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MATERIALS SCIENCE AND ENGINEERING

TOPIC 6. CERAMIC MATERIALS

Introduction Structure of Ceramic Materials Glasses Mechanical Properties of Ceramic Materials Processing of Ceramic Materials Examples of applications

Dpt. Materials Sci and Eng. and Chemical Eng.

UC3M

Topic 6: Ceramic Materials.

INTRODUCTION
Inorganic Materials made from Metals and Non Metals united by ionic and/or covalent bonds Can be: crystalline, amorphous or mixture of both

GENERAL PROPERTIES
Hardness Brittleness electric thermal

General Properties

Rcompression Chemical Stability

Tm

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

Topic 6: Ceramic Materials.

GENERAL PROPERTIES
High Youngs Modulus and high melting points Strong bonds (covalent and /or ionic) Limited electrical and thermal conductivity Absence of electronic cloud (directional bond) Low thermal shock resistance Coefficients of thermal expansion and thermal conductivity are low Refractory Stability at high temperature (NO CREEP) Resistance to oxidation/corrosion Chemical stability

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

Topic 6: Ceramic Materials.

CLASSIFICATION Glasses
Based on SiO2 + additives for Tf

Traditional Ceramics (clay products )

Porous ceramics (bricks, pottery, china) Compact ceramics (porcelain, earthware) Refractory ceramics
Clay: Al2O3 SiO2H2O Silica: SiO2 Feldspar: K2O Al2O3 6SiO2

Egineering Ceramics or Advanced Ceramics :

Refractory ceramics (SiC, Al2O3, ZrO2, BeO, MgO). Piezoelectrics and Ferroelectrics: BaTiO3, SrTiO3 Electro-optics: LiNbO3 Abrasive ceramics: nitrides and carbides Si3N4 , SiC Molecular membranes Superconductive ceramics (YBa2Cu3O7) Biomaterials : Hydroxyapatite
Dpt. Materials Sci and Eng. Chemical and Eng. UC3M 4

Topic 6: Ceramic Materials.

STRUCTURE Ceramic Bonds

Ionic Mixed Covalent

Pauling: % Ionic character =

( X A X B ) 1001 e 4

Percentage of ionic and covalent character of the bond for some ceramic materials determines the CRYSTALLINE STRUCTURE Ceramic Material MgO Al2O3 SiO2 Si3N4 SiC Atoms in bond MgO AlO SiO SiN Si-C XA - X B 2,3 2,0 1,7 1,2 0,7 % Ionic Character 73 63 51 30 11 % Covalent Character 27 37 49 70 89

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

Topic 6: Ceramic Materials.

STRUCTURE

T2 STRUCTURES:

Ions packing Electroneutrality of ionic ceramics Crystalline type structures

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

Topic 6: Ceramic Materials.

CRYSTALLINE STRUCTURE OF PEROVSKITE ABO3

TYPE B

A and B cations with different size (rA>>>rB)

O2- and Ca2+: packing fcc Ti4+: 1/4 octahedral sites C.I.(Ti2+): 6 ; C.I.(Ca2+): 12

Ceramics that adopt this type structure: TiO6 Octahedra BaTiO3, CaTiO3, SrTiO3, PbZrO3,, KNbO3, LiNbO3, Ferroelectric Materials, Magnetic Superconductor properties (YBa2Cu3O7)

TYPE A
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Topic 6: Ceramic Materials.

COVALENT CERAMICS
They are structural ceramics

DIAMOND Structure type blend

C sp3 c.i. 4 Tetrahedral CC4. Bond 100% covalent. wear resistance tensile strength

hardness
Insulator

SiC Diamond type structure (spherullite)

Applications: Good abrasive properties. 89% covalent bond High hardness, chemically inert.

