ACKNOWLEDGEMENT
I take this opportunity to express my sincere gratitude to University Grants Commission, for
providing the financial assistance for undertaking and completing this Minor Research Project
work successfully.
I am grateful to Dr. U Jayaprakash (Former Principal), Dr. T.L Remadevi (Former Principal) and
Dr. Madhusudanan Pillai K.R, Principal, N.S.S College, Ottapalam and colleagues of my college
for their encouragement and help for completing my work.
.
K.M.GAYATHRIDEVY
(Principal Investigator)
Associate Professor
Dept. of Electronics
N S S College
Ottapalam – 679103.
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 1
MINOR RESEARCH PROJECT
FINAL REPORT
THE ROLE OF PRODUCTION - PROCESS MODIFICATIONS IN
E-WASTE MANAGEMENT
(F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014)
Submitted To
University Grants Commission
Submitted by
K.M.GAYATHRIDEVY
PRINCIPAL INVESTIGATOR
ASSOCIATE PROFESSOR
DEPARTMENT OF ELECTRONICS
N.S.S. COLLEGE, OTTAPALAM
.
CONTENTS
Introduction 4
Review of Literature 8
Lead And Its Alternatives 11
Mercury And Its Alternatives 20
Cadmium And Its Alternatives 24
Chromium And Its Alternatives 29
Flame Retardants And Its Alternatives 32
Phthalates And Its Alternatives 37
Initiatives Taken By Different Electronic
Companies 42
Conclusions 49
Bibliography 51
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 2
DECLARATION AND CERTIFICATE
I hereby declare and certify that, the Final Report of the Minor Research Project
entitled “THE ROLE OF PRODUCTION - PROCESS MODIFICATIONS IN
EWASTE MANAGEMENT” NO.F.MRP/12th Plan/14-15/KLCA025 Dated
10/12/2014 is a bonafide record of research work carried out by me during the
year 2015- 2017. Further certify that the work presented in the report is carried out
according to the plan in the proposal and guidelines of the University Grants
Commission.
Principal Investigator Principal
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 3
INTRODUCTION
Electronic waste or e-waste describes discarded electrical or electronic devices. Used electronics
which are destined for reuse, resale, salvage, recycling, or disposal are also considered as e-
waste. Electronic scrap components, such as TV, CPUs, mobile phones etc, contain potentially
harmful components such as lead, mercury, beryllium, or brominated flame retardants. Recycling
and disposal of e-waste may involve significant risk to workers and communities in developed
countries and great care must be taken to avoid unsafe exposure in recycling operations and
leaking of materials such as heavy metals from landfills and incinerator ashes.
The electronic waste problem is huge: More than 20 million tons of e-waste are produced every
year. Americans alone generate about 3.4 million tons of e-waste per year. So in industries,
management of e-waste should begin at the point of generation. This can be done by waste
minimization techniques and by sustainable product design. Waste minimization in industries
involves adopting:
inventory management,
production-process modification,
volume reduction,
recovery and reuse.
Inventory management
By reducing both the quantity of hazardous materials used in the process and the amount
of excess raw materials in stock, the quantity of waste generated can be reduced.
Production-process modification
Changes can be made in the production process, which will reduce waste generation. This
reduction can be accomplished by changing the materials used to make the product or by the
more efficient use of input materials in the production process or both.
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 4
Volume reduction
Volume reduction includes those techniques that remove the hazardous portion of a waste
from a non-hazardous portion. These techniques are usually to reduce the volume, and
thus the cost of disposing of a waste material.
Recovery and reuse
This technique could eliminate waste disposal costs, reduce raw material costs and
provide income from a salable waste. Waste can be recovered on-site, or at an off-site
recovery facility, or through inter industry exchange. A number of physical and chemical
techniques are available to reclaim a waste material such as reverse osmosis, electrolysis,
condensation, electrolytic recovery, filtration, centrifugation etc.
Currently, most focus is placed on phasing out certain chemicals and there is little focus on other
aspects such as ease of disassembly. It is also important to note that, even were toxic materials to
be entirely designed out of electronics, the environmental and health impacts generated from the
rudimentary techniques used in informal recycling processes would still be unacceptably high.
Thus, eliminating negative environmental and health impacts through design requires the use of
materials which would not generate toxic matter even if processed using the most primitive of
methods, such as open burning.
For effectively tackling the problem of e-waste various countries irrespective of developed or
developing and underdeveloped in nature create individual regulations, Laws, Regulations and
Initiatives to tackle the mammoth growth problem of e waste. The group of developed countries
namely European Union, United States and other major stakeholder developed Asian countries
contributing to E -products initiatives till date can be listed as :-
Waste Electrical and Electronic Equipment (WEEE) Directive
Restriction of Hazardous Substances (RoHS) Directive
EU Directive on Energy-using-Products (EuP)
EU Directive on Registration, Evaluation and Authorisation of Chemicals (REACH)
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 5
E-waste regulations in Japan, China, India, Korea, United States, Canada and other many
nations
Basel Convention/s Basel Convention Partnership on the ESM of E-waste in the Asia-
Pacific region
Mobile Phone Partnership Initiative (MPPI)
Partnership for Action on Computing Equipment (PACE)
StEP Initiative
Regional 3R Forum in Asia
Objectives of the Project:
The project focuses on the study of possibility of alternatives for the hazardous and toxic
substances in the e-waste. RoHS often referred to (inaccurately) as the 'lead-free directive',
restricts the use of the following ten substances:
1. Lead (Pb)
2. Mercury (Hg)
3. Cadmium (Cd)
4. Hexavalent chromium (Cr6+)
5. Polybrominated biphenyls (PBB)
6. Polybrominated diphenyl ether (PBDE)
7. Bis(2-ethylhexyl) phthalate (DEHP)
8. Butyl benzyl phthalate (BBP)
9. Dibutyl phthalate (DBP)
10.Diisobutyl phthalate (DIBP)
DEHP, BBP, DBP and DIBP were added as part of DIRECTIVE (EU) 2015/863 which was
published on 31 March 2015
The substitutes for each of the hazardous substances are studied separately. Since the toxicity is
the main cause of the problem of e-waste, if less or nontoxic materials can replace the hazardous
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 6
substances then material change itself will be a good solution to the problem of e-waste. How far
the electronic industry succeeded in finding the suitable alternatives is also studied.
