Materials and Design 32 (2011) 1717–1732

Contents lists available at ScienceDirect

Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Review

Glasses as engineering materials: A review

Eugen Axinte ⇑
Gh. Asachi Technical University of Iasi, Faculty of Machine Manufacturing & Industrial Management, 59A, Prof. Dimitrie Mangeron Blvd., Romania

a r t i c l e i n f o a b s t r a c t

Article history: Glass products have applications in design engineering, and they can solve many special problems. These
Received 15 September 2010 materials can work in situations in which plastics and metals would fail and need to be part of designer’s
Accepted 24 November 2010 repertoire. In some situations, by using these materials, some difficult problems would be solved. This
Available online 28 November 2010
paper contains a number of chapters as follows: a brief about ceramics family, a short history of glass,
a brief about physics and the technology of glass fabrication, recently developed glasses with special des-
Keywords: tinations, testing methods and news about glass parts processing (grinding, waterjet processing, laser
Glasses
cutting, nanoimprint lithography, etc.). The last chapter of this review paper contain some strategic lines
Constitution
Environmental performance
of glass usage in industry and estimations about the future of glass development.
Ó 2010 Elsevier Ltd. All rights reserved.

1. The ceramics family
Cermets and ceramics are becoming the tool materials for the
present and future. By using the cemented carbides at wood work-
ing tools (as saw blades, cutting wheels), the wear was reduced sig-
nificant. Coated cemented carbides displaced the high-speed steel
for cutting tools and also high production press dies use the ce-
mented carbide tooling. Ceramics are taking a lot of high-temper-
ature machine tasks, are substrates for computer chips, and are
used for prosthetic devices. Glasses and carbon products have
applications in design engineering and they can solve many special
problems.
These materials can work in situations in which plastics and
metals would fail and need to be part of designer’s repertoire;
sometimes, using these materials, some difficult problems would
be solved. Ceramics are defined as solids composed of compounds
that contain metallic and/or non-metallic elements, and the atoms
of compounds are held together with strong atomic forces (ionic or
covalent bonds). The spectrum of ceramic uses is presented in
Fig. 1.
The ceramics with high strength and the best toughness (as alu-
minum, zirconias, oxides, silicon carbides) were named in 1980 as
‘‘structural ceramics’’. In Japan, these ceramics were called ‘‘fine
ceramics’’. In 1990, the (ASTM) Committee for ceramics (C28)
named this ceramics ‘‘advanced ceramics’’. The definition given
by C28 for this class of materials is highly engineered, high-perfor-
mance, predominantly non-metallic, inorganic, ceramic material
having specific functional attributes (by standard ASTM C1145) [1].
⇑ Tel./fax: +40 232217290 (office), mobile: +40 722892926.
E-mail address: axintee@tcm.tuiasi.ro
URL: http://www.cm.tuiasi.ro/html/ro/tcm.htm
Glasses are not ceramics (by previous definition of ceramics),
but they are used for similar type of things as ceramics and have
some properties that are typical for ceramics. The most common
property of ceramics, glasses, and cements is brittleness.
The measure of crack propagation tendency, fracture toughness,
is lower at ceramics family than at metals, as is shown in Fig. 2.
2. Brief history of glass: past and present of glass
It is not exactly known when, where, or how humans first
learned to make glass. The legends tells us that a Phoenician sailor
(by other historians, a Roman sailor), cooking the evening meal on
a beach, sets the pots on top of stones of natron (a natural mixture
of sodium carbonate decahydrate, sodium bicarbonate along with
small quantities of household salt). As the cooking fire heated both
these stones and the sand below, an unknown liquid began to flow
and that was the origin of man-made glass.
In [2] is demonstrated and argued that in ancient times, soda
glasses with high alumina concentrations are quite rare around
the Mediterranean area or in the Middle East. The few available
examples include European Iron-Age dark blue glass colored with
cobalt-rich alum that contains up to 8% of alumina. Mineral
soda–alumina (m-Na–Al) glass has been found across a vast area
stretching from Africa to East Asia. m-Na–Al glass appears around
the 5th c. B.C. and is relatively common for periods as late as the
19th c. A.D. It is particularly abundant in South Asia, where raw
materials to produce m-Na–Al glass are readily available and was
likely manufactured there; however, the number and the impor-
tance of the manufacturing centers are unknown as archaeological
information is extremely scarce. The interpretation of data ob-
tained using compositional analysis on a large corpus of artifacts
(486) shows that at least five subgroups of m-Na–Al glass can be

0261-3069/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2010.11.057
1718 E. Axinte / Materials and Design 32 (2011) 1717–1732
Fig. 1. The spectrum of ceramics uses.
Fig. 2. The fracture toughness of different materials.
identified using the concentrations of calcium, magnesium,
uranium, barium, strontium, zirconium, and cesium measured
with laser ablation-inductively coupled plasma-mass spectrometry
(LA-ICP-MS). From this data, it is possible to infer the existence of
several m-Na–Al glass-making centers, not all of them located in
South Asia as previously assumed. They were operating over differ-
ent time periods and were connected to different exchange
networks.
It is historically accepted that the first manufactured glass was
in the form of a glaze on ceramic vessels, about 3000 B.C. The first
glass vessels were produced about 1500 B.C. in Egypt and Mesopo-
tamia. The glass industry was extremely successful for the next
300 years and then declined. It was revived in Mesopotamia in
the 700 B.C. and in Egypt in the 500 B.C. For the next 500 years,
Egypt, Syria, and the other countries along the eastern shore of
the Mediterranean Sea were glassmaking centers. Glass manufac-
turing developed in the Roman Empire and spread from Italy to
all Roman provinces. The first four centuries of Christian Era is
called the First Golden Age of Glass. In the middle ages, by the time
of the Crusades, glass manufacture had been revived in Murano is-
land, near Venice, where soda lime glass, known as crystal, was
developed (this period is known as the Second Golden Age of Glass).
In North America (United States), the first factory known was a
glass plant built at Jamestown, Virginia, in 1608, but failed within
a year. The Jamestown colonists tried glassmaking again in 1621,
but an Indian attack in 1622 and the scarcity of workers ended this
attempt in 1624. The glass industry was reestablished in America
in 1739, when Caspar Wistar built a glassmaking plant in Salem
County, New Jersey. This plant operated until 1780.
In 1820, Bakewell, Page, & Bakewell Co. from Pittsburgh, Penn-
sylvania, introduced the first real development in production glass-
blowing since the blowpipe, a development that would change
how glass was used forever. They patented a process of mechani-
cally pressing hot glass. After 1890, glass uses and manufacturing
developments increased so rapidly as to be almost revolutionary.
The late 1900s brought new important specialty glasses. Among
the new specialty glasses were transparent glass–ceramics, which
are used to make cookware, and chalcogenide glass, an infrared-
transmitting glass that can be used to make lenses for night-vision
goggles. The science and engineering of glass as a material was
much better understood, and in the late 1950s, Sir Alastair Pilking-
ton introduced a new revolutionary production method (float glass
production), by which 90% of flat glass is still manufactured today.
In the 1970s, optical fibers were developed for use as ‘‘light pipes’’
in laser communication systems. These pipes maintain the bright-
ness and intensity of light being transmitted over long distances.
Types of glass that can store radioactive wastes safely for thou-
sands of years were also developed during the 1970s.
3. Brief about physics of glass: how it is made
Generally, solids (metals) have a three-dimensional periodic
structure (crystalline structure). But also exists solids with a ran-
domized three-dimensional structure – these solids are called
amorphous or glassy (Fig. 3).
A lot of materials such as organic polymers and metal alloys are
able to form under special conditions amorphous structures. An
inorganic amorphous or glassy solid is a high-speed cooled liquid
(cooled fast enough to prevent crystallization).
 E. Axinte / Materials and Design 32 (2011) 1717–1732 1719

Fig. 3. Crystalline structures (a) amorphous randomized structures (b) and the molecular structure of silica-based glass (c).

