New eco-compatible materials obtained from

WEEE glass
Fernanda Andreola, Luisa Barbieri, Davide Giuranna, Isabella Lancellotti

Dipartimento di Ingegneria ”Enzo Ferrari”

Università di Modena e Reggio Emilia

Executive Summary

Waste Electrical and Electronic Equipment (WEEE) is an emerging problem as well as a business
opportunity of increasing significance, given the volume of electronic waste being generated and
the content of both toxic and valuable material in it. Although after treatment in dedicated plants it
is downgraded to non-hazardous waste, there are problems in the recycling of waste glass.
In order to understand the importance of the problem, only in Italy 260 thousand tons were
collected during the 2010 [1].
WEEE are regulated by specific legislation (WEEE/ RoHS in Europe). This waste category is
classified in different groups, among which R3 Group (TVs and monitors) and R5 Group (light
sources) emerge. In particular, for these categories the Italian collection is about 85,000 tons in
2010.
The Cathode Ray Tube (CRT) glass can not be treated in the same way as cullet glass, as it is
composed by different types of glass with different composition, mainly screen (Ba, Sr) and cone
(Pb). The consolidation of the market of flat screen TV, even in emerging countries, caused a
significant contraction of demand, hence difficulties in recovering and recycling of these materials
and the need to experiment new ways of using them, alternative to landfill. It is important to
underline that of the 80,000 tons of old TVs collected last year in Italy, 98% is constituted by CRT
formed by 85% glass.
In this study are reported some interesting results reached by substituting significant amounts of raw
materials with WEEE glass in order to obtain products for ceramic sector. The laboratory and
industrial scale up results demonstrated that it is possible to produce a glazed tile with a glaze
containing 40wt% of fluorescent lamps glass instead of commercial ceramic frits. Besides, this
category of glass was used to obtain foam glass by a simple and economic processing, consisting of
a direct heating at relatively low temperatures (700-800 ºC) of a mix composed by glass powders
(95wt%) with egg shell (5wt%) as foaming agent.
New clay based ceramics containing up to 10 wt% of CRT panel glass, replacing completely both
fluxing and inert components were obtained. Samples tiles present technological properties
comparable to tiles used mainly for floor or wall covering. Laboratory studies demonstrated that
bricks containing up to 20wt% of a CRT glasses mix show lower water absorption and drying
shrinkage and similar compressive strength compared to the brick without glass.

Introduction

The current scenario of waste management in the light of European Directive 2008/98, has led to a
reinforcement of the principles of producer responsibility and a real implementation of the
hierarchy based primarily on waste prevention, followed by preparation for reuse, recycling and
recovery (energy and/or matter) and finally safe disposal for waste that have no other treatment
options.
Waste Electrical and Electronic Equipment (WEEE) describes loosely discarded, surplus, obsolete,
broken, i.e. end of life, electrical or electronic devices. Rapid technology change, low initial cost,
and short operative life have resulted in a fast-growing surplus of electronic waste around the
globe: in Europe it constitutes the fastest growing waste stream (3 - 5% per year). The WEEE
collection per capita is very different as a function of the EU state considered: from maximum
value for Nordic countries (10-16 kg / inhabitant) to minimum one for other countries as Italy,
Germany, France and UK (4-8 kg / inhabitant) [2].
Given the importance of this waste category, it has a specific legislation. The European
Commission adopted two directives: 2002/95/EC on restrictions of certain hazardous substances
used in electrical and electronic equipment (RoHS); 2002/96/EC and 2003/108/EC on WEEE
disposal.
WEEE glasses are the most representative residues in Italy (about 15 to 16 thousand tons /year) and
the main sources of these glasses are R3 Group (TVs and PC monitors) and R5 Group (light
sources). In particular, Televisions and monitors that are based on CRT technology are increasingly
(over 30% of its share) being replaced by flat-screen TVs that use LCD (liquid crystal display) or
LPD (liquid plasma display) resulting in an increasing amount of CRTs in the waste stream. In fact,
of the 80,000 tons of old TVs collected, 98% are CRTs formed by 85 wt% of glass.
Regarding end of life (EOL) fluorescent lamps, this category is expanding rapidly, taking into
account European regulation that requires gradually switching to low energy light sources until
2012 (fluorescent lamps, consisting of over 90% of glass). The Italian collection increased from 160
tons in 2008 to nearly 1,000 ton in 2010.
In Italy the creation of e-waste collection and treatment centres gives the opportunity to have
cleaned material useful for an open-loop recycling. Although after treatment in dedicated plants, it
is downgraded to not-hazardous waste, there are problems in the recycling WEEE glass. In fact, the
CRT glass can not be treated in the same way as cullet glass, as it is composed by different types of
glass with different composition. A CRT unit is divided in a) the viewing section (known as screen,
panel or face plate) is made of glass typically containing a significant level of barium and strontium
oxides (up to 10 %) but no lead oxide; b) the funnel section (the hidden CRT part) contains up to
25% lead oxide; c) the neck section, housing the electron gun, is up to 40% lead oxide. The three
glass components are joined together using a low melting temperature solder glass that also
contains high levels of lead oxide (up to 60%). In addition to the glass, there are other materials to
be separated and recycled including ferrous and non ferrous metals, coatings (typically a mixture
phosphors and aluminium oxides, go to disposal) to the screen and funnel sections, and plastic
housing casings.
A typical fluorescent lamp is composed by a glass tube phosphor coated by different blends of
metallic and rare-earth phosphor salts with electrodes located at both ends of the tube. Light tubes
are generally made by a soft sodium calcium glass whereas the materials on the ends which are
connected to the light cap are made of hard glass with higher lead content. The EOL lamps are
classified among the WEEE which contain dangerous substances. The principal environmental
hazard associated with these lamps is the small mercury content (normally less than 5 mg in
accordance with RoHS Directive). The mercury will be slowly absorbed into the glass, phosphor
powder and tube electrodes throughout the lamps life. Mercury will therefore be unevenly
distributed throughout the lamp but with most found in the phosphor powder (>90%). The disposal
of phosphors and particularly the toxic mercury in the tubes is an environmental issue. European
regulations require special disposal of fluorescent lamps separated from general and household
wastes. For large commercial or industrial users of fluorescent lights, recycling services are
available in many countries. In Italy CRUSH & SIEVE technology is adopted where the fluorescent
tubes are crushed. The crushed materials are separated into glass, metal and powder. In particular
fluorescent powder is treated by distillation (∼600°C) in order to separate the mercury fraction.
After reclaiming process the glass resulting is considered no hazardous waste (CER 19 12 05) and
can be used as an alternative raw material.
Discussion

