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Eutticos e Peritticos

Disciplina: Metalurgia Fsica


Conrado Ramos Moreira Afonso
Departamento de Engenharia de Materiais (DEMa) Centro de Cincias Exatas e de Tecnologia (CCT) Universidade Federal de So Carlos (UFSCar)
*e *e-mail: conrado@ufscar.br

Programa Disciplina
Data 11/03/11 19/03/11 25/03/11 01/04/11 08/04/11 15/04/11 22/04/11 29/04/11 06/05/11 13/05/11 20/05/11 Horrio 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h Local 173/AT7 173/AT7 173/AT7 163/AT7 163/AT7 163/AT7 163/AT7 163/AT7 163/AT7 163/AT7 163/AT7 Descrio 1 Aula Introdutria 2 Aula n 2 3 Aula n 3: Anlise Trmica de Metais / Polmeros 4 Aula n 4 5 Aula n 5 6 Aula n 6 No haver Aula 7 Aula n 7: Difrao de Raios-X (DRX) 8 Aula n 8 9 Aula n 9 10 Aula n 10 Obs Nascente Ademar Conrado/ Ademar Ademar Ademar Conrado Feriado Nascente/ Conrado Conrado Conrado Nascente

Programa Disciplina
Data 20/05/11 27/05/11 03/06/11 10/06/11 17/06/11 24/06/11 Horrio 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h 14:00 17:40h Local 163/AT7 163/AT7 163/AT7 163/AT7 163/AT7 163/AT7 Descrio 10 Aula n 10 11 Aula n 11: Microscopia de Fora Atmica (AFM) 1 Avaliao Semestral Apresentao Seminrio Apresentao Seminrio 2 Avaliao Semestral (Sub) Obs Nascente Nascente/ Conrado P2 S1 S1 P3

Referncias Bibliogrficas
ASM American Society for Metals, Casting Metals Handbook, v.15, Metals Park, Ohio, USA, 1988. W.Kurz e D.J.Fisher, Fundamentals of Solidification, Trans Tech Publication LTD, Swirtzerland, 1986. H.Jones e W.Kurz (Editores), Solidification Microstructures 30 Years after Constitutional Supercooling, Materials Science and Engineering, Special Issue, 65, 1984. H.Biloni, Solidification, em Physical Metallurgy, Part I, Ed. R.W.Cahn e P.Haasen, Nort-Holland Physics Publishing, 1983. A.Ohno, Solidificao de Metais, Livraria Cincia e Tecnologia Editora Ltda. M.P.Campos Filho e G.J.Davies, Solidificao e Fundio de Metais e suas Ligas, Livros Tcnicos e Cientficos Editora S.A e Editora da USP, 1978. M.C.Flemings, Solidification Processing, McGraw Hill, New York, 1974. G.J.Davies, Solidification and Casting, Applied Science, London, 1973. B. Chalmers, Principles of Solidification, John Willey Co., New York, 1964.

Solidificao de Ligas Polifsicas

Apresentam mais de uma fase slida aps a solidificao; Como as ligas monofsicas, tb podem eventualmente apresentar interface S/L plana; A instabilidade da interface depender de V e G;

Solidificao de Ligas Polifsicas

A redistribuio do soluto na interface mais complexa (movimento difusivo de soluto na direo de crescimento e na lateral); Entre as ligas com interface plana: monotticas e as eutticas (importante devido a grande variedade de morfologias estruturais);

Solidificao de Ligas Polifsicas


5.4 LIGAS POLIFSICAS 5.4.1 Solidificao de Eutticos

CRESCIMENTO simultneo de duas ou mais fases As microestruturas de eutticos podem ser classificadas: LAMELAR: f 0.5 (Pb - Sn) as duas fases em propores (Al - Al2Cu) FIBROSO: uma das fases em pequena proporo (NiAl - Cr) REGULAR: as duas fases so no facetadas IRREGULAR: uma das fases facetada

Solidificao de Ligas Polifsicas

Tambm merecem ateno as ligas com transformao perittica.

