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ARTICLE IN PRESS

Solar Energy Materials & Solar Cells 85 (2005) 205240

Environmental assessment of electrochromic


glazing production
E. Syrrakou, S. Papaefthimiou, P. Yianoulis*
Solar Energy Laboratory, Physics Department, University of Patras, Rion 26500, Greece
Received 29 October 2003; accepted 20 March 2004
Available online 28 July 2004

Abstract

The life cycle analysis method was used to determine the environmental impacts associated
with the production of an electrochromic (EC) glazing (called ECD). This paper describes the
inventory analysis for all the basic materials used during the manufacture of the ECD, i.e. K-
Glass, tungsten oxide (WO3), poly-methyl methacrylate (PMMA), propylene carbonate (PC),
lithium perchlorate (LiClO4) and acetic silicone sealant. K-Glass, PC and PMMA account for
the 98% of the total device mass and the CO2 emissions during their production processes are
810 g. The total embodied energy was estimated to be 49 MJ/ECD, with 32.1 MJ/unit of them
derived from the K-Glass. The comparison of the total embodied energies of the ECD and
various insulating glass units concluded that mass-produced EC glazings could easily compete
with them in terms of environmental performance, anticipating cost attenuation and overall
thermal and optical behavior. The above analysis could be implemented for the reduction of
the embodied energy of the ECD life cycle, since it is proposed as an energy saving device.
r 2004 Elsevier B.V. All rights reserved.

Keywords: Electrochromic glazing; Inventory analysis; Embodied energy; Environmental impacts

1. Introduction

1.1. Electrochromic windows state-of-the-art

Research for advanced glazing materials has focused so far to the realization of
systems that ensure acceptable visual transmittance, reduced glare and low thermal

*Corresponding author. Tel.: +30-61-997-449; fax: +30-61-997-472.


E-mail address: yianpan@physics.upatras.gr (P. Yianoulis).

0927-0248/$ - see front matter r 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2004.03.005
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losses. State-of-the-art systems incorporate double or multi-glazed windows with low


emittance coatings. Recent research has concentrated upon the application of
thermochromic lms, transparent insulation materials and the use of vacuum or
inert inll gases within appropriate double-glazed units.
Electronically tintable windows using electrochromic (EC) lms could offer a
remarkable alternative to advanced window technology. An EC window is an active
solar control device whose transmittance in the visible and near infrared (IR) part of
the spectrum can be reversibly modulated with the application of a low voltage
(typically 35 V DC). A typical electrochromic device (ECD) has a ve-layer
structure consisting of: (1) a transparent and electronically conductive lm deposited
on glass, (2) an EC lm (usually tungsten oxideWO3), (3) an ion conducting
electrolyte (either a polymer or a solid-state one), (4) an ion storage layer and (5) a
second transparent conductive lm. The devices using polymer electrolytes require
two glass sheets, one with the ITO/EC oxide and the other with the ITO/ion storage
layer. The polymer electrolyte serves as the laminating means that holds together the
two coated glass sheets. Devices using solid-state electrolytes require only one glass
substrate.
An EC window has several advantages compared to conventional shading and
solar control devices. It does not impede visibility through the window as with blinds
and curtains, while it provides glare control and thermal comfort management. It
has no moving parts and as a result, minimum maintenance costs. It requires low
voltage power supply (it can even be powered by photovoltaics) and it can be
integrated into the central power management of the building. It has practically
innite coloration stages and can block both direct and diffuse solar radiation,
unlike passive shading devices. Furthermore, it has a low energy consumption
(typically 8 W/m2), which is nearly zero when the glazing is kept at constant
conditions, due to the considerable open circuit memory it presents.1 An EC window
can outperform the best currently available window systems (in most applications)
and has lower annual energy performance than an opaque insulating wall [1]. The
primary energy benets are: reduced cooling, heating and ventilating loads and the
ability to reduce electric lighting use by managing daylight admittance. Last but not
least, the architectural and aesthetic appeal of a dynamic coating that the EC
technology offers is difcult to quantify but it will be a major factor for many
buildings. Many design decisions are made not on the basis of paybacks but rather
on the basis of style and appearance.

1.2. Economic aspects and cost estimates

The eld of architectural glazing is a highly competitive marketplace with an


estimated global size of 6 billion h/year [2]. EC glazing must be cost competitive in
order to meet the market expectations for solar control window products. Such
glazing could be easily retrot in existing buildings, thus creating further market
expansion that could increase the market size to 10 billion h/year. The price of high
1
Pilkington E-ControlTM, Product and Functional description.
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performance static solar control insulated glass units (IGUs) is about 80 h/m2, while
the corresponding value for the EC glazing is estimated at 1000 h/m2 [2]. The retail
price of Pilkington E-ControlTM, a combined EC-IGU product, was about 1080 h/
m2. Increased sales will require pricing to be much more aggressive. For signicant
market penetration to occur, EC glazing prices will need to be reduced by one order
of magnitude to around 100150 h/m2, which is less than prices for low-e IGUs
incorporating mechanical blind systems for light and energy control [2]. Meeting this
aggressive market-driven price can be achieved in the long term, by efcient in line,
large volume manufacturing [3].

1.3. Reduction of greenhouse gas emissions and energy savings

Greenhouse gas (GHG) emissions in the European Union (EU) were 4046 Tg in
1998. About 82% of EU GHG emissions are CO2 while CH3 and N2O emissions
amount to 9% each. CO2 emissions have been stabilized between 1990 and 1998 with
a 0.2% increase, while CH3 and N2O emissions have been reduced by 16.5% and
9.9%, respectively. However, actually achieving the Kyoto targets for 2012 will still
be difcult and require large efforts, as GHG emissions and energy consumption are
expected to grow in the next decade [4]. The adoption of new window technologies
has been estimated, by the year 2025, to provide the United Kingdom with an annual
saving in primary energy equivalent of about 0.2 million tonnes of coal with a CO2
saving of 5.2 million tonnes [5]. In the USA, with the adoption of the Green Seal
environmental standards for windows,2 it is estimated that 350 million barrels of oil
per year will be saved.
EC windows can reduce the peak electricity demand for cooling during summer
and heating during winter, thus contributing toward the further reduction of GHG
emissions. They can lead to the reduction of annual electricity consumption by 30%
and peak demand by 23% in large area buildings [1]. The use of EC windows as
active elements in a building envelope can also save up to about 50% of the primary
energy used for air-conditioning.3 Better thermal insulation provided will also reduce
the amount of space heating required during winter.
Given that 40% of the energy consumed each year is used in buildings and that
electricity consumption in buildings is about 20% of the total energy used [6], we can
estimate that the widespread use of EC windows will cause a net reduction of
electricity consumption by 2.4%. The reduction of GHG is expected to be three
times this amount (e.g. 7.2%), given that electricity production has an efciency of
about 30%. Furthermore, the incorporation of the EC part in an advanced window
(e.g. by the possible utilization of an evacuated component or by use of inert gas)
would improve the thermal insulation and reduce thermal losses during winter.
Considering that 60% of the thermal losses in buildings take place through windows
and that 60% of the energy in buildings is used for space heating, a reduction of 46%
2
Green Seal Proposed Environmental standards for windows (GS 13) and Retrottable window
frames (GS 14).
3
Pilkington Presseinformation PR/15/00, 16/02/00.
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in the glazing U-value (possible by use of advanced materials), can cause a 17%
reduction of the energy for heating of buildings, or a 6.8% reduction of the net
energy consumption. This can be translated to an equal reduction of GHG emissions
by 14%.
These savings are expected to increase further, due to the reduction of energy for
cooling and lighting during daytime. Indeed, the eighty EC panels of the
Stadsparkasse building in Dresden were found to reduce the energy required for
cooling by 30% as compared to conventional heat protection glazing (see footnote 3).
The Fraunhofer Institute for Building Physics has estimated that the Pilkington E-
ControlTM glazing saves about 50% of the primary energy used for air-conditioning.
Furthermore, such a glazing will facilitate better daylighting of buildings and
ofces. A standard EC window will allow a continuous modulation of the
illuminance between two extreme values during daytime (almost 944 and 316 lx in
the bleached and colored state, respectively, while the International Commission on
Illumination recommends 500 lx as natural limit for normal vision) [7]. This can also
lead to signicant cost savings due to the improvement of workers productivity [1].
In order to estimate the potential energy savings of the EC windows
implementation and the environmental impacts of their production, life cycle
assessment (LCA) is undertaken. The results of the Inventory Analysis of the main
raw materials used during all the production processes are presented in this study.
The production route, the raw and auxiliary materials used, the energy requirements
and all emissions per produced kilogram of each material are reported. Health
effects, toxicology data, working safety, exposure issues and environmental impact
of the intermediate and the end products are also presented. Finally, the contribution
of each material to the embodied energy of the ECD is discussed.

