedfr at least 48 h at 520 C (970 OF), then cled quickly (waterquenched) t 25 C (77 OF) " f---,...,d ; "E e>a. eq),:,l s. c "E '" :r f-----f----1:...,,., lt j 90 f----f----f- -"r '_ ) As-quenched hardness ,..- L-...L.l L...- -'- ----' ,000 Time, days
6 Heat Treater's Guide: Practices and Prcedures fr Nnferrus Allys, 06325G 6/ Heat Treater's Guide: Nnferrus Allys Cpyright 1996 ASM nternatinal Develping Tw-Phase Structures n sme nnferrus allys (fr example, titanium-base allys and high-zinc Cu-Zn allys), the desired structure cnsists f a mixture f tw phases f cmparable quantity (unlike the tw-phase structures develped in precipitatin hardening, where the precipitate is in the minrity). The mrphlgy and amunt f each are varied by cntrl fthe high temperature used and the cling rate frm that temperature. The preferred micrstructure can be quite cmplex, and the required treatment differs cnsiderably fr different systems, s that a systematic treatment f the principles invlved is difficult. n the Cu-Zn system, allys cntaining abut 40% Zn serve as the basis fr sme cmmercial allys (fr example, Muntz metal and naval brass). The Cu-Zn phase diagram (Fig. 10) shws that the allys f interest are in the regin f ex and Pphase stability. The Pphase is a bdy-centered cubic, with the cpper and zinc atms lcated at randm n the lattice sites. On cling t temperatures belw the dashed line (abut 450 C, r 840 "F), the cpper and zinc atms take specific relative psitin n the sites, frming an rdered structure, r a superlattice. This phase is dented Win Fig. 10. f the cmpsitin is exactly 50 at.% Zn, then the rdered structure is based n a bdy-centered cubic cell with zinc atms at the center and cpper atms n the cmers (r vice versa). See Fig. 11 fr typical micrstructure f Muntz metal (Cu-40Zn), Fig. 12 fr micrstructure f Cu-42Zn quenched frm beta regin, then reheated t develp an alpha precipitate structure E OJ Cu 10 r- r L 1083 C 10 u u+p L P+L P / - 1/ + P - y+- Y O+ Zinc, at.% Zinc, wt% e+ll }-'-- Y i+lr e 0 u p + p + y+ E p y -j 0!;'- ::J 1 11> a. E Zn Fig. 10 The cu-zn diagram. The pphase is bdy-centered cubic; the Wphase is an rdered structure based n this arrangement Fig. 11 Typical micrstructure f annealed Muntz metal (Cu 40Zn). The clear, white regins are the W, and the dark and gray regins shwing annealing twins are ex. Optical micrgraph. 250x 250X
7 Heat Treater's Guide: Practices and Prcedures fr Nnferrus Allys, 06325G Cpyright 1996 ASM nternatinal ntrductin /7 Fig. 12 Micrstructures f Cu-42Zn ally quenched frm the pregin, then reheated t develp an a precipitate structure. The higher reheating temperature gives a carser structure and thus a sfter material A{3' Quenched frm 0 e (a) White ex in {3' wax Quenched frm 0 "C. reheated fr 30 min at 400 -c (b) White ex in {3' wax Quenched frm 0 e, reheated fr 30 min at 0 -c (e) wax
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