Ligas Eutticas
Transformao Euttica: Lquido + (slidos)

Apresenta ponto de fuso menor que os 2 constituintes da liga euttica Euttico vem do grego e significa: de fuso mais fcil As fases apresentam porcentagem segundo Diagrama de Fases

Microestruturas de Ligas Eutticas


Podem ser classificadas em: Regulares Regulares Complexas Irregulares

Microestruturas de Ligas Eutticas Regulares: lamelares fibrosas globulares

Microestruturas de Ligas Eutticas Lamelares: placas parelelas e alternadas das duas fases EXEMPLO: Al Al2Cu

Microestruturas de Ligas Eutticas Fibrosas: barras finas ou lminas de uma das fases envolvidas por uma matriz EXEMPLO: Al Al3Ni

Microestruturas de Ligas Eutticas Globulares: glbulos de uma das fases envolvidos pela matriz EXEMPLO: Cu CuO2

Microestruturas de Ligas Eutticas

Aplicao na produo de materiais com anisotropia de propriedades mecnicas, pticas, eletrnicas ou magnticas ( Ex: Al - Al3Ni , NiSb InSb )

Microestruturas de Ligas Eutticas Regulares complexas: Duas regies de aspectos distintos: - uma com um padro repetitivo - outra com orientao ao acaso

EXEMPLO: sistema Bi-Pb

Microestruturas de Ligas Eutticas Irregulares: Consiste basicamente de orientaes ao acaso

EXEMPLO: FoFo

Microestruturas de Ligas Eutticas Aciculares: agulhas de uma das fases envolvidas pela matriz EXEMPLO: Al AlSi

Microestruturas de Ligas Eutticas Tipo de microestrutura pode ser relacionado com a morfologia da interface S/L: Obteno de ou microestruturas regulares Facetada lisa depender Difusado oucontrole Rugosadas condies trmicas
Tipo Microestrutura I II III Regular Regular Complexa Irregular Morfologia de crescimento euttico Difusa / Difusa Difusa / Facetada Difusa / Facetada Facetada / Facetada Exemplos
Sn-Pb , Al-Zn , Al-Cu , Al-Ag Al-Si , Sn-Bi , Pb-Bi , Al-Ge Al-Si , Fe-C
Comp.orgnicos

Microestruturas de Ligas Eutticas


No facetado/No facetado

Benzil/ azobenzeno

CBr4 / hexacloretano

Facetado/Facetado

Microestruturas de Ligas Eutticas Crescimento de Eutticos Regulares:


Quando a frao volumtrica da fase % menor: fV < 0,25 fibras; caso contrrio lamelar

EUTTICOS LAMELARES

Microestruturas de Ligas Eutticas Crescimento de Eutticos Regulares: Entretanto se a fase minoritria for

facetada: lamelas mesmo para fv < 0,25

EX.: FoFo Cinzento

EUTTICO LAMELAR

Crescimento de Eutticos Regulares:

Crescimento euttico COOPERATIVO COOPERATIVO: uma fase rejeita soluto outra fase absorve soluto Depende das condies de Superesfriamento na interface (SR)

Microestruturas de Ligas Eutticas

Lei Clssica de Crescimento Euttico

.V = cte
2 E

sendo: E : espaamento lamelar V : velocidade de crescimento cte dependente do material

Microestrutura euttica depende de V e Tt e no diretamente da taxa de resfriamento como ocorre com os crescimentos celulares e dendrticos

Variao do espaamento lamelar com a velocidade de crescimento

Variao do superesfriamento com a velocidade de crescimento

Ligas Eutticas

Ligas Eutticas

Ligas Eutticas

Ligas Eutticas

Ligas Eutticas

Ligas Eutticas

Ligas Eutticas Mecanismo de variao do espaamento lamelar com a velocidade

Ligas Eutticas

EX.: Zn-4%Al
(Refinada; P0mm)

EX.: Zn-4%Al
(Grosseira; P50mm)