Si3N4 Cutting Elements, blades, rotors

Si sp3 c.i. 4 SiN4 Tetrahedra N sp2 c.i. 3 N coordinated to 3 Si Open structure. 70% covalent bond

Sialons Si6-zAlzOzN8-z(1971)
It is a solid solution between nitrides and oxides. Derived from Si3N4, by substituting z atoms of Si for Al atoms. In order to compensate the valence difference, the same number of N atoms are substituted by O. Cutting tools, antifriction rollers, motors components. Dpt. Materials Sci and Eng. Chemical and Eng. UC3M

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Topic 6: Ceramic Materials.

STRUCTURE OF SILICATES
Si and O are the most abundant elements in the earths crust They are the base of traditional ceramics Useful engineering materials because Low price Great availability Special properties

Fundamentally in:

Construction (bricks, cement, glass) Electrical and thermal insulating materials

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

STRUCTURE OF SILICATES

Basic structural unit

SiO44Si in tetrahedral coordination Bond type (Pauling): 50% ionic -50% covalent

rC/r = 0.29 stable structure with tetrahedral coordination . A

packing factor tetrahedra united in the corners . Multitude of possible structures:

a) Structures of isolated silicates b) Ring and Chain structures c) Laminar structures d) 3D structures

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

STRUCTURE OF SILICATES

a) Isolated

Classification of silicates as a function of the tetrahedra ordering [SiO4]4-.

b) Ring

c) Chain

d) Laminar

e) 3D

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Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

STRUCTURE OF SILICATES
b) Ring and Chain Structure 2 of the 4 O- atoms in the tetrahedral SiO44- are united to another tetrahedral in order to form chains of silicate c) Laminar Structure Formula: (SiO3)n2n3 of the 4 O- atoms of in the tetrahedral SiO44- are united to another tetrahedral in order to form layers of silicates There is one O- without bond in each tetrahedral charge (-) Formula: Si2O52Kaolinite Al2(OH)42+ Talc: Mg3(OH)42+
Dpt. Materials Sci and Eng. Chemical and Eng. UC3M 18

Joining laminas (+)

Formation of KAOLINITE

Topic 6: Ceramic Materials.

STRUCTURE OF SILICATES Three-Dimensional Silicates

Silica They share all the corners in the tetrahedra Unit formula : SiO2 Presents Allotropy Important component in many traditional ceramics and many types of glasses Feldspars Similar structure to Silica (Al3+ replaces Si4+) lattice with (-) charge compensates the charge with voluminous cations (Na+, K+, Ca2+, Ba2+) in interstitial positions . Principal component of traditional ceramics

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

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Topic 6: Ceramic Materials.

NON CRYSTALLINE CERAMICS : GLASSES

Behaviour of glass during solidification

Crystalline Solid As T crystallizes in Tm

GLASS As T: viscosity Plastic stage Rigid stage

s Glas

e s. tallin Crys

Contraction due to freezing

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

CONSTITUENTS OF GLASSES
3 types of oxides
Glass Formers SiO2 and B2O3
SiO2: Fundamental sub-unit sub: SiO44- tetrahedra B2O3: Fundamental Sub-unit : plane triangles BO33triangles BO33- become BO44tetrahedra when we add oxides of alkaline M and alkaline earths. The cations give electroneutrality. The glasses that are made only of B2O3 have little durability . Normally we add B2O3 to SiO2: borosilicate glasses

Glass modifiers (Na2O, K2O) and (CaO y MgO) Are the oxides that the silicate lattice brake

Intermediates:

Al2O3

DO NOT form glasses only by themselves.