The relationship between the oxygen and the cation of the oxide
compound essentially influences the glass-forming ability of an
oxide. There are four types of oxides used in glass fabrication
(see Table 1).
At room temperature, glasses are very viscous structures
(1018 Pa  s – glass viscosity vs 1 Pa  s – water viscosity). Viscous
flow of glass at room temperature occurs in a geological timescale.
With increasing temperature, the glass viscosity decreases as is
shown in Fig. 4.
There are five very important temperatures, called ‘‘standard
points’’, associated with the viscous flow (melting) of glass. The
strain point is the maximum temperature supported by glass for
structural applications. A review and the description of standard
points is given by Table 2.
After the glass was formed, it is cooled to a temperature nearly
above the strain point, where it will retain its shape and resist flow.
At this point, the glass parts are annealed to relieve the internal
stresses. A glass part that is incorrectly annealed will fracture or
crack at ambient temperature.
The behavior of specific density of glass as a function of the
temperature is illustrated by graph from Fig. 5.
It is observed that at glass transition temperature exists an
inflexion point. After this point, the glass viscosity decreases,
specific volume abruptly increases, and the specific density has a Fig. 4. Dynamic viscosity of glass vs heating temperature.
greater rate of decreasing. This behavior has major consequences
for design and manufacture of molds. In [3], Fluegel developed
an accurate glass viscosity model relevant to commercial float glasses, TV panel glasses, borosilicate fiber wool and E-type
application through statistical analysis and based on all composi- glasses, low expansion borosilicate glasses, glasses for nuclear
tion–property data available in SciGlass. The viscosity model for waste vitrification, lead crystal glasses, binary alkali silicates, and
predicting the complete viscosity curve of glass was developed various other compositions.
using a global statistical approach and more than 2200 composi- All that is required to make glass is sand, soda, a little lime, and
tion–viscosity data for silicate glasses collected from over 50 years a lot of heat. The typical process of glasses fabrication is shown in
of scientific literature, including soda–lime–silica container and Fig. 6.

Table 1
Types of oxides used in glass fabrication.

No. Oxide type Characteristics Examples

1 Main glass former oxides Suitable structures and low crystallization rates SiO2
B2O3
Form glass under slow cooling rates GeO2
P2O5
2 Conditional glass formers oxides Form glass under certain conditions Al2O3; Bi2O3 WO3; MoO3
3 Intermediate oxides Cannot form glass themselves but form glass in mixture with former oxides TiO2; ZnO; PbO; Zr2O3
4 Network modifier oxides Cannot form glass themselves nether in mixture with former oxides MgO
CaO
Na2O
They can modify the properties of glass by affecting Si–O bonds K2O
1720 E. Axinte / Materials and Design 32 (2011) 1717–1732

Table 2
The standard points of glass.

No. Standard point Viscosity Temperature descriptions

name
1 Working point
2 Softening point
3 Glass transition
temperature
4 Annealing point
5 Strain point
(Pa s)
103 At this temperature, the viscosity is sufficiently low for glass forming. Casting processes are possibly below 10 Pa s viscosity
106.6 At this temperature, the viscosity is sufficiently low for glass to slump under own weight. Near below this temperature glass
is stiff, but a little effort is necessary for yield and flow
1012 Range of temperatures at which glass transitions from super cooled liquid in a solid state
1013.4 Internal stresses are relieved in minutes
1013.6 Internal stresses are relieved in hours

1 Pa s (SI) = 0.1 P (P – poise, physics system of units).

tured in glass pieces by different techniques as blowing, molding,

casting, injection, extrusion, and wire drawing.
Commercial glasses are silica-based glasses with additional oxi-
des (see Table 1). The presence, type, and the quantity of one or
many oxides give the glass type and also have major influences
on the glass properties and utilization. For example, a colored glass
is obtaining by addition of a metallic oxide (iron oxide for green
glass, cobalt oxide for blue glass). Crystalline glass–ceramics are
obtained by the introduction of titanium oxide in melted glass.
Titanium oxide initiates the crystallization and the material ob-
tained is up to 96% crystalline [1].
The mechanical and physical properties of glasses are essen-
tially determined by their composition, but a general view can be
given:

a.Glasses are harder than metals.

Fig. 5. The evolution of specific density vs temperature (———— specific volume vs
temperature).
The mixture of refined sand (SiO2) and additional basic oxide is
heated in furnace (gas or electric) at a temperature higher than
1200 °C. Essentially, the main role of this additional oxides (as
CaO, Na2O, K2O) is to reduce the working point of the mixture. A
pure silicone oxide (quartz) is refractory, with a softening point
near 1500 °C or higher. Then, the melted composition is manufac-
b.Glasses have tensile strength in the range 24–69 MPa.
c.Glasses are brittle and have low ductility.
d.Glasses have a low coefficient of thermal expansion.
e.Glasses have a low coefficient of thermal conductivity.
f.Glasses are good electrical insulators.
g.Glasses are resistant to acids, solvents, chemicals, water and
saline water and alkaline solutions.
h. Some glasses can be used at high temperatures (700 °C –
soda lime for windows; 1580 °C – fused quartz–silica).
Selection of the main mechanical and physical properties of
amorphous glass and crystalline glass–ceramic is presented in

Fig. 6. Basic technology for glass fabrication (integrated with the recycling process).
 E. Axinte / Materials and Design 32 (2011) 1717–1732 1721

