PMT-POLI / USP LM2C2

Materiais Cermicos para Altas Temperaturas - Non-Oxide Ceramics

Aula extra
Prof. Dr. Guilherme F. B. Lenz e Silva PMT-POLI/USP

Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP LM2C2 Laboratrio de Moagem de Alta Energia, Materiais de Carbono e Compsitos para Altas Temperaturas PMT-POLI/USP

L M2 C2

Materiais para altas temperas

Metais e elementos de alto ponto de fuso ( boro, C, tungstnio, etc.) Aos e ligas especiais xidos Carbetos, boretos, silicetos e nitretos: Non-oxide ceramics
Compsitos: CMM: compsitos de matriz metlica CMC: compsitos de matriz cermica

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

http://www.keramverband.de/brevier_engl/5/5_2.htm

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Seleo para aplicaes em altas temperaturas

Propriedades mecnicas: limite de resistncia, creep, fragilizao quente, resistncia ao choque trmico, etc. Propriedades qumicas: resistncia oxidao, vapor de gua, nitrognio, etc. Propriedades fsicas: temperatura de fuso, densidade, etc. Disponibilidade & Custo

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Metals and Alloys Wire-reinforced cement Cermets MMCs Composites Polymers CFRP GFRP Ceramics and Glasses

Steel-cord tyres

Filled polymers

STRUCTURAL MATERIALS FUNCTIONAL MATERIALS Mechanical tribology fatigue KIC y UTS E Thermal K H Tm TTransition
Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Chemical corrosion oxidation Physical optical magnetic electrical

MATERIAL Other feel look Environmental recycling energy consumption waste

Seleo de Materiais

Metais x Cermicas

Lingotes de ligas ODS Oxide dispersion strengthened (ODS) alloys: Ligas de nquel, Fe-Al-Cr e ligas de platina
Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Frmula
Al2O3 Al Al4C3

Nome
Alumina

Ponto fuso (oC)

2015 660 2200 (decomp. 1400 oC) 1655 2200

Estutura
Trigonal CFC Romb.

Frmula

Nome

Ponto fuso (oC) 2715 1852 3532 3246 2980 3500 2076 450~510 2468 1460 1842 3050 3410 1700 decompe 1473

Estutura monoclnico HCC cbico Hexagonal cbico Hexagonal ,,, Trigonal e monoclnico CCC Monoclnico CFC Cbico CCC Monoclnico Monoclnico

ZrO2 Zr ZrC

AlB2 e AlB12 AlN MgO Mg Mg2C3 MgB2 Mg3N2 SiO2 Si SiC SiB6 e SiB4 Si3N4 Silcio Carbeto de silcio Magnsia Magnsio

Hexagonal Hexagonal Cbica Hexagonal Instvel Hexagonal Cristob. Cbico polimorfis mo Decomp.

ZrB2 ZrN C
B B2O3 Nb Nb2O5 Th ThO2 W WO2 WO3

2800 650 ???? ~800 ~1500 1713 1410 2730 ???? 1900

Seleo: - Estabilidade qumica ( oxignio, gua, vapores cidos, enxofre, etc.) - Ponto de fuso - Produtos da oxidao/corroso - Estabilidade trmica, etc. Al2O3 [O] xidos AlSi2 [Si] silicetos [C] carbetos Al4C3
Instvel: - carbeto de alumnio

Al4C3 + H2O Al(OH)3 + CH4

Al
[B] boretos [N] nitretos AlN AlB2 e AlB12
Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

cooler circular de AlN

Rotas de sntese

http://www.morgantechnicalceramics.com/products-materials/process-animations

Principais fornecedores

http://www.ceradyne.com/materials/materials.aspx

Algumas propriedades comparativas ...

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Carbetos
Tipos de carbetos: Covalentes: pouca diferena de eletronegatividade Intersticiais: grande diferena de eletronegatividade, dimenso atmica adequada a formao de compostos intersticiais Intermetlicos: normalmente instveis e hidrolisveis (gua ou cido diludos) - Grupo VI a VIII: Inicos salt like : Grupos I, II e III: altos pontos de fuso, hidrolisveis
Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Ex: B, Si

Ex: Ti, V, Cr (exceo), Zr, Nb, Mo, Hf, Ta, W

Ex: Fe, Co, Ni ...