They are incorporated in the silicate lattice Al2O3 tetrahedra AlO44replacing SiO44Charge defects (Al3+: Si4+) compensating with alkaline cations and alkaline earths . Improve special properties : strength at high Al2O3 T (aluminosilicate glasses) PbO
Modifies optical properties Tf (glass soldering) Radiation protection of E

Alkaline (Na2O, K2O) alkaline earths (CaO y MgO) They are accommodated in interstitials (do not form part of the silicate lattice) viscosity facilitates moulding and workability

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

CONSTITUENTS OF GLASSES Substances constituents of glasses

COLOURS THAT METALLIC IONS GIVE TO GLASSES M+ as a MODIFIER ION C. I. COLOUR Cr3+ 6 Blue 6+ Cr 6 Green 2+ Cu 8 Blue green Cu+ 6-8 Transparent 2+ Co 6-8 Rose 2+ Ni 8 Yellow green Mn2+ 6 Light orange 3+ Mn 6-8 2+ Fe 6 Blue-green Fe3+ 6-10 Light yellow 6+ U 6 Light yellow 3+ V 6 Green V4+ Blue

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

PROPERTIES OF GLASSES Mechanical Properties Brittle Materials ( elastic modulus ) = f (composition, macroscopic (surface) imperfections, volume of material and T) Low modulus of Weibull Mechanical strength (presence of water/air + humidity ) Electrical Properties Generally insulators ( 10-10 -10-20 cm-1) with Temperature with modifier (=f(size and amount of modifier)) Thermal Shock = Rthermal shock

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

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Topic 6: Ceramic Materials.

PROPERTIES OF CERAMICS Hardness

Very hard solids Hardness (Covalent) > hardness (Ionic) (Diamond, SiC) (Al2O3, ZrO2)

Elastic Modulus
E f (time the load is applied ) Eceramics > Emetals Greater stiffness (bond type ) Low density Especific high They are employed in the form of fibers in Composite Materials

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

PROPERTIES OF CERAMICS

Fracture Resistance
It is characterized by low fracture stress KIC Reason: porosity that acts as a stress concentrator. Brittle and catastrophic rupture Formation of pores during fabrication (bad sintering ) R= f (size and volume fraction of pores )
INFLUENCE OF POROSITY

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

PROPERTIES OF CERAMICS Thermal Shock

Partial or total Fracture due to changes in T It can be produced by :

Restriction during expansion T rapid ( temporary T gradients ) Residual Stresses fracture

T1

T2>T1

T=T =
FREE EXPANSION FOLLOWED BY COMPRESSION

Stress profile at high T

FRACTURE DUE TO RESTRICTION OF EXPANSION

TEMPER ING
T TRACCI TRACCI N 0

Stress profile after tempering

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

PROCESSING
FABRICATION OF CERAMIC POWDERS
Production and synthesis of ceramic powders Physical methods (Milling) Chemical methods : Decomposition of salts Co-precipitation of salts Sol-gel Decomposition of organometallic compounds Evaporation-condensation

SHAPING FORMING
Product conditioning Compacting of powders

THERMAL TREATMENTS
Drying and binder removal Sintering
Dpt. Materials Sci and Eng. Chemical and Eng. UC3M 27

Topic 6: Ceramic Materials.

PROCESSING: SHAPING-FORMING
OBJECTIVE: Produce a

Green piece .
Without heat Uniaxial pressing Isostatic pressing (CIP)

Starting with powders

With heat

Hot Pressing Hot Isostatic Pressing (HIP) Alternative methods

Starting with pulps and suspensions

Slip Casting Tape casting or Doctor Blade

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

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Topic 6: Ceramic Materials.

PROCESSING: SHAPINGFORMING
Uniaxial Pressing (Dry Pressing)

Complicated pieces and production velocity Variables to control: good filling good compresibility use coagulants/additives/agglomerates

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

PROCESSING: SHAPINGFORMING
Cold Isostatic Pressing (CIP) Elastomeric flexible mold in a liquid

Advantages: Uniform pieces Injection cracks eliminated Low material consumables Lower porosity Disadvantages : Long processing times

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

PROCESSING: SHAPINGFORMING
Hot Isostatic Pressing (HIP)

Fluid = Inert gas Stages: 1. Powder in the mold (metallic or glass) 2. Vacuum in the mold 3. Mold in autoclave of P and T

Advantages: Good distribution of P in the compact uniformity in properties. Obtaining more complicated forms For pieces of hardness Disadvantages: Price of equipment Little dimensional control over the product Discontinuity of the process.
Dpt. Materials Sci and Eng. Chemical and Eng. UC3M 31

Topic 6: Ceramic Materials.

