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  • Sinterização R German 1

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    Sinterizaçao ceramicas

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    18 visualizações10 páginas

    Sinterização R German 1

    Enviado por

    Filipe Andrade Silva
    Sinterizaçao ceramicas

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    © All Rights Reserved
    Baixe no formato PDF ou leia online no Scribd
    Sinalizar o conteúdo como inadequado
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    = Fundamentals of Sintering Randall M. German, Engineering Science and Mechanics Department, Pennsylvania State University SINTERING provides the interparicte bonding that generates the attractive forces needed to hold together the otherwise 1oose ‘ceramic powder mass. Instead of setting a sintering Schedale by trial and error, a better Is to understand the fundamentals of interparticle bonding. The effects of both Intrinsic material chayactenstics and extrinsic powder and atmosphere characteristics. are Lunderstood, To study sintering, one monitors the density, surface atea, shrinkage, or some ‘other easily measured parameter that come- lates favorably withthe sintered properties. Sintering is the result of atomic. motion simulated by a high temperature. Diffusive processes generally are dominant. Several \ariables infivence the rate of sintering. Those Inchide the initial density, material, particle Size, sintering atmosphere, temperature, i and heating rate. The geometric progression using he inal stp grils fer boots Bike parce oni As denlfeaton pro- Geeds, ew contacts il form, hence there srl be varistons inthe degree of sitting From point-to-point in the mlerosiscte de tothe delayed contact formation. With pro. longed sintering, the pore strscture becomes tothed, lading to the intermediate sage, stioh coresponds toh open, eongtous por stature that ests tetwces dnsis of Zpprximately 70 sed 9255 of thcoresial. In dhe itermedine sage, the string rte Is continuously decreasing ands very sensitive {9 te poregain boundary morphology. Gra from occurs inthe later portion of snes. {5g ding which the pores become spherical nd isolted, Elimination of elated pores acl tis poet. he final stag’ of sine tering comesponds 1 closed, spercl pores ‘hat shine owly by vacancy fasion to fin boundaries. Sch densfeation is sen. the rae nse and he a tachment of pores 10 Bain boundaries A smo aed he ors Wl ‘Several potential mass transport pats can te active during sintering. The characterise discon is beeen surface and alk. pro ‘esc. Bulk unncpotprovigesdensifeation, white srface tanoport eontbutes t intr: tanlete bonding without densiiation. Be- cause of complexities inthe paricle-pore ge fmety, mase transport processes, and sages Of sintering, tis typical to resort fo computer Simulations 10 quantify the sintering models (et 1,2, 3-5). These simulations have ac. eurately predicted the behavior of several systems. One major benefit is tha they allow various processing. options to be evaluated without the need for repetitive and painstak- ing laboratory measurements "Addive phases that improve dffision rates uring sinering ae used in many ceramic ‘materials. These phases can be used to st bitize desroble crystal structures oF, more typically, to form a liguid phase to increase ‘Oe cae of intorng. Liguid-phase sinter {san atractive option For many of he hit perfomance materials because of the rapid processing jie, igh flnal density, and excellent foal properties. “The atomie motion in sintering contributes to the formation of weld bonds between the panicles and the elimination of pores. The Sire teal exh nd other Proc, eteral fore (pant) or chemical Additives can be used Sintoring Fundamentals ‘Sintering is the bonding together of parti- ‘les when heated to high terypecatures. On a restuctural scale, this bonding occurs as cohesive necks (weld bonds) grow a the points fof contact between particles, Figure 1 shows scanning electron micrographs of neck for ‘mation between sintering spheres. Such neck ‘growth causes all of the important property schenges associated with sintering. There are ‘several laws that guide the aylcation vf sm {ering fundamentals to practical situations (Ret 6-10), Its