Refractories-MTEN 403

Department of Materials Science and Engineering

University of Ghana
Lecturer: Dr. Emmanuel Nyankson
Email: loyankemon@yahoo.com, enyankson@ug.edu.gh

Office Hours:
Teaching Assistant:
 Introduction
➢Refractories are non-metallic materials that are hard to melt at high
temperature.
➢Japanese industrial standards (JIS) defines refractories as shaped materials that are
durable at high temperatures (> 1500℃), and unshaped materials like castables and
insulating firebricks with a maximum service temperature of > 800℃.
➢They have high mechanical strength and heat resistance
➢They are resistance to corrosion
➢High thermal shock resistance
➢They are used in kilns and furnaces and other applications in the industries like iron and
steel, cement, glass, ceramics and chemicals.
 Introduction
➢Materials drive our
society
• Stone Age
• Bronze Age
• Iron Age

Bronze Age
Stone Age

Iron Age
Introduction-Blast Furnace
 Introduction-Basic Oxygen Furnace
Purification of molten
iron and metal scrap
from;
• C
• S
• P
• Mn
Introduction-Electric Arc Furnace

• Steel is made
from scrap iron

• Metal Industries:Aluminum

• Glass making process

• Hydrocarbon industry
 Introduction
• The Commonest duty of refractories is to contain high temperature.
• to erect a solid barrier between hot “inside” and ambient or tolerable “outside.”

• The greatest challenge to refractories occurs as they face hot, corrosive

fluids.
• Metals are disqualified
• Corrosion attach enhanced by erosion
 Introduction
• Considerations of Functions
• Permeability
• Thermal conductivity
• Heat capacity
• Electrical conductivity
• Cost (relative to feasible
alternatives
• Considerations of Integrity
• Melting and vaporization
• Dimensional and phase
stability
• Strength and flow properties
• Elastic properties
• Thermal expansion
• Corrosion resistance
• Erosion resistance
• Abrasion resistance
Introduction
Introduction
 Introduction
• Refractories are materials having high melting points, with properties that makes them
suitable to act as heat resistant barriers between high and low temperature zones.

• The performance of a refractory depends on its qualities and quantities in three phases
• Solid
• Liquid/glass
• Pores

• The qualities of refractories are dependent on their chemical, physical, mineralogical

and thermal properties.
 Introduction
▪ Wanted properties of refractories
➢ Thermal conductivity should be low
➢ Refractoriness should be high
✓ High melting point
✓ Low creep rate
✓ High thermal shock resistance
➢ Mechanical strength
✓ High compressive strength
➢ Chemical resistance should be high
 Introduction: Monolithic Refractories
▪ Refractories are heterogeneous-they have different phases of components and
some pores
▪ That is refractory material is made up of
✓Crystalline phase
✓Glass phase
✓Pores and cracks Scanning Electron Microscopy Images of Refractories
 Introduction
▪ Classification of Refractories
➢Physical: different product forms e.g shaped and unshaped
➢chemical classification : different chemical compositions
• Physical classification
➢Shaped refractories: fired and unfired bricks
➢Unshaped refractories (Monoliths): castables, gunning mixes, ramming mixes, mortar
• Chemical classification includes
➢Acid refractories: RO2 (SiO2)
➢Basic refractories: RO (MgO, CaO)
➢Neutral refractories : R2O3 (Al2O3, Cr2O3)
 Introduction
• Chemical classification also includes
➢Oxide refractories: silica (SiO2), Magnesia (MgO), alumina (Al2O3)
➢Non-oxide refractories: SiC, C
➢Composite refractories: MgO-C, SiC-C, Al2O3-C.
 Introduction: Pre-shaped Refractories

Raw material Bonding agent

Shaping Drying Firing

Mixing to form Casting 80-1000C Tunnel kilns
homogeneous mass Extrusion Get rid of water Periodic kilns
vibration
 Introduction: Pre-shaped Refractories
▪ Bonding phases
➢Ceramic bonding (sintering)

Al2O3 Al2O3

✓Fusing two alumina grains without a bonding agent.

✓This is done at high temperature T≈(3/4)Tmelting
 Introduction: Pre-shaped Refractories
▪ Transport Mechanism
(a) Surface diffusion
(b) Surface to grain boundary
(c)Lattice to grain boundary
(d) Grain boundary diffusion
Al2O3 Al2O3
 Introduction
▪ Sintering can be related to the density of the particles as temperature
increases.
ρ
Intermediate Final
Initial stage stage
stage

T
 Introduction
▪ Initial stage: Densification: increase density
➢Density increases ~5 %
➢Slight reduction in porosity
➢Particles stick together
▪ Intermediate stage
➢5-92% increase in density
➢Porosity decreases
▪ Final stage
➢Density increases to ~100 %
➢Porosity vanishes
➢Grain growth (to avoid large grains, the sample is kept in the final stage for a short time
to avoid too much grain growth)
 Introduction
▪ Carbon bonding materials Tar and Pitch

➢pitch/tar or both

https://www.youtube.com/watch?v=BZvsrOciU_Q
Introduction
 Introduction
▪ Chemical bonding
➢High alumina cement
➢Phosphates-H3PO4
➢Borates-B2O3
➢Silicates-SiO2
 Introduction
▪ Chemical Bonding

SiO2

CS
C3S2

C2S

CaO Al2O3
C12A7 CA CA2
 Introduction
▪ C2S, C3S2 and CS – Portland cement
▪ C12A7, CA and CA2 – High Alumina Cement (HAC)
▪ Hydraulic phase
➢Hydraulic means reacting with H2O to from solid compound
C12A7, CA and CA2
decreasing reactivity

➢CA gives the best results

➢C12A7, causes flash setting, that is reaction between C12A7, and H2O is very fast, leading to
porosity and weak material
➢CA2 is the least reactive phase
➢The higher the CaO content, the higher the reactivity.
 Introduction: Monolithic Refractories
▪ Unshaped/monolithic refractories: they are without a definite form and obtain
their shape upon application.
 Introduction: Monolithic Refractories
Manufacturing Process

Drying
Raw material storage Drying screening
grinding

Weighing
storage Weighing mixing product
and packing

binder
 Introduction: Monolithic Refractories
▪ Unshaped/monolithic refractories: they are without a definite form and obtain
their shape upon application.
➢Mortar materials
➢Plastic refractories
➢Gunning mixes
➢Ramming mixes
➢castables

https://www.youtube.com/watch?v=PwAZnqIBD3E
 Introduction: Monolithic Refractories
▪ Unshaped/monolithic refractories: they are without a definite form and obtain
their shape upon application.

Gunning Mixes
Introduction: Monolithic Refractories

Ramming Mixes
Introduction: Monolithic Refractories
Introduction: Monolithic Refractories
 Introduction: Monolithic Refractories
▪ There are different bonding systems for Castables
✓Traditional castables-where alumina cement content is quite high, between 15-20%
➢ Low density
➢ Low refractoriness
✓Low cement castables (LCC)-cement content is between 5-8%
➢ Improved properties over the traditional castables: corrosion resistance, volume stability and hot
strength are equivalent to that found in preshaped refractories
✓Ultra low cement castables (ULCC)-cement content is between 1-3%
✓Benefits of LCC and ULCC
✓ Direct bonding between grog particles
✓ Low H20 content; low porosity
✓ Low CaO content: high refractoriness of materials