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DIFFUSION DEMO
Glass tube filled with water. At time ti t=0 0, add dd some d drops of fi ink kt to one end d of f the tube. distance, x x, over some time time. Measure the diffusion distance The concentration of ink is a function of time and distance x.
to t1 t2 t3 xo x1 x2 x3
x (mm)
time (s)
2
100% 0
Cu
Ni
Concentration Profiles
t=0
C A D B
C A B D
Diffusion: The movement of atoms or molecules from an area of higher concentration to an area of lower concentration. (Interdiffusion or impurity diffusion)
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DIFFUSION MECHANISMS
Substitutional Diffusion:
applies to substitutional impurities atoms exchange with vacancies rate depends on: --number of vacancies --activation energy to exchange.
INTERSTITIAL SIMULATION
Applies to interstitial impurities. More rapid than vacancy diffusion. Simulation:
--shows shows the jumping of a smaller atom (gray) from one interstitial site to another in a BCC structure. The interstitial sites considered here are at midpoints along the unit cell edges.
(Courtesy P.M. Anderson)
Interdiffusion of impurities such as H, C, N and O; which have atom small enough to fit into the interstitial position
Atomic radius Iron C 0.124 nm 0.071 nm
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Diffusion Diff i mechanisms h i i in material: t i l (a) ( ) vacancy or substitutional atom diffusion and (b) interstitial diffusion
Background - Steel
Pure iron is relatively soft and would not last very long if used as a tool Luckily, when a small amount of carbon (up to about 1.5%) is added to the iron it is called steel and can be made much harder by a heat t t treatment t called ll d quite it simply, i l hardening. h d i If some other metals, such as chromium, nickel and manganese are added to the steel it can be made much stronger and tougher and is called alloy steel In simple terms: The amount of carbon in the steel determines how hard it will be after hardening Th The various i metals l with i h which hi h it i is i alloyed ll d determine d i how h strong or tough it will be, after hardening
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100 hardness 50
80
Hypo
%EL
Hyper
40
Adapted from Fig. 10.20, Callister 6e. (Fig. 10.20 based on data from Metals ed., V. Masseria (Managing Ed.), American Society for Metals, 1981, p. 9.)
0 1 0
0.77
0.77
0.5
Callister 6e.
(Fig. 5.0 is courtesy of Surface Di i i Division, MidlandRoss.)
Improve: Wear resistance Wear r=kw/H, w-load, l d H-hardness Hh d Fatigue life compress stress
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Carburizing
The process: Pack carburizing Gas carburizing Liquid carburizing Vacuum carburizing g Plasma carburizing
Depth of Hardening: Case depths from as light as 0.08 mm (0.003") to as deep as 6.4 mm (0.250") may be specified, depending on the service requirements of the product. product
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Application High wear resistance, low to moderate loading-Small and delicate machine parts subject to wear High wear resistance, moderate to heavy loading-Light industrial gearing i High wear resistance, heavy loading, crushing loads or high magnitude alternating bending stresses-Heavy duty industrial gearing High wear resistance resistance, shock resistance resistance, high crushing loads-Bearing loads Bearing surfaces, mill gearing, rollers
Depth of Case Cases to 0.51 mm (0.020") 0.51 mm to 1.02 mm (0 020" to (0.020" t 0.040") 0 040") 1.02mm to 1.52mm (0.040" to 0.060") 1 52 mm to 6.4mm 1.52 6 4mm (0.060" to 0.250")
Carburizing Time: 4 to 72 hours Carburizing Temperature: 850-950 C (1550-1750 F) (i.e., above the upper critical iti l temperatures t t - austenite t it area) ) Quenching: After carburizing, the part is either slow cooled for later quench hardening, or quenched directly into various liquid quenches. quenches The part is then tempered to the desired hardness to achieve the optimum properties with acceptable levels of dimensional change.