Ligas Eutticas
Formao de falhas lamelares

MODIFICAO DE EUTTICOS:
Tratamento de Modificao: pequenas alteraes na composio qumica do euttico para produzir mudanas microestruturais e das propriedades

MODIFICAO DE EUTTICOS:
Al-Si: principal liga de fundio utilizando modificaes (Al-11,7% Si) Boa fluidez Resistncia corroso Pequena contrao Boa relao resistncia/peso Propriedades dependero: i) processo de fundio, fundio, ii) composio da liga iii) estrutura euttica iv) distribuio e granulometria do silcio

Mtodo de modificao do Euttico:


1. altas velocidades de solidificao, e consequentemente taxas 2. adio de agentes qumicos modificadores no banho lquido

Mtodo de modificao do Euttico:


1. altas velocidades de solidificao, e consequentemente taxas 2. adio de agentes qumicos modificadores no banho lquido
Principais Modificadores: Na e Sr

Mtodo de modificao do Euttico:


o Na e o Sr tm o poder de causar grandes modificaes mesmo em baixas porcentagens (ppm~1%), no alterando a composio da liga
Modificadores comerciais: Fluoreto de Sdio (NaF Modimil; Foseco)

Mtodo de modificao do Euttico:

O que acontece????
Microestrutura Veios de Si so(espaamento) transformados em uma forma Macroestrutura (gro) NO SE ALTERA!!!. ALTERA!!! fibrosa e ramificada envolvida por uma matriz. NO SE ALTERA!!!. ALTERA!!!

Estrutura modificada apresenta melhores Propriedades Mecnicas

Ligas Eutticas AlAl-Si

Ligas Eutticas AlAl-Si

ATAQUE cido Hidroclordrico 5%

100x

ATAQUE cido Hidroclordrico 5%

100x

ESTADO Bruto de Fuso. Molde de areia

ESTADO Bruto de Fuso. Molde de areia. Modificado com adio de sdio no banho lquido

Ligas Eutticas AlAl-Si

ATAQUE cido Hidroclordrico 5%

250x

ATAQUE cido Hidroclordrico 5%

300x

ESTADO Bruto de Fuso. Molde de areia. Modificado com adio de sdio no banho lquido,

ESTADO Bruto de Fuso. Molde refrigerado. Modificado pelas altas taxas de resfrimento

Ligas Eutticas AlAl-Si


Explicao: no incio: pensava-se que atuava como centros de nucleao atualmente: sabe-se que alm de diminuir a temperatura de nucleao, cresce de forma contnua sem a ocorrncia de repetidas nucleaes e em condies de maiores valores de SRC (Super Resfriamento Composicional) No afeta a matriz rica em Al A modificao est associada a mudana no mecanismo de crescimento do Si Passa da forma facetada para uma forma mais difusa

a) Veios de Si no modificados b) Modificados por altas taxas c) Modificao por ao qumica

Ligas Eutticas AlAl-Si


% dos Modificadores: Sdio: r = 1,58 A mais eficiente que o Sr dissolve-se rapidamente no lquido sem oxidar perde seu poder rapidamente (~ 20 min) Adies maiores que 0,02% em peso forma composto AlSiNa frgil Estrncio: r = 1,84 A menos eficiente que o Na dissolve-se rapidamente no lquido, porm oxida tem um poder de durao maior Teores acima de 0,05% em peso diminui resistncia mecnica pois forma Al2SrSi2

Ligas Eutticas FeFe-C


Euttico FeFe-C:
LIQUIDO Lquido L+ o 912 C 0,77%C o 727 C + Fe C 3 % C na Austenita na temperatura T 2,11 %C 4,3%C L + Fe C 3 Ponto 1 - 1147 C o Ponto 2 - T + Fe C 3 Ponto 3 - 726 Co 1148 o C