the objective of this section to highlight the fundamentals of sintering. Particles sinter together by atomie motions that act to eliminate the high surface energy associated with an unsintered powder. The surface energy per uoit volume is inversely proportional to the particle diameter. Thus, ‘smaller particles have more exergy and sinter ‘more rapidly than larger particles. However, hot all of the surface energy is necessarily available as a driving force for sintering. For 2 crystalline solid, neatly every particle con- tact will evolve a grain boundary with an as- seeitted grain boundary energy. These grain ‘boundaries prove important © aiomic motion because the boundaries are defective regions with high atomic mobility. ‘During sintering, neck growth by the ‘movement of mass to the neck is desirable because it reduces the surfece energy by de creasing the total surface area. The structural changes associated with neck growth depead ‘on several possible wansport mechanisms, most of which are diffusion processes. Dit fasion is thermally activated, meaning there is minimum energy necessary for atomic fr jonic movement and there must be avsil- able sites, This motion depends on the atoms ‘or jons attaining an energy equal to or above the activation energy necessary beak free ‘rom their present sites and moving ino other availabe sites. The population of available Sites and the number of atoms with suff ‘energy 10 move into these sites both vary with the Attheaius temperature relation, NN exo(-E/kT) e ‘where N/N is the ratio of availsble sites {o (otal atoms, E is the ap- jon energy, kis the Boltz- mann constant, and T is the absolute tem- perature, Thus, sintering is faster at higher femperatures because of the increased 1° ber of active atoms and available sites. ‘Because the elimination of surface encray fs the main objective of sintering, one ob- vious gage in achieving this goal is the sur- face afea, The surfuce area declines rapidly from an intial value and provides a gage of the degree of sintering. The surface area can ‘be measured using microscopic analysis, 62S adsorption, or gas permeability techniques (Ref ?. ‘Another measure of sintering isthe relative neck size ratio, X/D, defined as the neck ameter, X, divided by the particle diameter, D Fig 2). In addition to undergoing neck ‘fowth, a sintered compact usually shrinks, eases, and increases. in stengt, THE shvinkage that accompanies. neck growsh is iMustrated in Fig 3 for two temperatures. To" shrinkage, AL/Lo, ig the change in compact Tength from the initial dimension, AL, d= vided by the inital dimension, Le. Because of shrinkage, the compact densities from the & we Hsenirieeen os yan Fig. 1. Scowing sicronmivogrogh fsck foonotion etaen mers perl pres dv by hg fractional green density fe 10 the fractional sintered density J, Fig 3) according to the relation Behe abt” ean ‘The densification, W, isthe change in density ‘omic motion. Shrinkage is easly measured {sng campos heated to various emerates ferro nes alr, nets tr det imaging techniques can be aed (2 Continuously recor’ shankage during he fog. A comion techoiga with dlstometry tokscan over all possible sinesing temper? tives by heating We eompect a estan a © regreniva declan i tera slog of sintering (6 ite age () named i ed ein rh Fig 5 ios etal sige) acre soe. The race surfoce cogroph hows he Searone Placene fsck pre on gre Bunn hel ge of eer of temperature increase, such a 5 of 10 K/ nin (9 or 18 °F/min). ‘The specimen length or shrinkage versus temperature is recorded, ‘This approach uses a single experiment t0 Identify’ the temperatures where significant ensification occurs. This is a considerable improvement over isothermal experiments, \Vatious adaptations have evolved using elosed- Joop feedback control, where density versus time is programmed and the control computer determines. the necessary temperature in crease needed to obtain the desired density, ‘This leads to nontinear heating schedule that reflect sensitivities to grain. growth, pore coarsening, densification, and other ther- mally driven microstructural changes. ‘Sintering Is not a single zrechanism pro- ‘cess. Many materials sinler by a combination ‘of actions involving multiple modes of mae flow. With a change in particle size, tem. perature, of