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Materials
Most steels specified for carburizing contain less than 0.25% carbon, b with i h sufficient ffi i alloys ll to improve i case and d core hardenability. Depending on the application, any of numerous grades may be used. used In general general, steels that are applicable to carburizing are the following: 1. Low-carbon steels 2. Resulfurized low-carbon steels 3. Low-carbon alloy steels powder metal (P/M) ( ) compacts p 4. Low-carbon p
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Sulfur - is usually an undesirable impurity in steel rather h than h an alloying ll i element. l In I amounts exceeding 0.05% it tends to cause brittleness and reduce d weldability. ld bili Alloying All i additions ddi i of f sulfur lf in i amounts from 0.10% to 0.30% will tend to improve the h machinability hi bili of f a steel. l Such S h types may be b referred to as "resulfurized" or "free-machining". F Free-machining hi i alloys ll are not intended i d d for f use where h welding is required.
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Pack carburizing
The part is packed in a steel container so that it is completely surrounded by granules of charcoal. The charcoal is treated with an activating chemical (a catalyst) such as barium carbonate (BaCO3) that promotes the formation of carbon dioxide (CO2). This gas in turn reacts with the excess carbon in the charcoal to produce carbon monoxide, CO. Carbon monoxide reacts with the low-carbon steel surface to form atomic carbon which hi h diffuses diff i into the h steel. l Carbon b monoxide id supplies li the h carbon b gradient that is necessary for diffusion. The carburizing process does not harden the steel. It only increases the carbon content to some predetermined d t i d depth d th below b l th surface the f t a sufficient to ffi i t level l l to t allow ll subsequent quench hardening.
Heat Part to be carburized Steel container
C
CO
CO
Heat
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Advantages of Pack Carburizing 1. It can be done in almost any type of furnace 2. The equipment requirement is minimal (furnace, box, compound) 3. A wide variety of parts can be accommodated (as many as could be fitted and p in a box, or as large g as the box that will fit in the available furnace) ) separated 4. Requires lower operator skills than other processes. Disadvantages of Pack Carburizing 1 Carburizing 1. C b i i times i are longer l than h for f some of f the h other h processes 2. Not suitable for continuous production 3. Labour intensive (pack loading, box maintenance, sealing, pack handling etc) 4. Unsuitable for thin, carefully controlled case depths.
At carburizing temperatures, say 900 C, the following reactions occur: (1) C + O2 (initial air in charcoal ) CO2 CO2 + C CO . (2) Fe + 2CO Fe(C in solution) + CO2 CO2 + C CO . . (3) BaCO3 BaO + CO2 CO2 + C CO
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Gas Carburizing
The parts are heated above the upper critical temperature in a furnace with an atmosphere of carbon carbon-containing containing gas such as methane, ethane, propane, natural gas, acetylene, manufactured gas or mixed hydrocarbon gases. Most carburizing gases are flammable and controls are needed to keep carburizing gas at 927 C C (1700 F) F) from contacting air (oxygen). (oxygen) The carburizing gases are often diluted with an endothermic carrier gas, mainly nitrogen (N2) and CO along with smaller amounts of CO2, H2 and H2O. O Of all ll the th gases, N2 is i inert i t and d acts t only l as a dilutent. dil t t The Th carrier i gas serves to control the amount of carbon supplied to the steel surface and prevents the formation of soot residue. Mechanism (1) Transport of gas molecules containing carbon to the surface of the steel part (2) Reaction of the molecules at the surface to raise carbon content of steel, and (3) Diffusion Diff i of f the h carbon b i into the h steel. l
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. .
