Cement & Ceramic Technology
Chapter - IV
Manufacturing methods:
Processing ceramic ware
Processing of Ceramic Materials
▪ Produce commercial products with diverse sizes, shapes, compositions, structures, costs.
▪ Purpose: Increasing ability to refine, develop, and characterize ceramic materials.
▪ Processing involves many steps:
▪ Milling:
✓ reduce the materials from a large size to a smaller size.
✓ breaking up cemented material or pulverization.
✓ Done by mechanical including attrition, compression, and impact.
✓ Attrition milling equipment includes wet scrubber, which has paddles in water creating
twisters, then material collides and breaks up.
▪ Batching:
✓ Weighing the materials as per the
composition to be prepared,
and preparing them for mixing and drying.
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▪ Mixing:
✓ Occurs after batching; performed with dry mixing ribbon mixers (a
type of cement mixer), Mueller mixers, and pug mills.
✓ Wet mixing also used in the same equipment.
▪ Forming (casting):
✓ Making the mixed material into shapes, ranging from small bowls to
spark plug insulators.
✓ Forming can involve:
• Extrusion, such as extruding “slugs” to make bricks
• Pressing to make shaped parts
• Slip casting.
✓ Forming produces a “green” part, ready for drying.
• Green parts are soft, pliable, and over time will lose shape.
• For example, a green brick can be squeezed, and after being
squeezed, it will stay that way.
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Cont…
▪ Drying:
✓ It is removing the water/moisture or binder from the formed
material.
✓ Spray drying used to prepare powder for pressing operations.
✓ Also used tunnel dryers and periodic dryers.
✓ Apply controlled heat in two-stage process. First, heat removes
water.
This step needs careful control; rapid heating causes cracks and
surface defects.
▪ Firing:
✓ Applied on where the dried parts pass through a controlled
heating, and the ceramic materials may chemically change to
cause sintering and bonding.
✓ The fired part will be smaller than the dried part.
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Forming Ceramic Articles
Forming Ceramics:
▪ Formed and shaped before firing. It determines the final ceramics.
▪ Important variables in the forming steps: particle shape, particle packaging, phase
distribution, and location of pores.
▪ Forming processes are cold forming or hot forming.
▪ The major cold forming processes include,
✓ Slip casting
✓ Extrusion
✓ Dry pressing
✓ Injection molding
✓ Tape casting and variation of these
▪ Product of such processes is called a green body, before firing.
▪ Homogeneity of cold-formed part determines uniformity of shrinkage during firing.
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Slip Casting
A suspension of ceramic powders in water is called a slip. It is poured into a porous
plaster of Paris mold so that water from the mix is absorbed into the plaster to form a
firm layer of clay at the mold surface.
▪ The slip composition is 25% to 40% water
▪ Two principal variations:
✓ Drain casting – the mold is inverted to drain excess slip after a semi-solid layer
forms, producing a hollow product.
✓ Solid casting – to produce solid products, adequate time is allowed for the entire
body to become firm.
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Extrusion
Compression of clay through a die orifice (Molder) to produce long sections of uniform
cross-section, which are then cut to the required piece length.
▪ Equipment utilizes a screw-type action to assist in mixing the clay and pushing it
through the die opening.
▪ Products: hollow bricks, shaped tiles, drain pipes, tubes, and insulators.
▪ Also used to make the starting clay slugs for other ceramics processing methods
like jiggering and plastic pressing.
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Dry Pressing
Process sequence is similar to semi-drying pressing; the main distinction is that
the water content of the starting mix is typically below 5%.
▪ Dies must be made of hardened tool steel or cemented carbide to reduce wear
since dry clay is very abrasive.
▪ No drying shrinkage occurs, so drying time is eliminated and good dimensional
accuracy is achieved in the final product.
▪ Typical products: bathroom tile, electrical insulators, refractory brick, and other
simple geometries.
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Powder Injection Molding (PIM)
Ceramic particles are mixed with a thermoplastic polymer, then heated and
injected into a mold cavity.
▪ The polymer acts as a carrier and provides flow characteristics for molding.
▪ Upon cooling, which hardens the polymer, the mold is opened, and the part is
removed.
