Ceramics and Glass

Since prehistoric times, engineered ceramic and glass materials have had significant roles in
most technologies.

Ceramic and Glass Materials’ Role in Civilization

Ceramics is one of the most ancient industries going back thousands of years. Once humans
discovered that clay could be found in abundance and formed into objects by first mixing with
water and then firing, a key industry was born. The oldest known ceramic artifact is dated as
early as 28,000 BCE (BCE = Before Common Era), during the late Paleolithic period. It is a
statuette of a woman, named the Venus of Dolní Věstonice, from a small prehistoric settlement
near Brno, in the Czech Republic. In this location, hundreds of clay figurines representing Ice
Age animals were also uncovered near the remains of a horseshoe-shaped kiln.

The first examples of pottery appeared in Eastern Asia several thousand years later. In
the Xianrendong cave in China, fragments of pots dated to 18,000-17,000 BCE have been found.
It is believed that from China the use of pottery successively spread to Japan and the Russian Far
East region where archeologists have found shards of ceramic artifacts dating to 14,000 BCE.

Use of ceramics increased dramatically during the Neolithic period, with the establishment of
settled communities dedicated to agriculture and farming. Starting approximately in 9,000 BCE,
clay-based ceramics became popular as containers for water and food, art objects, tiles and
bricks, and their use spread from Asia to the Middle East and Europe. The early products were
just dried in the sun or fired at low temperature (below 1,000°C) in rudimentary kilns dug into
the ground. Pottery was either monochrome or decorated by painting simple linear or geometric
motifs.

It is known that, around 7,000 BCE, people were already using sharp tools made from obsidian, a
natural occurring volcanic glass. The Roman historian Pliny reported that the first man-made
glass was accidentally produced by Phoenician merchants in 5,000 BCE, when, while resting on
a beach, they placed cooking pots on sodium-rich rocks near a fire. The heat from the fire melted
the rocks and mixed them with the sand, forming molten glass.

Archeologists have not been able to confirm Pliny’s recount. Instead, simple glass items, such as
beads, have been discovered in Mesopotamia and Egypt dating to 3,500 BCE. At the beginning
of the Bronze Age, glazed pottery was produced in Mesopotamia. However, it was not until
1,500 BCE that Egyptians started building factories to create glassware for ointments and oils.

One of the first breakthroughs in the fabrication of ceramics was the invention of the wheel, in
3,500 BCE. The introduction of the wheel allowed for the utilization of the wheel-forming
technique to produce ceramic artifacts with radial symmetry.
Meanwhile, ceramic pottery evolved in its use of increasingly elaborated paintings, so that these
objects eventually became genuine pieces of art. Decorations also involved the use oxidizing and
reducing atmosphere during firing to achieve special effects. Greek Attic vases of the 6th and 5th
centuries BCE are considered the apex of this evolution.

Throughout the 16th century CE (CE = Common Era), earthenware remained the main class of
ceramic products manufactured in Europe and the Middle East.  The Chinese were the first to
introduce high temperature kilns capable of reaching up to 1350°C, and, around 600 CE,
developed porcelain (a material with less than 1% porosity) from kaolin clay. During the Middle
Ages, trade through the Silk Road allowed for the introduction and diffusion of porcelain
throughout Islamic countries first and later in Europe, due in large part to the journeys of Marco
Polo.

By the 15th century the earliest blast furnaces were developed in Europe, capable of reaching up
to 1,500°C. They were used to melt iron and were initially constructed from natural materials.
When synthetic materials with better resistance to high temperatures (called refractories) were
developed in the 16th century, the industrial revolution was born. These refractories created the
necessary conditions for melting metals and glass on an industrial scale, as well as for the
manufacture of coke, cement, chemicals, and ceramics.

Since then, the ceramic industry has gone through a profound transformation. Not only have
traditional ceramics and glass become ubiquitous, but over the years new products have been
developed to take advantage of the unique properties of these materials, such as their low thermal
and electrical conductivity, high chemical resistance, and high melting point. Around 1850 the
first porcelain electrical insulators were introduced, starting the era of technical ceramics.

After World War II, ceramics and glass have contributed to the growth of many technologically
advanced fields, including electronics, optoelectronics, medical, energy, automotive, aerospace
and space exploration.  In addition, innovations in ceramic processing and characterization
techniques have enabled the creation of materials with tailored properties that meet the
requirements of specific and customized applications. In recent years, ceramic processing has
gained new vigor from nanotechnology, which is allowing manufacturers to introduce materials
and products with unconventional properties, such as transparent ceramics, ductile
ceramics, hyperelastic bones, and microscopic capacitors.

All these advances are expected to drive the global ceramic and glass industry to become a
nearly 1.1 trillion dollar market in 2023, up from an estimated $800 billion in 2018.

A summary of the most relevant milestones in the history of ceramics and glass is provided in
the table below.