2. Life cycle assessment

LCA is a technique for assessing the environmental aspects and potential impacts
associated with a product through its whole life cycle. LCA is used in the building
sector for environmental improvement of the building materials and comparative
studies of the total energy demand and material used, considering the entire building
life cycle [8]. LCA studies of advanced windows aim to assess their environmental
benets compared to the conventional glazing or to explore the relationship between
the embodied and operating energy in buildings. The LCA study in advanced
windows conducted by Lawson [9] aimed to examine the life cycle of materials used,
the resultant environmental impacts and to assess the efcacy of advanced glazing
systems in terms of environmental, energy and comfort criteria. In Ref. [10] LCA
was implemented in the analysis of the production and the maintenance phase of a
glazing system and also for the evaluation of the thermal balance of its utilization
phase. Weir and Muneer [11] estimated the embodied energy for the manufacture of
the main components used in the construction of an inert gas lled, double-glazed
window, while the environmental consequences of the manufacture, application,
disposal, reuse and recycling of advanced windows are being discussed in Ref. [12].
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2.1. Life cycle inventory analysis

LCA methodology is being implemented in the ECD according to the ISO 14040
guidelines, thus four phases are distinguished: goal and scope denition, inventory
analysis (LCI), impact assessment (LCIA) and interpretation [1316]. In LCI, an
integrated analysis of the entire manufacture procedure of the device is carried out in
order to collect the life cycle inventory data. Thus, all inputs used (raw materials and
energy) and outputs produced (air, liquid and solid emissions) during the device life
cycle (fabrication, use and disposal) are quantied.
With this analysis, the environmental burden and the embodied energy of the nal
product are allocated to the life cycle stages of the materials used for its production.
More specically, the contribution of each material (used in the production stage) to
the environmental input and output analysis is a signicant information for the
decision-making about the devices improvement and further re-design. Moreover,
the capabilities for reduction of the embodied energy of the nal product life cycle
can be examined, since it is proposed as an energy saving device. The obtained data
can be used to explore new possibilities, to plan, monitor and represent
environmental issues in R&D of the product.
The studied system is a 40 cm  40 cm ECD which comprises of four layers (Fig. 1)
[17,18]. Pilkington K-Glass serves as the transparent conductor, coated with a
350 nm thick WO3 lm (the active EC material which optical properties are
modulated). Polymer electrolyte (with 1.5 mm layer thickness in order to compensate
the lack of an ion storage layer) is prepared using a solution of a lithium salt mixed
with a polymer: lithium perchlorate diluted in propylene carbonate and poly-methyl
methacrylate (LiClO4PCPMMA). A second K-Glass is used to create the
necessary cavity for the infusion of the electrolyte. The whole device is sealed via
a silicone sealant. The total mass of the fabricated ECD was 3.33 kg: K-Glass

material [g]/ECD

Glass K-Glass 3000


K-Glass
Transparent conductor LiClO4 25.5
Lithium Perchlorate
Electrolyte Propylene carbonate PC 251.6
PMMA
Active electrochromic PMMA 20.9
Tungsten oxide
material
Transparent conductor WO3 0.4
K-Glass
Glass Silicone 36.7

Dimensions not in scale TOTAL 3335.2

Fig. 1. ECD layout and materials mass contribution.


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represents 89.9% of this weight while PC, LiClO4 and PMMA 7.5%, 0.7% and
0.6%, respectively. Silicone used for the fabrication accounts for 1.1% of the total
weight, while the WO3 weight contribution is very low (0.4 g/ECD).
The ow chart for the ECD fabrication stage is depicted in Fig. 2. WO3 layer is
evaporated on K-Glass (Fig. 2, process 1). The two K-Glass sheets form the
electrolyte cavity, which is being peripherally sealed with the silicone sealant (Fig. 2,
process 2). The polymer electrolyte is produced (Fig. 2, process 3) and is inserted in
the cavity (Fig. 2, process 4). The assembled ECD is nally sealed (Fig. 2, process 5).
The system boundaries include the raw materials production processes (Fig. 2,
processes 1a, 1b, 2a, 3a, 3b and 3c). Therefore, we estimate the inputs and outputs
for resource extraction and mining processes, procurement of auxiliary materials and
all manufacturing processes for each material used.
In this study, we present the LCI for each of the six basic raw materials used in the
fabrication of the ECD: (1) K-Glass, (2) tungsten oxide (WO3), (3) PMMA, (4) PC,
(5) lithium perchlorate (LiClO4) and (6) acetic silicone sealant. Most of these
materials are complex chemicals requiring several steps for their production. The
inventory analysis is based on ow charts for each production process, showing the
inputs and outputs allocated in each phase. Thus, each production process is
described, the raw and auxiliary materials used are quantied and the energy
requirements are registered. As far as the outputs of each production process are
concerned, the air, water and solid emissions per manufactured kilogram of each
product are reported.

WO3
production 1a
see Fig. 4
WO3 WO3 layer
K-Glass evaporation 1
K-Glass
production 1b PMMA
see Fig. 3 production 3a
see Fig. 5
K-Glass PMMA
polymer electrolyte PC
peripheral sealing PC production 3b
silicone silicone 2 production 3 LiClO4
see Fig. 6
production 2a
see Fig. 8 LiClO4
production 3c
see Fig. 7
electrolyte
insertion 4

final sealing
5

ELECTROCHROMIC
DEVICE

Fig. 2. ECD fabrication ow diagram.


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3. Materials production inputoutput analysis

3.1. K-Glass

Pilkington K-GlassTM is a low emissivity glass coated with a neutrally colored


uorine-doped tin oxide layer. This layer is deposited pyrolytically to one surface of
clear oat glass during its manufacture. Due to its properties (high transmittance in
the visible spectral region, high reectance in the IR region and nearly metallic
conduction), K-Glass is extensively used to multiple glazed windows providing
improved thermal insulation, reduced condensation effects and maximized thermal
comfort. It is energy efcient, as it minimizes heat losses in winter, combining high
light transmission and neutral color in transmission and reection. Due to the
durable pyrolytic coating it can be handled, cut, bent, insulated, laminated and
toughened using standard techniques. Tin oxide layer doped with uorine is used in
K-Glass, and enhances the electrical conductivity due to the excess of electrons
available for conduction. Thus, it is incorporated in ECDs, acting as the transparent
conductor simultaneously minimizing heat losses [19,20].

3.1.1. K-Glass production


K-Glass production is practically incorporated, as a separate part, in the oat
glass process used to produce at glass panes [21,22]. The oat glass process is
presented in the ow diagram of Fig. 3. Batch, made from mixed ne-grained
ingredients, ows on to molten glass at 1500 C in the melter (melting and rening,
Fig. 3, process 1). A continuous melting process inside the furnace, lasting as long as
50 h, delivers molten glass at 1100 C free from inclusions and bubbles.
Glass from the melter is poured onto a bath of molten tin, called oat bath (Fig. 3,
process 2), where the glass develops a uniform thickness and assumes the almost
perfect atness of the molten tin. A ribbon is thus formed, with the upper and lower
surfaces becoming parallel under the inuence of gravity and surface tension. In the
oat bath the thickness of the glass ribbon (typically from 1.5 to 19 mm) is controlled
by adjusting the rate of glass ow and by using several pairs of water-cooled top
rollers, adjustable in direction, height, penetration depth and angle.
From the exit of the oat bath (at 600 C), the solid ribbon is pyrolytically coated
(online coating, Fig. 3 process 3) with a neutrally colored uorine-doped tin oxide
layer. K-Glass is coated using the chemical vapor deposition (CVD) method. In
CVD, precursor compounds (both gases and liquids) are vaporized, and are then
carried to the chamber in which the coating will be applied by an inert carrier gas
(e.g. nitrogen). The resulting gas mixture is sprayed uniformly over the glass ribbon,
while the temperature ranges 480730 C. A pyrolytic reaction occurs at the surface
of the substrate leading to the deposition of a thin lm, which bonds tightly to the
glass. There are two separate coating stages: (i) a SiCO undercoat and (ii) a uorine-
doped tin oxide topcoat.
After the coating process, the glass ribbon is passed through a temperature
controlled tunnel furnace, the lehr, to be annealed (Fig. 3, process 4). During
annealing, the glass is gradually cooled from 600 C to 60 C to reduce residual
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silica sand soda ash limestone dolomite Process 3

SnCl4 HF CH3OH SiH4

1500C
alumina Melting and
refining precursor's vaporization
1 1100C

1100C nitrogen gas mixture formation


SO2 Float bath
2 600C
undercoat pyrolytic
SiO2 organics
reaction
SnCl4 480C thermal
HF bag filter
CVD coating incinerator
CH3OH SiCO film
SiH4 3 730C recycle to
deposition destroy
furnace

600C
Annealing halides topcoat pyrolytic tin
(HF, HCl) reaction compounds
4 60C
packed bed high
chemical temperature
fluorine doped
scrubber tin oxide reactor
Inspection 38C
5 electrostatic
precipitator
cullet
coated glass
precipitation
Cutting to order
6

Fig. 3. K-Glass production ow diagram.

stresses. The lehr is divided in sections in which there is heating and indirect or direct
cooling by forced and natural convection.
Automated online inspection (Fig. 3, process 5) is carried out at every production
stage in order to reveal process faults and minimize wastage. Finally, the cooled glass
ribbon is cut to size (Fig. 3, process 6) by a computer controlled travelling cutter,
while the ribbon selvedges (named cullet) are trimmed off and then recycled to the
furnace [21,22].

3.1.2. Input analysis: energy and raw materials


The main environmental issue associated with at glass production is that it is a
high temperature, energy demanding process [22]. It is assumed that the K-Glass
production line incorporates a cross-red regenerative furnace, which uses gas or oil.
Furnace consumes the 83% of the energy used in a typical oat glass process but
these furnaces are generally more energy efcient than other conventional fossil fuel
red furnaces due to the more efcient combustion air preheating system. Annealing
and forming consume 5% of the total energy used. The cutting process expends 2%
while all the other processes (e.g. electrical energy used to drive air compressors and
fans, etc.) 10% of energy.
Glass composition is very well specied in order to ensure the production of high-
quality product [21]. Sand, the principal source of silica (SiO2, 72.6% w.w. in the
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nal product composition), is quarried either as granular sand or as sandstone and


subsequently crushed, graded and treated to remove impurities since the most
deposits are lacking sufcient purity for glass making. Since the melting point of
sand is too high (in the region of 1700 C), a uxing agent, usually sodium oxide
(Na2O), is used to reduce the melting temperature. Soda ash (sodium carbonate,
Na2CO3) is the main source of sodium oxide (13.0% w.w.), which during melting
becomes part of the melt and carbon dioxide is released. Sodium sulfate is added as a
rening and oxidizing agent and is a secondary source of sodium oxide, which is
incorporated into the glass, while the sulfur oxide gases are released through the
melt. Other major constituents of at glass are calcium and magnesium, which are
used to avoid crystallization during cooling. Thus, calcium oxide (CaO) is added to
the glass as calcium carbonate (CaCO3) in the form of limestone or chalk (8.4%
w.w.) that is a natural material, which is mined, crushed and graded. CaO can also
be incorporated as dolomite (4.0% w.w.), which contains both calcium carbonate
and magnesium carbonate (MgCO3). Aluminum oxide (Al2O3) is also added as
alumina to improve chemical resistance and to increase viscosity at lower
temperatures. The raw materials used for the K-Glass coating process are: tin
tetrachloride (SnCl4), hydrouoric acid (HF), methanol (CH3OH) and a silane
(SiH4) [21,22].
Flat glass plants recycle 99% of the glass waste (trims, rejects and damaged glass)
from the end of the glassmaking process into the furnace only if the cullet has the
appropriate quality and chemical compatibility that is required for the nally
produced glass. The total cullet introduced in the furnace is typically around 20%
and it is estimated that each tonne of cullet replaces approximately 1.2 tonnes of
virgin material [22].