▪ Because temperatures needed to plasticize the carrier are much lower than
those required for sintering the ceramic, the piece is green after molding.
▪ The plastic binder is removed, and the remaining ceramic part is sintered.
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Drying
▪ Dried in open or heated chambers.
▪ Dip or spray glazed, drying and fired in a kiln at 900 °C.
▪ The drying process occurs in two stages:
✓ Stage 1: Drying rate is rapid and constant as water evaporates from the surface
into the surrounding air and water from the interior migrates by capillary action
to the surface to replace it.
• This is when shrinkage occurs, with the risk of warping and cracking.
✓ Stage 2: The moisture content has been reduced to where the ceramic grains are
in contact.
• Little or no further shrinkage occurs.
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Finishing
▪ Finishing operation manually or mechanically.
▪ This step involves grinding and machining with diamond and boron nitride tools,
chemical etching, and laser and electric discharge machining.
▪ The high hardness and chemical inertness of densified ceramics make the finishing
operations some of the most difficult and expensive in the entire process.
▪ Grinding alone can account for a large fraction of the cost of the component.
▪ In addition, surface cracks are often introduced during machining, and these can
reduce the strength of the part and the yields of the fabrication process.
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Finishing Operations for New Ceramics
▪ Parts made of new ceramics sometimes require finishing, which has one or more of
the following purposes:
✓ Increase dimensional accuracy
✓ Improve surface finish
✓ Make minor changes in part geometry
▪ Finishing usually involves abrasive processes.
✓ Diamond abrasives must be used to cut the hardened ceramic materials.
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Stages During Firing
▪ Dehydration (150 – 600 oC): By dehydration, mechanical water, and chemical
combined water is removed.
✓ Mechanical dehydration (water smoking)
✓ Chemical dehydration (chemical water smoking)
▪ Oxidation (300 - 950 oC).
✓ Oxidizable sulphur and carbon are removed.
✓ Ferrous ions into ferric ions
✓ Ca and Mg carbonates dissociate into their respective oxide and carbon dioxide.
▪ Vitrification:
✓ Some minerals melt to a glassy state and, on cooling, bond the unmelted particles
into a film mass.
✓ The progressive reduction in porosity is vitrification.
▪ Finally fired in the kiln.
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Firing of Traditional Ceramics
Firing: The heating of clay or glaze to a specific temperature.
The temperature at which the clay or glaze material melts is the fusion point.
A heat treatment process that sinters the ceramic material.
▪ Performed in a furnace called a kiln
▪ Bonds are developed between the ceramic grains, and this is accompanied by
densification and reduction of porosity.
▪ In firing of traditional ceramics, a glassy phase forms among the crystals which acts
as a binder.
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Kilns
▪ It is a furnace for firing clay. It includes two firings: one for bisque and one for glaze.
It can be electric, wood, or gas-powered.
Bisque fire:
▪ Clay has been fired, unglazed. First firing of clay to drive out chemically combined
water and carbonaceous materials before glazing.
Glaze fire:
▪ Glaze materials are heated sufficiently to melt and form a glass surface coating
when cooled.
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Types of Kiln
▪ Depends upon the types of product, fuel available, and temperature.
▪ Different Kilns:
✓ Down draft kiln
✓ Chamber kiln
✓ Tunnel kiln
✓ Top hat kiln
✓ Vertical shaft kiln
✓ Tank furnace
✓ Shuttle kiln
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Tunnel Kiln:
▪ The tunnel kiln is a continuous industrial kiln used for sintering bricks, ceramics,
refractory materials, and other products.
▪ Its structure is a long tunnel.
▪ The kiln is divided into three functional areas: preheating, firing, and cooling.
▪ The bricks are loaded and slowly pass through the tunnel to complete the sintering
process at high temperature.
▪ Compared with traditional kilns or intermittent kilns, tunnel kilns have the
advantages of a high degree of automation, low energy consumption and high
output, and have mainstream production equipment in the modern brick and tile
industry.
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Epoxy Resins
▪ Epoxides – cyclic ethers with three ring atoms.
▪ Epoxide group, addition of an oxygen atom across a C=C, epoxidation.
▪ Oxygen transfer agents: H2O2, HOCl, etc.