Ponto 1
C

C C

C C

DIFUSO DO C

C C C C C C C C C C C C C C C C C C C C C

Empobrecido para C C 2,11% de C Enriquecido com 6,67% de C


C

AUSTENITA CEMENTITA

Ponto 3

Empobrecido para 2,11% de C

Perlita

LEDEBURITA

Ligas Eutticas FeFe-C


Hipoeuttico:
Lquido L+ o 912 C 4,3%C 2,11 %C %C na Austenita no resfriamento 0,77%C o 727 C + Fe C 3 P.ex.: Fe - 3,5 %C %C na Austenita em solidificao %C no lquido remanescente + Fe C 3 Ponto 3 - 1147 C o o LIQUIDO Ponto 1 - Formao dos primeiros cristais slidos de Austenita Pto 2 - Temperatura T L + Fe C 3 1148 C o

Ponto 4 - 728 C

Ponto 2

Dendritas de Austenita

Lquido remanescente

Ledeburita (Fe3 C + )
Ponto 3

Ligas Eutticas FeFe-C

Resfriamento rpido: FoFo Branco (perlita e ledeburita) Resfriamento lento: Fofo Cinzento ferrtico (perlita e grafita)

Ligas Eutticas FeFe-C


Hipereuttico:
Lquido Ponto 1 - Formao dos primeiros cristais slidos de Cementita Pto 2 - Temperatura T 4,3%C 2,11 %C %C na Austenita no resfriamento 0,77%C o 727 C + Fe C 3 + Fe C 3 LIQUIDO

L+ o 912 C

L + Fe C 3 1148 C Pto 3 - 1147 Co

Ponto 2

%C no lquido remanescente

Fe3 C

Agulhas de Cementita Lquido remanescente

Ledeburita (Fe3 C + )
Ponto 3

Ligas Eutticas FeFe-C


Mtodos de Modificao em FoFo Branco: variao nas velocidades de solidificao, e consequentemente taxas adio de agentes qumicos modificadores no banho lquido Principais Modificadores: Si principal agente nucleante da grafita em veios e aumenta T metaestvel (fofo cinzento) Mg favorece a formao de grafita nodulares (ndulos) Ce nodularizante

Ligas Eutticas FeFe-C

Ligas Eutticas FeFe-C


Branco
(perlita e ledeburita)

Cinzento
(veios grafita e perlita)

Nodular
(ferrita e ndulos grafita)

Nodular
(perlita e ndulos grafita)

Ligas Eutticas FeFe-C


Microestruturas
de FoFo para vrios % Mg: 0,017%; 0,026% e 0,13% e detalhes de um ndulo de grafita

Ligas Peritticas:
Transformao Perittica: Lquido + (slido)

Ligas Monotticas:
Transformao Monottica: Lquido1 + Lquido2

Ligas Peritticas Ligas Peritticas:


Transformao Perittica: Lquido + (slido)

Apresentam essa transformao os sistemas: Fe-C Fe-Ni Cu-Sn Cu-Zn

Mistura total no lquido e mistura parcial no slido No patamar perittico ocorrem 3 fases: Lquido + +

Ligas Peritticas
No Equilbrio Fora do Equilbrio

Ligas Peritticas

Liga Pb-20% Bi

Ligas Peritticas

Ligas Monotticas:
Transformao Monottica: Lquido + Lquido

Apresentam essa transformao os sistemas: Al-Bi, Al-In, Bi-Zn,Cu-Pb Mistura parcial no lquido e mistura parcial no slido No patamar monottico ocorrem 3 fases: Lquido1 + + Lquido2

MICROSCOPIA TICA DE MATERIAIS AOS

Diagrama Fe-C (Aos e Fofo)

MICROSCOPIA TICA DE MATERIAIS AOS

Propriedades x Microestrutura de Aos Microligados (Laminao e Trincas)

Resumo Fases no Sistema FeFe-C

Diagrama de Schaeffer: Sistema FeFe-C (Inox)

MICROSCOPIA TICA DE MATERIAIS

Micrografia de Chapa de Ao SAE 1010 Cementada e Temperada (Bainita)

Micrografia de Ao Microligado ao Nb (V, Ti, Mo, W)

MICROSCOPIA TICA DE MATERIAIS

Micrografia de Ao C AISI 1020 Na Zona Fundida (ZF)