3.1.3. Output analysis: emissions


In the K-Glass production process, the product accounts for 70% of the raw
material input. From the remainder output 1020% is cullet and the rest 1020%
consists of emissions to air, mainly CO2 from melting activities that constitute the
greatest potential for environmental pollution in oat glass production [22].
Particulate matter, such as dust (mainly crystalline silica), is emitted during
handling and melting of materials. This is supposed to be 100% recycled using the
best available techniques (BAT, [22]) for dust emission control: electrostatic
precipitator and dry scrubber. Wherever possible, batch plant dust is returned to
the raw material silos and reused in the process. For the control of oxides of nitrogen
(thermal NOx, nitrogen compounds in the batch materials, nitrogen contained in
fuels), primary NOx control techniques are used (e.g. reduced air/fuel ratio, reduced
preheat temperature, staged combustion, low NOx burners). They are very efcient
when used at the cross-red regenerative furnaces, although higher NOx quantities
are formed due to the high preheat temperatures. SOx emissions arise from
decomposition of sulfur compounds in the batch materials and from melting
activities. In these, the emission levels for oxides of sulfur (expressed as SO2) are
considered to be higher for oil than for natural gas ring furnaces; although, it is
assumed that oil containing less than 1% sulfur is used. Waste minimization with full
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dust recycling and cullet recycling is considered of high priority for reducing SOx
emissions. Also, CO is emitted as product of incomplete combustion, particularly in
hot blast cupolas. However, in the cross-red regenerative furnaces the low energy
use per tonne of glass melted leads to reductions in many of the combustion
pollutants. Furnace emissions also contain traces of chlorides, uorides and heavy
metals (e.g. V, Ni, Cr, Se, Pb, Co, Sb, As, Cd) present also and in secondary
processing (e.g. cutting, polishing, etc.).
If the oat bath (Fig. 3, process 2) is correctly operated, the emission of tin vapor
has been found to be very low and it is generally monitored only to ensure low
workplace exposure levels. Emissions during CVD coating (Fig. 3, process 3) that
typically contain acid gases (HF, HCl) and ne particulate matter (e.g. oxides of
silicon and tin) can be controlled using a combination of techniques (dust abatement
equipment, bag lter or EC, dry/wet-chemical scrubbing, high temperature oxidation
and thermal incineration). Emissions from the undercoat stage pass through a
thermal incinerator to destroy any organic remains, the waste gas is cooled and a bag
lter removes the solids (amorphous silica). The collected material is recycled to the
furnace. During the top coating stage, the waste gases, which contain halides and tin
compounds, are passed through a high temperature reactor to oxidize the tin
compounds. The solid tin oxide is removed with electrostatic precipitator and the
halides in a packed bed chemical scrubber [19,2225].
During the annealing process in the lehr (Fig. 3, process 4), SO2 is sprayed on
both sides of the ribbon, providing a surface treatment to protect the glass
against the contact of the rollers. If the process is properly operated, SO2
emissions are insignicant. The only potential emissions are combustion products
from natural gas heaters in the lehr. In K-Glass production, water is used for
cooling, cleaning and batch humidication. Water used for cooling and washing the
hot glass ribbon, which is the greater part of water used, is not contaminated except
that it may contain some Na2SO4. Water emissions contain glass solids, oil
contamination and chemicals from cooling water system treatment that can be
controlled with simple abatement techniques (e.g. settlement, screening, oil
separators, neutralizing) [22].

3.2. Tungsten oxide

Tungsten has the highest melting point of all metals, exhibits high hardness and
corrosion resistance and its thermal expansion is almost equal as for glass. Pure
tungsten can be forced, drawn and extruded and is extensively used in lighting
laments, television sets, magnetrons for microwave ovens, wire, rods and other
electrical consumer products. Other applications include chemical uses (mainly in the
form of catalysts) and use in the ammunition industries [26,27]. Tungsten oxide
(WO3) is the most widely studied EC material. It is incorporated in ECDs as the
active material, due to its favorable properties: reversible transmittance modulation
under applied voltage, prolonged durability, cycling reversibility and relative ease of
production by various physical vapor deposition techniques (thermal evaporation,
electron gun, sputtering). Another important feature is the stability of WO3 lms
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during operation in devices with electrolyte (liquid or polymer) containing proton or


lithium ions.

3.2.1. Tungsten oxide production


Tungsten oxide production is presented in Fig. 4 and consists of four distinct
stages: (1) ore preparation (Fig. 4, process 1a), (2) leaching (Fig. 4, processes 2a and
2b), (3) purication to ammonium paratungstate (APT, (NH4)10W12O41  5H2O, Fig.
4 processes 3a and 3b) and (4) calcination of APT (Fig. 4, process 4). The main
intermediate product, APT, is manufactured from ore concentrates (scheelite or
wolframite) and tungsten-containing scraps [26]. Mother liquor emitted from APT
crystallization is reused in synthetic scheelite production (Fig. 4, process 1b) [28]. Ore
preparation (Fig. 4, process 1a) involves gravity and otation methods. Leaching of
concentrates (Fig. 4, process 2a), or leaching and roasting (Fig. 4, process 2b) follows
and sodium tungstate or tungstic acid is produced, respectively [28]. Sodium
tungstate is then converted to APT (Fig. 4, process 3a) via chemical processes,
involving: precipitation, ltration and purication, solvent extraction and crystal-
lization [29]. On the other hand, the tungsten acid is digested with aqueous ammonia
(Fig. 4, process 3b) and with further purication/processing yields APT, which is
then converted to tungsten oxide by calcining (Fig. 4, process 4) in a rotary furnace
with temperature varying between 400 C and 900 C [26,28]. APT can be converted
to yellow (WO3) or blue oxide (containing tungsten b-oxide WO2.9 or W20O58,
tungsten g-oxide WO2.72 or W18O49). Yellow tungsten trioxide can be produced by
calcination either of APT (sufcient air should be supplied) or of tungstic acid [30].

3.2.2. Input analysis: raw materials


Tungsten oxide occurs in the natural state only in the form of chemical
compounds with other elements, in more than 20 tungsten bearing minerals, most of
which contain less than 1.5% WO3. Of these, only wolframite ((Fe, Mn)WO4, 76.5%
in WO3) and scheelite (CaWO4, 80.5% in WO3) are important for industrial use, and
are mainly mined from narrow veins by conventional underground methods. The ore
is rst crushed and milled to liberate the tungsten mineral crystals in ore dressing
plants that are always in close proximity to the mine. Scheelite ore can be
concentrated by gravimetric methods, often combined with froth otation, while
wolframite ore can be concentrated by gravity, sometimes in combination with
magnetic separation. Fatty acids are used to oat wolframite. Magnetic and
electrostatic methods are also used to separate wolframite and cassiterite. Because of
the friable nature of tungsten minerals, a signicant amount of these minerals may be
lost in ner-grained material during milling [26,29].
Scraps and residues are also used as secondary raw materials in tungsten
processing industries that recycle some 30% of tungsten, which can be recovered
from almost every kind of tungsten-containing scrap and waste [26]. The scraps are
classied according to their size as hard scraps (solid pieces) and soft scraps (sludge,
sweeps and powders). The most important of them are: (i) the rejects of the
manufacturing of tungsten products, e.g. wires, coils, powders, etc., (ii) the rejects or
by-products of manufacturing tungsten alloys and alloy products, e.g. powders,
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Fig. 4. WO3 production ow diagram.


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turnings, ingots pieces composed of CuW, FeW, NiW, AgW, etc., (iii) the rejects
or by-products of manufacturing hard metals as well as worn tools (cutting and
drilling tools, wire drawing stones) composed of WCCo, WCTa(Nb), CTiCCo,
etc. Other scrap materials are steel products that are reprocessed with pyrome-
tallurgical steel-making technologies and used catalysts that require very careful
selection and testing [28]. Contaminated cemented carbide scrap, turnings, grindings
and powder scrap are oxidized and chemically processed to APT in a way similar to
that used for the processing of tungsten ores. Clean cemented carbide inserts and
compacts are converted to powder by the zinc process (treatment with molten zinc,
which is dissolved in the cobalt phase and is then distilled off, leaving a spongy
material that is easily crushed). This powder is added back to the manufacture of
ready-to-press powder. Great part of tungsten is being recycled industrially in high-
speed steel plants, and a typical melt contains 6070% scrap, including internally
generated scrap. On the other hand, recycling in such applications as lamp laments,
welding electrodes and chemical uses is low [26].
The main auxiliary materials used during WO3 production are Na2CO3 and
H2SO4 which is used during APT purication (Fig. 4, process 3a), while NaOH,
Al2(SO4)3  18H2O, Mg(SO4)  7H2O, Na2S and NH4OH are also used [28].

3.2.3. Output analysis: emissions and health issues


Various by-products are formed during the tungsten production processes that
need special handling since that for example the amount of salts discharged annually
may reach several thousand tones for a medium-sized manufacturer. The by-
products are: (i) gaseous: NH3, NOx, H2S (classied as dangerous), (ii) liquid:
Na2SO4, NaCl, CaCl2 and HCl, H2SO4, NaNO3, NaNO2 (classied as dangerous)
and (iii) solid: MoS2, P2O5 Ni(OH)2, Co(OH)2, Mn(OH)2 (classied as dangerous)
and Sb2O5, Sb2O3, As2O5 (classied as carcinogenic) and Al(OH)3, Mg(OH)2, SnO2,
Cu(OH)2, Fe(OH)2, CaCO3, WO3.
Solid leaching residues from the ores and certain scrap materials (Fig. 4, process
2a and 2b) such as Fe(OH)2, Mn(OH)2 and CaCO3 have to be collected and stored at
special dumps because there is not a method for economically recycling within the
process and there is no other possible outside use for them. For dissolved salts, such
as NaCl and CaCl2 generated in large amounts from the auxiliary materials, there
are already more or less applicable processes for recycling or reprocessing to make
other useful materials for hydrometallurgical uses. Nitrate salts are discharged when
larger pieces of scrap are processed. During the preparation of APT (Fig. 4, process
3a), the precipitates involve Mg(OH)2, Al(OH)3, As2O5, P2O5, MoS2, while the
gaseous by-products (e.g. NH3, H2S) are fully or partially recycled. The dissolved
Na2SO4 can be handled like CaCl2. The organic by-products originating from the
solvents and reagents such as tars, foams, impure charcoal, etc., may be incinerated
in suitable equipment [28].
Elemental tungsten is considered physiologically inert, and insoluble tungsten
compounds, such as the oxide, have not been found to be mutagenic, carcinogenic or
teratogenic. Documented health effects include respiratory illness due to excessive
exposure to elemental tungsten dust [27]. Chronic exposure to tungsten dust has been
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reported to cause dermatitis, pulmonary brosis, characterized by cough, labored


breathing and wheezing. Dusts of tungsten pose a hazard considered to be somewhat
greater than that of nuisance dust [31].