EOL Fluorescent lamps glass as alternative raw material

1- Ceramic engobe and glaze
EOL (end of life) fluorescent lamps glass was used in order to tailor in laboratory scale
compositions of ceramic engobes as substitute to industrial frits. An engobe is a thin layer of fluid
clay based applied to a ceramic support in order to improve both the aesthetical and technical
properties.
As stated above, this glass is a typical sodium (∼16wt%)-calcium (∼5wt%) silicate glass and shows
a tendency to not crystallize with a low melting nature, confirmed by low softening and transition
temperatures (respectively Ts: 567°C, Tg: ∼500°C) and high thermal expansion coefficient (α=9.7
10-6 *°C-1). These characteristics are similar to some industrial frits with high expansion coefficient,
so the recovery of this e-waste glass into engobes formulations was tested. Before the addition it
was necessary to carried out a pre-treatment of the glass by sieving in order to separate pollutants
such as bakelite, insulators, metallic conductors (5-6%). Engobe compositions were prepared using
three glass fractions: as-received (VS), fraction above 1mm and hand cleaned (VL), residue fraction
below 1mm without hand cleaned (VR). Besides, with the aim to compensate the absence into the
glass composition, zircon (ZrSiO4) was added in different percentages - VL1(10wt%), VL2(5wt%),
VL3(3wt%) - to improve the material brightness. From these considerations we can assume that the
substitution of EOL lamp glass does not affect the final engobe particle size distribution and it will
not cause changes on the related parameters (already industrially optimized) such as: fluency during
application, porosity, drying time, etc. Thermal results have shown that the formulation containing
e-waste glass has a more refractory behaviour in firing (∆T=60°C) because the zircon added is not
chemically bonded in the frit. In Table 1 are reported the results of CIELab parameters calculated
by the Hunter method [3]. The colorimetric measurements evidenced that on the glazed final
products, the presence of e-waste glass causes a slight decrease of the L* value (VL sample); this
worsening is overcome by the addition of 5% of zircon which brings values closer to the standard
(VL2). Another subject evaluated by L* values is the cleanliness effect of the glass; the data
evidenced that as the purity degree decreases with L* decreases (VR2). The derived ∆E* parameter
indicates the shift with respect to the standard, being considering ∆E * values lower than 1 within
the industrial tolerance. ∆E * values for VR2 sample indicates that it is not possible to use the glass
without a previous cleaning treatment.
Starting from this laboratory screening, the research has been extended to industrial scale in
collaboration with a ceramic company, originating a glazed porcelain stoneware tile which uses a
glaze containing 40 wt% of e-waste glass. The developed technology, called Relux, consists in the
production of innovative tiles with reduced environmental impact by implementing an
environmentally ethical management system and allows to recycle one EOL fluorescent lamp for 1
m2 of glazed tile. Since 2007, when began the production, up to the end of 2011, 655,000 m2 of this
commercial ecological product were produced. Relux technology has been applied to improve
environmental performance in five key areas: reducing the use of raw materials, reducing transport,
reducing energy consumption, recycling high-quality materials and reducing waste processing.