Micrografia de Ao C AISI 1020 Na ZAC de Gros Grosseiros (GG)

MICROSCOPIA TICA DE MATERIAIS


Micrografia de Ao Microligado ao Nb

Micrografia de Ao Microligado ao Nb

MICROSCOPIA TICA DE MATERIAIS

Micrografia de Ao ao Mangans

Micrografia de Ao Liga

MICROSCOPIA TICA DE MATERIAIS

Micrografia de Ao FeCrC

Micrografia de Ao FeCrC+Nb

MICROSCOPIA TICA DE MATERIAIS

Micrografia de Ferro Fundido Branco Hipoeuttico (FoFo Branco)

Micrografia de Ferro Fundido Branco Euttico (Ledeburita)

MICROSCOPIA TICA DE MATERIAIS

Micrografia de Ferro Fundido Cinzento (Veios de Grafita)

Solidificao Direcional em Liga TiTi-Fe

Diagrama de Equilbrio do Sistema Binrio Eutetide Ti-Fe


E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

Solidificao Direcional em Liga TiTi-Fe

Diagrama Esquemtico do Forno de Fuso Arco para Solidificao Direcional


E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

Solidificao Direcional em Liga TiTi-Fe


-Ti
0.2 0.1 Temperature ( C) DTA (V/mg) 800 0.0 -0.1 -0.2 -0.3 600 400 200
(200) D-S
a = 0,3182 nm

Exo

605 C

1080 C

1200 1000

FeTi

a = 0,2986 nm FeTi

Intensity (a.u.)

(110)

FeTi

(110)

As-cast
a = 0,3203 nm

a = 0,2996 nm FeTi

(211)

0 0 50 100 Time (min) 150 200 250


30 40 50

60

70

80

2 (Degrees)

Anlise Trmica de DTA da Liga euttica Ti-32,5Fe (%peso) e DRX da Liga Fundida em Forno Arco (As-Cast) e Solidificada Direcionalmente.
E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

(220)

(200)

(211)

90

Solidificao Direcional em Liga TiTi-Fe

Anlise de Microscopia tica mostrando micrografias da Liga euttica Ti-32,5Fe (%peso)


E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

Solidificao Direcional em Liga TiTi-Fe

TEM micrographs in (a) bright field (BF) sign showing the -Ti matrix (bcc) and the cross section of the ordered TiFe fiber phase (cubic). Respective SADP showing orientation relationship between the (314) // (113)TiFe zone axis
E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

Solidificao Direcional em Liga TiTi-Fe


a c e

SEM micrographs showing transversal and longitudinal cross-sections at growth rates of (a) and (b) 10 mm/h, (c) and (d) 30 mm/h and (e) and (f) 60 mm/h.
E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

Solidificao Direcional em Liga TiTi-Fe


1.75 1.50

Interphase Spacing, [m]

1.25 1.00 0.75 0.50 0.25 0.00 0.00 0.05 0.10

Linear Regression: -1/2 = 0.15 + 4.7 V

0.15

0.20

0.25
-1/2

0.30

0.35

Growth Rate, [mm/h]

Relationship between the average interspacing (m) and the solidification velocity (mm/h) for directionally solidified Ti-Fe eutectic alloy.
E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

Solidificao Direcional em Liga TiTi-Fe

SEM micrographs in BSE sign showing transversal cross-section of Ti-Fe eutectic alloy directionally solidified at v= 30 mm/h in different magnifications.
E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

Solidificao Direcional em Liga TiTi-Fe

Evolution of hardness with interphase spacing (m): Vickers microhardness (HVmicro) and nanohardness (HVnano).
E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

Solidificao Direcional em Liga TiTi-Fe


Compressive mechanical properties of the Ti-Fe eutectic alloy as a function of the interphase spacings, (m).

Evolution of hardness with interphase spacing (m): Vickers microhardness (HVmicro) and nanohardness (HVnano).
E. S. Lopes, Directionally Solidified Ti-Fe Eutectic Alloy processed by Arc Melting Technique, Submitted to Intermetallics.