3.3. Poly-methyl methacrylate

PMMA is a transparent, colorless, thermoplastic polymer. It is a pigment-wetting


binder for coatings that contributes hardness, weather resistance and resistance to
chemicals. The structure of the polymer solid gives PMMA a distinctive optical
clarity. It is commonly available in either sheet or bead form, is readily fabricated
and can be colored as required. Its durability, plus its high-quality nish, ensures its
in demand for use in the production of long lasting high-quality products, such as
baths, sinks and showers. Its mechanical properties of high softening point and high
impact strength, when combined with its good weatherability and resistance to most
aqueous inorganic reagents, favor its use in external applications. Illuminated signs,
glazing and motor vehicle rear lights are only few of the examples of its possible uses.
Because of its optical clarity and stability, PMMA has found uses in the medical eld
where special grades have long been successfully employed for intra-ocular lenses,
contact lenses and implants. The mechanical properties and nishes of PMMA can
be further optimized for specic applications by the addition of inert llers and
plasticizers [32].
Gel materials offer an alternative approach to highly conductive electrolytes for
ECDs. In such polymersolventsalt systems, the polymer serves as a stiffener for the
solvent, which dissolves the salt and acts as a conducting medium. These materials
may then exhibit conductivity very close to that observed in liquid electrolytes.
PMMA can be used in such polymer electrolytes serving also as laminating means,
thus minimizing potential leakage problems.

3.3.1. Poly-methyl methacrylate production


A signicant number of intermediates are required during the production
route of PMMA as shown schematically in Fig. 5 [32]. Methyl methacrylate
(MMA) is the raw material used to make PMMA resin. The most widely applied
technology for the synthesis of MMA is the acetone-cyanohydrin (ACH) process,
which accounts for 85% of the global production of MMA. This process begins with
the hydrocyanation of acetone and hydrogen cyanide (Fig. 5, process 1). Acetone
cyanohydrin is produced, which is then converted to methacrylamide sulfate (Fig. 5,
process 2) and MMA is produced in an acid solution of sulfuric acid (Fig. 5,
process 3) [33]. Finally, it is polymerized to produce PMMA beads or cast sheet
(Fig. 5, process 4).

3.3.2. Input analysis: energy and raw materials


The main environmental issue associated with PMMA production is the demand
for high energy consumption and the requirement of handling large quantities of
extremely toxic and hazardous hydrogen cyanide, which generates ammonium
sulfate wastes. This results in the development of a great interest in the chemical
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benzene propylene methane ammonium

acetone production HCN production


1a 1b

acetone HCN

acetone cyanohydrin
production 1

acetone
cyanohydrin

methacrylamide sulphate
production 2

methacrylamide
sulphate

water sulfuric acid


MMA production
sulfuric acid 3 ammonium sulphate

methyl methacrylate

MMA polymerisation
4

POLY METHYL
METHACRYLATE

Fig. 5. PMMA production ow diagram.

industry for a replacement process. The greatest part of energy required to produce
PMMA is provided from fuels; condensate gas and crude oil are the primary fuels
used [32].
Hydrogen cyanide and acetone are used in the ACH process, which also requires
handling of large amounts of sulfuric acid. Acetone can be produced by a number of
different routes, but the most commonly used is the manufacture of phenol (Fig. 5,
process 1a) which gives acetone as by-product. Hydrogen cyanide is mainly
produced by the reaction of methane (natural gas) with ammonia over a catalyst (the
Blausaure Methane Anlage process) or by reaction of methane and ammonia in the
presence of oxygen over a catalyst (the Andrussow process) (Fig. 5, process 1b). A
small proportion of hydrogen cyanide, however, is obtained as a by-product from
acrylonitrile production process (the Sohio production process) [34]. The required
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water resources for cooling processes exceed 72% of the total, while the rest is used
during processing.

3.3.3. Output analysis: emissions and health issues


By-products, as well as the properties of MMA produced, are the main
environmental concerns about the outputs of PMMA production facilities. At
cyanide chemicals manufacturing facilities the following hazardous air pollutants
(HAP) emission sources have been identied: process vents, storage vessels,
equipment leaks, transfer operations and wastewater treatment operations [34].
HAP emissions from process vents and equipment leaks account for more than 96%
of the total. Emissions from storage vessels that contain HCN are greatly reduced by
venting through a closed vent system to a are or any combination of control
devices. Control of equipment leaks will reduce the amount of HAP-containing
material that could be discharged to a facilitys wastewater treatment stream through
equipment washdowns or from storm water runoff. Acute inhalation exposure to
high concentrations of cyanide compounds can be rapidly lethal, while at lower
concentrations can cause a variety of adverse health effects on human, such as
weakness, headache, and nausea, increased rate of respiration, and eye and skin
irritation. Chronic inhalation exposure to cyanide compounds can result in effects on
the central nervous system, such as headaches, dizziness, numbness, tremor and loss
of visual acuity. Other chronic exposure effects include cardiovascular and
respiratory effects, an enlarged thyroid gland, and irritation to the eyes and skin [34].
Methacrylamide sulfate produced during the ACH process (Fig. 5, process 2) is
not isolated and thus stoichiometric amounts of waste ammonium hydrogen sulfate
(NH4HSO4) are produced. Only the spent sulfuric acid from the process is recovered
and regenerated for further use [32]. NH4HSO4 by-product is either discarded or
reclaimed at substantial cost but its demand for use as a fertilizer is decreasing.
Problems regarding treatment of the NH4HSO4 (cost of disposing or regenerating)
and difculties in procuring hydrocyanic acid make the ACH technology
environmentally and economically untenable for any new expansions. Various
processes that switch raw materials or do not generate NH4HSO4 as a by-product
have been developed to date to replace the ACH process [35,36].
MMA is a harmful material if swallowed or inhaled [37,38]. It affects the central
nervous system, causes allergic skin reaction and may be harmful if absorbed
through skin or contact eyes, while inhalation of vapors irritates the respiratory
tract. Symptoms from overexposure can cause coughing, chest pain, headache,
drowsiness, anorexia, irritability and narcosis, while in very high levels it may cause
pulmonary edema and death. MMA has been linked to cardiac arrest and other
cardiovascular problems because of its ability to lower the blood pressure. It has
caused mutagenic and teratogenic effects on laboratory animals. MMA liquid and
vapors are ammable: heating sunlight or contact with incompatible materials may
cause explosive polymerization. It should be handled as hazardous waste and should
be saved or recycled to the greatest possible extend. When released into the soil or
into water, it may biodegrade to a moderate extend, may leach into groundwater and
is expected to quickly evaporate. It has an estimated bio-concentration factor of less
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than 100 and is not expected to signicantly bio-accumulate. When MMA is released
into the air, it is expected to degrade by reaction with photochemically produced
hydroxyl radicals [37,38].
PMMAs chemical, physical and toxicological properties have not been
thoroughly tested [39]. It may be harmful by inhalation, ingestion or skin absorption
and may cause eye and skin irritation and irritation to mucous membranes and
upper respiratory tract. In case of chronic exposure target organ are found to be
lungs, thorax or respiration. Heat should be avoided, as during combustion toxic
fumes of carbon monoxide and carbon dioxide are produced. PMMA is
incompatible with strong oxidizing agents and strong acids. Disposal considerations
suggest to dissolve or mix the material with a combustible solvent and burn in a
chemical incinerator equipped with an afterburner and scrubber [39].

3.4. Propylene carbonate

PC is produced in a continuous process by the reaction of propylene oxide


with carbon dioxide and is sold as different purity and color grades dependent
on the supplier. PC may be used as a solvent for chemical reactions or as a carrier
of cosmetically active agents, medicinal agents, biocides and fungicides. It may
also be used as a reactive intermediate in alkoxylations, trans-esterications,
polymerizations reaction with amines or carboxylic acids. PC is a popular solvent
in lithium ion batteries industry and is also extensively used as lithium salt
solvent in ECDs.

3.4.1. Propylene carbonate production


The PC production ow diagram is presented in Fig. 6 [40]. Propylene
manufacture begins with the thermal cracking of saturated hydrocarbons such as
ethane, propane, naphtha and other (Fig. 6, process 3). These have been pro-
duced during crude oil (Fig. 6, process 1) and natural gas processing (Fig. 6, process
2). Hydrocarbons and steam are heated in a cracking furnace to temperatures
around 1000 C and the products are quenched in heat exchangers, producing
high-pressure steam. Fuel oil is separated from the main gas stream in a multi-
stage centrifugal compressor, while the main gas stream undergoes hydrogen
sulde removal and drying. Then, the various reaction products including propylene
and isobutane are processed with fractional distillation. In the next step, the
isobutane hydroperoxide process (Fig. 6, process 4) is used to form propylene oxide
and tert-butyl alcohol from isobutane, oxygen and propylene. Isobutane is rst
oxidized to the intermediate tert-butyl hydroperoxide, while the untreated isobutane
is recycled. The tert-butyl hydroperoxide and alcohol mixture is combined with
propylene at a rate of 26 mol of propylene per mole of hydroperoxide. The nal
mixture is reacted over a catalyst usually made of molybdenum, producing
propylene oxide and tert-butyl alcohol. Recoverable catalyst is also obtained at
the end of the purication columns. PC is then produced (Fig. 6, process 5) by the
reaction of propylene oxide with carbon dioxide over a tetraethyl/ammonium
bromide catalyst.
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crude oil natural gas

isobutane oxygen
crude oil procesing natural gas processing
1 2
4

NaOH oxidised isobutane Fe(OH)2


salt mining
tert butyl tert butyl 4a1
alcohol hydroperoxide propylene manufacture
3
Mo mixture propylene sodium hydroxide
manufacture 4a propylene
sodium
hydroxide
Chlorine H2 isobutane hydroperoxide
propylene tert butyl
oxide alcohol process 4
Oxygen
oxygen propylene oxide
manufacture 4b
carbon carbon dioxide
catalytic reaction
5 dioxide manufacture 5a

PROPYLENE
CARBONATE

Fig. 6. PC production ow diagram.