timo, it i possible to shift the ominant sintering mechanism because of the Siffering sensitivities to process parameters. Viscous flow dominates for amorphous ma- terials. Volume diffusion is prevalent with very high temperature sintering of large part Surface diffusion and grain boundary diffu. sion are usually dominant with smaller par- ticle sizes in crystalline materials. Further ‘more, small particles exhibit faster neck {prow and need les sintering time or a lower sintering temperature to achieve an equiva. Fundamentals of Sintering/263 Surface aitusion 7 g voure nN Siaron { ~ Pras Now ‘ cain boundary Ditusion theron wx, ft Sen " Evaporation ondenaston Fig 6. settecrtnaen erste bean oF saat EBs ooo SPE irene Jent degree of sintering. Generally, large par- ticles will sinter slower and requice higher sinteting temperatures or longs sintering times ‘© atiain an equivalent degree of densfica- tion. The improved sintering densification with decreasing particle size is @ majoryeason for ‘sing small parictes, “Another demonstration of the effect of small panicles on sinceing is piven in Fig? 7 plots the fesctionnt sintered density for medal mixtures of alumina with sizes (of approximately 0.3 and 3 ym @20 10 200 spin}. The sintered density increased withthe fraction of small particles, demonstrating the potent sole of small particles. Model experi- nents with continuous particle size distnbu 3s ndicate maximum sintering densifica tion with distbutions ofitermastat to large widths (Ref 12) . ‘During sintering, bulk transport will reate ‘change in the interparticle spacing as neck growth takes place. The result is shrinkage, Increased density, and higher strength forthe entire powder compact. Figure 8:plos the Sintered density of nonosited titania (TiO) powder sintered at vations temperatures and fimes. Longer times, higher tetnperatures, and Table 1 Nomenclature for the initie! stage sintering equation: (X/0)" B/D” ® vl Pie ow Evaporation condensation (rai Bossdy son Sortie ditroe : 3 nse ap ei ete we wt ty ten i Fe ms Pp Be. Hee: Bi ame ee SE, ‘Sc Se RNG AG Se Skt Rea a gra 264 /Firing/Sintoring: Densification +00 » a Sitsred deny, % so 030 Smo particle eontont Plt of focfonat sintered deity vrs Fig 7 ccapestion of Uinodal chaizo powders fo show thot te Naest dant seas wi We grectest ‘enter of orl pores, Brel lumina, lech we Sere 1600°C (2710) fr 60 in, tonite of parila dametors cf6.5 ond'5 pm (20 and 200 pin} Stren Ret higher initial packing densities all contribute toa higher sintered density. Note tat the rate of densification continuously decreases dur- ing sintering. This is the consequence of relaxation in the driving force and the need for larger diffusion distances as the neck en- anges. Shrinkage mandates an oversizing of the tooling to bring the fina sintered part into an acceptable size. Density gradients in the ‘compact translate into differentia shrinkages 1). Typically, 2, will vary inversely withthe cube of the grain size, reflecting the strong role played by grain boundaries in the dea- sification of erystalline ceramics. ‘The intermediate stage is important in de termining the properties of the sintered com: is characterized by @=e+Ke en where Go is the inal grain size, and X is a thermally activated parameter that is similar to the factor B in Eq 4 and 5. During the in- termediate stage of sintering the pore struc- ture becomes smooth but remains intercon rected until the final stage. The solid-vapor surface area of the compact is now less than 50% of the ini used to follow sintering well into the inter- mediate stage. Effect of Sintering on Pore Structures “The geometry of the grin boundary and the pore during intermediate stage sintering ‘onto the sintering rate. At the beginning tf the intermediate stage, the pore geometry Ishighly convoluted and the pores are located at grain boundary intersections, With conn (Gan deundary Fig 9 the aed pores dome dra Two ponte poe ued sintering, the pore geometry approaches 2 cylindrical shape in which densification ‘occurs by decreasing of the pore radius (Ref 14). Daring sintering, the interaction between pores and grain boundaries can have three forms: Pores can retard grain growth ‘© Pores can be dragged by the moving grain boundaries during any grain growth (© Grain