Solidificao Rpida Ligas TiTi-Fe Fe-Sn

XRD patterns of as-cast Ti65Fe35, (Ti65Fe35)99Sn1 and (Ti65Fe35)97Sn3 alloys.


J.H. Han, Ultrafine Eutectic TiFeSn alloys, Journal of Alloys and Compounds 483 (2009) 4446.

Solidificao Rpida Ligas TiTi-Fe Fe-Sn

SEM secondary electron micrographs of as-cast Ti65Fe35 (a and b), (Ti65Fe35)99Sn1 (c and d) and (Ti65Fe35)97Sn3 (e and f) alloys.

J.H. Han, Ultrafine Eutectic TiFeSn alloys, Journal of Alloys and Compounds 483 (2009) 4446.

Solidificao Rpida Ligas TiTi-Fe Fe-Sn

Roomtemperature engineering stressstrain curves (a) and SEM micrographs of fracture surface of as-cast Ti65Fe35 (b), (Ti65Fe35)99Sn1 (c) and (Ti65Fe35)97Sn3 (d) alloys.
J.H. Han, Ultrafine Eutectic TiFeSn alloys, Journal of Alloys and Compounds 483 (2009) 4446.

Solidificao Rpida Ligas TiTi-Fe Fe-Sn

XRD patterns for (Ti0.705Fe0.295)100x Snx (x = 0 and 3.85) as-cast rods and arc-melted ingots.

J. Das et al., Bulk ultra-fine eutectic structure TiFeSn alloys, Journal of Alloys and Compounds 434435 (2007) 2831.

Solidificao Rpida Ligas TiTi-Fe Fe-Sn

SEM back scattered electron images of: (a) Ti70.5Fe29.5 ingot (near the Cu hearth), inset (near air-cooled region); (b) Ti67.79Fe28.36Sn3.85 ingot; (c) Ti70.5Fe29.5 as-cast rod; (d) Ti67.79Fe28.36Sn3.85 as-cast rod. The micrographs clearly reveal the change in morphology of the eutectic up on Sn addition
J. Das et al., Bulk ultra-fine eutectic structure TiFeSn alloys, Journal of Alloys and Compounds 434435 (2007) 2831.

Solidificao Rpida Ligas TiTi-Fe Fe-Sn

Room temperature compressive engineering stressstrain curves of the Ti70.5Fe29.5 and Ti67.79Fe28.36Sn3.85 ingots and as-cast rods
J. Das et al., Bulk ultra-fine eutectic structure TiFeSn alloys, Journal of Alloys and Compounds 434435 (2007) 2831.

Solidificao Rpida Ligas TiTi-Fe Fe-Sn

Room temperature compressive engineering stressstrain curves of the Ti70.5Fe29.5 and Ti67.79Fe28.36Sn3.85 ingots and as-cast rods
J. Das et al., Bulk ultra-fine eutectic structure TiFeSn alloys, Journal of Alloys and Compounds 434435 (2007) 2831.

Amorfos em Eutticos Binrios

Diagrama de Equilbrio do Sistema Binrio Cu-Zr


M.F. de Oliveira et al., Topological instability and glass forming ability of amorphous alloys, Intermetallics 17 (2009) 183185

Amorfos em Eutticos Binrios

Variation of lminDe in the ZrCu diagram. The vertical dashed lines indicate the experimental ranges of BMGs reported for the ZrCu system and the arrows indicate the intermetallic stable compositions [13]. The symbols mark the lowest calculated critical cooling rates
M.F. de Oliveira et al., Topological instability and glass forming ability of amorphous alloys, Intermetallics 17 (2009) 183185

Amorfos em Eutticos Binrios

Diagrama de Equilbrio do Sistema Binrio Ti-Ni


M.F. de Oliveira et al., Topological instability and glass forming ability of amorphous alloys, Intermetallics 17 (2009) 183185