3.4.2. Input analysis: energy and raw materials


PC production is an energy demanding process due to the raw materials used [40].
These are: crude oil, natural gas, oxygen, sodium hydroxide and carbon dioxide.
Crude oil used to produce feedstocks for olens production goes through the
following renery operations: desalting, atmospheric and vacuum distillation, and
hydrotreating (Fig. 6, process 1). Natural gas is frequently being co-produced with
crude oil. Light straight-chain hydrocarbons are normal products of a natural gas
processing plant (Fig. 6, process 2), typically using compression, refrigeration, and
oil absorption to extract these products, with heavy hydrocarbons being removed
rst.
Salt (sodium chloride) is used as raw material in an electrolytic process (Fig. 6,
process 4a), producing caustic soda (sodium hydroxide), chlorine and hydrogen gas.
Each of chlorine and caustic soda accounts for about half of the output process, with
hydrogen amounting to only 1% by weight. Salt used in the above process is most
commonly removed from brine using solution mining (Fig. 6, process 4a1), in which
pressurized fresh water is introduced to the bedded salt through an injection well.
The brine is then pumped to the surface for treatment.
Oxygen is manufactured by cryogenic separation of air (Fig. 6, process 4b), a
technique by which air is liqueed and liquid oxygen is collected by fractionation.
Carbon dioxide is primarily produced by steam reforming of natural gas (Fig. 6,
process 5a) and is a by-product of ammonia manufacture. Natural gas, or other light
hydrocarbons and steam are fed into a primary reformer, over a nickel catalyst to
produce hydrogen and carbon dioxide, generally referred to as synthesis gas. About
70% of the hydrocarbon feed is converted to synthesis gas in the primary reformer.
The remaining hydrocarbons are converted in the secondary reformer in which air is
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E. Syrrakou et al. / Solar Energy Materials & Solar Cells 85 (2005) 205240 223

introduced. The efuent from the reformers is fed into carbon monoxide shift
converters, where the carbon monoxide reacts with water to form hydrogen and
carbon dioxide. The product of the shift converters is cooled and condensed water is
removed. The carbon dioxide and some excess hydrogen are then removed from the
synthesis gas as co-products [40].

3.4.3. Output analysis: emissions and health issues


Propylene is usually handled commercially in liquid form, and will cause freezing
burns when in contact with skin or eyes. Volatilization is expected to be the primary
environmental fate in soil and water, but it is not expected to bio-accumulate or bio-
concentrate in organisms and food chains. Propylene has been shown to affect plant
growth. If it is released to the atmosphere (in the combustion gasses of hydrocarbon
fuels, wood and synthetic polymers such as polyethylene), it will exist in the vapor
phase but it is unknown if it will biodegrade in the environment. Gross inhalation of
propylene-contaminated air may cause reduced blood pressure and heart rhythm.
Propylene has shown anesthetic effects in human, while in animal studies, it was
found to be a cardiac sensitizer in dogs. There is inadequate evidence in human or
animals for the carcinogenicity of propylene [40].
Propylene oxide is an epoxy compound that may produce tissue sensitization after
repeated exposure. It is classied as severely irritating to the eyes and skin in either
the liquid or vapor form. Central nervous system effects have been reported in
human. According to the US national toxicology program, propylene oxide is
classied as an animal carcinogen via the inhalation route [40,41].
The chemical, physical and toxicological properties of PC have not been
thoroughly investigated yet. As far as human health is concerned, PC is a skin
and eye irritant and cause damages to the respiratory system and especially to the
lung. Human toxic effects due to overexposure to PC include tightness and pain in
the chest, coughing and difculty in breathing if inhaled, skin irritation if in
prolonged contact with the chemical and eye irritation. Rabbit skin and eye irritation
studies have shown moderate irritation effects [40,42,43].

3.5. Lithium perchlorate

Perchlorate salts are used in pyrotechnics and munitions, in the manufacture of


matches, monitors and paints, in the chemical industry as additives in lubricants, oils
and tanning products. Lithium Perchlorate (LiClO4) is extensively used for the
production of lithium salt containing electrolytes in ECDs.

3.5.1. Lithium perchlorate production


Industrially, perchlorates are prepared by electrolysis in diaphragmless cells [44].
The whole process of lithium perchlorate synthesis is presented in the ow diagram
of Fig. 7. The main steps in lithium perchlorate manufacturing process are: (1) cell
construction (Fig. 7, process 1), (2) electrolyte preparation (Fig. 7, processes 2ab),
(3) sodium chlorate formation (Fig. 7, process 3), (4) sodium perchlorate formation
(Fig. 7, process 4), (5) solution processing (Fig. 7, process 5), (6) lithium perchlorate
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NaCl
cell construction
1
2a
Sodium Sodium
chloride chloride solution
Stainless
RuO2, TiO2 steel saturation

preparing fresh recycling of the old


1 filtration
electrolyte 2a electrolyte 2b
anode cathode
construction construction NaF, Na2CrO4 efficiency
Na2CrO7.2H2O improvement

Anode Cathode HCl


Sodium chlorate pH adjustment
NaOH
formation 3

Sodium chlorate electrolyte


solution

NaCl3 Sodium perchlorate


formation 4
4 old electrolyte
NaOH filtering of solid Sodium perchlorate
particulates Fe(OH)2
HCl, NaOH 2b
NaOH filtering of solid
Precipitates solution processing Fe(OH)2
chromate barium (di) 5 HCl, NaOH particulates
BaCl2 removal / filtration chromate
Ba(ClO3)2 sodium dissolve impure
Ba(ClO4)2 sulfite chlorate
sodium chlorate NaCl3 double decomposition
sulfite destruction 6 solution
NaCl
saturation
LiClO4
crystal filtration
clear solution
NaClO4
purification HCl
7 pH adjustment
NaOH

LITHIUM electrolyte
PERCHLORATE solution

Fig. 7. Lithium perchlorate production ow diagram.

formation (Fig. 7, process 6) and (7) purication (Fig. 7, process 7). The conditions
in the cell are usually optimized to increase the reaction rate (pH is kept around 6
and temperature between 60 C and 80 C). The manufacture of perchlorate salts
begins with the electrolysis of brine (sodium chloride), rstly to form sodium
chlorate (NaClO3) and then sodium perchlorate (NaClO4). The sodium perchlorate
reacts with lithium chloride to form lithium perchlorate (LiClO4) and sodium
chloride (NaCl). The NaCl is taken out rst, then the crop of lithium perchlorate is
separated by cooling, the crystals are dried in an oven at 100 C and nally they are
packaged.

3.5.2. Input analysis: energy and raw materials


The general structure of electrochemical cells for perchlorate synthesis contains
two working electrodes without diaphragm [44]. Industrial cells power consumption
ranges between 4.5 and 5.5 kWh/kg of sodium chlorate produced. A constant
reaction rate suitable for the cell design is maintained by setting an appropriate
current value. The voltage over the cell uctuates depending on conditions and cell
design and usually lies in the range of 57 V. No more than 2 A/100 ml of electrolyte
must be passed through a chlorate cell. To convert 100 g of sodium to sodium
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perchlorate, 50 Ah are required if the cell operates at an ideal 100% efciency, but in
real conditions more electricity is needed.
The principal raw materials used in the manufacture of lithium perchlorate are salt
(sodium chloride), lithium chloride and hydrochloric acid. Stainless steel is a suitable
cathode material, while mild steel may also be used (Fig. 7, process 1). Anode
materials suitable for perchlorate synthesis are: platinum, lead oxide and
dimensionally stable anode (DSA). The obvious disadvantage of platinum is its
high price, although it provides an almost ideal anode material, since it corrodes only
at a very slow rate and thus high efciency can be reached. Using platinum,
processing of the electrolyte is greatly simplied due to the absence of insoluble
anode erosion products. Lead dioxide provides an economical alternative to
platinum, but it usually has a slightly lower efciency. The DSA consists of a layer of
noble metal oxides (usually RuO2 and TiO2) coated onto a substrate, usually
titanium. Although, the required chemicals for the manufacture of these anodes are
expensive and difcult to handle, they nd increased use in industrial cells because
their cost remains lower than platinum and they resist to corrosion.
Sodium chloride is used to prepare sodium chlorate (Fig. 7, process 3), as it is very
soluble in water and can therefore be easily separated from existing insoluble
impurities. The amount of NaCl is usually recycled by 50%. In case of preparing
fresh electrolyte (Fig. 7, process 2a) a saturated solution of sodium chloride is made,
which is brought to a boil and then it is cooled back to room temperature. Some
sodium chloride will crystallize as the solution cools, while ltering follows.
Optionally, 24 g/l of potassium dichromate, potassium chromate, sodium chromate
or sodium dichromate may be added to improve efciency. These compounds are
suspected carcinogens. If lead dioxide anodes are used, potassium dichromate will
reduce efciency, thus instead 24 g/l of sodium or potassium uoride may be used
(not carcinogenic). The pH of the solution should be kept around 6 and can be
adjusted by addition of dilute solutions (2% w/v) of sodium hydroxide or
hydrochloric acid. When old electrolyte is available from previous batch of
perchlorate, it can be recycled (Fig. 7, process 2b). First, the solid particles in the
electrolyte should be removed by ltering. Any impure chlorate from the purication
and extraction steps should also be dissolved. Sodium chloride is used to re-saturate
the solution following the procedure mentioned above with the fresh electrolyte.
During sodium perchlorate formation (Fig. 7, process 4) small amounts of
chromates or dichromates are added in order to prevent the products of the
electrolysis from being reduced at the cathode again. A layer of hydrated oxides of
chromium will then form around the cathode effectively preventing hypochlorite and
chlorate ions from reaching the cathode surface. The nal product of the electrolysis,
sodium perchlorate, is conveniently converted in high yield to lithium perchlorate by
double decomposition reactions (Fig. 7, process 6). Lithium chloride is dissolved in
the smallest volume of water possible and when this solution is mixed with the
electrolyte (solution of sodium perchlorate) a white precipitate of the corresponding
perchlorate should be formed. The solution is boiled and small amounts of water are
added until all the perchlorate has dissolved. The pH of the solution should be
neutral or slightly alkaline (above 7) and can be adjusted with dilute sodium
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hydroxide solution or hydrochloric acid. Then the solution is cooled slowly to room
temperature and the perchlorate will crystallize. The solution is further cooled to 0 C
and ltered. The crystals are rinsed in the lter with some ice-cold water and may be
further puried [44].

