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Densification during Sintering in the Presence of a Liquid Phase. II.

Experimental
W. D. Kingery and M. D. Narasimhan

Citation: Journal of Applied Physics 30, 307 (1959); doi: 10.1063/1.1735156
View online: http://dx.doi.org/10.1063/1.1735156
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13 On: Mon. 1953). F. 000 I 000000000000 000 RADIATION * With funds from the U. Reuse of AIP content is subject to the terms at: http://scitation. Experimental* W. Eversole and P. second. J. 203 (1940). Atomic Energy Commission under SHIELDS t-~--Y---r Contract No. Nat!. No. based on the models copper powder and magnetic iron powders having proposed. continuous liquid films 2 and an increased rate dull red heat ('" 700°C) to 1150°C in 1 to ! min.M~O~LYBDENUM 000 000000000000 000 SUSCEPTOR T~ 878 (1945). NARASIMHAN Ceramics Division.! a theory of densification sintering in the presence of a liquid has been reported data with theoretical expectations. 6 H. H. 27. V. Lenel in The Physics of Powder Metallurgy. The low at least the conditions required for the process to take heat capacity of the furnace allowed heating from a place. ~~~~~~~~~~~. Tyrol.. D. Chern. H. 2t in. Engrs. 4 F. particle size and tempera- ture are in agreement with theoretical predictions. ' 6 F. Hidnert and W. Utilizing rear lighting. New York. I. Phys. 7 P. 307 [This article is copyrighted as indicated in the article. S. ll. there are a variety of hydrogen was utilized for all measurements and all data available which indicate that in aqueous systems measurements were carried out at 1150°C. Z. determined with a filar micrometer telescope. Dependence of the sintering rate on time. temperature. Finally. 10. 2 W. direct observation of densification. U. S. INTRODUCTION mined experimental densification rates for the iron- copper system and propose to compare these and other I Nduring the previous paper. App\. Mining and Met. Metallkunde 16. should be capable of experimental verifi. Lenel. edited by SILICA COOLING {OILS W. viewed through a sighting window and the length Further qualitative arguments can be based on experi. KINGERY AND M. the ends of the bar could be are shown to be consistent with the proposed steps. 09 Dec 2013 11:56:25 . Quantitative calculations Samples were prepared from -325 mesh electrolytic of the absolute rate of sintering. 7 An atmosphere of dry sintering process itself. lnst. 1. which is typical of those systems showing spheroidal grain development. D. Gross.3 have been Measurements were continued for approximately 4 hr. Am. FIG. Cambridge. 36. direct experimental measure. Ruette. 686 (1941). D.130. E. Inc. Second.aip.20. solution at Experimental determinations of the densification rate contact points and precipitation. NUMBER 3 MARCH. Bur. Am. Trans. 1 W. 301 (1959) (preceding paper). Benesovsky (Metallwerk Plansee Ges. 9. EXPERIMENTAL MEASUREMENTS take place by three consecutive processes. Norton and A. indicate that in this system the rate of densification during liquid phase sintering is controlled by diffusion through a liquid film between particles. and finally coalescence were made by means of direct observations of linear of solid particles which prevents further densification. of solution on the application of pressure. Similar mental studies of the effects of liquid content on the arrangements have been employed for measurement of size and shape of grains as well as on the kinetics of the thermal expansion coefficients. I I II t-J~4------- LIGHT/OURCE __ ~ B. V. as hydrogen reduced iron powder with a nominal par- A system for which much information is available in the literature is the iron-copper system. first a re- arrangement of solid particles. A theoretical estimation of the sintering rate is in good agreement with experimental measurements. 1958) Experimental measurements of the densification rate and microstructure changes taking place during sintering of the iron-copper system. nominal particle sizes of 3. J. Derjagrin. developed in which the over-all change is supposed to II. Kingston (McGraw-Hill Book Company. 