Table 1- Colorimetric parameters for the different engobe compositions after glazing and firing compared to the
standard one. L* (lightness), a* (+a: expresses red;-a: expresses green), b* (+b: expresses yellow;-b: expresses blue),
ΔE* ( tolerance).

SAMPLE L* a* b* ∆E*
STD 92,37 0,05 2,45 0
VL 91,55 - 0,04 2,15 0,87
 VL2 92,27 - 0,28 1,78 0,75
VR2 89,98 0,19 1,77 2,48

2 - Glass foams
The glass foams are cellular materials constituted by voids of variable size obtained by sintering of
glass powder in the presence of a foaming agent. The particular properties of these materials are
low density (0.1-0.3 g cm-3) and high porosity (85-95%), typical of commercial foam glass products
[4].
In this study is reported the effect of glass from EOL fluorescent lamps to produce foam glass.
Various mixtures of glass powder and different kinds of foaming agent were prepared. The glass
obtained by dismantled of fluorescent lamps (V) were milled in the range about 75-100 µm.
Foaming agents used were a traditional CaCO3 (C) and the study proposes to evaluate also the
replacement of this with egg shell (E), composed of 95% calcium carbonate. These materials were
dry ball milled to obtain similar particular size distribution of glass powder. In this study were
tested two mixtures varying the foaming agent added: V95C5 (95wt% glass, 5wt% CaCO3) and
V95C2.5E2.5 (95wt% glass, 2.5 wt% CaCO3, 2.5wt% egg shell). The samples were obtained by
pressing at 40 MPa in a cylindrical steel die. The obtained samples were dried at 110°C for two
hours, then subjected to heat treatment at 700°C for 45 minutes in order to evaluate the effect of
waste glass on the materials properties. The glass foams obtained were characterized by measuring
of apparent and absolute density by picnometry and compressive strength by Instronn machine.
Besides, the porosity was calculated using the formula (1).

(1)

Table 2 shows the results obtained with thermal cycles at 700°C for 45 minutes.

Table 2 - Physical and mechanical properties of the foam glass obtained.

700°C Apparent density Absolute density Porosity (%) Compressive

45 minutes (g/cm3) (g/cm3) strength (MPa)
V95C5 0.37 2.47 85.0 2.69 ± 0.66
V95C2.5E2.5 0.31 2.44 87.3 2.69 ± 0.58

In Table 2 it is possible to note that the values reported are comparable with those of typical
commercial foam glass [4]. Also the property values are in agreement with other studies conducted
using CRT glass with CaCO3 as foaming agent [5], CRT glass with egg shell as foaming agent [6]
and cullet glass and fly ash with CaCO3 [7].
The images obtained by SEM microanalysis shows the high porosity which justified the low
density. As verified in other researches for glass foams obtained by conventional heating, small
pores are present within the walls and large pores into the structure, which are both responsible of
mechanical properties decrease [4,5]. From the SEM analysis it is possible to confirm that the two
glass foams obtained shown similar microstructure.
Besides, this study demonstrated that glass foams obtained with CaCO3 and egg shell (V95C2.5E2.5)
present both similar density and mechanical strength compared to the foam glass with only calcium
carbonate as foaming agent. This is a very important aspect of environmental sustainability. The use
of waste glass and the possibility to obtain a 100% recycled material, with complete replacement of
foaming agent, allows to reach a considerable saving on the cost of virgin raw materials. Besides,
the use of this kind of glass (low melting Tg≅ 500°C ) consents to decrease the firing temperature
with respect to other mixtures [7] and to achieve energy saving result.