Ex: CaC2, Al4C3, Be2C,

Formao de carbetos
Diferena de eletronegatividade Regra de Hag

Covalentes

Intersticiais

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Carbetos intersticiais

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Carbetos Covalentes: SiC e B4C a) Carbeto de boro

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Carbeto de silcio

4H-SiC

()6H-SiC

()3C-SiC

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

http://www.lspceramics.com/Silicon_Carbide_Brochure.pdf

SiC Melting point

3C-SiC

3103 (40) K

p = 35 bar. Peritectic decomposition temperature at 35 atm at 35 atm. see also Phase diagram

Scace & Slack (1960) Tairov & Tsvetkov (1988) Tairov & Tsvetkov (1988)

4H-SiC 6H-SiC

3103 40 K 3103 40 K

http://www.ioffe.ru/SVA/NSM/Semicond/SiC/thermal.html

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Propriedades mecnicas HMPC: High melting point compounds (nanostructured) (%): porosidade L (nm): tamanho do gro Microdureza Vickers (Hv) Tenacidade a fratura KIC

Processo Acheson
Principais processos: Acheson; Lely (1955) - Lely modificado Crescimento Epitaxial - Feixe molecular - CVD

1859-1931

https://www.ifm.liu.se/semicond/new_page/research/sic/Chapter3.html
Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Fluxo de produo de SiC

Gest. Prod. vol.12 no.1 So Carlos Jan./Apr. 2005

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

http://www.treibacher.com.br

Carbeto de boro

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Aplicaes: proteo balstica

Ceralloy 546 Boron Carbide is the lightest technical ceramic material (2.5 g/cm) as well as the hardest (second only to diamond). This fully dense boron carbide is produced by hot pressing and is characterized as follows:

Light Weight High Hardness Erosion Resistance High Modulus Neutron Absorber

Ceralloy 546 Boron Carbide is used for the following applications:

http://www.ceradyne.com/materials/boron-carbide.aspx

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

B4C

Difcil Demorado Caro

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Boretos
Boretos refratrios : TiB2, ZrB2, HfB2, CrB2, MoB2 CaB6

Their crystal structure and chemical bonding depend strongly on the metal element M and on its atomic ratio to boron. When B/M ratio exceeds 12, boron atoms form B12 icosahedra which are linked into a three-dimensional boron framework, and the metal atoms reside in the voids of this framework. Those icosahedra are basic structural units of most allotropes of boron and boron-rich rare-earth borides. In such borides, metal atoms donate electrons to the boron polyhedra, and thus these compounds are regarded as electron-deficient solids.

Supercondutor

28

AlB2

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Sntese de hexaboreto de clcio

One of the main reactions for industrial production is:6 CaO + 3 B2O3 + 10 Mg CaB6 + 10 MgO Other methods of producing CaB6 powder include: Direct reaction of calcium or calcium oxide and boron at 1000 C; Ca + 6B CaB6 Reacting Ca(OH)2 with boron in vacuum at about 1700 ( carbothermal C reduction);11 Ca(OH)2 +7B CaB6 + BO(g) + H2O(g) Reacting calcium carbonate with boron carbide in vacuum at above 1400 C (carbothermal reduction) Reacting of CaO and H3BO3 and Mg to 1100 5 C. Low-temperature (500 synthesis C) CaCl2 + 6NaBH4 CaB6 + 2NaCl + 12H2 + 4Na

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Silicetos
Exemplo: Super Kanthal Dissiliceto de molibdnio

Silicetos refratrios: MoSi2, WSi2, Cr3Si2

Application Heating elements air furnaces Gas burner Diesel engine glow plugs Molten metal lances Aerospace gas turbine engines blade outer seal Moderate density 6.24 g cm-3 High melting point 2030 C Properties

Excellent oxidation resistance

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

http://www.caret.hokudai.ac.jp/labo/hightemp-e.html

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Nitretos

Nitretos Refratrios: Ti, V, Zr, Nb, Hf, Ta, B, Al, Si.

Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

TiN Properties High melting point High strength Wear resistance High electric conductivity AlN Application

Coating material Cermet material High heat resistance Decorative purposes

TiAlN Application

Properties High thermal conductivity Excellent electrical isolation High heat resistance High-corrosion resistance

Electronic substrate Power device Heatsink

Properties High vickers hardness (TiAlN>TiN) High oxidation onset temperature High-corrosion resistance
Powder color Vickers hardness Oxidation temperature Frictional coefficient Purple / Broun 2800 HV 788 C 0.8

Application Coating material Mold tool Optical apparatus

Nitreto de alumnio

Microestrutura do nitreto de alumnio

Nitreto de silcio

trigonal -Si3N4.

Nitreto de silcio sintereizado sob alta presso de nitrognio (100 Bar)

hexagonal -Si3N4

cubic a-Si3N4
Si3N4 bearing parts
Prof. Dr. Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP

Processamento e aplicaes: nitreto de silcio

Exemplo de Aplicaes

PMT-POLI / USP LM2C2

Prxima aula ... Compsitos de matriz cermica e coatings cermicos

FIM
Guilherme Frederico B. Lenz e Silva, PMT-POLI/USP LM2C2 Laboratrio de Moagem de Alta Energia, Materiais de Carbono e Compsitos para Altas Temperaturas PMT-POLI/USP

L M2 C2