30. and 20 microns as well cation in systems for which suitable data are available. Kingery. J. 3 R. Chap. Samples consisting of bars Experimental tests of the theory may be of three kinds. !959 Densification during Sintering in the Presence of a Liquid Phase. JOURNAL OF APPLIED PHYSICS VOLUME 30. Lenel in Plansee Proceedings.. Massachusetts Institute of Technology. 344 (1924). there are qualitative arguments in which the were heated on a bed of alumina grain in an induction shape of grains developing during the sintering process furnace with a molybdenum susceptor as shown in Fig. demonstrated. pressed in a steel die with no binder First. 1952. Top view of induction furnace assembly employed for 1951). Laher. 486 (1950). edited by F. Phys. Johnson. and the phenomenological description of the process 1. with theoretical expressions. Trans. Faraday Soc. 14. This method of heating and observation allowed meas- ments of the densification rate and effects of particle urements at relatively short times and allowed an entire size.4-6 which shows HEATING COIL typical spheroidal grain development. 175 . Ceram Soc. Souder. S. Department of Metallurgy. Standards Circ. Cannon and F. 77 (1944). shrinkage during sintering. We have deter. G. Downloaded to ] IP: 177. 10ngX! in. and time should be in agreement densification curve to be obtained on one sample. Massachusetts (Received July 23. L. AT-(30-1)-1852. V.org/termsconditions.

In the iron-copper Lo 3 Vo systemS at 1150°C. linear plots formed for several systems by Lenel 4. 9 15. Lo 3 Vo positions employed correspond to approximately 4. For the solution- the solubility of copper in solid 'Y-iron is not well known.1. or. Reuse of AIP content is subject to the terms at: http://scitation. 9 W. Densification parameter vs log sintering time for several 1150°C.. Inc. We have no data as to the ap. commonly reported in terms of the "densification In several cases. 308 W.0.6% copper. 09 Dec 2013 11:56:25 .02 60 2: 0 . the com. D. 14. D. ~L 1 ~V proach to equilibrium during sintering.142. D.4 micron iron powder were prepared with 11.= .3-1. Inc. precipitation process with diffusion rate controlling.5% Cu. compositions in the iron-copper system. 'Y-iron is in equilibrium with a liquid containing about 95. Downloaded to ] IP: 177. but taking the . 4. (2) and 43. but says it may be lower.2 100 0. and carbonyl iron powders. New York. p. In both III.3. That is.0 weight percent copper.6 are 20. 3. Also.tt i (3) solid composition as containing 7.-=C 2f r. and 38 volume percent liquid at the sintering tempera ture. and C 3 are constants for any fixed com- cooling and measuring resultant bulk densities. particular. edited by 8 B.'"::E a:: 80 1i'.0 weight percent copper.5 0. rearrangement process the fractional shrinkage is given taining 22.130. the densification rate true density.3 ~L 1 ~V .-=C 3!r.. In the preceding paperl it was shown that for the Samples were prepared with each iron powder con. EFFECT OF TIME cases. and 40 micron copper gave average sizes of 9.= . Danidoff s indicates it has been reported as 7. Metals. It is clear that these data can 0. in several cases the density reaches a constant value corresponding to true density.. respectively. we have plotted the log copper compositions at 1120°C and 1200°C. reduced. not universal.4 factory agreement with Eq. and 33._=C1t Hv .20. (John Wiley and Sons. Cleveland. Direct microscopic plot over restricted time periods. the approximately determination of the particle size of the nominal 10. an initial portion of the curve can be parameter" equal to the fraction of porosity eliminated represented by the relation (~VI V o) '" t1. N. 1196. 2. (2). a substantial portion of the log-log plot is best represented by a slope of j.4~ u: 40 . .05 . All powders were obtained from only be represented by straight lines on this semilog Charles Hardy.org/termsconditions.4.bulk density] D=loo [ . p. [This article is copyrighted as indicated in the article. and 43 weight percent copper at FIG.1 Lo 3 Vo t" (4) Lenel and co-workers4-6 have determined densification rates by heating samples for different time intervals.13 On: Mon. 3 with electrolytic.1 a:: . KINGERY AND M.aip.green density Plots of the densification parameter vs time are shown for our data in Fig. 1954). 