Table 3 A list of glass types in the flat glass industry is starting from ba-
Mechanical properties of glasses vs other engineering materials. sic glass types as float glass, mirrors, and trough security types to
Material Flexural Compressive Hardness, Young special glass types like electrochromic and photovoltaic glass
strength strength HV modulus (see Table. 6). A large spectrum of designer’s interests for these
(MPa) (MPa) of elasticity, glass products are also observed.
E (GPa)
A simplified classification is based on the chemical composition
Silica (amorphous 98 1860 600 69 and follows the crystallization model (Table 7).
glass)
Crystalline 103 344 250 64
glass–ceramic 4.1. Advances in glass and glass–ceramics design and manufacture
Plastic 89.6 2.28
(polycarbonate) In [4], Hampshire revealed some advances in the domain of oxy-
Carbon steel 275 275 100 200
nitride glasses. This work is a complete review of the development
Cemented carbide 1400 4000 1000 612
of oxynitride glasses and outlines the effect of glass composition,
especially nitrogen content and also cation ratios, on properties
and relates this to structural features within the glass. Nucleation
Table 4 and crystallization studies are also outlined. Oxynitride glasses
Physical properties of glasses vs other engineering materials. are prepared by mixing appropriate powders – silica, alumina,
Material Density Thermal Coefficient Electrical the modifying oxide(s) plus silicon nitride or aluminum nitride –
(kg/ conductivity of thermal resistivity in isopropyl alcohol in a ball mill with sialon milling media, fol-
m3) (W/m °C) expansion, (O m) lowed by evaporation of the alcohol. Glasses (50–60 g) are melted
20–100 °C in boron nitride-lined graphite crucibles under 0.1 MPa nitrogen
(10 6 m/m °C)
pressure at 1600–1750 °C for 1 h, after which it is quickly removed
Silica (amorphous 2304 34 1 107 from the furnace and poured into a preheated graphite mold at
glass)
Crystalline 2592 33 9.4 1012
850–900 °C. The glass is annealed at this temperature for 1 h to
glass–ceramic remove stresses and then slowly cooled. The main conclusions of
Plastic 1296 0.2 6.7 8  1014 the study are that oxynitride glass formation occurs in a number
(polycarbonate) of M–Si–O–N, M–Si–Al–O–N and M–Si–Mg–O–N systems, and
Carbon steel 8064 47 11.9 20
8
using normal melting processes, up to 30 equiv.% nitrogen can
Cemented carbide 16,000 86 7.4 6  10
be dissolved in the glass. An innovative approach, using metal pre-
cursors, allows much more N to be dissolved into some M–Si–O–N
glasses. As nitrogen content increases, properties such as glass
Tables 3 and 4. For comparison, in tables are presented some prop- transition temperature, elastic modulus, viscosity, hardness, and
erties of a plastic (polycarbonate), a carbon steel, and a cemented slow crack growth resistance increase while thermal expansion
carbide WC with 6% cobalt. coefficient decreases as a result of increased cross-linking of nitro-
Optical properties of glasses make them preferable in the con- gen within the glass network. Spectroscopic studies have identified
struction of lenses and windows. The very low coefficient of ther- the structural features of glasses and the role of nitrogen as a net-
mal expansion of high silica glasses makes them extremely work ‘‘former’’. Many studies on crystallization of oxynitride
resistant at thermal shocks and also makes them favorite for labo- glasses have been carried out, which have identified suitable
ratory glass instruments (tubes, retorts) and light bulbs. The crys- two-stage heat treatments for nucleation and growth of crystal
talline glass with elasticity modulus above 130  103 MPa has phases, to form glass–ceramics with significant increases in
good shock resistance. strength and elastic modulus over the parent glasses. Addition of
fluorine extends glass formation in oxynitride systems and allows
dissolution of higher levels of nitrogen into glasses. Fluorine lowers
4. Advances in glass family development
glass transition temperature but does not have any effect on elastic
modulus or microhardness. Nitrogen may be dissolved in phos-
The glass family is huge and is in continuous enrichment. Year
phate glasses with consequent improvements in chemical durabil-
after year, new types of glass with new properties extend their uti-
ity and increases in many physical and mechanical properties [4].
lization domain. The utilization domain of glass in engineering de-
New advances in structural glasses domain are described by
sign have a lot of facets: from banal windows or bottles to
Royer-Carfagni and Silvestri [5]. The authors developed an innova-
antinuclear radiation containers; from architectural and structural
tive point-fixing system (called Gecko system) for frameless glass
glasses to photosensitive glass devices used in machine controls;
glazing that exploits the enhanced mechanical properties of a
from food preparation tanks to newest optical fibers.
new generation of ionoplast polymer interlayers. Laminated glass
The enormous variety of existent glass types, rapid develop-
connected with the new device exhibits a noteworthy resistance
ment of new and innovative glasses, developments in glass fabrica-
and interesting post-glass-breakage performances. To achieve a
tion and development of glass-manufacturing processes make the
fail-safe performance, the key point is to attach the polymeric
classification of glasses extremely difficult. After the product types,
interlayer of laminated glass directly to metallic holders, so that
a first classification can be done for the main glass industries, as in
the interlayer itself may act as a confining membrane even after
Table 5 (based on http://www.glassonweb.com/ description-in
glass-breakage. This technology is possible only if the polymeric
section directory).
materials present sufficiently high mechanical properties and ad-
here well to both glass and metals. The Gecko system is presented
Table 5 in Fig. 7 (from [5]).
Classification of main glass industries. After the testing of the system in different conditions (tests at
Main glass industries room temperature, tests on aged samples and tests at low and high
temperatures), the authors have demonstrated that the polymer
Flat Hollow Automotive Art Optical Glass Glass
glass glass glass glass glass fibers Wool can be easily curved by slightly heating the material, and even
when the radius of curvature is very small, no considerable decay
1722 E. Axinte / Materials and Design 32 (2011) 1717–1732

Table 6
Glass types in flat glass industry and the designers spectrum of interests.

Designer’s interests Automotive/ Architecture Physics/chemistry/

aerosapce construction electronics
Flat glass Common glasses (basic and Float glass x
industry decorative) Body tinted glass x
Reflective glass x x
Low glass x x x
Mirror x x x
Insulating glass
Enameled/screen x
printed glass
Pattern glass x x
Antique mirror x
Special glass types Photovoltaic glass x x x
X-ray protection glass x x x
Electrically heated glass x x x
Electrochromic glass x x x
Liquid crystal glazing x x
Self-cleaning glass x x x
Sand-blasted glass x
Acid-etched glass x x
Bent glass x x
Tempered glass x x x
Laminated glass x x x
Fire-resistant glass x x x
Wired glass x x x
Alarm glass x x x
Antireflective glass x x x

Table 7
Simplified glasses classification.

No. Type Description/key words

1 Ordinary – amorphous Amorphous structure; silica base; high commercial spectrum
glasses
a. Quartz
b. Silica glass
c. Na–Ca
silicate glass
2 Glass–ceramics Glass–ceramics are manufactured through the controlled crystallization of a specially formulated glass – a high density of crystalline
nuclei (Ti, Zr, P2O5) is generated in the molten glass. Glass–ceramics are useful in thermally hazardous conditions. Good resistance to
erosion and pressure and the excellent hardness make glass–ceramics widely used in industrial purposes. Moreover, glass–ceramics
are very good electrical insulators
3 Bulk metallic glasses Bulk metallic glasses (BMGs) are metallic materials with a disordered atomic-scale structure, produced directly from the liquid state
BMGs during cooling (the rapid cooling, on the order of millions of degrees a second, is too fast for crystals to form and the material is ‘‘locked
in’’ a glassy state), are called ‘‘glasses’’, or amorphous metals and they are commonly referred as ‘‘metallic glasses’’ or ‘‘glassy metals’’.
BMGs have been paid great attentions for its theoretical and practical reasons since the bulk amorphous Pd–Cu–Si and Pd–Ni–P alloys
was first synthesized by water quenching method in 1974. More recently, batches of amorphous steel have been produced that
demonstrate strengths much greater than conventional steel alloys. The most useful property of bulk amorphous alloys is that they are
true glasses, which means that they soften and flow upon heating. This allows for easy processing, such as by injection molding, in
much the same way as polymers. Bulk metallic glasses have been commercialized for use in medical devices, and as cases for electronic
equipment