3.5.3. Output analysis: emissions and health issues


The main output from perchlorate production is the ltration residues of the
solutions [44]. Filtration is the rst step in sodium perchlorate solution processing
(Fig. 7, process 5). The electrolyte usually contains suspended solid particles (erosion
products of the anodes, the cell walls and the unsubmerged parts of the cathodes)
that may be very small and are not always easily removed. A common impurity that
is hard to remove is suspended iron hydroxide originating from corrosion of
(stainless) steel cathodes. It can be removed by ltration if some sodium hydroxide
or pool coagulant is added, which cause the iron hydroxide particles to coagulate. It
can also precipitate if hydrochloric acid is added rst to lower the pH of the solution
to between 2 and 3 and then sodium hydroxide is added to raise the pH to above 7
again. If chromates or dichromates are used they should be removed by adding a
solution of barium chloride to the electrolyte. It will precipitate any chromate or
dichromate resulting to barium compounds that are then being ltered. If barium
chlorate or perchlorate is formed (a white, sometimes clearly crystalline precipitate)
it should also be removed. For the destruction of residual chlorate, sodium sulte is
used as reducing agent in industrial setups.
Purication (Fig. 7, process 7) is required also for the nal product. Lithium
perchlorate can be puried by re-crystallization, which is done by placing the crude
product in a pan where water is repeatedly added while it is boiled until the entire
product has dissolved. The pH of the boiling solution is maintained neutral or
slightly alkaline. The solution is left to cool down to room temperature and the
puried product crystallizes. The crystals should be ltered and rinsed well with ice-
cold water and dried in an oven at 100 C, while the ltrate should be discarded [44].
Most of the perchlorate salts have high water solubility and once dissolved,
perchlorate is extremely mobile, requiring decades to degrade. The principal
pathway for aqueous perchlorate is by ingestion of contaminated water, but health
effects of perchlorate-contaminated water are not fully investigated. In human and
animal studies, it has been shown that perchlorate can inhibit the uptake of iodide by
the thyroid gland and cause pathological changes of the thyroid, even thyroid
tumors and severe neurological damages. Pure perchlorate salts are absorbed
through the skin. Perchlorate dust can be suspended in the air, and can be inhaled by
individuals, working in areas where perchlorate is manufactured. Perchlorate
compounds in the form of dust irritates the skin, eyes and mucous membranes; dust
and vapors can cause coughing and shortness of breath. Explosions and associated
res have been reported in perchlorate production facilities causing extensive
property damage in immediately adjacent areas. There may be still unknown effects
of perchlorate on ecosystems and it may be more widespread than already indicated.
It is also difcult to be removed from soil and groundwater. Groundwater
remediation at low concentrations (100 mg/l) is not economically possible with
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current technologies (ion exchange, reverse osmosis and electrodialysis), thus bio-
and/or phytoremediation technologies are attempted (acetate-oxidizing and per-
chloratechlorate-reducing bacteria) [4550].

3.6. Acetic silicone sealant

Acetic silicone sealant is a clear, durable and exible rubber paste, specically
intended for use as a sealant for bonding to non-porous surfaces such as glass, metal,
ceramic, etc. It forms a long lasting seal that is resistant to the effects of sunlight,
rain, snow, ozone, ultraviolet radiation and temperature extremes. Acetic silicone
sealants are based on poly-dimethyl siloxanes (PDMSs), they typically contain a
cross-linker, methyl triacetoxy silane, and are cured by atmospheric moisture. Their
name is derived from the acetic acid, which is generated during the curing reaction
and accounts for the distinctive smell derived from these products. Acetoxy, or acetic
acid cured silicones are the most widely used (instead of alkaline or neutral) in the
glass and sanitary industries and can be exposed to maximum service temperature of
120180 C. They are used for the peripheral sealing of some ECDs [51,52].

3.6.1. Acetic silicone sealant production


The synthesis of acetic silicone sealant is presented in the ow diagram of Fig. 8
and it comprises of: (1) chlorosilane synthesis (Fig. 8, process 1), (2) chlorosilane
hydrolysis (Fig. 8, process 2), (3) polycondensation (Fig. 8, process 3a) and
polymerization (Fig. 8, process 3b) and (4) cross-linking (Fig. 8, process 4) [53]. The
rst three steps are required to obtain the PDMS polymers. Acetoxy silicone sealant
is formulated from a reactive polymer prepared from a hydroxy end-blocked PDMS
and a large excess of methyl triacetoxy silane as cross-linker (Fig. 8, process 4). The
resulting product is still liquid and can be stored in sealed cartridges. Upon opening
and contact with the ambient moisture, the acetoxy groups are hydrolyzed to give
silanols, which allow further condensation to occur. An organometallic tin catalyst is
typically used. This cross-linking requires that moisture diffuses within the product
and curing proceeds from the outside surface toward the inside.

3.6.2. Input analysis: energy and raw materials


It is estimated that 1.4 kWh of energy is required per pound of polymer produced
[54]. In the case of silicone sealant it corresponds to 10.0 MJ/kg silicone sealant.
A common acetic silicone sealant contains [55,56]: hydroxyl-terminated PDMS is
the main constituent (60% w/w) used as polymer-bonder required to form the
elastomeric network, and PDMS polymer (10% w/w). Amorphous silica (25% w/w)
acts as reinforcing ller. Methyl triacetoxy silane (1.7% w/w) and ethyl triacetoxy
silane (2.6% w/w) are used for cross-linking of the polymeric component to provide
the network structure. Specic additives such as catalysts (organo-Sn, Ti, Pt, Zn,
Rh, 0.7% w/w) accelerate or retard the curing process.
PDMS polymers (often referred to as silicones) are formed from two compounds
that are largely available: quartz and methanol. PDMSs are used in many
applications because of their stability, low surface tension and lack of toxicity.
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quartz processing
1a

quartz HCl methanol

chlorosilane synthesis
1

dimethyl
dichlorosilane

chlorosilane
HCl
hydrolysis 2

linear oligomer cyclic oligomer

acid/basic acid/basic
condensation polymerisation
catalysts 3a 3b catalysts

PDMS hydroxy PDMS hydroxy


PDMS PDMS
terminated terminated

methyl triacetoxy silane amorphous silica


crosslinking by condensation organometalic tin
ethyl triacetoxy silane 4
catalyst

acetic acid
ACETOXY SILICONE
SEALANT

Fig. 8. Acetic silicone sealant production ow diagram.

In the following sentences, the necessary raw materials for the three steps synthesis
processes of PDMS are presented [53]:

1. Synthesis of chlorosilanes: Silicones are obtained commercially from chlorosilanes


prepared following the direct process of Rochow, using Si metal, obtained from
the reduction of quartz at high temperature, and methyl chloride, obtained by
condensation of methanol with hydrochloric acid. The reaction giving chlor-
osilanes takes place in a uidized bed of silicon metal powder, in which a stream
of methylchloride ows, usually at temperatures of 250350 C and at pressures of
15 bar. A mixture of different silanes is obtained containing mainly the
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E. Syrrakou et al. / Solar Energy Materials & Solar Cells 85 (2005) 205240 229

dimethydichlorosilane. The exothermic reaction proceeds in the presence of a


copper-based catalyst with a yield of 8590%, and the various silanes are
separated by distillation. The dimethyl dichlorosilane, which is separated,
becomes the monomer for the preparation of PDMS by hydrolysis. Redistribu-
tion reactions can be used to convert the other silanes and increase the
commercial yield of the production equipment.
2. Hydrolysis of chlorosilanes: PDMSs are obtained by the hydrolysis of the
dimethydichlorosilane in the presence of an excess of water. A heterogeneous and
exothermic reaction occurs that gives formally a disilanol intermediate, which
readily and rapidly condenses with HCl acting as a catalyst to give a mixture of
so-called linears and cyclics oligomers by inter- or intra-molecular condensation.
This mixture separates from the aqueous acid phase and the ratio between the two
types of oligomers depends on the hydrolysis conditions (concentrations, pH,
solvents). These oligomers are water-washed, neutralized and dried. The HCl is
recycled and reacted with methanol to give the methylchloride used in the direct
process described above.
3. Polymerization and polycondensation: The linear and cyclic oligomers obtained
have too short chains for most applications. They must be condensed (linears) or
polymerized (cyclics) to give acromolecules of sufcient length. The reaction in
both processes needs to be catalyzed by many acid or base compounds.

The other two basic raw materials used in silicone production silica and quartz are
substances primarily composed of silicon dioxide (SiO2) [57]. Silica is a general term
for silicon dioxide, both natural and man-made, while quartz refers to certain
crystalline forms of silica and is very abundant. Quartz used to produce silicon metal
must satisfy moderate requirements in terms of particle size and purity. Feed chip
sizes ranging from 10 to 100 mm insure appropriate gas permeability in the electric
furnaces used for silicon reduction. In terms of purity, a typical composition for
quartz used for silicon metal production is SiO2 content >98.0%, Al2O3 1.0% max,
Fe2O3 1.5% max, CaO 0.2% max and MgO 0.2% max.