boundaries can break away from the pores, leaving pores isolated in the grain Nerior At the temperatures typical of sintering, most materials exhibit moderate high grain growth rales. Any differences in inital grain sizes ‘generate forces on the grain boundaries that cause grain growih. As the. temperature is increased, the rate of grain boundary motion Increases. Breakaway of the boundaries from the pores occurs because the pores aze slower moving than the grain boundaries (Ref 15). Under the tension of a moving grain bound ‘ay, pores can move by volume or surface diffusion or even by evaporation-condensa- tion across the pore, but this requires close contro! of the heating rate, using a process termed rate-controlled sintering (Ref 16). Consider the two possible pore-boundary ‘configurations illustrated in Fig 9. Pores can ‘occupy sites located at the grain edges or in Interior of the grains. The system energy fs lower for the pore occupying the gran edge because the pore reduces. the totsl grain boundary area (and energy). Should the pore ‘and boundary become sepggited, the system ‘energy is inereased in proportion t the amount fof newly created interfacial ifea, bs a con- sequence, the pore has a binding’ energy in relation to the grain boundary. that increases {as the porosity increases. Hence, at the be> ginning of the intermediate stage, litle sep- aration of boundaries from pores is expected. cin boundary cones inthe inemasitestoge of Stein (0) With dan- ‘ifeaon, (©) Wht dansicaton. Te pores lcstedon ran bowndres provide dencsion whe i ; As densification proceeds, 1 ane Tower mobility ofthe pores coupled to the ‘iminishing pinning force allows breakaway. ‘Separation of the pores from the boundaries Timite the potential final density. Conse. ‘quently, itis importent to minimize breaka- Shay by careful processing contral. A com- bination of large pore size and grain size leads to breakaway during grain growth (Fig 10). IWealy, the large pores are immobile in the cay sages of sintering and are pinned against the gain boundaries to maintain a small grain size, inthe Iater stages of i the pores fecome fewer in number and diminish in size due to shrinkage. Although the grains are ret ively lage, the pores are sufficiently mo- bile t0 migrate with the boundaries. Densi- fication is dependent on the rate of pore shzinkage while this situation persists and a high grain boundary diffusivity is helpful. As the pore size decreases, there is less inhibi tion to grain growth and pore mobility is 9 greater concern. For the pores to remain on the moving grain boundaries, itis necessary to ncrexse their mobility, for example, by in- creasing, surface diffusivity. Rapid grain growth iso be avoided because invariably ‘the densification rate is low (Ref 17) “The mechanisms whereby the breakaway ‘event can be avoided are of particular im- portance to coramic materials that exhibit a high sensitivity to residual porosity. Al- though the rate of densification is dependent fon factors such as grain size, density, tem- perature, and time, the dominant factor is the effect of temperate. If bulk diffusion is active at the end of the inital stage of sin- tering, there will be no densification, al though pore growth and possibly grain growth right be sctive. Pore rounding occurs si- ‘multaneously with densification ‘The final stage of sintering eccurs when the pores spheroidize into a closed structure, at approximately 8% porosity. Most mate: Fal ae sintered to densities over 92% of the- Potedes, Ain, 011 1m ww Grain gowrh Tie £ 9] "notong + 2 mata 10 Bo + sows] i sara di § «| ee Died eo LI 4 coor ag er 1 Wi We aes, wn tt gin ao em Fig 10 Ceninschericanae aka ‘tcn growth ca eman @ bresiznvay Wom fe heres, Zetudly lean to bbisied demifcoton. Desable Screg ‘ret the brvchawey eondiion by Sota Wilage ow tomperhaer wre ‘tan grow is bed ‘retical and pass into the final stage. Surface transport is active during intermediate stage sintering. Its effect is to smooth the pore structure and to allow pore migration with grain boundaries during grain growth, Sur- face transport does not contribute to densifi- cation of shrinkage. The specific sintering ‘events are dependent on the microstructure (grain sizo, pore size, and pore spacing), Fur- thermore, since the