of the mechanical properties has been observed. In any case, the
viscoelastic nature of the polymer renders the response strongly
dependent upon the load duration and environmental tempera-
ture. However, the confinement effect produced by the attached
glass or metal enhances the mechanical strength of the bent
appendix, which results much higher than that of the plain poly-
mer especially at relatively high temperatures. The post-glass-
breakage testing shows that the interlayer remains attached to
the metallic holders even after complete breakage of both glass
plies, thus acting as a confining membrane that prevents the
detachment of the glass fragments.
In [6], Fujimoto describes a new infrared luminescence from
bismuth (Bi)-doped glass. In this work, the author will introduce
the basic properties of Bi-doped silica glass (BiSG), such as a phase
diagram and spectroscopic properties, and then mainly talk about
the origin of luminescent center. After the discovery of a new infra-
red luminescent bismuth center, several research groups started to
study its applications, such as optical amplification or laser oscilla-
tion using Bi luminescent materials. Optical amplification around
1.3 lm with Bi-doped multicomponent glass fiber is useful for
metropolitan area network optical amplifiers [7].
A large study about advances in multicomponent silicate
glasses and their glass–ceramics derivatives for dental applications
is presented by ElBatal et al. [8]. X-ray diffraction patterns reveal
the formation of lithium disilicate as a major phase together with
other subsidiary phases precipitated during the crystallization pro-
cess according to the other constituent oxides. Infrared spectra
show mainly characteristic bands due to silicate network.
In [9] is statistically analyzed the relation between the chemical
composition and the density of silicate glass melts at temperatures
of 1000–1400 °C. The analysis was carried out on all 140–260
available values in the SciGlass information system for composi-
tions containing more than 40 mol% silica, less than 40 mol% boron
oxide, varying amounts of Al2O3, Li2O, Na2O, K2O, MgO, CaO, PbO,
 E. Axinte / Materials and Design 32 (2011) 1717–1732 1723

Fig. 7. The Gecko system with indication of the bent polymeric interlayer [5]. (a) Section; (b) front view of a prototype.

and other minor components. A model based on multiple regres-
sion was developed. The 95% confidence interval of the mean mod-
el prediction on the density was 0.5–3%, depending on the
composition of interest. The prediction of density as a function of
temperature made possible the estimation of the coefficient of
thermal expansion in the molten state to within 20–40% error with
a 95% level of confidence. The effects of the composition of silicate
glass melt density and thermal expansion are investigated: boron
oxide, B2O3, decreases the density of silicate glass melts based on
its low molecular mass; lithium oxide, Li2O, slightly decreases
the density of silicate glass melts; alumina, Al2O3, clearly increases
the glass melt density at high temperatures (1200–1400 °C); so-
dium oxide, Na2O, does not have a strong influence on the glass
melt density within the studied temperature range because of
the interplay between its medium molecular weight, its influence
on the thermal expansion, and component interactions. At
1400 °C, adding Na2O appears to decrease the density, whereas at
lower temperatures, the influence of Na2O addition is not readily
recognized; potassium oxide, K2O, decreases the density of silicate
glass melts; magnesium oxide, MgO, might not decrease the glass
melt density despite its low molecular weight, because it does not
appear to increase the thermal expansion coefficient significantly;
calcium oxide increases the glass melt density due to its relatively
high molecular weight and the moderate influence on the thermal
expansion coefficient; lead oxide, PbO, has a very high molecular
weight; therefore, it increases the glass melt density significantly.
An example for glass designer’s use is given in Fig. 8 (from [9]).
The authors recommend that for glass design through property
modeling, evaporation losses during glass batch melting and possi-
ble influences of the oxidation states of transition metal oxides
must be taken into account.
Advances in environmental glass industrialization are extracted
from [10–12] and are listed as follows: Ref. [10] presents glasses
obtained from melting mixtures of industrial wastes (panel glass
from cathode ray tubes, mining residues from feldspar excavation,
and lime from fume abatement systems of the glass industry). Mi-
cro- and macrocellular sintered glass–ceramics were manufac-
tured. Microcellular glass–ceramics, with a closed porosity, were
prepared by the direct foaming of the glass mass, determined by
viscous flow sintering of fine powders (<37 lm), due to the addi-
tion of a SiC-based waste (from polished glass articles). The surface
crystallization of glass, upon sintering, limited the porosity (being
about 50%), but imparted a remarkable crushing strength to the
products (up to about 80 MPa), useful for construction applica-