Search:
Year(s) Development
 28,000 BCE Ceramic figurines are used for ceremonial purposes.
18,000 BCE Chinese pottery appears.
18,000 BCE to 14,000 Ceramic pottery spreads in Eastern Asia.
BCE
9,000 BCE Ceramic products, such as vases, bricks, and tiles, become popular in
the Middle East and Europe.
7,000 BCE Sharp tools made from natural glass appear.
5,000 BCE Phoenician merchants possibly make the first glass.
3,500 BCE Simple glass items are fabricated in Mesopotamia and Egypt.
3,500 BCE The wheel is invented, which will later be applied in wheel-forming of
pottery.
3,000 BCE Glazed pottery is produced in Mesopotamia.
1,500 BCE Egyptians start building factories for production of glassware.

Glass-ceramic
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Glass-ceramics have an amorphous phase and one or more crystalline phases and are produced
by a so-called "controlled crystallization" in contrast to a spontaneous crystallization, which is
usually not wanted in glass manufacturing. Glass-ceramics have the fabrication advantage of
glass, as well as special properties of ceramics. When used for sealing, some glass-ceramics do
not require brazing but can withstand brazing temperatures up to 700 °C.[1] Glass-ceramics
usually have between 30% [m/m] and 90% [m/m] crystallinity and yield an array of materials
with interesting properties like zero porosity, high strength, toughness, translucency or opacity,
pigmentation, opalescence, low or even negative thermal expansion, high temperature stability,
fluorescence, machinability, ferromagnetism, resorbability or high chemical durability,
biocompatibility, bioactivity, ion conductivity, superconductivity, isolation capabilities, low
dielectric constant and loss, high resistivity and break-down voltage. These properties can be
tailored by controlling the base-glass composition and by controlled heat
treatment/crystallization of base glass. In manufacturing, glass-ceramics are valued for having
the strength of ceramic but the hermetic sealing properties of glass.

Glass-ceramics are mostly produced in two steps: First, a glass is formed by a glass-
manufacturing process. The glass is cooled down and is then reheated in a second step. In this
heat treatment the glass partly crystallizes. In most cases nucleation agents are added to the base
composition of the glass-ceramic. These nucleation agents aid and control the crystallization
process. Because there is usually no pressing and sintering, glass-ceramics have, unlike sintered
ceramics, no pores.

A wide variety of glass-ceramic systems exists, e.g., the Li2O × Al2O3 × nSiO2 system (LAS
system), the MgO × Al2O3 × nSiO2 system (MAS system), the ZnO × Al2O3 × nSiO2 system
(ZAS system).

The LAS system mainly refers to a mix of lithium, silicon, and aluminum oxides with additional
components, e.g., glass-phase-forming agents such as Na2O, K2O and CaO and refining agents.
As nucleation agents most commonly zirconium(IV) oxide in combination with titanium(IV)
oxide is used. This important system was studied first and intensively by Hummel,[2] and
Smoke.[3]

After crystallization the dominant crystal phase in this type of glass-ceramic is a high-quartz
solid solution (HQ s.s.). If the glass-ceramic is subjected to a more intense heat treatment, this
HQ s.s. transforms into a keatite-solid solution (K s.s., sometimes wrongly named as beta-
spodumene). This transition is non-reversible and reconstructive, which means bonds in the
crystal-lattice are broken and new arranged. However, these two crystal phases show a very
similar structure as Li could show.[4]

The most interesting properties of these glass-ceramics are their thermomechanical properties.
Glass-ceramic from the LAS system is a mechanically strong material and can sustain repeated
and quick temperature changes up to 800–1000 °C. The dominant crystalline phase of the LAS
glass-ceramics, HQ s.s., has a strong negative coefficient of thermal expansion (CTE), keatite-
solid solution as still a negative CTE but much higher than HQ s.s. These negative CTEs of the
crystalline phase contrasts with the positive CTE of the residual glass. Adjusting the proportion
of these phases offers a wide range of possible CTEs in the finished composite. Mostly for
today's applications a low or even zero CTE is desired. Also a negative CTE is possible, which
means, in contrast to most materials when heated up, such a glass-ceramic contracts. At a certain
point, generally between 60% [m/m] and 80% [m/m] crystallinity, the two coefficients balance
such that the glass-ceramic as a whole has a thermal expansion coefficient that is very close to
zero. Also, when an interface between material will be subject to thermal fatigue, glass-ceramics
can be adjusted to match the coefficient of the material they will be bonded to.

Originally developed for use in the mirrors and mirror mounts of astronomical telescopes, LAS
glass-ceramics have become known and entered the domestic market through its use in glass-
ceramic cooktops, as well as cookware and bakeware or as high-performance reflectors for
digital projectors.
Contents
1 Ceramic matrix composites
2 Cooktops
3 Brands and manufacturers
4 Sources
5 Literature
Ceramic matrix composites[edit]
One particularly notable use of glass-ceramics is in the processing of ceramic matrix composites.
For many ceramic matrix composites typical sintering temperatures and times cannot be used, as
the degradation and corrosion of the constituent fibres becomes more of an issue as temperature
and sintering time increase. One example of this is SiC fibres, which can start to degrade via
pyrolysis at temperatures above 1470K.[5] One solution to this is to use the glassy form of the
ceramic as the sintering feedstock rather than the ceramic, as unlike the ceramic the glass pellets
have a softening point and will generally flow at much lower pressures and temperatures. This
allows the use of less extreme processing parameters, making the production of many new
technologically important fibre-matrix combinations by sintering possible.