microstructure is contin- ually changing, the influence of temperature ‘can be quite pronounced. The densification rate is enhanced by a high diffusivity and ‘small grain size (Ref 18). Pores, dispersoids, and second phase inclusions slow grain growo) land can be used (o improve densification. Final stage sintering is slow process ‘wherein spherical pores shrink by a diffusion ‘mechanism. Ifthe pores have a trapped gs, then solubility of the gas i the matrix will {inflence the cate of pore elimination. For this ‘reason, itis preferable to sinter in vacuum or to use’an atmosphere that is soluble in the sintering material. When a gas is sealed in the pores, the densification rat is controlled by the intemal gas pressure, Pores begin to pinch closed at approximately 80% of theo- Fetical density, as iustrated by the wranie (UO}) data in Fig 11. At approximately 92% density the pores make a rapid shift a closed structure. If the closed pores are mobile ‘enough (0 stay coupled to the grain structure, then shrinkage will continue into the final stage. A honiogeneous grain size and sinter- ing in a vacuum aid densification in the final ee ‘In most materials, the distributions in par ticle size and packing create a pore size dis- tribution in the final stage. With long sinter- {ng times, the number of pores decreases and pore size Coarsens while the total poresity may even inerease. Differences in pore curvature vill lead to growth of the larger pores at the ‘expense of the smaller, less stable pores. This process is known as Ostwald ripening. faining 100% density by sintering requires precise manipulation ofthe initial powder mi- DOA : q 050 Bom a Ct O58 we Pros. % ‘The vrai nthe open end dosed pore Fig 11 ecion:varas the ttl porosy forse taving wna of 1400 (25807). Sources Rel 19 Fundamentals of Sintoring/265 crostructure and heating cycle, because sev- feral factors can inhibit final pote elimination. Sintering Diagrams ‘The sintering diagram is a useful concept for representing sintering behavior (Ref 1,2). shows the density or neck size versus fem= [erature for several isothermal sintering times, ‘These diagrams combine the several mech nisms of sintering with the changing geom- try to show the effects of the main process varlables, Because of the complexity of euch an analysis, sintering diagrams are generated Irom a materials data base using computer simulations. A sintering dizgram for 0.4 ya (16 win.) alumina is given in Fig 12. Den sification is dominated by grain boundacy dif- fusion, aldiough surface diffusion makes a ‘considerable contbution to the overall mass flow. This plot shows the relative density versus isothermal sintering temperature for foor selected times. Because grain growth during Sintering reduces the densification rate, ac- ‘wal sintering behavior tends to give Tower ‘densities, From such plots, an assessment of the interactions between the key processing variables of particle size, sintering tempera- ture, and sintering time ean be made. A chang? in particle size has a large effect on each dia- ‘gam. Ata given temperature, a higher den sity is attained fom small powders. ‘The sintering diagram provides a computer generated first estimate of te sintering be- havior for 2 given combination of parame- 4ers. One important aspect of sintering dia- seams isthe inclusion of mahi i Jn the calculations. Most materials do not sin- ter by a single mechanism. Rather, several mass transport processes usually are active daring sintering. ‘The effect of these simul- taneous mechanisms is to increase the overall rte of sintering Effects of Sintering on Compact Properties “Te main season for sintering is to improve such compact properties a hardressetength, tranapaeney, toughness, clectal conduc: i) heal eapnsion, magne sare ad corrosion rsa, The sensitvity heath of these propertics to the dence of ring canbe quite cifeeny, but in general iclmproves with the depres of densifeation. ‘Various quanta models ofthe effects of poreity on properties ae sted fn Table 2. rte tae, sath propery i piven at a ne tion ofthe balk atrial progeny (ube “Or, fatonal density nd vaso aja thio parameters that pend on the poe ie, Shope, and spacing. Te dynamic properties Gon pat sheng) prove Be foperies that are most sense to sintering. PSPoe 3 