Research Design and Methodology:
As the subject is concerned with the role of production process modifications in e waste
management, the study has relied upon the textbooks, journals, research papers, project reports
and opinions from experts in electronics.
Area and Scope of the study:
The present study is concerned with how far we can modify the production process of electronic
equipments so that the e waste problem can be minimized. The study focuses on the research
developments in finding the alternatives of the hazardous substances in electronic devices and
how the different manufacturing companies modify their production process.
Relevance of the Study:
Today, primary environmental and sustainability-centred legislation arising in different regions
of the world, and the economics of materials supply and management across the whole lifecycle,
are primary drivers for the types of materials that will continue to be used in the future and those
which need to be developed to replace those that cannot meet the requirements. The
encouragement of eco-design principles, which include materials selection, will lead to the
integration of environmental considerations during the design and materials-selection phases of a
product.
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 7
REVIEW OF LITERATURE
E-waste comprises of wastes generated from used electronic devices and household appliances
which are not fit for their original intended use and are destined for recovery, recycling or
disposal. Such waste encompasses wide range of electrical and electronic devices such as
computers, hand held cellular phones, personal stereos, including large household appliances
such as refrigerators, air conditioners. Electronic wastes contain toxic substances such as lead,
mercury, cadmium, and lithium. These toxic materials can be released upon disposal, posing a
threat to human health and the environment. Inconsistencies in worker safety and environmental
protection mean potential liability concerns for those sending electronics to recycling facilities –
especially if these facilities are located in developing countries. (S.Mahima, Coimbatore)
The effect of usage, dumping and recycling of the electronic waste on the natural environment
are an important field of study in Developing Countries (Dr. Mathias Schluep). Basel
Convention characterizes e-waste as hazardous when they contain and are contaminated with
mercury, lead, cadmium, polychlorinated biphenyl etc. R.E. HESTER AND R.M. HARRISON
illustrates the technical complexity of much of the so-called e-Waste and the difficulties that this
presents for recovery and re-use of precious materials. So much attention is being given to the
design of electrical and electronic products in order to facilitate their treatment at end of life.
For effectively tackling problem of e waste various country‘s irrespective of developed or
developing and underdeveloped in nature create individual regulations, Laws, Regulations and
Initiatives to tackle the mammoth growth problem of e waste.( Umesh Kumar, Dr. D. N. Singh)
The group of developed countries namely European Union, United States and other major
stakeholder developed Asian countries contributing to e products initiatives like Waste
Electrical and Electronic Equipment (WEEE), Restriction of Hazardous Substances (RoHS)
Directive, EU Directive on Registration, Evaluation and Authorisation of Chemicals (REACH),
Waste Electrical and Electronic Equipment, E-waste regulations in Japan, China, India, Korea,
United States, Canada and other many nations, Basel Convention etc. In industries management
of e-waste should begin at the point of generation. This can be done by waste minimization
techniques and by sustainable product design. Changes can be made in the production process,
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 8
which will reduce waste generation. This reduction can be accomplished by changing the
materials used to make the product or by the more efficient use of input materials in the
production process or both(Ramachandra T.V, Saira Varghese K.-Energy and Wetlands Group,
Center for Ecological Sciences, Indian Institute of Science, Bangalore.)
The introduction of the RoHS has created many opportunities and just as many challenges for
manufacturers in financing R&D activities and undertaking innovation, understanding the
constraints throughout the supply chains and in identifying effective substitutes and their
limitations on product design and performance.( ARCADIS ECOLAS & RPA Economic impact
analysis 06/11925 - a study on RoHS and WEEE directives). The RoHS directive aims to restrict
the presence of Lead (Pb), Cadmium (Cd), Mercury (Hg), Hexavalent chromium (Hex-Cr),
Polybrominated biphenyls (PBB), and Polybrominated diphenyl ethers (PBDE).
Throughout recorded history, lead has been known to be toxic. H.L. Needleman points out that
evidence of lead toxicity existed in 2000 BC. Industry has come up with several lead free
solders with preference given to alloys containing tin, silver and copper but there is no ‘drop-in'
substitute to leaded solder. (Sunil Heart, Griffith University). Research is going on in Electronics
Manufacturing with Lead-Free, Halogen-Free, and Conductive-Adhesive Materials (John
Lau , C.P. Wong , Ning-Cheng Lee, Ricky Lee)
Agency for Toxic Substances and Disease Registry, Electro-tech-online.com and many other
websites and projects give ample information about replacement-for-mercury. Bruce Sartwell,
Weapons Systems and Platforms Program Manager, SERDP/ESTCP and Faraday Technology,
Inc.315 Huls Drive Clayton explains the alternatives of Cr6+ used in their products.
“The transition away from environmentally sensitive substances, such as brominated flame
Retardants and PVC is well under way at Acer. However we do not have the leverage to move
the entire supply‐chain on our own. Legislators can help in this process”, explains Richard Lai,
head of Corporate Sustainability Office at Acer. “By introducing restrictions, and thereby
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 9
ensuring that the entire supply‐chain is on board, costs are kept down and availability of safer
alternative material is promoted.”
“Dell supports including BFRs and PVC among the substances restricted by RoHS, as well as a
full ban on these substances in 2015,” said Mark Newton, Dell’s director of sustainability.“Given
the ongoing discussions in the EU Institutions on the RoHS recast, we hope EU decision makers
revise RoHS to prohibit the use of PVC and BFRs in electrical and electronic equipment.”
“HP is working with suppliers globally to remove these chemicals from personal computing
product lines”, said Ray Moskaluk at HP. “We support these restrictions in a revised RoHS
Directive.”
Sony Ericsson is committed to a complete phase‐out of halogenated organic substances from
its products, and at the current time has phased out almost all brominated flame retardants
(BFR)," said Daniel Paska, Environmental Expert at Sony Ericsson. "We believe the electronics
industry has a responsibility to move proactively to find substitutes to replace BFR and PVC
and are therefore calling on EU legislators to show leadership on this issue by voting to tighten
the RoHS directive.”