Fig. 8. Glass viscosity example curves, derived from experimental data (except lead crystal glass) – from [9].
1724 E. Axinte / Materials and Design 32 (2011) 1717–1732
tions. Micro- and macrocellular glass–ceramics, with an open
porosity and very low relative density (from 40% to less than
10%), were prepared by the sintering of fine glass powders mixed
with Polymethyl Methacrylate micro-beads or deposited on poly-
urethane sponges. The crystallization, besides imparting a good
mechanical strength, allowed the maintenance of the open-celled
morphology, useful for filtering applications. The production of cel-
lular sintered glass–ceramics, both by direct foaming (exploiting a
SiC-based waste) and by the usage of sacrificial polymeric materi-
als, is also illustrated.
Ref. [11] summarizes the progresses and points out the direc-
tions for the proper uses of waste glasses in Portland cement and
concrete. The use of recycled waste glasses in Portland cement
and concrete has attracted a lot of interest worldwide due to the
increased disposal costs and environmental concerns. Being amor-
phous and containing relatively large quantities of silicon and cal-
cium, glass is, in theory, pozzolanic or even cementitious in nature
when it is finely ground. Thus, it can be used as a cement replace-
ment in Portland cement concrete. The use of crushed glasses as
aggregates for Portland cement concrete does have some negative
effect on properties of the concrete; however, particle applicability
can still be produced even using 100% crushed glass as aggregates.
The main concerns for the use of crushed glasses as aggregates for
Portland cement concrete are the expansion and cracking caused
by the glass aggregates.
National Academy of Engineering (NAE – Washington, DC) iden-
tified glass and glass–ceramics as central to many of the great engi-
neering achievements of the 20th century, as development of solid
state lasers and optical glass fibers, biomaterials, glasses for imag-
ing technologies, glass films in microelectronic devices [12]. In
2008, NAE also identified The Grand Challenges for Engineering
for 21st Century (Fig. 9).
Some of these challenges offer great opportunities for glass sci-
entists and manufacturers to develop their role of improving the
human condition, to contribute to the development of new and
sustainable sources for energy and to develop techniques that en-
hance the environment.
A complete survey of environmental, energy-saving and pro-
duction applications of glasses is given by Brow and Schmitt
[12]. In this paper, authors review some of the opportunities for
the development and use of glass to address future energy and
environmental challenges. Some of these applications will require
Fig. 9. Schematics of The Grand Challenges for Engineering for 21st Century (adapted from [12]).
large-scale manufacturing of glasses that are closely related to cur-
rent products, and other applications will require materials re-
search to develop new compositions and forms that meet
stringent engineering requirements.
4.1.1. Glasses and solar energy
Solar energy applications include thermal, photovoltaic, and
photochemical energy conversion, and the scale of solar systems
range from power plants to portable, individual power units.
Intrinsic physical, chemical, and mechanical properties of glasses
(optical transparency, chemical durability, strength, thermal
expansion coefficient, manufacturability, etc.) make them indis-
pensable for all solar energy systems. The specific function of the
glass component is common to all solar systems: glass transmits
desirable solar radiation to an active component (photovoltaic cell,
thermal storage unit, etc.) while providing chemical and structural
protection of that active component from the ambient conditions.
The engineering conditions for glasses in solar energy systems
are synthesized in Table 8 (adapted from [12]).
The performances of solar power units can be improved by
improving the design of the glass unit. Glass covers for photovol-
taic units can be patterned to help concentrate and guide the solar
energy to the photovoltaic layer. Reflective layers coated on the
patterned, back surface of the cover further guide solar radiation
to the photovoltaic cells by means of total internal reflection. Mir-
rors are commonly used in solar power units, and researchers try
to find the best solutions for improving their durability and effi-
ciency (silvered glasses, polymer-coated sheet aluminum, silvered
polymer films). Other solar power applications drive to important
glass development and manufacturing as building-integrated
photovoltaic (BIPV). BIPV have been developed to incorporate
energy-efficient structures into building fronts and facades and
are produced by encapsulating and alternating with transparent
resin solar cells between glass sheets. In this way is producing elec-
tricity and is reduced solar heat gain while still allowing daylight
to enter the building. Because of their large thermal inertia, glasses
are used in other forms to rapidly capture solar energy and to
release them slowly: hollow glass beads, glass wool, etc. The inte-
gration of inorganic synthetic methods with a size reduction to the
nanoscale has lead to the creation of a new class of optical report-
ers, called quantum dots. These semiconductor quantum dot nano-
crystals have emerged as an alternative to organic dyes and
 E. Axinte / Materials and Design 32 (2011) 1717–1732
Table 8
The engineering conditions for glasses in solar energy systems (adapted from [12]).
Desired Descriptors
properties
Optical properties  Maximum transparency over desired wavelength of
solar light (UV, IR)
 Reduced refractive index (for minimum reflection loss)
 Filtering non-desirable UV wavelengths
 No solarization effects
Mechanical  Minimum density at maximum strengths
properties  Improve fracture toughness
 Thermal expansion characteristics of system
Chemical  Maximized weathering resistance
properties
Manufacturing  Viscosities, thermal stabilities that complement specific
properties manufacturing process
fluorescent proteins and are brighter and more stable against
photobleaching than standard fluorescent indicators. Quantum
dots have tunable optical properties that have proved useful in a
wide range of applications from multiplexed analysis such as
detection of nucleic acids (DNA) and cell sorting and tracking to
most recently demonstrating promise for in vivo imaging and diag-
nostics [14]. By introducing quantum dots (crystalline, semicon-
ductor nanostructures, as CdSe/ZnS, which absorb light and emit
photons of lower frequencies) directly in transparent glass matrix
or in films incorporated by glass sheets are obtained solar collec-
tors that can be integrated in building facades.
4.1.2. Glasses and water purification
Solar-driven technologies make use of glass as substrates for
photocatalytic decontamination methods, and glass windows and
tubes enable the operation of both photocatalytic and desalination
systems for producing clean water. Photocatalysis using glass sub-
strates – the electrophoretic coating method – was used to deposit
titania onto glass substrates that had been coated with indium-
doped tin oxide to improve conductivity. The glass substrates were
found to have a significant advantage over other options due to
their transparency to UV-A light and their chemical stability. This
transparency allows for illumination from either side of the coating
and increases the surface area available for photocatalysis. Further
improvements in efficiency could be realized when glass sheets are
replaced by glass beads and fiberglass mesh to increase the active
surface areas of the photo-reactors.
Fig. 10. Double basin solar still for desalination (adapted and modified from [12]).
1725
Research, development and design challenges
Compositional control for trace transition metal contents
Nanocomposites, glasses and glass–ceramics with engineered transparencies
New materials for optically active substrates (infrared luminescence)
Stronger, ‘less brittle’ glasses and glass–ceramics
Thermal/chemical/mechanical treatments to improve strength and resistance at
environmental events (sand storms, etc.)
Improved resistance at corrosion to acid rains or environmental salinity
New manufacturing techniques for customized designs and compositions
4.1.3. Glass for water desalination and hydrogen production
Transparency to solar radiation is essential for solar collection
systems and thus solar stills generally consist of glass covers. The
glass covers also act as condensation surfaces and are usually
angled to aid in distillate collection. The most basic types of solar
stills are single and double basin (Fig. 10 – adapted and modified
from [12]).
In [13] authors describes the using of amorphous silicone car-
bide for construction of an photoelectrode for hydrogen production
(SiC:H) using the sun light. The simulation results which indicate
that a SiC:H as a photoelectrode in a photovoltaic (PV – SiC:H)
structure could lead to a efficiency of solar heat conversion greater
than 10% are also presented.
4.1.4. Glasses and wind energy
Glass fibers reinforced composites are commonly used for wind
turbines. The fatigue resistance of these composites is crucial for
the maintenance and reliability of turbine. That gives the opportu-
nity for designers to create new, ultra-high strength, high-modulus
glass compositions for these applications, including environmen-
tally friendly, boron-free glasses. In [15], authors made a compar-
ison at chemical attack for basalt and E-glass fibers, under a
complex chemical attack. Basalt and glass fibers were treated with
sodium hydroxide and hydrochloric acid solutions, respectively, for
different periods of time. Both the mass loss ratio and the strength
maintenance ratio of the fibers were examined after the treatment.
Some results, obtained under acid attack conditions are presented
in Figs. 11 and 12 (reproduced from [15] – ÓElsevier).
1726 E. Axinte / Materials and Design 32 (2011) 1717–1732
For the basalt fibers, the acid resistance was much better than
the alkali resistance. Nevertheless, for the glass fibers, the acid
resistance was nearly the same as the alkali resistance.
Technical report [16] proposes a hybrid glass–reinforced epoxy
composite as a good material for Passenger Car Bumper Beam. Envi-
ronmental constrains make the hybridization of synthetic with
agro-based structures become a reality in the near future. These
hybrids are designed for non-structural and semi-structural com-
ponents. Experimental setup from [16] is focused on a hybrid of ke-
naf/glass fiber to enhance the desired mechanical properties for car
bumper beams as automotive structural components with modi-
fied sheet molding compound (SMC). In this research, authors de-
velop a hybrid material using natural kenaf and synthetic glass
fiber as reinforcement. Kenaf is extracted from the bast of the an-