. (4) . (5)
These reactions decrease the amounts of CO 2 and H 2 O but increase the amounts of CO and H 2 . Carbon monoxide is the primary gas responsible for raising the carbon content at surface of the steel. Second, the CO decomposes to allow carbon to diffuse into the steel surface by the following reversible reactions 2CO C (in Fe) + CO 2 CO + H 2 C (in Fe) + H 2 O . . . . . . . . . . .. . (6) . (7)
Thus, the carbon content on the surface of the steel may be controlled by either a constant CO 2 content or a constant water vapor content determined by the dew point of the gas. If we combine Equations (4) and (6) or Equations (5) and (7), we have CH 4 C (in Fe) + 2H 2 . . . . . . (8)
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Advantages of Gas Carburizing (over pack carburizing) (1) More accurate control of the composition and depth of the hardened case (2) Suitable for continuous production and high-volume production surface hardening g Disadvantages (1) High equipment requirements (2) Soaking time required is longer than for pack carburizing (3) High safety demands. The gases used for gas carburizing can be explosive. (4) Requires experienced and skilled personnel and very reliable gas control systems. systems
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silicon
2. Heat it. 3. Result: Doped semiconductor regions.
light regions: Si atoms
Fig. 18.0,
Callister 6e.
silicon ili
Directional Quantity y J y Jz Jx x
Callister 6e.
Position, x
Diffusion coefficient [m2/s]
Jx = D
dC dx
200 03 Brooks/Cole, a division o of Thomson Learning, Inc. T Thomson Learning is a trademark used herein under lice ense.
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Jx(left) = Jx(right)
x
Concentration C Concentration, C, in the box doesnt doesn t change w/time. w/time
stop 12/03
Callister 6e.
Q: How much carbon transfers from the rich to th d the deficient fi i t side? id ?
0 x1 x2
D=3x10-11m2/s
m 10 m
J = D
J = 3 10 11
5m
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dx
J(right) Concentration, C i C, in th the b box
Governing Eqn.:
dC d2C =D dt dx 2
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Cs
C(x,t)
erf f ( z) =
t t2 3 position, x
e t dt d
Adapted from Fi 5.5, Fig. 55 Callister 6e.
t1 t o Co
General solution:
Assuming: Cs and D are constants
x C(x, t) Co = 1 erf 2 Dt Cs Co
(1)
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z=
x 2 Dt
pre-exponential [m2/s] (see Table 5.2, Callister 6e) activation energy Q [J/mol],[eV/mol] exp d (see Table 5.2, Callister 6e )
RT
30 00
Experimental Data:
15 500 60 00
10-8 D( (m2/s) )
T(C)
D has h exp. dependence d d on T Recall: Vacancy does also! Dinterstitial >> Dsubstitutional C in -Fe C in -Fe Fe Cu in Cu Al in Al Fe in -Fe Fe in -Fe Zn in Cu
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C in Fe
Zn
Ci
n -Fe
10-14
in Fe
Al in Al Cu Cu in -Fe in C u in Fe Fe -
10-20
0.5
1.0
1.5
2.0 1000K/T
Adapted from Fig. 5.7, Callister 6e. (Date for Fig. 5.7 taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)
2003 Brooks/Co ole, a division of Thomson Learning, Inc. Thomson Lear rning is a trademark used he erein under license.
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Figure 5.8 5 8 The Arrhenius plot of in (rate) ( ) versus 1/T can be used to determine the activation energy required i for a reaction
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Diffusion coefficient
D = 2.3 10 5 exp(
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Diffusion coefficient
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Carburizing
Three ee s steps: eps: Transfer C from the gas to steel surface C diffusion diff i from f surface f to t interior i t i of f steel t l section Quench/tempering Q h/ i treatment to achieve hi hard h d case with a tough interior
Aim To obtain specified carbon profile and hardness distribution through section p thickness of the component
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100 hardness 50
80
Hypo
%EL
Hyper
40
Adapted from Fig. 10.20, Callister 6e. (Fig. 10.20 based on data from Metals ed., V. Masseria (Managing Ed.), American Society for Metals, 1981, p. 9.)