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 10
LEAD AND ITS ALTERNATIVES
E-Waste is of major health and environmental concern due to the toxicity of some of the
materials present in the waste stream. These include metals such as lead, mercury, hexavalent
chromium and cadmium and chemicals such as polychlorinated biphenyls.
The Latin word for lead, plumbum, may have derived from the original Sanskrit bahu-mala,
meaning “very dirty.” Throughout recorded history, lead has been known to be toxic.
Lead Average
Lead in computers- 1.72 kgs
• Can be upto 2-3 kg of each CRT
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 11
Health Effects or Physiological Changes Associated with Blood Lead Levels
Blood Lead Levels (μg/dL)
Health Impacts Children Adults
IQ Reduction (1–4 points, mean of 2.6)a 10–20 N/A
IQ Reduction (2–5 points, mean of 3.5)a 20 N/A
Increased Systolic Blood Pressure (1.25 mm Hg) N/A 10-15b
Increased Systolic Blood Pressure (2.50 mm Hg) N/A 15-20b
Increased Systolic Blood Pressure (3.75 mm Hg) N/A Above 20b
Gastrointestinal Effects 60 N/A
Anemia 70 80
Nephropathy 80 120
Encephalopathy 90 140aIn children aged 0–1 only; bin men, aged 20–79; N/A = not applicable, or data
not available.
• In solder.
• Lead sulphate stabilizer in PVC sheathing for cables and wires.
• 0.3% by weight of lead in mobile phones (Average weight- 125gms)
Lead in EEE is of a major concern to the public due its ability to leach from landfills and
contaminate the human food chain causing serious health hazards. Commonly known as
‘Restriction of Hazardous Substances (RoHS)‘ legislation attempts to create green electronics by
the application of environmentally considerate design and manufacture to EEE. Lead-free
soldering in EEE is one of the major drivers of the legislation forcing researchers and
manufacturers to find suitable lead-free substitutes for the traditional leaded solders used for
several decades.
Of the six substances regulated by the RoHS Directive, Lead(Pb) is the most widely used in
semiconductor manufacturing. In addition, Lead(Pb) based solder has been widely used in the
electronics industry for the last 50 years with great success and high reliability. Soldering is the
process where two metals are joined together by means of a third metal or alloy having a
relatively low melting point. The process involves exposing the electronic components and the
PCB to high temperatures to melt the soldering alloys which then form an acceptable solder
joint. The most common processes used for such operation are reflow and wave soldering . In
Wave soldering the electronic components are inserted or placed on the printed circuit board and
is passed across a pumped wave molten solder which is held in a tank while reflow soldering
attaches a surface mounted component to a circuit board, apply the solder paste, position the
devices, and reflow the solder in a conveyorized oven.
Lead-based solders have been used for a time in the electronics industry with most common
being 63% tin (Sn) and 37% lead (Pb) by weight referred to as Sn63Pb37. Mechanically and
electrically lead-based solders make an excellent choice in the electronics industry but due to the
environmental reasons described above regulators now require the manufacturers to find suitable
alternatives.
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The transition to Lead (Pb)-free plating alternatives and Lead(Pb)-free solder requires additional
qualification tests to ensure manufacturability and long term reliability. In addition, Lead (Pb)-
free components generally require a higher soldering temperature, along with a complete bill of
materials compatible with the higher temperature profile. As a result, the elimination of Lead
(Pb) requires more change throughout the entire supply chain and manufacturing process. This
accounts for the greater emphasis on Lead(Pb)- free materials than on the other regulated
substances.
Lead-free Solder Choices
There are many lead-free solder systems that have been proposed as replacements for
conventional lead-based solders and they have melting ranges from much lower than
conventional solders to much higher. Consequently, solders based on tin-silver-copper alloy
compositions are widely used for both reflow and wave soldering and tin-copper alloys are also
used for wave soldering. The tin-silver-copper solders, which are also known as SAC alloys,
have compositions with melting ranges between 215 and 220oC . For wave soldering, the tin-
copper eutectic alloy (Sn-0.7Cu) melts at 227oC and this represents one of the lowest-cost lead-
free alloys available, although SAC alloys are also widely used in wave soldering. These higher
soldering temperatures can have a significant impact on materials, components and processes
and it is vital that soldering operations are modified accordingly if successful soldering is to be
achieved.
Examples of tin-silver-copper and related lead-free solder alloys
Alloy type Composition Melting Point/oC
Tin-silver-copper Sn96.5/Ag3.0/Cu0.5 219.8
Tin-silver-copper Sn95.5/Ag3.8/Cu0.7 218.8
Tin-silver-copper Sn95.5/Ag4.0/Cu0.5 220.2
Tin-silver-copper -antimony Sn96.2/Ag2.5/Cu0.8/Sb0.5 217.0
Tin-copper Sn99.3/Sn0.7 227.0
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One problem with lead-free alternatives is a tendency to get brittle over time after repeated or
prolonged heating cycles. This potential drawback has become an increasingly important factor
as technological advances have boosted the operating temperatures of common electronics
devices. For example, the steady climb in computer-processor speeds has meant a corresponding
increase in the amount of heat that computers generate.
To combat this solder “aging” problem, Ames Lab researchers are studying additional additives
to the tin-silver-copper formula, including silicon, titanium, chromium, manganese, nickel, zinc
and germanium. Joints soldered with the different alloys were subjected to 150 °C for 1,000
hours, then tested for both shear strength and impact strength.
For long-term joint reliability, modifying a strong (high copper content) tin-silver-copper solder
alloy with a substitution alloy addition for copper seems effective for producing a solder joint
that retains both strength and ductility after at least 1,000 hours of aging at temperatures up to
150 °C. Of the choices tested, cobalt, iron, and zinc substitutions for copper seem most attractive
from the standpoint of the microstructure. Although nickel has the same strong interfacial
segregation behavior as the others, the discovery of a brittle failure case and the reduced impact
strength on thermal aging seem to take it out of prime consideration.
The substitutes to Sn-Pb solders must satisfy various engineering and other criteria which
includes similar properties to current alloys, same temperature range as Sn-Pb, same or better
reliability and equal or lower cost, compatibility with standard finishes, ease of application with
wetting properties similar to current Sn-Pb including fluidity and cohesive force and stability.