Amorfos em Eutticos Binrios

Variation of mine in the TiNi diagram. The experimental points for the alloy (open symbols) were produced by melt-spinning [15].
M.F. de Oliveira et al., Topological instability and glass forming ability of amorphous alloys, Intermetallics 17 (2009) 183185

Phase Field Simulation of Solidification

Multiphase microstructures formed in the terminal stages of solidification in (a) AlSi 7Mg 0.6as cast, (b) FeC 0.9Cr 4Mo 5W 6.5thixo cast, (c) CuSn 12Ni 2as cast and in ternary AlCuAg alloys after unidirectional solidificationin cross section of Al70Cu13Ag17 (at%)
U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

With increasing Cr-content in ternary FeCCr alloys the d-ferrite field extends to higher carbon content than in the binary FeC system.
U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

Isothermal cut through the phase diagram of the ternary alloy system AlCuAg at T = 505 8C.

Univariant and nonvariant reactions on the liquidus surface of the AlCuAg system.

U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

Multiphase patterns in ternary AlCuAg alloys after unidirectional solidification: eutectic cells in longitudinal (a) and cross section (b) of AlCu 13.66 at.%Ag 10.27 at.% and a three-phase eutectic pattern (c) in cross section of AlCu 13.6 at.%Ag 16.4 at.%.

U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

Cross section through an array of elongated cells of the ternary alloy Al70Cu13Ag17 (at%) after unidirectional solidification in a temperature gradient G = 27x103 K/m with a velocity v = 1.42x10-6 m/s (a) and snapshot of the three-phase eutectic pattern obtained for a 3D simulation for G = 5x103 K/m and v = 0.5x10-6 m/s (b). For both images (a) and (b), the phases are Ag2Alwhite, Al2Culight grey, a(Al)dark grey.
U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

Cross section through the three-phase eutectic pattern of the ternary alloy Al70Cu13Ag17 (at%) after unidirectional solidification in a temperature gradient G = 27x103 K/m with a velocity v = 1.42x10-6 m/s (a) and snapshot of the three-phase eutectic pattern obtained for a 3D simulation for G = 5x103 K/m and v = 0.5x10-6 m/s (b). For both images (a) and (b), the phases are Ag2Alwhite, Al2Culight grey, a(Al)dark grey.
U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

Solidification of FeC 1 at.%Mn 1 at.% at a cooling rate of 1 K/s in a temperature gradient of 20 103 K/m. Shown are the composition maps of carbon and manganese in atom fractions as well as the phase map.
U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

2D dendritic solidification of a binary NiCu alloy as predicted by the phase field theory at 1574 K and a supersaturation of 0.8. By the end of solidification about 300 dendritic particles form. The calculation has been performed on a 3000 3000 grid. In (a) the color map represents compositions, with yellow and blue corresponding to the solidus and liquidus compositions, respectively. In (b) the colors denote crystallographic orientations.
U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

Equiaxed solidification in hypo-eutectic (cCu = 0.3), eutectic (cCu = 0.35), and hyper-eutectic (cCu = 0.4) Ag-Cu liquids at 900 K as simulated by the phase field model. Composition maps are shown in the top row, the respective orientation maps are in the bottom row. The simulations were performed in 2D on a 1000 1000 grid.
U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Phase Field Simulation of Solidification

Heterogeneous crystal nucleation on rough (sinusoidal) surfaces in a binary liquid as predicted by the phase field simulations. Composition maps are shown (liquidusblue, solidusyellow, graywalls
U. Hecht et al., Multiphase solidification in multicomponent alloys, Materials Science and Engineering R 46 (2004) 149

Precipitation Hardening
The strength and hardness of some metal alloys may be improved by the formation of extremely small, uniformly dispersed particles (precipitates) of a second phase within the original phase matrix. Other alloys that can be precipitation hardened or age hardened:
Copper-beryllium (Cu-Be) Copper-tin (Cu-Sn) Magnesium-aluminum (Mg-Al) Aluminum-copper (Al-Cu) High-strength aluminum alloys

Phase Diagram for Precipitation Hardened Alloy


Criteria: Maximum solubility of 1 component in the other (M); Solubility limit that rapidly decreases with decrease in temperature (MN). Process: Solution Heat Treatment first heat treatment where all solute atoms are dissolved to form a single-phase solid solution. Heat to T0 and dissolve B phase. Rapidly quench to T1 Nonequilibrium state ( phase solid solution supersaturated with B atoms; alloy is soft, weak-no ppts).