CRT glass as alternative raw material

1- Tile bodies
In the last few years many researches addressed to the ceramics industry reporting the possibility to
use alternative raw materials replacing quartz or feldspar, in the manufacture of different ceramic
products. Interesting results were obtained by substituting the traditional fluxes by other raw
materials as zeolites [8], grate slag [9] and soda-lime waste glass [10,11]. This aspect acquires
particular importance due to the reduced availability of traditional quality fluxes. In fact, the
feldspar deposits, suitable for ceramic industry, are located in foreign countries (as Turkey), with
higher costs than the other raw materials (i.e. sands and clays).
The aim of the study was firstly to tailor new formulations using only ball clays and panel glass
replacing completely both feldspatic and inert components of a traditional ceramic body.
Successively the goal of the study was to verify the properties of the laboratory samples obtained by
fast firing industrial cycle (1200°C, 40 min) in agreement with UNI EN rules requirements. The use
of this kind of glass to formulate a new tile ceramic body derive from two factors: a) chemical
nature of glass (high amounts of alkaline and alkaline-earth oxides) along to the absence of
crystallization in the firing range; b) presence of a high amount of glassy phase in the sintered
ceramic products (60-70%). The mixtures glass-clays prepared and a commercial formulation were
fired in a roller kiln using a fast single firing cycle in order to better simulate the industrial
conditions. The linear shrinkage (LS%), water absorption (WA%) and other technological features
are reported in Table 3. The values obtained as a function of the panel glass content put out that
amount higher than 10wt% of panel glass has a negative effect on the body and it is responsible for
the overfiring at the studied temperature. Small amounts of glass in the mixture are necessary to
improve the densification process. The presence of glassy phase in higher quantities causes swelling
at the firing temperature (1200°C). It is possible to observe a low LS% at 20wt% of glass and an
increase of porosity (∼ 20%). For the traditional ceramics, the optimum firing range is achieved
when the open porosity is minimum (WA% nearly zero) and simultaneously the shrinkage reaches
the maximum value. The obtained tiles compared with commercial products (porcelain stoneware
tile), can be classified into BIa Group according to UNI EN 14411 (all.G) rule (BIa WA≤0.5%)
corresponding to impervious tiles used mainly for floor or wall covering. Regarding LS% the
presence of glass favoured the sintering process but the samples show LS values higher (9.5-10.5%)
than the industrial requirements (7.5-8.5%); this fact can cause calibration problems after firing. In
order to optimize the linear shrinkage, a reformulation of the raw materials content and type was
designed. In the new composition commercial sand was added with the aim to shift the shrinkage
values within the industrial tolerance range. When feldspar is simultaneously substituted by panel
glass and industrial sand, the percentages of formed closed porosity significantly decrease.
Table 3- Linear shrinkage (LS%), water absorption (WA%), apparent density (AD), bending strenght (BS) and open
(PO), close (PC) and total porosity (PT) of the sintered samples as a function of panel glass content compared with a
commercial product.

Sample 5 wt% glass 10 wt% glass 20 wt% glass Porcelain

stoneware tile
LS (%) 10.45± 0.01 9.40± 0.01 4.20± 0.01 7.80± 0.01
WA (%) 0.09 ± 0.01 0.05± 0.01 0.02± 0.01 0.04± 0.01
AD (g/cm3) 2.47 2.40 2.25 2.40
BS (MPa) 80.70 ± 4.07 60.71 ± 3.20 43.71 ± 5.49 53.59 ± 3.50
 PO (%) 1.604 3.090 4.834 2.802
PC (%) 4.034 6.224 14.399 5.037
PT (%) 5.637 9.780 19.234 7.840

The new samples containing lower amount of sand (10wt%) with respect to commercial
formulations (15-17wt%), showed satisfactory results for all rules requirements. Regarding
mechanical properties, bending strength (BS) is a characteristic parameter of each material with a
clear dependency on porosity and phase composition. The results show a decrease of the average
BS values as a function of the added amount of panel glass. It is possible to explain this behaviour
on the basis of the separate effect of open and closed porosity as above reported. However, all the
samples tested show values higher than >35 MPa as prescribed in the EN ISO 10545.4 rule for the
ceramic materials belonging to BIa group and >50 MPa generally associated to commercial
products.