Technically, lead-free solders must have a coefficient of thermal expansion (CTE) that matches
the joining components, must be able to resist thermal cycling, have sufficient creep resistance to
maintain thermo mechanical loading in the longer periods in the field of use. In general,
materials used in lead free alternatives must be readily available, be economical and should not
have any negative environmental impact now or in the future.
A lead free substitute that satisfies all the above criteria is referred to as a ‘drop in' substitute for
Sn-Pb solder. Unfortunately, up to date manufacturers or researchers have not been able to find
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 14
such a substitute, although they have come up with near solutions. The issue here is that if all the
potential metals for lead free substitute were screened even on basic requirements such as
melting point, cost, availability, toxicology and chemical resistance, only very few will appear as
possibilities. Sn, Cu and Ag become the leading candidates followed closely by Bi, Sb, In, Zn
and Al. However, Bi and Sb are partially produced as by-products in lead manufacturing,
therefore, strictly should not be considered. There are various issues for metals other than Sn, Cu
and Ag. Bi and In are only produced at a rate of 3,000 and 500 tonnes per year, which is far
below the 10,000 tonnes per year of lead used in conventional lead solders. Zn and Al are known
to oxidise rapidly in manufacturing and use. Cost-wise, Sn is about 10 times the price of lead and
Cu, Ag and In are all about 300-400 times the cost of lead
Issues with Lead-free Substitutes
One of the key issues with lead free substitutes is the temperature and the process time required
to flow the solder. The melting point of the traditional Sn-Pb solder is 1830C, which requires a
maximum reflow temperature of around 2200C. The most preferred lead-free alloys have a
melting temperature range from 217-2200C (see Table 1), which corresponds to reflow
temperature of 2540C, an increase of 340C heating difference. Since soldering is one of the last
steps of the PCB manufacturing process, all the materials and electronic components on the
board must withstand this increased thermal differential. The question is whether most of
laminates that are currently used in PCBs can achieve this as they have low glass transition
temperatures. Hence more expensive substrates need to be designed for this new temperature
environment. Taking this into account, the design engineers are replacing the traditional
substrates used in PCBs by newer materials which have higher glass transition temperatures. A
further issue related to the high temperatures is increased potential for the growth of conductive
anodic filament (CAF) known to be an electrochemical failure of the PCB during the use
environment. CAF are by products from Cu corrosion that emanate from the anode of a circuit
and grow subsurface towards the cathode most frequently along separated fiber-epoxy interfaces
in the PCB. A recent study has shown that higher reflow temperatures needed for lead free
solders could result in increasingly higher incidences of CAF.
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Another problem related to high temperature soldering relates to the polymers used in the PCBs.
Prior to reflow soldering most of these components are exposed to the environment and hence
absorb moisture from air. As the components undergo the reflow process this moisture turns into
steam and creates internal stress by trapping inside the polymers. This can result in electrical
failure if the connections are broken. This process can be worsened by the increased
temperatures used in lead free solders. Only solution for this is to use high water permeability
polymers.
As with many other manufacturing processes, higher operating temperatures will increase the
energy consumption and the associated CO2 emissions which is also one of the drawbacks of
lead-free soldering.
Intermetallic formation, an another issue in lead free soldering, is a diffusion driven process
where solder-wettable coatings are transformed into intermetallics by solid-state reactions.
During the soldering process molten solders come into contact with Cu or Ni surfaces they wet
resulting in the formation of interfacial intermetallics. These grow in solid state into the solder as
rods or plates. If these formations become too thick they can weaken the solder joint and may
fracture under certain conditions. There is a concern that high Sn-content lead free solders could
accelerate the growth of theNi and Cu metals resulted in the formation of intermetallics that are
not significantly thicker than with traditional Sn-Pb solder but provided a path for fracture under
mechanical loading due to increased strength of lead free alloys. Furthermore, Ho found that
addition of Ni to Sn, SnCu, SnAg, and SnAgCu alloys in amounts as minute as 0.1 wt.% is able
to substantially hinder the intermetallic growth hence a useful alloying additive to these solders.
However, the present understanding of the behaviour of these intermetallic structures under
elevated temperatures or longer term use is very low, hence needs more research.
As with intermetallic formation, the complete understanding of the reliability of lead free solders
is still far away. The fatigue characteristics of popular lead free solders are unknown to a certain
extent as they vary dependant upon the test conditions. Under some conditions lead free solders
were found to have more fatigue resistance than the traditional Sn-Pb solder but in other cases
they were found to be equal or worse.
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Tin whiskers are metallic crystals that can grow out of the surface of a Sn surface very rapidly
and can be very long. The problem occurs when these whiskers join across conducting contacts
resulting in electric shorts. Although the potential growth of whiskers on tin and tin alloys has
been a consideration in electronics in the past they have not been a major issue since alloying of
Sn with a few percent of Pb was found to greatly reduce the whisker formation. However, with
the advent of lead free regulations industry is moving rapidly to pure Sn and other high Sn
content lead free alloys and as such formation of tin whiskers has become a major issue. A
significant amount of scientific literature could be found on the topic of tin whiskers, much of
recently, however, there is still no consensus on the specific growth mechanisms for whisker
growth. The most preferred lead free alloy – SnAgCu- has only very small amounts of Ag and
Cu, hence the possibility of these elements consumed at the interface is large leaving behind a
large regions of Sn available for whisker formation. Fukuda studied the whisker growth on
whisker growth on various types of specimens in terms of density and length distributions. They
found high whisker densities and lengths in bright Sn plating demonstrating the unsuitability of
their use in electronics. However, they found shorter whisker lengths in matte Sn finishes
although they could still cause problems with fine-pitch devices. They also questioned the
applicability of current durability testing times as whisker growth continues to increase over
time.
Tin pest is an allotropic transformation of Sn which causes deterioration of Sn objects at low
temperatures. At 13.20C and below, pure Sn transforms from the silvery, ductile allotrope of β-
modification white tin to brittle α-modification grey tin, eventually decomposing into powder. A
large volume change is associated with this transformation causing eruptions (warts), cracking
and eventual disintegration.
Scientific observations of tin pest formation reveal a huge inconsistency and an incomplete
understanding of the process with some alloy additions promoting tin pest by reducing the
incubation time, whereas others retarding or inhibiting its formation.