Precipitation Heat Treatment the 2nd stage


The supersaturated solid solution is usually heated to an intermediate temperature T2 within the + region (diffusion rates increase). The precipitates (PPT) begin to form as finely dispersed particles. This process is referred to as aging. After aging at T2, the alloy is cooled to room temperature. Strength and hardness of the alloy depend on the ppt temperature (T2) and the aging time at this temperature.

Precipitation Hardening
Particles impede dislocation motion. 700 Ex: Al-Cu system T( C) Procedure: 600 +L
-- Pt A: solution heat treat (get solid solution) -- Pt B: quench to room temp. (retain solid solution) -- Pt C: reheat to nucleate small particles within phase.
500 400 A L +L

CuAl2

C 20

+
30 40 50

(Al)

300 0 B 10

composition range available for precipitation hardening

wt% Cu

Temp. Pt A (solution heat treat) Pt C (precipitate )

At room temperature the stable state of an aluminum-copper alloy is an aluminum-rich solid solution () and an intermetallic phase with a tetragonal crystal structure having nominal composition CuAl2 ().

Pt B

Time

Precipitation Heat Treatment the 2nd stage


PPT behavior is represented in the diagram: With increasing time, the hardness increases, reaching a maximum (peak), then decreasing in strength. The reduction in strength and hardness after long periods is overaging (continued particle growth).

Small solute-enriched regions in a solid solution where the lattice is identical or somewhat perturbed from that of the solid solution are called Guinier-Preston zones.

PRECIPITATION STRENGTHENING
Hard precipitates are difficult to shear.
Ex: Ceramics in metals (SiC in Iron or Aluminum).
precipitate
Side View Large shear stress needed to move dislocation toward precipitate and shear it. Unslipped part of slip plane Dislocation advances but precipitates act as pinning sites with spacing S.

Top View

S
Slipped part of slip plane

1 Result: y ~ S
24

Several stages in the formation of the equilibrium PPT () phase. (a)supersaturated solid solution; (b)transition () PPT phase; (c) equilibrium phase within the matrix phase.

2014 Al Alloy:

Influence of Precipitation Heat Treatment on Tensile Strength (TS), %EL


%EL reaches minimum with precipitation time.

TS peak with precipitation time.


Increasing T accelerates process.

tensile strength (MPa)

400 300 200 100 204 C 149 C

%EL (2 in sample)

30 20 10 0 149 C

204 C

1min 1h 1day 1mo 1yr precipitation heat treat time

1min 1h 1day 1mo 1yr precipitation heat treat time

Effects of Temperature

Characteristics of a 2014 aluminum alloy (0.9 wt% Si, 4.4 wt% Cu, 0.8 wt% Mn, 0.5 wt% Mg) at 4 different aging temperatures.

Aluminum rivets
Alloys that experience significant precipitation hardening at room temp and after short periods must be quenched to and stored under refrigerated conditions. Several aluminum alloys that are used for rivets exhibit this behavior. They are driven while still soft, then allowed to age harden at the normal room temperature.

Peritectic Solidification
Peritectic Reaction
All three phase in contact (, and liquid)

Peritectic Transformation
Liquid and are separated by B phase Transformation Reaction
l

Growth of
Diffusional Growth Mass Balance at interface dC D = V C dx x= 0 2 interfaces / and /l dC dx D = C C ] [ dx dt x= x dC dx l D = [Cl Cl ] dx x= x l dt


Cl

C C

Cl

Stainless Steels Peritectic/Eutectic Transformation

5 Modes of Solidification

AC -Acicular Net -Network Vm- Vermicular D - Dendritic ID - Interdendritic

Phase Selection in Stainless Steels

Slab Production: Stainless

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