22. we will refer to data for 20 weight percent To test these relations.01 iiu 11. New York. prepared fractional shrinkage vs log time for our data in Fig. where y is some small fraction. for the phase boundary reaction rate controlling. where C I . ~L 1 ~V Data are also available in the literature in which .3 Cu. NARASIMHAN ticle size of 40 microns.8.1 microns. Kingery.'" . C2. In addition. in agreement with Eq.5-9%. and for some data reported by Lenel 5 in Fig..= . Kingery in Ceramic Fabrication Processes. 9. ------. At this temperature. Metals Reference Book (American Society for W. (1) cessation of sintering. 2. In position and temperature. samples by of the 9. 1958).002~1--~--~5~~1~0--720~~5~0--1~00---200L-~~ 0 TIME (MINUTES) 3 100 200 400 TIME (MINUTES) FIG. Log fractional densification vs log sintering time for compacts containing 11.. Danidoff. D.3.005 • ziii u.4 in satis- as suggested by LeneJ. (3) Densification as a function of time has been most indicating that the rate-controlling process is diffusion.I 0 .

-_ _-. t:. (5) is 0-10 kcal mole-I. During the solution-precipitation stage of the process.6 little change in the sintering rate on going from 1120° cm 2 secI. the effect of particle size 0. k2= 1. (3). 6. I (MICRON-I) the four-thirds power of the radius. While the functional dependence of the sintering rate on particle size. QUANTITATIVE CALCULATIONS FOR iron-copper system. The agreement within a (1-15 kcal mole-I). taken from data of LeneJ. II 309 . in Eq.IO I °1-I~" <f> 1 / {:~~g:g= ~ 0. that rate of sintering should be inversely proportional to the particle size. For the iron-copper system T.20 -I" I z i . The experimental data are seen to fit this model satisfactorily. Co..02 / 0. 0= 10. Sintering rate vs r-4/ 3 during the 1200°C. Fig. D= 10. -_ _-.13 On: Mon. Co=0. IV. EFFECT OF PARTICLE SIZE During the initial rearrangement stage of the sin. 0 4 .45 X 10. and paperl] with sintering data. Downloaded to ] IP: 177. Log fractional densification l'S log sintering time for compacts containing 20 weight percent copper at 1120° and FIG.03 0. This relationship is found to be observed experimentally..130. t:.V Since Co increases from 0.15 ~~O.20 TIME (MINUTES) 4 r-T FIG. S. (3) [Eq. [This article is copyrighted as indicated in the article. varies with time as predicted for the case where the rate of the solution-precipitation process is controlled by diffusion. we may (5) T also. 6. . THE IRON-COPPER SYSTEM fusion coefficient.035 to 0.06 0. (20) in the previous where the temperature dependent terms are D..20.02 10 20 40 100 200 400 1000 . as shown in FIG. S.org/termsconditions. Sintering rate t'S inverse particle size during the initial "rearrangement" process.6 cm4 sec1]lr-tt1• (6) temperature interval..7 cm. z i tering process. 09 Dec 2013 11:56:25 . That is.. as hypothesized in the VI. Reuse of AIP content is subject to the terms at: http://scitation.._ .044 cclcc in this . . DENSIFICATION DURING SI~TERING. time and temperature is strong 6k2l'lV O'YLV DC o evidence that the process occurs as predicted.Lo 3 t:. 6 for comparison activation energy expected for diffusion in liquid metals with the experimental data. EFFECT OF TEMPERATURE trolled process-further evidence favoring the diffusion con trolled model. mainly as a function of the dif. 4.L 1 t:.60 0. as shown in Fig. 'YLV= 1280 erg cm-2. The data in Fig. taking kl = t.= .04 V / / CARBONYL ELECTROLYTIC REDUCED {:~~:g = 1120·C - ~ v . V. when the rate is controlled by diffusion.30 0. Effects of temperature enter into the relation for diffusion-controlled sintering. but with considerably less assurance. to 1200°C and in another case C 2 increased by 45%.. 4 indicate that in one case there was at 11S0°C..08 0. quanti- tatively compare Eq. . since the driving force obeys this relationship while the rate of flow or the rate of rearrangement should be independent of the absolute particle size.0 should lead to a sintering rate inversely proportional to r. Vo fusion calculated from the sintering data and Eq.= [0.& "solution-reprecipitation" process.8 the activation energy for dif.8 1.aip. A larger activation energy would be expected for a phase boundary reaction rate con- THEORETI~/ .40 0... in satisfactory agreement with the This result has been plotted in Fig.01 ! / 0. as is the case for the iron-copper system.04 cclcc.