nual fast-growing plant named Hibiscus cannabinus. The main con-
stituents of kenaf are cellulose (45–57 wt.%), hemicelluloses
(21.5 wt.%), lignin (8–13 wt.%), and pectin (3–5 wt.%). E-glass fiber
has been extensively applied as a reinforcement in polymer com-
posite, and its good mechanical properties and low price are
important considerations. Epoxy is selected as the matrix for the
hybrid material. A specimen without any modifier is tested and
compared with a typical bumper beam material called glass mate-
rial thermoplastic (GMT). The results indicate that some mechani-
cal properties such as tensile strength, Young’s modulus, flexural
strength, and flexural modulus are similar to GMT, but impact
Fig. 11. Mass loss ratio-treating time behavior (acid treatment) (reproduced from
[14]).
Fig. 12. Strength maintenance ratio-treating time behavior (acid treatment)
(reproduced from [15]).
strength is still low and shows the potential for utilization of hy-
brid natural fiber in some car structural components such as bum-
per beams. The comparison charts (Fig. 13) show some mechanical
properties advantages (higher elasticity and tensile/flexural
strengths) and disadvantages (lower impact resistance and higher
mass density) of hybrid material vs the common bumper beam
material (GMT).
4.1.5. Glasses as immobilizers for nuclear wastes
A big challenge in nuclear-related industries is that the radioac-
tive wastes generated must be isolated and safely stored. Glass is
the material of choice for waste forms because it can be designed
with good chemical durability, good mechanical properties, and
superior radiation and thermal stability than other waste forms.
The vast compositional variability of glass makes it possible to
incorporate the many different nuclear waste compositions, and
glass forming and processing allow for easy, large-scale production
of waste forms. For these dangerous wastes, as immobilizers are
generally used the borosilicate glasses. Borosilicate glass is a
particular type of glass, known under the brand names Pyrex or
Kimax. It was first developed by German glassmaker Otto Schott
in the late 19th century and sold under the brand name ‘‘Duran’’
in 1893. After Corning Glass Works developed Pyrex in 1924, it be-
came a synonym for borosilicate glass in the English-speaking
world [17]. Borosilicate glass is the oldest type of glass to have
appreciable resistance to thermal impact and higher temperatures
and also has excellent resistance to chemical attack. In this glass
structure, a little of the SiO2 is replaced by boric oxide B2O3 (13%).
Typical algorithm process in vitrification facilities for radioac-
tive wastes is shortly presented below: radioactive elements are
separated from the waste stream, mixed with a borosilicate glass
frit, and melted at 1200 °C; the molten waste glass is cast into
large stainless steel canisters (approximately 1500 kg each); the
canisters are decontaminated, welded shut, and stored at the vitri-
fication facility; the canisters are moved to geological repositories
[18]. Recent, the iron phosphate glasses are investigated as alterna-
tive for nuclear waste immobilizers and are considered a ‘‘high pri-
ority for US Department of Energy – DOE’’ [19]. Studies revealed
that iron phosphate glasses have excellent chemical durability,
and some compositions have corrosion rates 1000 times lower
than borosilicate waste glass.
4.1.6. Glasses as energy storage systems
The possibilities to engineer and fabricate a material with a par-
ticular set of thermal, electrical, and chemical properties, into a
strictly defined geometry, make from glass a crucial material to en-
able these technologies for energy storage.
Glasses play important roles in smaller power supplies, includ-
ing dielectrics for super-capacitors, electrolytes for electrochemical
devices, and sealants for high-temperature solid oxide fuel cells
(SOFC). In [20], glass–ceramic sealants free from barium oxide
(BaO) and sodium oxide (Na2O) have been designed and investi-
gated in the crystallization field of diopside (CaMgSi2O6). Further,
the influence of Bi2O3 (different amounts 1, 3 and 5 wt.%) addition
on the flow properties, sintering, and crystallization behavior along
with electrical conductivity and long-term thermal stability of
sealants has been investigated. The investigated glass–ceramic
compositions were highly effective in performing metal-to-metal
sealing with smooth interface and negligible interfacial reactions,
thus proving them to be potential sealants for applications in SOFC.
The amount of amorphous character in the glass–ceramics in-
creases during prolonged heat treatments at SOFC operating tem-
peratures, which can be beneficial to provide self-healing ability
to the sealant.
Glass–ceramics are suitable for use in super-capacitors, and
some glasses are investigated as solid electrolytes in lithium
 E. Axinte / Materials and Design 32 (2011) 1717–1732
Fig. 13. Comparison charts of mechanical properties GMT vs Hybrid (adapted from [16]).
batteries. A recent study of controlled crystallization of lithium
aluminum silicate (LAS) glass–ceramic shows that with the opti-
mum nucleating agents (2%ZrO2 + 2.36%TiO2), LAS glass–ceramics
with fine grain, high transparency and good mechanical properties
were obtained, due to the b-quartz solid solution formed after the
crystallization process [21]. A simple and low cost manufacturing
technique for obtaining the glass–ceramic matrix composites is
described as follows [22]: sintering with simultaneous crystalliza-
tion of fine glass powders allowed the preparation of dense
glass–ceramics based on unusual feldspar crystals, at a very low
temperature (750 °C) and with limited processing times. Al2O3
platelets were added to the glass powders. The observed effects
are improvement in bending strength (exceeding 100 MPa),
microhardness (approaching 9 GPa), and fracture toughness – even
for limited concentrations (which varied from 5 to 15 vol.%). The
elastic modulus and coefficients of thermal expansion (CTE) are
major contributors to the stresses that can lead to cracking of the
seal. The model presented by Milhans et al. [23] is useful for
designers of glass–ceramic SOFC seal materials : the effective elas-
tic properties and CTE of a glass–ceramic were predicted using
homogenization techniques. Using G18 (a glass–ceramic SOFC
sealant) as an initial reference material, the effectiveness of differ-
ent homogenization models was investigated for a two-phase
glass–ceramic. The predictive model offers accurate macroscopic
values on both the elastic modulus and the CTE of glass–ceramic
materials, provided the estimated amorphous values are
reasonable.
Hollow glass bubble technology was developed by 3M in the
1960s, and today this material is used in aerospace and military
systems, paints and coatings, marine hulls, oil and gas exploration
and production and other industrial uses. Glass bubbles are made
from a chemically stable soda–lime borosilicate glass and pro-
duced in a range of properties, including nominal diameters from
9 lm to 70 lm, densities from 0.15 to 0.60 g/cm3, and compressive
strength ratings from 1.7 MPa to 20 MPa. Resin compounder Noble
Polymers (Grand Rapids, Michigan, subsidiary of Cascade Engineer-
ing) has developed a low-density polyolefin resin formulation that
reduces the weight of thermal plastic olefin (TPO) parts by up to
twenty percent. This masterbatch bulk resin additive incorporates
hollow glass bubbles from 3M Company to displace resin and re-
duce part density in injection molded, thermoformed, and ex-
truded thermoplastic parts.
Recently, hollow glass micro-spheres (HGMS) are considerate as
a viable alternative for hydrogen storage [12]. Some advantages for
using HGMS as hydrogen storage and transportation containers are
(a) the materials are cheap and most of the batch consists of recy-
cled cullet; (b) the micro-spheres are non-explosive and each indi-
1727
vidual sphere contains a small volume of hydrogen to be hazardous
if the sphere break; (c) HGMS are strong due to their small size and
are able to contain hydrogen at high pressures – up to 100 MPa; (d)
no additional transportation vessel is needed, so they serve as
lightweight containers for relatively high hydrogen mass density;
(e) HGMS are reusable and recyclable. For loading with hydrogen,
the glass spheres (produced by different methods, as flame spray
pyrolysis of glass frit) are inserted into a high-pressure hydrogen
environment and are heated enough for diffusion of hydrogen into
spheres. The loaded spheres are extracted from hydrogen environ-
ment and cooled at ambient temperature.
4.2. Advances in bulk metallic glasses (BMG) design and manufacture
Metallic glasses exhibit unique softening behavior above their
glass transition, and this softening has been increasingly explored
for thermoplastic forming of metallic glasses. Metallic glasses can
be patterned on extremely small-length scales ranging from
10 nm to millimeters. It is possible that this may solve the prob-
lems of nanoimprint lithography where nanomolds made of silicon
break easily. Nanomolds made from metallic glasses are easy to
fabricate and more durable than silicon molds [24]. The process
of making nanoscale devices by simple stamping or molding may
revolutionize the manufacture of nanodevices from computer
memory to biomedical sensors.
Metallic glass (Ti40Cu36Pd14Zr10) is considered non-carcino-
genic, is about three times stronger than titanium, and its Young’s
Modulus matches bones. It has a high wear resistance and does not
produce abrasion powder. The alloy (Mg60Zn35Ca5) rapidly cooled
to achieve amorphous structure (BMG) is being investigated as a
biomaterial for implantation into bones as screws, pins, or plates,
to fix fractures [25].
The first reported metallic glass was an alloy (Au75Si25) pro-
duced at Caltech by Klement Jr., Willens, and Duwez in 1960. This
and other early glass-forming alloys had to be cooled extremely
rapidly (on the order of 1  106 K/s) to avoid crystallization. An
important consequence of this was that metallic glasses could only
be produced in a limited number of forms (typically ribbons, foils,
or wires) in which one dimension was small so that heat could be
extracted quickly enough to achieve the necessary cooling rate. As
a result, metallic glass specimens (with a few exceptions) were
limited to thicknesses of less than 100 lm. Bulk metallic glasses
have been paid great attentions for its theoretical and practical rea-
sons since the bulk amorphous Pd–Cu–Si and Pd–Ni–P alloys was
first synthesized by water quenching method in 1974.
Ref. [26] describes how copper was inserted into hard magnetic
bulk metallic glass Nd–Fe–Al alloys. The effects on the magnetic
1728 E. Axinte / Materials and Design 32 (2011) 1717–1732
properties and glass-forming ability (GFA) were assessed using
vibrating sample magnetometer and thermal expansion method.