0 1 0
0.77
0.77
0.5
Hyper
Duc ctility (%A AR)
90
Hypo
Hyper
spheroidite
60
30
wt%C
0 0
wt%C
Hardness: fine > coarse > spheroidite %AR: fine < coarse < spheroidite
Adapted from Fig. 10.21, Callister (Fig. g 10.21 based on data from 6e. ( Metals Handbook: Heat Treating, Vol. 4, 9th ed., V. Masseria (Managing Ed.), American Society for Metals, 1981, pp. 9 and 17.)
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Hyper
martensite
Functions of the Alloying Elements in Steel, American
Adapted from Fig. 10.23, Callister 6e. (Fig. 10.23 adapted from Edgar C C. Bain, Bain
400
200 0 0
fine pearlite
0.5
Society for Metals, 1939, p. 36; and R.A. Grange, C.R. Hribal, and dL L.F. F Porter, P t Metall. M t ll Trans. T A, Vol. 8A, p. 1776.)
wt%C
Martensite
(b)
( ) Hardness (a) H d of f martensite, t it as a function f ti of f carbon b content. t t (b) Micrograph Mi h of f martensite t it containing t i i 0.8% carbon. The gray platelike regions are martensite; they have the same composition as the original austenite (white regions). Magnification: 1000X. Source: Courtesy of USX Corporation.
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Quenching test
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T(C)
600
Adapted from Fig. 11.12, Callister 6e. (Fig. 11.12 adapted d t d from f H. Boyer (Ed.)
0% 100%
400
200
M(start) ( ) AM
te rli ite ea e rl P lit ea + ar P ite e Pe Fin ens e t t ar si M ten ar
M(finish)
Only O l th the position iti with T/t > critical cooling rate will change to Martensite
0.1
10
100
Time (s)
1000
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Q: Determine Cs values for 4820, 1020 and 3115 steels at 800 and 900 C.
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C(x,t) Co = x 1 erf 2 Dt Cs Co
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The h curvature of f the h surface f b being i carburized b i d also l influences i fl the h case depth d h when the radius of curvature is comparable in magnitude with the case depth. For convex surfaces, surfaces the case depth obtained is greater than that expected on plane surfaces. For concave surfaces, , the case depth p is lesser than that expected p from plan p surfaces.
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PROCESSING QUESTION-1
Copper diffuses into a bar of aluminum. 10 hours at 600C gives desired C(x). How many hours would it take to get the same C(x) if we processed at 500C? Constant Key point 1: C(x,t C(x t500C) = C(x,t C(x t600C). ) Key point 2: Both cases have the same Co and Cs.
C(x,t) Co = x 1 erf 2 Dt Cs Co
5.3x10 5 3x10-13m2/s 4.8x10-14m2/s
Constant
Answer:
t 500 =
C(x,t) Co = x 1 erf 2 Dt Cs Co
t1273 = D0 exp(
(Dt)900C =(Dt)1000C
Answer:
QUESTION-continued
At 900C, the cost per part is ($1000/h) (10 h)/500 parts = $20/part At 1000C, 1000C the cost per part is ($1500/h) (3 (3.3 3 h)/500 parts = $9 $9.90/part 90/part Considering only the cost of operating the furnace, increasing the temperature reduces the heat-treating heat treating cost of the gears and increases the production rate. Another factor to consider is if the heat treatment at 1000C could cause microstructural or some other changes? For example, would increased temperature cause grains to grow significantly? If this is the case, we will be weakening the bulk of the material. How does the increased temperature affect the life of the other equipment q p such as the furnace itself and any y accessories? How long g would the cooling take? Will cooling from a higher temperature cause residual stresses? Would the product still meet all other specifications? These and other questions should be considered The point is, as engineers, we need to ensure that the solution we considered. propose is not only technically sound and economically sensible, it should recognize and make sense for the system as a whole (i.e., bigger picture). A good solution is often simple, simple solves problems for the system, system and does not create new problems. problems
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50
x C (x,t) Co = 1 erf f 2 Dt Cs Co
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Worked example
A 25-mm diameter 8620 steel bar was carburized at 900C for eight hours. The diffusion coefficient of carbon in austenite is
D = 16.2 exp( 137800 ) 8.314T
Determine: (1) the location in the carburized case where a quenched hardness of 54 HRC may be obtained with a minimum of 95 percent martensite; (2) whether the desired hardness can be obtained by quenching in agitated water t or in i agitated it t d oil? il?