is limited by diffusion through the liquid boundary formity with neighboring grains is required in order film.3 0. Downloaded to ] IP: 177.2 0.20. 310 W. The fractional volume shrinkage corresponding shapes. 8.org/termsconditions. On the other hand. complete densification can is quantitatively consistent with experimental obser. and temperature on the sintering rate in the iron- the "sphericity index" is plotted against liquid content copper system are in satisfactory agreement with a in Fig. Distinct differences were ob. complete densifi. take place by the rearrangement process and no other vations.13 On: Mon.4 FIG. little densification can take VII. As is seen there. Solid line is theoretical factor of two must be considered fortuitous in view relation.1 0. While the experimental contents.2 ~ 0. D. and related to the approach toward equilibrium microstructure studied. particle many individual particles. Measured values of the sintering rate in the iron- to achieve densification. densification must take place by a solution-precipitation cation can be reached by the rearrangement process phenomena." which is the average ratio of minimum particle dimension to maximum particle dimension.THEORETICAL ~ 0.3 . Numerical values were calculated of a "sphericity VIII. trend of results is in agreement with that predicted. sintering process is required. Consequently.5 VOLUME FRACTION LIQUID 0. 7. 09 Dec 2013 11:56:25 .aip. taken over Experimental data for the effect of time. KINGERY AND M. and the used. Reuse of AIP content is subject to the terms at: http://scitation. the general served which were related to the fraction liquid content. "Sphericity index" for solid particles in the Fe-Cu and VOLUME FRACTION LIQUID Cu-Bi systems after sintering 4 hr. samples with different points cover a range depending on the raw materials amounts of liquid phase were sintered for 4 hr. it is clear that the process as described volume percent or more. for smaller liquid contents. surface tension in which the rate of material transfer precipitation adjustment for particle shape into con. Experimentally. D. 8. and major part of If large liquid content is present.. size.2 0. of the latitude available for selection of various con- stants.130. [This article is copyrighted as indicated in the article. NARAsIMHAN 0.2 •• :3 0.5 "' 0.3 0. and the initial and final packing ability.1 0. The initial break in the curves in Fig. we would expect the greatest to this break in the curve has been plotted against the uniformity in grain shape for systems at high liquid volume fraction liquid in Fig. The effect of liquid content on the micro- the fractional shrinkage which can take place by the structure developed and the fractional volume change rearrangement process. 7. If the volume percent liquid due to a particle rearrangement process are in agreement at the sintering temperature is equal to about 35 with theoretical predictions. For the two systems studied.. SUMMARY index.4 0. FIG. the maximum departure from model corresponding to solution at contact points spherical shape takes place at small liquid contents between solid particles due to the pressure of liquid which are those for which the maximum solution.4 ~ "z0: x <J) ~ 0.4 '. EFFECT OF LIQUID CONTENT place by the rearrangement process.. copper-system are in agreement with theoretical calcu- An additional effect of liquid content is to determine lations.u ~ 0. Fractional volume shrinkage during rearrangement for compacts with different liquid contents. However. 3 and no need arises for the solution-precipitation and Fig. 4 corresponds to the end of the rearrangement phenomena which would be expected to change grain process.1 0.