Cooktops[edit]
Glass-ceramic from the LAS-System is a mechanically strong material and can sustain repeated
and quick temperature changes. However, it is not totally unbreakable. Because it is still a brittle
material as glass and ceramics are, it can be broken. There have been instances where users
reported damage to their cooktops when the surface was struck with a hard or blunt object (such
as a can falling from above or other heavy items).

The material has a very low heat conduction coefficient, which means that it stays cool outside
the cooking area. It can be made nearly transparent (15–20% loss in a typical cooktop) for
radiation in the infrared wavelengths.

In the visible range glass-ceramics can be transparent, translucent or opaque and even colored by
coloring agents.
A glass-ceramic cooktop
Today, there are two major types of electrical stoves with cooktops made of glass-ceramic:

A glass-ceramic stove uses radiant heating coils or infrared halogen lamps as the heating
elements. The surface of the glass-ceramic cooktop above the burner heats up, but the adjacent
surface remains cool because of the low heat conduction coefficient of the material.
An induction stove heats a metal pot's bottom directly through electromagnetic induction.
This technology is not entirely new, as glass-ceramic ranges were first introduced in the 1970s
using Corningware tops instead of the more durable material used today. These first generation
smoothtops were problematic and could only be used with flat-bottomed cookware as the heating
was primarily conductive rather than radiative.[6]

Compared to conventional kitchen stoves, glass-ceramic cooktops are relatively simple to clean,
due to their flat surface. However, glass-ceramic cooktops can be scratched very easily, so care
must be taken not to slide the cooking pans over the surface. If food with a high sugar content
(such as jam) spills, it should never be allowed to dry on the surface, otherwise damage will
occur.[7]

For best results and maximum heat transfer, all cookware should be flat-bottomed and matched
to the same size as the burner zone.

Brands and manufacturers[edit]

CorningWare casserole dish and other cookware pieces, with the 'Cornflower' pattern decoration
Some well-known brands of glass-ceramics are Pyroceram, Ceran (cooktops), Eurokera
(cooktop, stoves and fireplaces), Zerodur (telescope mirrors), and Macor, Kanger (Glass-
Ceramic for cooktop, stoves, microwave and fireplaces door). German manufacturer Schott
introduced Zerodur in 1968, Ceran followed in 1971.

Nippon Electric Glass is a predominent worldwide manufacturer of glass ceramics, whose

related products in this area include FireLite and NeoCeram ceramic glass for architectural and
high temperature applications respectively. Keralite, manufactured by Vetrotech Saint-Gobain, is
a specialty glass-ceramic fire and impact safety rated material for use in fire-rated applications.
Glass-ceramics manufactured in the Soviet Union/Russia are known under the name Sitall.

The same class of material was also used, until the late 1990s, in CorningWare dishes, which
could be taken from the freezer directly to the oven with no risk of thermal shock.

Sources[edit]
^ "Glass Ceramic Composite Materials for Hermetic Seals | Elan". Elan Technology. Retrieved
2017-06-13.
^ Hummel, F. A. (1951). "Thermal expansion properties of some synthetic lithia minerals".
Journal of the American Ceramic Society. 34 (8): 235–239. doi:10.1111/j.1151-
2916.1951.tb11646.x.
^ Smoke, E. J. (1951). "Ceramic compositions having negative linear thermal expansion".
Journal of the American Ceramic Society. 34 (3): 87–90. doi:10.1111/j.1151-
2916.1951.tb13491.x.
^ Li, C. T. (1971). "Transformation mechanism between high-quartz and keatite phases of
LiAlSi2O6 composition". Acta Crystallographica. 27: 1132–1140.
doi:10.1107/S0567740871003649.
^ G. Chollon et. Al. (1997), Thermal stability of a PCS-derived SiC fibre with a low oxygen
content (Hi-Nicalon), Journal of Materials Science
^ "Archived copy". Archived from the original on 2005-03-23. Retrieved 2008-08-03.
^ "Range - Glass Cooktop Cleaning Instructions". www.geappliances.com. Retrieved 2017-06-
13.
Literature[edit]
McMillan P.W., "The glass phase in glass-ceramics", Glass Technology, 1974, Vol. 15 (1), P. 5-
15
Bach H. (Editor), "Low thermal expansion glass ceramics", Springer-Verlag (1995).
Holand, Wolfram and Beall, George H. Glass-Ceramic Technology. Wiley, 2002. ISBN 978-1-
57498-107-0