contests the advantages and ds. advantages of some of the agjsible pro essing vats In sintring. rom iter 266/Firing/Sintering: Densification Temperate F sauna ss tonne nasa ° Time alae on anh “aah os Be i ra ountuy | Siena Boal - os} te Green density °3 Soo xo aco tow) avn a6 Yt ——Tato Tompersture, (8 pin) parce see nd 0.1 hte iri dogron, bat each cna he rinor mecha cone Fig 12 Suncaldnty mpeonot'ns oct ton a taafonnelolon oe Ing standpoint, a decrease in particle size 1s favorable, because smaller partcles lead to ‘more rapid sintering rates and highec strengths, Figure 13 illustrates such an effect by plot ting the sintered strength of zirconia (Zr0,) ‘versus the particle size for a constant pro- cessing eyele. A long sintering time will fyp- {cally improve the degree of sintering but will Jead to more expense in processing, The sin- tering temperature is one of the most influ- ental ofall sintering variables. Higher sia- si ee canin wth the ina Rafar of dom spect tering temperatures give more raid sintering. ‘This is not always favorable, because of the greater expense in furnace detign, the higher ‘energy costs, and the possible grain boundazy Separation from the pores, Ia the same man- ner, compositional changes can improve tered properties. By adjusting the composi- tion itis possible to considerably strengthen the material and aid sintering densification. ‘Thus, another goal of sinering ist attain de- sible diffusional homogenization responses Table 2 Effect of porosity changes induced by sintering on selected properties of compacts minnie ono er sent Sens esi conte 2 o Nowe seaion * amis + ap eh : frag Ra Beet mete 5 eas ‘Sear mouie 6 ole ion mo ‘ £20 aets7 tery nine na pn iy a yn oe, uring the high-temperature portion of the sintering cycle. Mixed-Powder Sintering tering because itis easy to change composi- tion and because some unigue composite mi- crostructures are possible. Two types of sintered structures are possible from mixed powders: © Solid solutions, which involve the ho- rmogenization of the powder mixture by diffusional processes © Composites, which involve cosintering two dlistint phases Homogenization during sintering issn al- ternative to forming compacts from chemi cally prehomogenized powders. Sintering of ‘multiple component powder systems is more ‘complex than sintering. single component ‘compacts because of the simultaneous phase reactions and homogenization effects. Di fusional leveling of the chemical concentra- tion gradients is dominant early in the sin- tering cycle. ‘Mixed-phase sintering has some recog nized problems, The compositional gradients require control of both time and temperature to ensure homogenization, The degree of homogenization 17 is defined as the point-to- int chemistry variation, and it varies with Aiffusion rate and parle size as follows (Ref 24): wm Dupe 9) where ¥ is the seale of the Imicrostructural segregation, D, i the volume diffusivity, and 1s te time. The scale of segregation a5 mes- sured by ¥ depends on the particle size and concentration of the powders. Equation 9 shows that homogenization i faster wth small particles where the diffusion distances arc Stall, Ifthe diffusion rates of the two com- ponents are very different, den swelling may fccur. The phase diagram is important to un- Serstanding the possible phase reactions dure ing mixed phase sintering (Ref 25, 26). ‘Composites with two interlaced phases can be formed if a condition of cosintering is at- tained (Ref 27). Success in cosintering te- ‘quires specific particle size ratios and uses of ‘compositions that exhibit similar shrinkage versus temperature behaviors. Enhanced Solid-State Sintoring . “To provide the maximum properties, itis ‘often teceseary to enhance deraifcation. Me ‘common approaches are (Ref 7) © Phase stabilization Activated sintering : Reactive sintering 1 Liguid-phase sintering Table 3. Results of modifications in sintering process Processing designed to ald the Precetng change at recy ane “Feemal decomposition ‘Bower bin Phose Stabilization. Diftuiviy of = rstedal is determined by several factor, including the temperature, crystal structure, fn defect configuration. ‘The degree of sin- tering. densification depends on the phases prevent atthe sintering temperature. Addi Tonal, mixed phase