The as-cast alloys exhibited higher GFA ability and hard magnetic
properties at room temperature. The enhancement of GFA is attrib-
uted to more negative mixing heat between Cu and Nd, and
accordingly, less crystallite and more Fe-rich clusters result in
higher coercivity up to 313 kA/m. Adding more Cu, however, will
cause an abrupt reduction in coercivity for the precipitation of soft
magnetic and non-magnetic crystalline phase.
The effects of alloy addition on the glass-forming ability, ther-
mal stability, and mechanical properties of Mg–Cu–Tb-based bulk
metallic glasses were investigated in [27]. The Mg-based BMG have
received intensive attention due to their high specific strength and
relatively low cost. Mg–Cu-based BMG could be fabricated by con-
ventional copper mold casting method in air atmosphere without
obviously decreasing the GFA. These BMGs exhibit higher specific
strength comparing to their crystalline counterparts. In [27],
authors investigated the effects of alloy additions on the GFA and
mechanical properties of a typical glass-forming composition,
Mg65Cu25Tb10, which approaches the ideal brittle behavior associ-
ated with silicate glasses The authors demonstrate that appropri-
ate additions of Ag, Zn or Be in Mg65Cu25Tb10 could not only
improve the glass-forming ability but also enhance the strength
and plasticity of these amorphous metallic alloys within a certain
composition range.
Zirconium-based metallic glasses (Zr-based BMG) present good
mechanical properties that combines the high fracture stress, elas-
tic strain (up to 2%), significant fracture toughness, and good corro-
sion resistance. In [28] is studied the influence of aluminum
content on the GFA and on the mechanical properties of the
Zr–Ni–Cu–Ti alloys. Multicomponent Zr75 xAlxNi10Cu10Ti5
(x = 15–20 at.%) alloys were produced by melt spinning method
obtaining ribbons, and by casting technique into a copper mold,
manufacturing rod-shaped samples with a maximum diameter of
2 mm. Supercooled liquid region depends on chemical composition
and exceeds 45 °C. Vickers microhardness of studied alloys is
comparable to the highest ones for other Zr-based BMG.
The glass-forming ability (GFA) is one of the most important
factors in the study of metallic glasses. No standard definition
has been made for this parameter up to now, and many indicators
have been developed. A review of advances in characterization of
GFA is given by Bing et al. [29]. In this work, four types of criteria
for the glass-forming ability are categorized and reviewed: (1)
indicators with characteristic temperatures; (2) indicators involv-
ing structural factors; (3) indicators based on Miedema’s model;
and (4) indictors based on phase diagram. Authors underline that
a single indicator cannot be used to predict GFA of all the metallic
Fig. 14. The illustration of abrasive waterjet turning.
glass systems. Some techniques as CALPHAD predict and describe
well the glass-forming and new glass-forming composition regions
in some multicomponent alloy systems. The authors final conclu-
sion are that the formation of metallic glass is a non-equilibrium
process, and studies in view of equilibrium theories may lead to
incorrect results and that is a long way to develop proper indica-
tors for GFA, which are theoretically strict and composed of very
simple and fundamental parameters.
4.3. Advanced techniques of manufacturing for glass and glass–
ceramics
Sometimes, glass pieces require some supplementary opera-
tions as drilling, cutting, grinding, and stamping for meeting their
functional or aesthetic role.
The mechanical and physical properties of glasses (especially
brittleness and low ductility) make them very difficult or impossi-
ble to manufacture them by conventional mechanical processes.
Drilling of holes in glasses is possible to non-tempered glasses
and ceramics. The glass bits have a spade-shaped point and are
made of tungsten carbide to withstand the friction of drilling in
glass. Diamond drillers are also used for holes with diameter smal-
ler that 10 mm.
Conventional glass cutting is done by scoring and breaking
which produces micro-cracks and splinters and leaves cutting oil
residues. These influences lead to lowered strength and pollution
of the glass sheets. If the glass has to be tempered, further grinding,
polishing, and washing processes are needed.
Cutting still remains one of the most common operations for
glasses. Old-fashioned hand-cut glass remains indispensable for
any glass-processing workshop but today’s technologies allow us
to cut glass with machines.
Waterjet cutting technology can be described as a controlled
accelerated erosion process. This system consists of high-pressure
water, mixed with abrasives, that passes through a gauge orifice at
three times the speed of sound. Such pressure produces a pure
working power able to cut any shape of glass or other materials.
In comparison with the traditional diamond cutting system, it
has the following advantages: flexibility, high accuracy, works on
any material, low cost, lack of heat generation. Short communica-
tion [30] reports a particular application of abrasive waterjet (AVJ)
turning that proved its technological and economical capability, i.e.
profiling and dressing of grinding wheels with ceramic bonds. The
schematic process and the experimental setup and is described by
Fig. 14 (adapted from [30]).
The results are very suggestive illustrated by Fig. 15. This tech-
nology seems to be attractive for those manufacturing sectors for
 E. Axinte / Materials and Design 32 (2011) 1717–1732
Fig. 15. Some results of waterjet turning.
roughing and semi-finishing off-the-shelf grinding wheels for the
production lines that require mass utilization of specially profiled
grinding wheels.
Laser cutting of flat glass is a subject of a handful of specialists.
In practice use for daily production, today there are approximately
50 installations for flat glass laser cutting worldwide and the same
number in research laboratories. The main problem is that the
Fig. 16. Laser-induced scoring by tension – schematic method (from [31]).
Fig. 17. Microscopic views of brut (a) and finished (b) ceramic surfaces (from [32]).
1729
glass tolerates only a certain amount of energy per square per time.
If this value is too large, the glass breaks or gets a grainy structure
in the heated zone. To meet this requirements, many patents are
known, all of them try, by forming a special laser spot, to optimize
the energy placement. The invention called LiST (laser-induced
scoring by tension – Grenzebach Maschinenbau GmbH) has to con-
trol not only the laser energy and spot size but also its timing in a
way that more heat on the glass surface can flow to deeper areas
into the glass, where finally a multiplicative energy rate can create
many times higher tension in the glass (see Fig. 16 – from [31]).
The technical limit in cutting speed is the mechanical possibility
to move a small cooling head along the score trace. There is an eco-
nomical limit too: double speed requires double laser power,
which is very expensive to buy.
Development of advanced ceramics has gained significant
importance because of their desirable properties. Their engineering
applications are still limited owing to the limitations in developing
optimized (minimum damages, high rate of material removal, min-
imum roughness, etc.) machining techniques.
In [32], a cylinder from magnesium–silicon-vitrified ceramic
(Steatite 63–63 HRC with initial surface roughness Ra = 3.25 lm)
was plunge grinded with a ceramic bonded abrasive wheel (66A
16K 5 V217 – pink Al2O3). At constant work piece velocity
(vw = 14 m/min) and constant plunge feed (ft = 0.03 mm/min), dif-
ferent cutting speeds were used (vd = 30; 50 and 70 m/s). Good re-
sults was revealed at cutting speed 70 m/s by obtaining a final
surface roughness Ra = 0.8 lm and a finished surface as in Fig. 17b.
Experimental study [33] investigates the grinding characteris-
tics and surface and subsurface integrity of ground silicon carbide
1730 E. Axinte / Materials and Design 32 (2011) 1717–1732
to explore the material removal and damage formation mecha-
nisms involved during high removal rate grinding. The experimen-
tal investigations revealed that an increase in material removal
rate did not affect surface finish and surface morphology.
Imprinting technology is an ancient technique for the reproduc-
tion of writings on appropriate supports. Since 1990s, one of the
imprinting techniques, i.e., injection molding, has been used for
compact disk (CD) production. More recently, the semiconductor
industry is interested in imprint related techniques because of
the mass production requirement of future microelectronic circuits
with a possible critical dimension down to a few nanometers [33].
Up to now, the process has found its way into scientific research
domains and production lines in micro-optics (Fig. 18) and into
prototyping for nanophotonics and biotechnology and is also ex-
pected to have additional impact in fabrication of memory devices
and in display technology.
Nanoimprint lithography (NIL) was introduced in 1995 by
Stephen Chou. He demonstrated results from an experiment where
a laboratory press was used to press together a patterned stamp,
made from a SiO2-coated Si-wafer, with a silicon substrate coated
with a thermoplastic polymer [34]. The NIL process is described
Fig. 18. 300-mm soft stamp replicated lens wafer and 200-mm stacked wafer level
camera module (from [33]).
Fig. 19. The thermal nanoimprint lithography (adapted from [33]).
very well by Fig. 19 (adapted from [35]). It is based on the use of
thermoplastic polymer spin coated on the substrate. The thermo-
plastic polymer is heated above the glass transition point of the
polymer, and the heated template is brought into contact with
the polymer. Once the polymer has filled all the cavities of the tem-
plate, the substrate and the template are cooled down and the tem-
plate is separated from the substrate. A negative replica of the
template is created on the polymer. In order to use imprinted poly-
mer for pattern transfer to other layers on the substrate, polymer
left on the indented areas has to be removed. Because the flow of
the polymers is not free of resistance, a residual layer appears
(Fig. 19d).
5. Conclusions and strategic lines in glass development
Glass as a material will always exist, but many new applications
and manufacturing processes will involve glass in combination
with other materials. Optical fibers are currently manufactured
with one or more different coating, which are often plastics. With
the increasing sophistication of optoelectronic devices, there is an
increasing need to combine optical and electronic devices for many
applications such as transmission of audio, video, and data infor-
mation. Glasses and ceramics (stand-alone or composite with other
Fig. 20. Foil of flexible ceramic ZircoFlex™.
 E. Axinte / Materials and Design 32 (2011) 1717–1732 1731