The factors governing the tin pest formation are unknown although elements such as Pb, Sb and
Bi which are soluble in Sn seem to inhibit tin pest appearance while insoluble metals such as Zn,
Al and Mg promote its formation. The major issue is insoluble metals such as Zn, Al and Mg
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 17
promote its formation. The major issue is to what extend the proposed lead free alloys are
vulnerable to the tin pest phenomenon. Plumbridge studied the behaviour of several lead-free
solder alloys (Sn–3.5Ag, Sn–0.5Cu, Sn–3.8Ag–0.7Cu, and Sn–8Zn–3Bi) and found that only the
Sn–0.5Cu solder is vulnerable to the appearance of tin pest. He also found that impurities may
inhibit the formation of tin pest, but for long term applications there is no certainty that tin pest
and joint deterioration will never occur.
Examples of Pb-free Implementation/Products
Matsushita Electric (Panasonic) has completed a switch over to Pb-free solder for PCBs
in March 2003. – 12,000 models have been manufactured in 22 facilities in Japan and 79
overseas facilities of the Matsushita group.
Approximately 80% of the Sony’s products use Pb-free solders. – Pb-free products
include LCD TV, mobile phone, laptop PC, and digital camcorder.
Motorola shipped more than 10,000 units of mobile phones with the use of Pb free solder
paste to date.
All of the Toshiba’s new hard disk drives have already implemented Pb-free soldering
and halogen-free PCB.
Challenges-General Pb-free Electronics
No exact drop-in replacement for Pb-based materials/components.
Solder alloy selection may vary based on application.
Replacements likely to see wide adoption include – SnAgCu – Reflow – SnCu – Wave –
SnAgCu or SnAg - Rework
Changes in component finishes, die attach materials, solders joints
Higher processing temperatures (pop-corning, board warpage, delamination)
Compatibility with Pb-free processing (mixed technology)
– Indirect failure mechanisms (tin whiskers, creep corrosion)
–Solder joint reliability (durability, intermetallic growth)
Conclusions
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Substitution of the six RoHS substances is in many cases not straightforward, especially lead.
Many uses of lead have no alternatives such as in some types of glass and ceramics and so
exemptions are permitted. Lead based solders have however been replaced by lead-free solder
alloys but these are not drop- in replacements.
The issue of lead-free solders is an excellent example of a challenging problem for society,
regardless of whether you approach it as a human ecologist, a social ecologist, an industrial
ecologist, or simply as a materials scientist. A great deal of empirical information has been
presented in order to help organizations implement lead-free soldering per their own time-line.
Lead-free electronics assembly is achievable, but it requires a strong understanding of the
changes required of each person involved in the manufacturing process. This pertains to
considerations regarding design, components, PWBs, solder alloys, fluxes, printing, reflow,
wave soldering, rework, cleaning, equipment wear & tear and inspection.
Mercury and Its Alternatives
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 19
Mercury is a metallic element that occurs naturally in the environment. It has been used by
various industries for many years to manufacture chemicals or as a catalyst for chemical
processes because of its unique characteristics. Some of the parts of EEE function by utilizing
some characteristics of mercury. There are three primary categories of mercury and its
compounds: elemental mercury, which may occur in both liquid and gaseous states; inorganic
mercury compounds, including mercurous chloride, mercuric chloride, mercuric acetate, and
mercuric sulphide; and organic mercury compounds. The characteristics of mercury are unique
that mercury exists as liquid at normal temperature and pressure and transforms into the vapour
at 0.3 Pa, 25°C. Elemental mercury is the most volatile form of mercury. Mercury vapours are
colourless and odourless. The higher the temperature, the more vapours are released from liquid
elemental mercury.
E-waste and mercury
EEE using mercury accounts for 26 categories at least and includes audio equipment, laptops or
notebook computers, telephones, DVD players, fax machines, photocopiers, products containing
liquid crystal display (LCD), and so on. Mercury in the EEE is contained in LCD backlights,
lamp components, and display panels and so on. Although the amount of mercury contained in
each unit of EEE is at a low level (about 2- 10 mg per equipment), it is estimated that all the
mercury annually used in EEE accounts for about 22 per cent of the world mercury consumption
When EEE is disposed of in an environmentally unsound manner, the mercury contained in it is
released into the environment because of its chemical properties. A gas containing low pressure
mercury vapour in fluorescent lamps, for instance, escapes into the environment when
fluorescent lamps are broken. The other occasions on which mercury leaks is when obsolete EEE
is disposed of into landfills, or incinerated, or openly dumped into illegal dumping sites in an
environmentally unsound manner. Once mercury is released into the environment, it remains
there permanently, changing its chemical forms depending on the environment. Mercury cannot
be converted to a non mercury compound. If people inhale mercury vapour, approximately 80
per cent of it crosses the alveolar membrane and is rapidly absorbed into the blood. Due to the
high lipophilicity, elemental mercury vapour passes the blood-brain barrier and the placenta.
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The simplest and easiest way to avoid mercury exposure is to use protective gears, such as masks
(particulate respirators), goggles, gloves and protective clothing. The other way is to install a
ventilation system or at least open windows during processing. However, it should be noted that
mercury vapour would simply be released into the environment in this case. Although ideally
there should be an advanced ventilation system, such as a fume hood equipped with an air
control system, this would be a first step for the informal recycling industry to become “a formal
recycling sector” under a legal framework and subsidized by a public sector.
There are mercury free alternatives for nearly every product currently requiring mercury,
although the global transition to mercury free products will be quicker and easier for some
product categories than others. Between 65-75% of mercury used in products is used in batteries,
measuring and control devices, and electronic devices.
Items that may contain mercury Mercury-free alternative(s)
Float control switches Magnetic dry reed switches, optic sensors, and
mechanical switches
Flow meters with mercury switches Digital, optical, and ball-actuated flow meters
Fluorescent, vapor, metal halide, and high-
pressure sodium lamps
Fluorescent light bulbs
None (recycle old bulbs safely)
None (recycle old bulbs safely)
Fungicides and pesticides New fungicides and pesticides don’t contain mercury
(get rid of old fungicides and pesticides safely).