PROCESSING: SHAPING-FORMING
Slip Casting Slip: suspension of a colloidal ceramic particles in an immiscible liquid, generally water

a) b) c) d) e)

Porous mold Pouring of slip into porous mold. Mold absorbs some of the water Remaining suspension is poured out Trimming Part is removed and ready for firing

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

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Topic 6: Ceramic Materials.

PROCESSING: SHAPINGFORMING
Tape Casting Fabrication of ceramic layers Suspension without water

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

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Topic 6: Ceramic Materials.

PROCESSING: SHAPINGFORMING
Extrusion

20-30%water

Extruding
Dpt. Materials Sci and Eng. Chemical and Eng. UC3M

jiggering
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Topic 6: Ceramic Materials.

PROCESSING: SHAPINGFORMING
Injection Molding

1. 2. 3. 4.

Ceramic powder is mixed with binder or wax Mix is forced into a die Binder is removed by pyrolysis Part is sintered

Used for high-tech application such as rocket engine components

Dpt. Materials Sci and Eng. Chemical and Eng. UC3M 35

Topic 6: Ceramic Materials.

PROCESSING OF GLASS

1150oC

650oC

Floating method

Glass rods or tubing

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

Topic 6: Ceramic Materials.

APPLICATIONS: REFRACTORIES IN THE GLASS INDUSTRY

Requirements - T - R corrosion (v\molten glass dissolves the refractory and contaminates) - R thermal shock
Feeding Refining zone
(1300-1400 C)

(1400-1500 C)

Ceramics mostly used are refractory fused cast AZS bricks (AluminaZirconia-Silica) (contact with glass)
Composition of AZS blocks Al2O3: 45-51% ZrO2: 33-41% SiO2: 10-15% Na2O: 1-1.5% Microstructure: -Eutectic fibers of Al2O3-ZrO2 -Grains of ZrO2 o Al2O3 -Aluminosilicate glass

Discharging zone

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

APPLICATIONS: REFRACTORIES IN THE GLASS INDUSTRY

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

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Topic 6: Ceramic Materials.

APPLICATIONS OF REFRACTORIES
Thermal protection System of space transporter

Requirements: - -Resistance to severe thermal gradients -To withstand external T (-110C 1260 C) - To be adherent to the Al structure - Good finish (smooth and aerodynamic)

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

APPLICATIONS OF REFRACTORIES
Thermal protection System of space transporter

Material used materials with properties - ceramic plates - C reinforced with C (Matrix C reinforced with C fibers) (T>1260C) -Filter of nylon covered with silicone

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

APPLICATIONS OF REFRACTORIES
Thermal protection System for space transporter

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

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Topic 6: Ceramic Materials. APPLICATIONS : TRADITIONAL CERAMICS

Dpt. Materials Sci and Eng. Chemical and Eng.

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Topic 6: Ceramic Materials.

APPLICATIONS : ENGINEERING CERAMICS

High-strength alumina components for hightemperature applications

Dpt. Materials Sci and Eng. Chemical and Eng. UC3M

Gas-turbine rotors made of silicon nitride

Topic 6: Ceramic Materials.

APPLICATIONS : ENGINEERING CERAMICS

Ceramics in Aerospace

Combustor Support Struts Flameholder Re-heat shields Nozzle Turbine Airfoils Turbine Casing Exhaust Cone Jet Pipe

Rolls-Royce AMED gas turbine engine H.M. Flower, High Performance Materials in Aerospace, Chapman & Hall, 1995

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M

Topic 6: Ceramic Materials.

APPLICATIONS : ENGINEERING CERAMICS Ceramic Tiles

The space shuttle is covered with approximately 24,000 ceramic tiles made from a silica fiber compound.

Dpt. Materials Sci and Eng. Chemical and Eng.

UC3M