2 - Brick bodies

Heavy clays ceramics as bricks, are being produced from natural raw materials with a very wide–
ranging overall chemical and mineralogical composition [12]. This fact represent a concrete
possibility to recycle different wastes in brick bodies thank the tolerance regard to technical
parameters greater than other productive typologies and the production cycle particularly simple.
In particular, many studies have shown than the use of waste glass in brick produces positive effect
on the properties of materials [13,14,15]. The purpose of this study was to investigate future
opportunities in the ceramic sector, in particular searching to improve the properties
of materials and reducing the use of virgin raw materials. This experience demonstrates that the use
of CRT glass in brick produces lower water absorption, lower drying shrinkage and similar
mechanical strength compared to the bricks without glass.
The CRT glass used is a mix of panel and funnel glass of old TVs or PCs monitor obtained after
their dismantled. Different mixtures were prepared in the laboratory by traditional procedure for the
production of brick: grinding raw materials, mixing and humidification, extrusion, drying and
firing. In order to evaluate the effect of CRT glass in the clay body, four mixtures were prepared
with increasing percentage of CRT glass added (M1, M2, M3, M4). The samples were firing at two
different temperatures: 800°C and 950°C for 172 minutes by roller kiln. Table 4 records the
main properties of dried samples and fired samples. The bricks with CRT glass were compared to
brick without glass (M0).
Table 4 - Main properties measured of laboratory's bricks.

SAMPLE 800°C 950°C

Modulus of Modulus of
Dry 24 h Water Dry 24 h Water
rupture rupture
shrinkage absorption shrinkage absorption
(MOR) (MOR)
(%) (%) (%) (%)
(kg/cm2) (kg/cm2)
M0 4.5 15.6 145.9 4.7 15.3 152.7
M1 5.1 16.1 101.4 5.0 15.3 111.1
M2 4.2 15.8 118.9 4.7 14.7 134.0
M3 3.8 15.5 118.7 4.5 14.5 143.6
M4 3.5 15.3 121.0 4.2 14.4 151.8
For all properties, there is a proportionality with the increase of the percentage of waste added. A
significant result is the reduction of shrinkage in drying which decreases progressively with
increasing glass in the mixture. This value decrease up to 1 percentage point less than brick without
glass. The brick firing at 950°C shows a lower water absorption than standard sample (M0). These
results are comparable with studies on CRT panel glass [13] and ground cullet glass [14].
Besides, the increase of firing temperature produces an increase of mechanical strength and these
values are similar to control sample. The firing temperature and the introduction of glass powder
affect on the vitrification of the bricks during the firing phase; the result of this has been a reduction
of water absorption and improve of mechanical strength.
This study demonstrates that is possible to use a mixture of CRT glass powder (panel and funnel)
milled at particle size greater than literature studies, in order to still achieve similar or better
properties than traditional bricks bodies without glass. The best mix obtained was reproduced on a
semi-industrial scale. The results of large scale trial firings shows significant results. In particular,
have been observed:
- no apparent defects of surface;
- same color of brick without glass;
- similar compressive strenght;
- drying shrinkage 1% less than traditional brick values.
The inertization degree of waste glasses was verified through a leaching test following the European
rule (UNI EN 12457-2: “Compliance test for leaching of granular waste materials and sludge”). The
elements searched were those indicated in the Italian regulation used to identify granulated and
monolithic residues for recovering (Decree No. 186, 05/04/2006, All.3). In particular, the
concentration of lead and barium, present in CRT glass, as well as other dangerous elements, were
always below limits of rule. These results are shown in Table 5.

Table 5 - Results of leaching test on the large scale sample.

Element Brick without Brick with glass Limits

glass (mg/l) (mg/l) Decree No. 186,
05/04/2006 (All.3)
Sr 0.185 0.345 -
Cu 0 0 50 µg/l
Pb 0 0 50 µg/l
Ba 0.04 0.105 1 mg/l
Al 4.68 2.365 -
Fe 0.01 0.007 -
Ca 160.2 202.8 -
Na 10.3 9.225 -
Mg 0.085 0.05 -
Si 2.52 1.98 -
Zr 0.14 0.025 -
Sulfates 0 3 250 mg/l
Chlorides 7 4 100 mg/l

This study has shown that the introduction of glass powder in clay’s mixture allows to obtain
measurable benefits and, simultaneously, environmental advantages such as saving of raw materials
and energy, inertization of waste and reduced environmental impact due to the extraction of clay.
An advantage of this study derive from the use of glass at high particle size, this is an important
aspect because the high cost of waste glass milling to a sufficient fineness can hamper its more
extensive use. At the conclusion of this study, an italian patent application was take out
(RE2011A000020 – 01/04/2011) by some authors of this paper [16].
Ackwnowledgements
The authors would like to thank Dr. Eng. E. Bernardo (University of Padova, Italy) for his
assistance on the mechanical tests on glass foams and Polis Ceramiche S.p.A (Bondeno di Gonzaga
(MN), Italy), Manfredini & Schianchi Srl (Sassuolo (MO), Italy), Dr. F. Moedinger and
Wienerberger S.p.A. (Mordano (BO), Italy) for laboratory or industrial supports.

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