Products made before 1994 may contain mercury
Latex or marine paint and floor
varnishes
New paint and varnishes don’t contain mercury (get
rid of old paint and varnishes safely). Products made
before 1992 may contain mercury
Mercury gauges Electronic or aneroid gauges
Mercury oxide or mercury zinc
batteries
Zinc-air or silver oxide batteries
Older model microwave ovens New microwave ovens don’t contain mercury vapor
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 21
Other equipment with mercury switches (e.g.,
flame sensors, fire alarms, safety valves)
bulbs (follow local procedures for recycling
mercury vapor bulbs)
Non-mercury thermocouples, electronic ignition
systems, fire alarms with a snap-action, or push-
button switch
“Silent” light switches New light switches don’t contain mercury (get rid of
old light switches safely)
Thermometers in freezers and
refrigerators
Digital or other mercury-free thermometers
Thermostats Air-controlled, reed switch, vapor-filled diaphragm,
snap-switch, or programmable digital thermostats
Less-toxic TVs: Electronics industry rapidly going mercury-free
A television set that is 37 percent thinner, uses 46 percent less energy -- and is made without
the highly toxic heavy metal mercury? That sounds like too much eco-goodness rolled into one
PR-friendly package. But this is precisely what consumer electronics giant Samsung is
boasting in its new generation of super-thin, super bright LCD television sets.
Samsung's elimination of mercury from LCDs is part of a sea change in the industry as
manufacturers switch from mercury-laden cold-cathode fluorescent lamp (CCFL) lighting
systems to more efficient and less toxic light-emitting diode (LED) systems that illuminate the
glass screens and make images on the TVs visible and bright. As the tech industry rushes to go
green, Samsung and many other consumer electronics manufacturers are rolling out new
product lines that leave out some of the more toxic elements, while both improving
performance and efficiency. Apple has introduced mercury-free LCDs in its own products,
including the MacBook Pro and MacBook Air. Japanese LCD component and set makers
Matsushita and Sony have also rolled out LCD TVs that don't contain mercury.
The rapid adoption of this technology by manufacturers has helped drop pricing on LED-based
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 22
illumination for consumer electronics products dramatically. The greatest beneficiary of these
new technologies could well be China, the destination of choice for illicit e-cyclers.
Unregulated recycling operations contribute significantly to mercury and other heavy metal
contamination in parts of China.
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NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 24
Cadmium and Its Alternatives
Cadmium is widely used in engineering applications because of its unique properties. The coatings are
adherent, smooth and ductile, and may be applied to a wide range of metals. For electrical and electronic
applications, which make up about one-quarter of the market for cadmium coatings, ease of solderability
and high electrical and thermal conductivity, along with low contact resistance, are important properties.
Some Uses of Cadmium & Its Compounds In Electrical & Electronics-Related Industries
Application Component
Motors Brushes, commutators, slip rings
Batteries Electrodes for nickel-cadmium and mercury-
cadmium cells, reference cells
Battery packs Holders, contacts, sockets, connectors, bonding
Surfaces
Printed Circuit Boards Solder (fatigue resistant), bipolar transistors,
holders, Connectors
cabinet housings Latches, hinges, fasteners, chases, EMI
shielding
Switches, Relays Contacts
Photovoltaic cells Semiconducting materials, contacts
Cadmium is a highly toxic cumulative poison and a probable human carcinogen. Because it leaches
easily, it is a frequent environmental contaminant from aircraft and engine washdowns. Under the
European rules ELV (End-of-life Vehicles), WEEE (Waste Electrical and Electronic Equipment)
and RoHS (Restriction of Hazardous Substances), cadmium is restricted to no more than 0.01wt% of any
vehicle and electronic material or coating, with exemptions for aircraft and military use. These
exemptions are only temporary and are intended to be removed once alternatives become available.
Under the new European REACH statute (Registration, Evaluation, Authorization and Restriction of
Chemicals), cadmium plating is forbidden except for aircraft and some safety and electrical equipment.
REACH has no exemption for military use, posing a problem for sustainment of military vehicles in
Europe.
The result of this worldwide pressure is that cadmium (Cd) plating (which was once widely used in
everything from automotive bolts to padlocks and deck screws) has been removed from almost all
Phthalates and Their Alternatives
Phthalates are a class of synthetic chemicals that are widely used in a variety of consumer
products made of polyvinyl chloride (PVC). The addition of phthalates to PVC makes this brittle
plastic more flexible and durable. PVC products may contain up to 50 percent by weight of
plasticizers, most commonly phthalates.. Six of the commonly used phthalates in consumer
products are di-(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP), dibutyl phthalate
(DBP), diisodecyl phthalate (DIDP), di-n-octyl phthalate (DnOP), and benzyl butyl phthalate
(BBP or BzBP).
Since phthalates are not chemically bound to the PVC polymer, they can be released from
products or dissolve upon contact with liquids or fats. Phthalates have low volatility and are
slowly released from PVC products during use, diffusing into the air. They are also released into
the environment during their production, processing and waste disposal. Once in the
environment, phthalates bind to particles––primarily dust particles in the home––and can be
carried in the air over long distances. Human exposure to phthalates occurs through inhalation
and ingestion of contaminated air and food as well as from skin contact. Food may become
contaminated when it comes in contact with packaging that contains phthalates.
Human Health and Environmental Concerns
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Most of the early studies on the health effects of phthalates experimented with doses
administered to laboratory animals above human exposure levels. In recent years however,
researchers have noted health effects such as reproductive abnormalities and developmental
effects in animals given doses of phthalates similar to those to which humans are exposed.
Epidemiologic studies have also evaluated the human health impacts of phthalate exposure.
These studies have identified a possible association between exposure to phthalates and male
reproductive malformation, sperm damage, fertility impairment, female reproductive tract
diseases, early puberty in girls, asthma, and thyroid effects. Adverse effects on the lungs, liver
and kidneys have been observed in animals and in some limited human studies. Phthalates may
also pose risks for aquatic and terrestrial ecosystems particularly in the vicinity of phthalate
processing industries. Some phthalates are bioaccumulative and have been detected in aquatic
organisms.