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Solution 1 Solution-1
The as-quenched hardness is 54 HRC. Then, we use Fig. 1 to convert the asquenched hardness to carbon content because the hardness of as-quenched martensite is only a function of carbon content. content The carbon content is found to be 0.45 percent C = C(x,t) in the carburizing equation
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Solution 2 Solution-2
C ( x, t ) C0 x ) = 1 erf ( C s C0 2 Dt
from which we can solve for x, the location of C(x,t) = 0.45% of C. At 900C (1173 K), Cs = 1.24 percent C for 8620 steel from Fig. A and the diffusion coefficient is 137800 D = 16.2 exp( ) = 1.183 10 5 mm 2 / s 8.314 (900 + 273)
Then and
and
Solution-3
(2) We need to know now whether we can obtain the desired as-quenched hardness of 54 HRC at 0.98 mm from the surface by quenching in water or oil. We need to know the Jominy equivalent cooling rate at this location and then use a hardenability curve. Rounding the location to 1 mm, this location from the centre of the 25-mm diameter bar is (11.5/12.5 = 0.92R). For agitated water quenching, the Jominy equivalent rate at 0.92R (very close to surface) is 1mm. To get the hardness at this location we look for the hardenability curve 8645 not 8620 since C = 0.45% at this location not 0.2% . The minimum at l mm for 8645 from Fig. Fig 9 9-51 51 it is 57 HRC HRC. Doing the same for the agitation in oil and using Fig. 9-53, the Jominy equivalent q cooling g rate at 0.92R location is found to be 2.5 mm, and using g 0.45% C, is 56 HRC. We see that 57 HRC for water quenching and 56 HRC for oil quenching both exceed d the h 54 HRC HRC. Th Therefore, f we can use either i h quench, h because b oil il quenching is less drastic, we should use oil quenching.
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Water q quenched
oil q quenched
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57
58
59
x C(x i , t i ) Co i = 1 erf Cs Co 2 Dt i
= (constant here)
x i Dt i
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B B B B BBB B BB
ln[t(min)]
Other Applications
Processing of microelectronic circuits i i
The ability to produce a large number of circuits on such a small surface arises from the techniques of masking and then patterning by lithography. The procedure is illustrated here. The "mask" used is the oxide of silicon that is grown by thermal oxidation, referred to as thermox in the industry. The thicknessof this oxide can be carefully controlled ll d from f previous i experience. i A layer l of f an organic i material called photoresist is applied over the oxide layer on which lithography is done. Webster's Dictionary defines de es lithography og ap y as the ep process ocess of o printing p g from o a plane pa e surface (smooth stone or metal plate) on which the image to be printed is ink-receptive and the blank area inkrepellant. In microelectronics processing, a masking pattern tt is i placed l d over the th photoresist h t i t and d ultraviolet lt i l t light li ht is passed through. Depending on whether the photoresist is positive (or negative), the area exposed (or unexposed) is washed away y by y a suitable developer p to p provide a window over the oxide. The oxide is etched away by ydrofluoric acid to expose the silicon surface onto which dopants are predeposited and driven-in or where metallic i t interconnect t is i deposited. d it d
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S h Schematics ti of f the th lithographic lith hi methods th d to t create t metallic pattens and selected areas for infusion of dopent atoms
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Schematic of a n-p-n transistor. Diffusion plays a critical role in formation of the different regions created in the semiconductor substrates. The creation of millions of such transistors is at the heart of microelectronics technology
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2003 Brooks/Cole, a div vision of Thomson Learning, , Inc. Thomson Learning is s a trademark used herein un nder license.
SOLUTION
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