3.6.3. Output analysis: emissions and health issues


Silica extraction is one of the simplest mining processes, as the material does not
require rening, resulting to relatively small amounts of overburden. Compared to
other process of extracting metallic ores of industrial minerals, the environmental
impacts due to silica extraction are relatively low. The content of the desired
substance, silicon dioxide, in the extracted rock is high. The main process emissions
are silica dust, spent water and emissions from the machinery used to collect and
process the ore [57].
Most siloxanes have a very low level of toxicity; this explains the use of silicone
uids as ingredients in many cosmetic products and of silicone elastomers as
materials in biomedical applications. The most common PDMS polymers have a
very low acute toxicity via the main routes of administration. They are not absorbed
through the skin, neither orally but excreted unchanged. Repeated oral, dermal or
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230 E. Syrrakou et al. / Solar Energy Materials & Solar Cells 85 (2005) 205240

inhalation dosage showed no signicant adverse effects to various species, while


in vitro studies showed no indication of mutagenic potential [53].
There is no evidence suggesting a negative impact of silicone to the environment.
PDMSs are nearly insoluble in water and absent from the water cycle. Because of
their extremely low solubility in water and low surface tension, these polymers will
accumulate in the sludge of wastewater treatment plant or be strongly absorbed by
particulate material in sediments. Upon disposal of the sludge (e.g. by land
amendment) these polymers can be chemically degraded, (e.g. by clay containing
soils) to lower molecular weight species, mainly siloxanols binding to soils or
volatilized and oxidized in the atmosphere. Furthermore, studies have shown that
volatile silicone oligomers like poly-dimethyl cyclo-siloxanes and short-chain linear
oligomers of low molecular weight do not contribute in the lower atmosphere to the
formation of ozone. These volatile silicone oligomers have been granted an
exemption from the volatile organic compounds regulations by the US EPA. In
the higher atmosphere, volatile silicones oligomers are quickly photochemically
degraded and do not deplete the ozone layer neither contribute signicantly to global
warming. Other silicone products, e.g. elastomers, are disposed by landll or
incineration, with their combustion leading to amorphous silica, CO2 and H2O [53].
Acetic silicone sealant is characterized as ammable and its thermal decomposi-
tion and combustion produce aldehydes, acids, and oxides of carbon, and silicon. As
it contains PDMS, it can generate formaldehyde as a by-product of oxidative
thermal decomposition at temperatures greater than 150 C in the presence of air.
Exposure to formaldehyde can cause adverse effects such as skin and respiratory
sensitization and eye and throat irritation at breathing concentration less than one
part per billion. Formaldehyde is a potential carcinogen [52,55,58].

4. Discussion

4.1. Inventory table

The results of the inventory analysis for the production phases of the constituents
of an ECD are depicted in Tables 1 and 2. The raw data used were obtained from EU
and EPA reports, product-specic LCAs and bibliographic sources. The rst table
summarizes the input data (raw materials and energy consumption), while analyses
of the air, water emissions and solid waste are presented in Table 2. Tungsten oxide
energy contribution (Table 1) has not been estimated, but it is expected to be
negligible because of its low mass contribution to the ECD (E0.1%). The emissions
data in Table 2 refer only to K-Glass, PC and PMMA, which all together represent
the 98% of the total ECD mass.
Some basic remarks regarding the K-Glass data incorporated in this study are:
* The nal product represents 70% in weight of the raw materials input, while the
cullet used replaces 20% of virgin raw materials. The packed product to melted
glass ratio used was 0.9.
Table 1

E. Syrrakou et al. / Solar Energy Materials & Solar Cells 85 (2005) 205240
Inventory table, input analysis

K-Glass Tungsten oxide Poly-methyl methacrylate Propylene Carbonate Lithium perchlorate Acetoxy silicone sealant

Substance (kg/kg Substance (kg/kg Substance (kg /kg Substance (kg /kg PC) Substance (kg /kg Substance (kg /kg
K-Glass) WO3) PMMA) LiClO4) silicone)

Raw materials
4
Silica sand 0.788 Sulfuric acid 1.40 Bauxite 7.3  10 Sodium 1.18 Sodium 0.212 Hydroxyl-terminated 0.6

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chloride chloride PDMS
Soda ash 1.37
5 2
Soda ash 0.286 Sodium hydroxide 1.03 Barytes 7.5  10 Crude oil 7.51  10 Lithium 0.308 Amorphous Silica 0.25
chloride
5 4
Limestone 0.141 Ammonium 0.12 Clay 1.1  10 Natural gas 3.17  10 PDMS 0.1
hydroxide
6
Dolomite 0.091 Al2(SO4)3  18H2O 0.08 Dolomite 6.0  10 Ethyl triacetoxy 0.026
silane
6
Alumina 0.043 Sodium sulde 0.05 Bentonite 2.0  10 Methyl triacetoxy 0.017
silane
Cullet 0.011 Mg(SO4)  7H2O 0.03 Calcium sulfate o5  10 7
Specic additives 0.007
Others 0.011 Chalk o5  10 7

Water 2.00 Chromium o5  10 7

Water resources 3.6

Energy consumption

(MJ/kg K-Glass) (MJ/kg WO3) (MJ/kg PMMA) (MJ/kg PC) (MJ/kg LiClO4) (MJ/kg silicone)

10.7 110.2 47.7 85.5 10.1

231
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Table 2
Inventory table, output analysis

K-Glass Propylene carbonate Poly-methyl methacrylate

Substance (kg/kg K- Substance (kg/kg PC) Substance (kg/kg


Glass) PMMA)

Air emissions
CO2 1.28  10 1 CO2 1.24 CO2 5.6
NOx 3  10 3 Hydrocarbons 2.45  10 2
SOx 2.8  10 2

SOx 2.3  10 3 SOx 3.63  10 3


NOx 2.2  10 2

CH4 8.15  10 4 NOx 2.82  10 3


CH4 1.9  10 2

HCl 1.74  10 4 Isobutane 2.66  10 3


Hydrocarbons 7.2  10 3

Particulates 1.00  10 4 CO 1.37  10 3


Dust 5.1  10 3

HF 2.65  10 5 Particulates 5.29  10 4


CO 2.3  10 3

Lead 2.22  10 5 Ammonia 3.47  10 4


Other organics 1.9  10 3

Arsenic 5  10 6 Other 2.74  10 4


H2 7.9  10 4

organics
7 4 4
Nickel 5.56  10 Propylene 2.58  10 HCl 1.5  10
4 4
Propylene 1.29  10 Aldehydes 1.0  10
oxide
Aldehydes 2.27  10 5 Metals 1.3  10 5

CH4 2.02  10 5 HF 8.0  10 6

Lead, o5  10 7 Ammonia 7.0  10 6

chlorine, HCl,
kerosene
6
H2S 4.0  10
6
HCN 3.0  10
6
Aromatic-HC 1.0  10
N2O, Cl2, lead, F2, o5  10 7

mercaptans,
organo-Cl,
polycyclic-HC, Hg,
CFC/HCFC,
H2SO4, CS2, DCE,
VCM

Water emissions
4
Chloride 0.082 Sulfuric acid 1.69  10 SO4 2 2.7  10 2
4 4
COD 2.31  10 Dissolved 1.43  10 Na+ 1.9  10 2

solids
Sulfate 1.8  10 4 Iron 4.20  10 5
Cl 1.0  10 2

Susp. solids 5.33  10 5 Ammonia 2.11  10 5


Susp. solids 1.9  10 3

Fluoride 4.44  10 5 COD 1.00  10 5


COD 1.5  10 3

Mineral oil 3.56  10 5 Oil 1.00  10 5


Organics (dissolved) 1.2  10 3

Ammonia 1.78  10 5 Metal ion 3.63  10 6


NH4 1.1  10 3

(Kjeldahl)
6
Boric acid 7.11  10 BOD 2.18  10 6 Phosphate (P2O5) 1.0  10 3
6
Barium 5.33  10 Susp. solids 1.94  10 6 Dissolved solids 6.3  10 4

Phenols 1.78  10 6
Phenol, zinc, o5  10 7 BOD 5.1  10 4

chromium,
acid, lead
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E. Syrrakou et al. / Solar Energy Materials & Solar Cells 85 (2005) 205240 233

Table 2 (continued)

K-Glass Propylene carbonate Poly-methyl methacrylate

Substance (kg/kg K- Substance (kg/kg PC) Substance (kg/kg


Glass) PMMA)
7 4
Chromium, 8.89  10 Various metals 2.1  10
Copper, tin,
lead, nickel,
zinc
Ca+2 1.2  10 4

Acid (H+) 1.1  10 4


5
Hydrocarbons 6.3  10
7 5
Arsenic, 5.33  10 Detergent/oil 6.2  10
antimony
5
Phenol 2.1  10
Cadmium o5  10 7
K+ 1.2  10 5
6
F 7.0  10
6
Other nitrogen 6.0  10
6
CN 4.0  10
CO3 2 3.0  10 6

NO3 , Fe+2/Fe+3, 2.0  10 6

Pb
Ni+2, Cu+/Cu+2, 1.0  10 6

sulfur/sulde, other
organics
Arsenic, DCE, o5  10 7

VCM, dissolved Cl2,


CrO3, organo-
chlorine, Al+3, Hg,
Mg+2, Zn+2

Solid waste

(kg/kg K-Glass) (kg/kg PC) (kg/kg PMMA)

0.0682 0.0298 0.11

* The water quantity used and wastewater emissions data (assumed to be 1.6 m3/
tonne glass melted) were taken from inputoutput analysis referring to container
glass production [22].
* Data from at glass industry [59], referring to fully recycled (by use of cullet) and
virgin glass, have been used to extrapolate the values presented in Table 2: 20%
use of cullet has been assumed.
* It is assumed that a cross-red regenerative furnace (code name FG3 [22]), which
uses gas or oil (1% in Sulfur), is incorporated in the K-Glass production line. Its
capacity is 650 tonne/day and primary NOx abatement techniques are used, while
100% of the dust is recycled with electrostatic precipitators and dry scrubbers.
This furnace is also equipped with waste heat boiler.
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* The generally accepted value for the energy required per kilogram of oat glass
melted and kilogram of glass produced are 8 and 10.7 MJ, respectively. On the
other hand, the lowest corresponding values were reported to be 6.2 and 8.3 MJ
for FG3 plant furnace [22].