Six Common Phthalates, Their Primary Functions and
Products
Phthalat
e Function(s) Product(s)
DEHP
Primarily used as a
plasticizer for PVC
Dolls, shoes, raincoats, clothing, medical devices
(plastic tubing and intravenous storage bags),
furniture, automobile upholstery and floor tiles
DINPPrimarily used as a
plasticizer for PVC
Teethers, rattles, balls, spoons, toys, gloves, drinking
straws, rubber, adhesives, ink, sealant, paints and
lacquers, food and food related uses, clothes, shoes, car
and public transport interior
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DBP
Used as a plasticizer for
PVC, poly vinyl alcohol
(PVA) and rubber. Also used
as solvent and fixative in
paint and cosmetics
Latex adhesives, sealants, car care products, cosmetics,
some inks and dyes, insecticides, food wrapping
materials, home furnishing, paint, clothing and
pharmaceutical coating. (may sometimes be present
in toys as impurity or by-product in trace amounts)
DIDP
Primarily used asa plasticizer
for PVC
Electrical cords, leather for car interiors and PVC
flooring
DnOP
Primarily used as a
plasticizer for PVC
Floorings, tarps, pool liners, bottle cap liners,
conveyor belts and garden hoses
BBP Used as a plasticizer for
PVC, polyurethane,
polysulfide and acrylic-
based polymers
Vinyl flooring, sealants, adhesives, car care products,
automotive trim, food conveyor belts, food wrapping
material, and artificial leather. (low concentrations
have been detected in baby equip- ment and
children’s toys as by-products and impurities; not
intentionally added to those products)
Chemical Alternatives to Phthalates
A number of substances have been identified as alternative plasticizers. These alternatives
include citrates, sebacates, adipates, and phosphates. They are being substituted in products
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 27
that traditionally use phthalates, such as toys, childcare articles and medical devices. In
addition to their application as alternative PVC plasticizers, these substances are also being
used as solvents and fixatives in cosmetic products, inks, adhesives, and other consumer
products.
Most of these alternative plasticizers are not well studied with regard to their potential effects on
human health and the environment. Although many of these alternatives show promising
application potential, significant exposure may lead to adverse health effects. Like phthalates,
these alternative plasticizers are not chemically bound to the polymer and can leach out of
products. Some documented effects from exposure to the alternative plasticizers that are
currently being used in children’s products and other consumer products include eye, skin, and
respiratory irritations. There is also evidence of effects on the kidney, liver, spleen, testes, and
uterus. Most evidence on human health effects is derived from laboratory studies as few
epidemiologic studies have been conducted on these materials. In addition, some alternative
plasticizers may be toxic to aquatic organisms and may not biodegrade in the environment.
Alternative Plastics that Do Not Require Phthalates
Petroleum-Based Plastics
Choosing a plastic that does not require the addition of phthalates is another substitution
approach. Although all plastics require the use of additives in processing to improve material
properties, many types of plastic require fewer and less harmful additives than those required by
PVC. These plastics have a wide range of applications in toys, children’s products, and other
consumer products. Substituting alternative plastics for PVC may also alleviate some of the health
and environmental concerns that have been identified in the PVC manufacturing and disposal stages
of the life cycle. Petroleum-based plastics are produced from non-renewable fossil fuel resources. The
production of these plastics poses a variety of health and environmental concerns. Extraction of raw
materials, manufacturing, and disposal of petroleum-derived plastics generate greenhouse gases and
pollutants including hydrogen chloride, hydrogen sulfide, sulfuric acid, heavy metals,
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chlorofluorocarbons, polycyclic aromatic compounds, volatile organic compounds, and nitrogen and
sulfur dioxides.
Bio-Based Plastics
Biobased plastics are alternatives to petroleum-based plastics. They may be completely made from
plant materials or may be a blend of plant-based and petroleum-based plastics. Plants such as corn,
soy, rice, wheat and linseed can be converted to plastics. Many of these plastics are currently under
development for a wide range of commercial applications. The production of biobased plastics is not
without hazards. The use of large quantities of pesticides in industrial agricultural production and
hazardous chemicals/additives such as sodium hydroxide, carbon disulfide, and chlorine in processing
are of concern to human health and the environment. Genetically modified organisms (GMOs) used
in development of biobased plastics are also a concern because their effects in the environment are
not well understood. Furthermore, not all biobased plastics are biodegradable or compostable. The
biodegradability or effective composting of biobased plastics is dependent on the material’s chemical
structure and composition.
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Initiatives taken by different Electronic Companies in Removing the
Hazardous Materials from the ProductsToday, there are considerably more electronic products that are free from hazardous chemicals
than there were in 2006. This is the result of both legislation and intense campaigning from
environmental and consumer organizations, which have put the electronics industry under
pressure to phase out certain chemicals.
In Europe, the leading NGO pressure comes from Greenpeace’s campaign for Greener
Electronics. Since 2006, the campaigns, and its accompanying Guides to Greener Electronics,
have been pushing companies to eliminate the use of polyvinyl chloride (PVC) and brominated
flame retardants (BFRs). Greenpeace advocates that manufacturers introduce phase out plans, to
strict timelines, and face being publicly confronted with “penalty points” if they fail to keep to
them; an approach that has seen some success.
According to Greenpeace’s report, Green gadgets: designing the future, 15 of the 20
commitments from the big electronics firms to phase out PVC and BFRs were considered
credible, with reasonable timelines. Similar commitments were also made to eliminate other
hazardous chemicals – antimony and compounds, beryllium and compounds and phthalates, on
slightly later deadlines, Greenpeace says. In 2014, more than 50% of the mobile phone market
was represented by brands – led by Nokia, Sony Ericsson and Apple – that have completely
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eliminated the use of PVC and BFRs in these products, according to the report. In 2006, by
comparison, virtually all mobile phones contained these compounds.
However, progress varies between product classes. Televisions are the campaign’s main
remaining concern. There is so far only one PVC/ BFR-free television available on the market,
manufactured by Philips. Greenpeace says the only market leader with a credible plan for future
phase out is LG Electronics.
The PC market still uses PVC in cables and other external components. But according to the
report, over 50% of the market would be represented by companies whose products are virtually
PVC/BFR-free if the PC market leaders completed the phase-out of PVC in power cables.