Table 9
Criteria for material selection.

Criteria
1 Supply property (depletion time, years)
2 Recycled supply property (% of recycled material used)
3 Embedded energy property, MJ/kg of material
4 Environmental impact property, scorecard hazard rating
5 Legal property (legal restrictions)
6 Longevity (grade of degradation in environment)
7 Recyclable property (% material recyclable)
8 Social and political property
Ratings
A < 25; B – 25 to 50; C – 51 to 100; D > 100
A – 100; B – >50; C – 25 to 50; D < 25
A < 50; B – 50 to 99; C – 100 to 200; D > 200
A < 25; B – 25 to 50; C – 51 to 75; D > 75
A – no problems; B – minor problems; C – serious legal problems; D – under severe legal restriction
A – quickly degrades; D – unlimited lifetime
A – 100; B – 50 to 100; C < 50; D = 0
A – no social or political problems; D – social malign; political restrictions

materials) will find increasing application in biological and medical
areas. Materials such as photochromic, electrochromic, and ther-
mochromic glasses, which respond to external stimuli, are being
developed with various, sometimes unusual, applications. Revolu-
tionary materials, as the flexible ceramic heat shield material (Zir-
coFlex), are recently developed and fabricated by using a new
technology in which the ceramic material is sprayed in the form
of thousands of individual ‘platelets’ onto the surface of the alumi-
num backing foil (see Fig. 20). Early applications for ZircoFlex™ foil
are coming from the automotive industry, where the foil can be
used to protect sensitive components from heat in increasingly
crowded engine bays.
Al Gore (former US vice president) became the publicly recog-
nizable face of the environmental issue after his Oscar-winning
documentary movie An Inconvenient Truth (2006). This documen-
tary helped enormous to make the issue of global warming a recog-
nized problem worldwide. By winning of Nobel Peace Prize in 2007,
Al Gore brought once more to the forefront the problem of global
warming. The first impact on glass industry was produced by
switching on large scale to compact fluorescent light bulbs (by
the replacing of incandescent bulbs 4200 + tons of carbon were off-
set). Glass industry has successfully reacted to environmental
issues by offering a variety of applications to make buildings more
energy efficient and ecologically friendly. Today’s glass can be prac-
tically custom-made to fit into any environmental conditions and
offer specific appearances and performance. The latest develop-
ment in the industry has been the introduction of self-cleaning
glass. While progress in the glass industry continues, we can expect
glass in the near future that will react to external stimuli, the so-
called ‘‘smart glasses’’, offering maximum comfort and excellent
energy efficiency inside buildings. Some glass applications also
use alternative natural resources to preserve the environment in
which we live. Some states have begun to regulate or even stimu-
late the introduction of such energy-preserving applications [36].
The modern glass industry have a huge contribution through
development and the introduction of new energy-efficient glass
products and applications, some issues in glass manufacturing
and processing still must be addressed in the future.
A great challenge for the actual and the future glass industry is
to increase the contribution to environment preservation. Accord-
ing to the criteria of environment-friendly selection of materials
(Table 9 [37]), the weakness of glass is the ‘‘embedded energy’’.
The embedded energy for glass mass unit can be rated at D
(>200), the worst as possible.
The challenge for researchers and glass industry is to act for sig-
nificant decreasing of embedded energy in glass mass unit. There
are two possible ways to solve this desiderate: (a) continuous
developing of high-efficiency furnaces; (b) continuously develop-
ing of new glass compositions, with lower glass transition temper-
atures. The synergetic effect of simultaneous applying of both ways
could offer a good future for glass industry. Most recent tendencies
are to use the green energy (wind and solar) in producing and
manufacturing of glasses.
The modern glass industry must increase contribution through
development and the introduction of new energy-efficient glass
products and applications, some issues in glass manufacturing
and processing still must be addressed in the future.
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