4.2. Input materials

K-Glass accounts for 90% of the total ECD mass (see Fig. 1). Subsequently, the
raw materials used for its production are the major contributors to the whole input
analysis. These are mainly natural materials, which are mined, crushed and graded.
Thus, the abundant silica sand (SiO2) representing 72% of the total K-Glass mass,
accounts for 65% w.w. in the ECD composition. Tin tetrachloride (SnCl4),
hydrouoric acid (HF), methanol (CH3OH) and silane (SiH4) used during the K-
Glass coating process (CVD) are environmentally signicant, even if their quantities
are not reported in Table 1. Silane is a spontaneously combustible (pyrophoric) gas
and its existence may result to a subsequent re or explosion hazard. The lower limit
for spontaneous ignition of SiH4 in air ranges 23%, depending on the carrier
gas [60].
Tungsten oxide production demands many auxiliary materials, with sulfuric acid
and sodium carbonate (soda ash) being used in larger quantities. Raw materials for
the tungsten and PMMA production are mined by ores and then they are processed
to the nal product, while salt (NaCl) taken from brines is the main constituent for
PC and LiClO4 production. Furthermore, fossil fuels (crude oil and natural gas) are
used as energy sources and raw materials during PC production process. On the
contrary, acetoxy silicone sealant synthesis requires more complex chemical
substances apart from silica, namely siloxanes and silanes that are also produced
from quartz among others.

4.3. Energy analysis

The contribution of each material to the embodied energy of the ECD is presented
in Fig. 9. K-Glass corresponds to almost 66%, PC to below 25%, while PMMA,
LiClO4 and silicone account for less than 10% in total. The production of WO3 is
not characterized as high energy demanding and due to its negligible mass presence
its energy contribution to the ECD is considered insignicant. As presented in Table
1, the most energy demanding procedure is the manufacture of PMMA (110 MJ/kg
material produced). On the other hand, there is signicant difference between the
required energy for the production of 1 kg of K-Glass and PC: 10.7 and 47.7 MJ,
respectively. Due to this and although the PC mass ratio in ECD is quite small
(almost 8%, see Fig. 1) its nal contribution to the total embodied energy is
important and comparable to that of the K-Glass: 24.5% and 65.6%, respectively.
In Table 3 the embodied energies of an ECD and other insulating glass units
(IGUs) with the same dimensions (40 cm  40 cm) are compared. The data used [11],
refer to argon, krypton and xenon cavity lled double-glazed windows, which
represent a signicant percentage of the IGUs market worldwide. The values for the
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E. Syrrakou et al. / Solar Energy Materials & Solar Cells 85 (2005) 205240 235

PMMA
PC
4.7%
Material MJ/ECD 24.5%
K-Glass 32.13
WO3 -
PMMA 2.31
Propylene Carbonate 12.00 LiClO4
4.4%
Lithium Perchlorate 2.18
Silicone 0.37
Silicone
Total 48.98 K-Glass 0.8%
65.6%

Fig. 9. Contribution of materials in ECD embodied energy.

Table 3
Embodied energy of raw materials and manufacturing processes

Device type Embodied energy (MJ/unit) Frame (MJ/unit) Manufacture (MJ/unit)

ECD 49 252 130170


Argon lled IGU 42 252 137
Krypton lled IGU 116 252 137
Xenon lled IGU 697 252 137

ECD and the argon lled IGU are similar, while the energy required in the case of
krypton is more than double compared to ECD. On the other hand, xenon lled
IGUs demand extreme energy consumption, which could make them rather
unadvisable for real applications.
The frames are not included in the calculation of the above values, but in the case
of a typical timber frame suitable to t the EC window, 220250 MJ [11] should be
added to the embodied energy of each unit. In this frame we have incorporated some
aluminum components as the glazing unit spacer, frame ventilation, outer timber
protection and window mechanism. The energy requirements for the manufacturing
process of each of the IGU window systems (including frame and sealed glass unit
construction, aluminum processing, lighting and factory services) are 137 MJ/unit.
Corresponding values for an ECD are not commercially available, but taking into
account that no complex fabrication procedures will be included [3], an estimate of
130170 MJ/ECD is logical.
Thus, the values for the total embodied energies for the ECD and the argon lled
IGU are 431471 and 431 MJ/unit, respectively. The energy payback time for the EC
glazing is estimated to be less than 2 years [1,62]. On the other hand, given that the
added rst cost for installed, mass manufactured EC glazing will be almost 160 h/m2
of glazing, we can estimate a simple payback period of 3.2 years [1]. This analysis
depicts the promising future that advanced window systems such as ECDs could face
when they come to market, as they can combine favorable thermal and optical
properties with low energy demanding production procedures.
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4.4. Emission analysis, safety and environmental issues

The production processes of K-Glass, PC and PMMA (which all together


represent the 98% of the total ECD mass) account for emissions of 810 g of CO2
necessary for the fabrication of an ECD. The partial contribution of K-Glass, PC
and PMMA are 380, 310 and 120 g, respectively. CO2 emissions during the K-Glass
production are comparatively the lowest among the three, but due to its large mass
ratio in the ECD the nal value exceeds that of PC. For the same reason, NOx and
SOx emissions are mainly attributed to K-Glass and are about 9 g/ECD.
Chloride quantity found in liquid emissions reaches the 250 g/ECD, while air
emissions of HCl are about 500 mg. Particulates/dust emitted are above 10 4 kg/kg
for either of K-Glass or PC or PMMA produced. This value corresponds to 300 mg/
ECD produced, derived almost exclusively from K-Glass manufacture process. In
this case, particulates contain mostly silica dust, whose inhalation may cause a
serious lung condition known as silicosis, and is also suspected to be a carcinogen.
Exposure limits from The American Conference of Governmental Industrial
Hygienists (ACGIH) are set to 10 mg/m3 (for inhalation) and 3 mg/m3 (for
respiration), while Occupational Safety & Health Administration (OSHA) deter-
mines a value of 20 mppft3 [57,61].
Air and liquid emissions of toxic elements and metals (e.g. heavy metals, phenols),
produced during the K-Glass production are in the range of 15 mg/ECD, except
from lead and arsenic which are 66 and 15 mg/ECD, respectively. PC and PMMA
contributions to the above pollutants as well as organo-Cl compounds, hydro-
carbons, mercaptans, etc. are very low.
The air emissions of propylene, propylene oxide and HCN from PC and PMMA
production, respectively, are environmentally signicant, even though they
correspond to very small quantities per ECD. The fate of propylene to the
environment is not fully investigated yet as well as its detailed impacts to human
health (refer to Section 3.4.3), while propylene oxide is a severely irritating chemical
and animal carcinogen. HCN is emitted during PMMA production as air emission
and dilutes in liquid emissions (Section 3.3.2). It is an extremely toxic and hazardous
chemical with severe human health effects. The existence of emitted HCN and
ammonium hydrogen sulfate, which dilute in liquid emissions to sulfuric and
ammonium ions, have lead to the need of replacement of ACH process with other,
more environmental friendly. Other environmental signicant substances are emitted
during tungsten production and a large amount of by-products arise, some of which
are characterized as dangerous chemicals requiring special handling (Section 3.2.3),
although their value is very low per ECD.
Workers exposures, possible accident or release to the environment, are issues
causing serious concerns about some of the materials examined in this study.
Contamination of drinking water by perchlorate has severe impacts on human health
and ecosystems (Section 3.5.3). In the USA, large volumes of perchlorate have been
disposed since the mid-1940s (because of its extended use in rockets and missiles),
polluting the soil and aquifers. Today the detection limit of perchlorate in
groundwater has been lowered to 4 mg/l (with the analytical EPA Method 314.0).
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E. Syrrakou et al. / Solar Energy Materials & Solar Cells 85 (2005) 205240 237

A public health goal (PHG) in the range of 26 mg/l is proposed for perchlorate
percentage in drinking water, while a safe exposure limit is 0.03 mg anion of
perchlorate/kg of weight per day [4550].
PMMA and PC health impacts are discussed in Sections 3.3.3 and 3.4.3,
respectively, but their chemical, physical and toxicological properties have not been
thoroughly analyzed yet. MMA is a harmful and ammable chemical which should
be handled as hazardous waste, and the permissible exposure limit of OSHA and
ACGIH is 100 ppm time weighted average (TWA) [37,38]. The exposure limit for
methyl triacetoxy silane and ethyl triacetoxy silane, chemicals used during silicone
sealant production, is for both 10 ppm TWA and 15 ppm short-term exposure limit
(STEL) as denoted by ACGIH [52,55,58]. As far as tungsten is concerned, the lower
impacts among all the above-mentioned materials are recorded. The ACGIH has
recommended 5 mg/l for insoluble and 1 mg/l for soluble tungsten compounds [27,30].

5. Conclusions

The LCA method was used to determine the environmental impacts of an


electrochromic glazing (called ECD) production. This study covered the inventory
analysis for all the basic materials used during the manufacture of the ECD, i.e. K-
Glass, WO3, PMMA, PC, LiClO4 and acetic silicone sealant. Various ECD
prototypes were fabricated and tested in the lab. The difculties in nding reliable
data sources and the lack of available inventory data have to be denoted.
K-Glass, PC and PMMA account for the 98% of the total ECD mass and the CO2
emissions during their production processes are 810 g. Chloride quantity found in
liquid emissions reaches the 250 g/ECD, while air emissions of HCl are about
500 mg. The most energy demanding process was proved to be that of the PMMA
(101 MJ/kg) while LiCLO4, PC and K-Glass follow with 85.5, 47.7 and 10.7 MJ/kg
of product, respectively. The total embodied energy of the ECD was estimated to be
49 MJ/unit. The nal contribution of each material to this value was based on the
mass ratio and K-Glass was proved to be the most important with 32.1 MJ/ECD.
The comparison of the total embodied energies values for an ECD and various IGUs
was quite promising. A complete ECD with frame would need 431471 MJ/unit to be
produced, compared to 431 MJ/unit needed for an argon lled IGU. Taking into
account their improved overall performance (thermal and optical), mass-produced
electrochromic glazings with cost similar to that of the best available IGUs, would
certainly prevail.
The LCI analysis of the ECD has already moved to the next step of assessing the
laboratory assembling process. The operating energy and the energy savings during
the lifecycle of the device in buildings will also be estimated. For the disposal phase
the potential recycling and end-life methods will be evaluated and the emissions of
the disposed device will be reported. The LCI will be concluded with the total
inventory table where all inputs and outputs of ECD life cycle will be depicted. Thus,
the net energy of the device (embodied energy and operating energy) will be estimate
and the real savings of energy will be resulted. The LCA will be further implemented
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with LCIA, where the contribution of the above results to specic impact categories
will be estimated. Finally, with the interpretation of these results the total
environmental assessment of the ECD lifecycle will be carried out.

Acknowledgements

The authors would like to acknowledge the EU for nancially supporting this
work within the frames of the EESD program (project name ELEVAG, Contract
No. ENK6-CT-2001-00547).

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