▪ Epoxy resins: reactive polymers/prepolymers which contain epoxide groups.
▪ Can undergo crosslinking reactions (referred to as curing) with itself or amines,
acids, phenols to give co-polymers.
▪ Raw materials: mainly petroleum-derived materials.
✓ Epichlorohydrin prepared using plant-derived glycerol.
✓ Novolac epoxy resin – phenols, formaldehyde, epichlorohydrin.
Role of Epoxy Resins in Cement
Epoxy resin (ER) is widely used as a polymeric modifier and binder in advanced
cement systems, especially in repair materials, coatings, and high-performance
concrete.
Key roles:
▪ Strong adhesion (bonding agent): Provides excellent bonding between cement
and substrates such as old concrete, steel, and masonry.
▪ Improved mechanical strength: Significantly enhances compressive, tensile,
and flexural strength by forming a dense, cross-linked polymer network within
the cement matrix.
▪ Low permeability:
Epoxy-modified cement exhibits very low porosity, reducing water absorption
and preventing ingress of harmful chlorides and sulfates.
Cont……
▪ Chemical resistance:
Imparts high resistance to acids, alkalis, oils, and solvents, making it suitable for
industrial flooring and aggressive environments.
▪ Abrasion and wear resistance:
The hardened epoxy-cement composite exhibits excellent abrasion resistance,
improving durability in high-traffic areas.
▪ Reduced shrinkage & cracking:
Epoxy resins reduce drying shrinkage and help control crack formation during
curing.
▪ Fast setting and early strength:
Epoxy-modified systems often achieve rapid curing and early strength gain,
which are useful for quick repair work.
Viny Ester Resins
▪ Vinyl esters are a class of thermosetting resins formed by the reaction of epoxy
resins with unsaturated monocarboxylic acids (commonly acrylic or methacrylic
acid).
▪ They combine the mechanical strength and chemical resistance of epoxies with
the processing ease of unsaturated polyesters.
▪ Vinyl ester resins contain reactive vinyl groups that enable crosslinking through
free-radical polymerization, typically using styrene as a reactive diluent.
▪ These materials exhibit excellent corrosion resistance, good adhesion, and
superior toughness compared to conventional polyester resins.
Preparation of Viny Ester Resins
Vinyl esters are prepared through a two-step chemical process:
▪ Step 1: Esterification
Epoxy resin reacts with acrylic or methacrylic acid:
Epoxy resin + acrylic acid ==== Vinyl ester resin
▪ Step 2: Dilution and additives
✓ The resin is diluted with a reactive monomer like styrene to reduce viscosity.
✓ Initiators (peroxides), inhibitors, and accelerators are added to control curing.
Curing process:
✓ Vinyl ester resins cure via free radical polymerization.
✓ Initiators generate radicals that cause crosslinking of vinyl groups, forming a
rigid 3D network,
Role of Vinyl Ester Resins in Cement
Vinyl ester resins (VER) are used as a polymeric modifier and binder in advanced
cementitious systems to enhance durability and performance, particularly in
aggressive environments.
Key roles:
▪ Enhanced mechanical strength: Vinyl ester resins improve compressive, tensile,
and flexural strength by forming a cross-linked polymer network within the
cement matrix, leading to a denser and tougher composite.
▪ Excellent chemical resistance: They provide superior resistance to acids, alkalis,
salts, and solvents, making vinyl ester-modified cements suitable for chemical
plants, wastewater systems, and marine structures.
▪ Low permeability:
These resins reduce porosity and water absorption, preventing ingress of
harmful ions (e.g., chlorides and sulfates), thereby increasing durability.
Cont……
▪ Improved adhesion:
Vinyl esters exhibit strong bonding with aggregates, steel reinforcement, and
existing concrete surfaces, making them ideal for repair and overlay
applications.
▪ Corrosion protection:
By limiting moisture and chemical penetration, they help protect reinforcement
from corrosion in reinforced concrete structures.
▪ Thermal and environmental stability:
Vinyl ester-modified systems show good resistance to temperature variations
and harsh environmental conditions.
▪ Reduced shrinkage and cracking:
The polymer network helps control shrinkage during curing, minimizing crack
formation.