microstuctires resist fran growh during sintering, especially in the intermediate stage, Tes possible to ast the composition or stoichiometry of powder system to stabilize a phase witha high 3 tering rat. This ean davolve Use of 2 Second spin an owt cig Sing Rk Activated sintering. allows for either a lower sintering temperature, a shorter sinet- ing time, or improvement in properties from ‘chemical addition fo the powder. One of the ‘most dramatic examples of activated sinter Saar depre ‘Berne np Seam ce lglg ten a ang Ch tig r er x * 2 ¥ x x € x x x ¥ x n y % ing oceurs when tungsten or molybdenum are {reated with certain transition metals (Ref 28, 29). The successful additive acts co improve the rate of butk transport daring sintering by providing a fast diffasion path. To perform {his role, the activator segregates to the in- terparticle contacts where it provides a high iifusivty ehortciecuit path by forming a low ‘melting temperature phase, ‘The lower melt ing point ensures a lower activation energy for diffasion. Typically, an activator that de- creases the liquidus and solidus of the base ‘material is most successful. Figure 14 shows ‘an ideal phase diagram for activated sintering systems. AC temperatures slightly above the ‘ctivated sintering range, a liquid phase fooxs. Forming of a liguid phase is another means of enhancing sintering (sce the section “Lig ‘id-Phase Sintering” ie this article). oaceasig arte st, pegessicg 0 _oor2 0.004 0006 018 aw woke “ Be gL ad € €- | aia : ' proce £ xo} — mob E z Bog Aetivated Bw wi f ae Le toe 5 rn oe seliy 980 s08 . 8 100180 ave A Pardee po shies fig 13. Mat sre sana wens te por ested pre date fo 0 dive Fig 13 far keine meee te Fig V4 Seiscs Sik snting draeoton ot £2200 °C (29907). The mor iv singe he naar Parle: eos to lnproved srengi. Sous Bal 23 1 bot mote The adding ot foeahone fhe Mes ‘fonpor roe dng sneng, Sour Ref 25 Fundamentals of Sintering/267 Reactive used to prevent stoichiometty loss during sine tering. An excess ofthe higher sability spe. {ex might be needed o avoid decomposition ofthe compound during sitering. Also sur face contaminants may attack one ofthe con- stuens, leading to preferential atack or d- Piston. Fortis reaa, it scorn practice {b add excess carbon to carbides (Angaten tarbide oF silicon carbide) dug Tndeed, silicon eabide ean be formed by the {se of free carbon and free silicon to prodace 2 silicon carbide reaction product simulta scously with sintering. Likewise, thet are Special sintering stations where mas can be faived by the compact by reaction with the ‘Sntrng auposphore. The most common form ‘of such procesing involves the we of excess Silicon and a niogen atmosphere. In sinter ing, the slicon forms silicon nisde and the resctan product swells (oil the poe space. “These later techniques rely on ches actions during sintering, and the many vari- ft ofthese approaches ar gener own Liguid-Phore Sintering. In. two-phase systems involving mixed powders, liga fr~ ratonis possible because of difering melt ing ranges for the components or the for sation of @ low melting phase (cluding « sass phase), In such a system, the liquid may rove for Spi transport and therefore rapid Sintering if cercain erteria are met (Ref 6,25, 30). The lignid must form a fil surounding the sold phase, Ths, weting is the fist r= quirement. Secondly, the ligaid must have 8 Solubility forthe soli. Finally, the difusive transport forthe sold atoms dsoived inthe liguid shouldbe high eaouph to ensrefapid sintering. The formation ofa gi i pro- Vides the boreit of a surface tension force ‘sting (0 aid encification and pore elimina. tion. fo this sense, te liquid phase ats Tike ‘low presure extemal stess, An example of systems involving liquid phase formation luring sintering are WE-Co and SisNs-Yi0,. In liquid-phase siting, the densification rate 45 much faster than fn solid-state sintering, and ines as short a9 15 min at he maximum temperate can be successful in producing full densi ‘when a mixture of poids is Bete, ge ti forms and then Flows toe the particles Figure 15 provides 2 diagram of the densi fication stages of liquid-phase sintering. The combirstion of wetting, liquid flow, and par- {ete rearrangement all cogubate 1 densi

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