Sharp
Sharp states that it will “continue these efforts to expand the product categories and models that
require the elimination of BFRs and antimony compounds.” However, the numbers of PVC free
and part BFR free products that have come on the market in 2011 are less than in 2010. Sharp’s
commitment was to phase out the use of PVC, phthalates, BFRs and antimony by fiscal year
2010, provided it can find suitable alternatives. Not all products are free from PVC and
phthalates; BFRs and antimony have only been removed from casings in the majority of products
such as LCD TVs. Even as Sharp has now gone past its timeline without fully meeting its
commitment, it needs to communicate the dates when new products and components will be free
from PVC, phthalates, BFRs and antimony in order to complete its phase out. It also needs to
provide the percentage of each product line that is free from each specified substance, to
demonstrate progress towards elimination. The company has already banned beryllium oxide,
but there are many exemptions for which Sharp needs to find substitutes.
Philips
Philips continues making progress on its commitment to phase out PVC/BFR from products. The
company has launched new shavers and grooming products, among others, free of these
substances. Philips was the first company to introduce a PVC and BFR-free TV; the Econova
LED-TV. From July 2010 new adapters for consumer lifestyle products have also been PVC and
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BFR-free. Additionally, a large number of PVC/BFR free product ranges such as Oral
Healthcare, vacuum cleaners and shavers have been put on the market. Phthalates and antimony
trioxide are being phased out from new products. Arsenic has been eliminated from TV glass and
other displays from 2008. Beryllium and its compounds are already restricted with a threshold of
1000 ppm, but include exemptions. In 2010 Philips launched its comprehensive PVC/BFR free
policy, committing itself to their phase out in new consumer products placed on the market after
January 2011.
Panasonic
Panasonic has been selling PVC-free notebook computers (excluding separate AC cord), in
Japan only. There are more examples of PVC-free models, including healthcare products and
LED panel display units. Panasonic gives examples of fluorescent ceiling lamps that are free of
BFRs – and are manufacturing halogen-free printed wiring boards for certain applications and
markets. Panasonic needs to show progress by bringing new PVC and BFR free products onto
the market. Panasonic still plans to eliminate the use of PVC in notebooks (its original timeline
was the end of 2011) globally, but notes that there are technical issues to do with the
development of PVC-free AC cords. Panasonic has launched a BFR-free notebook (CF-B10) and
mobile phone (P-02D), apart from accessories. Panasonic intended to eliminate BFRs from
notebooks and mobile phones by the end of 2011 and now intends to do so as soon as it identifies
successful alternatives. Panasonic has replaced PVC with a substitute for internal wiring of all
products for the Japanese market by end of March 2009 and globally by end of March 2011.
However, 54% of products – such as washing machines, are exempted due to technological
problems. Panasonic states that its commitment to eliminating PVC will reduce or eliminate the
use of phthalates, used primarily as softeners in PVC. This leaves out other applications of
phthalates e.g. in adhesives. Likewise, use of antimony trioxide will be reduced as BFRs are
eliminated.
Nokia
Nokia sits close to maximum points having already phased out brominated compounds,
chlorinated flame retardants and antimony trioxide; however, there is no target to phase out other
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 32
antimony compounds. Nokia eliminated remaining uses of PVC in 2006 and the use of
phthalates has been restricted since 2005. It banned the use of beryllium oxide in 2004 and the
use of all other beryllium compounds has been restricted since 2010, for all new products. From
the beginning of 2010, all new Nokia products must be free of bromine, chlorine and antimony
trioxide.
Wipro
Wipro has 80% of its total products free from PVC and BFR. Wipro also launched its first
products - two desktop models, SG68F55W7 and WIV68F55 – free from antimony, beryllium
and phthalates. These two products constitute 20% of its product range free from these three
hazardous chemicals, which is an encouraging development. Wipro commits its timeline to
complete phase-out of antimony, beryllium and phthalates from its entire product range by FY-
2012.
Samsung
Samsung has achieved its target to phase-out PVC and BFRs in notebooks (except power cord
and adapter), ahead of its revised commitment of January 2012, and its target to phase out PVC
in internal wires of TVs by January 2011. All models of mobile phones and MP3 players are free
from BFRs as of January 2010 and PVC from April 2010. All HDD models launched after April
2009 are free from PVC and BFRs. Since 1 November 2007, all new models of LCD panels are
PVC-free. Other products that are partly PVC/BFR free are: all models of digital cameras and
camcorders launched after April 2010 have main PWB and cases free from BFRs and internal
wires free from PVC. The housings of some TVs and all monitors are BFR free. Samsung
previously backtracked on its commitment to eliminate BFRs in new models of all products by
January 2010, and although it has set new timelines for eliminating PVC and BFRs for some
product groups, the commitment no longer covers all its products or all parts (for example there
is no commitment to extend the PVC/BFR phase out in notebooks to power cords and adapters).
Samsung no longer plans to phase out the use of BFRs and all PVC in its TVs and household
appliances. Antimony trioxide has been phased out from new mobile phones developed from
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January, 2012 and mobile phones and MP3 players launched as of January 2011 are free of
beryllium and its compounds (with the exception of beryllium alloys), as well as phthalates. All
new models of all products will be free from beryllium from January 2013. There is an
exemption for the use of beryllium in connectors and certain electronic components. Phthalates
are now to be phased out in the same applications as PVC from January 2013. New models of
the same list of products and applications will be free from antimony trioxide from January 2013,
but with 2 exemptions. Samsung Electronics Co. Ltd (the “Company”) on 29/11/2016 declared
that all Samsung Electronics’ products placed on the European Community market by the
Company and its subsidiaries are compliant with Directive 2011/65/EU on the Restriction of
Certain Hazardous Substances in Electrical and Electronic Equipment
Toshiba
Toshiba Semiconductor Company defines “RoHS-Compatible” semiconductor products as
products that either (i) contain no more than a maximum concentration value of 0.1% by weight
in Homogeneous Materials for Lead, mercury, hexavalent chromium, polybrominated biphenyls
(PBBs) and polybrominated diphenyl ethers (PBDEs) and no more than 0.01% by weight in
Homogeneous Materials for cadmium; or (ii) fall within one of the stated exemptions set forth in
the Annex to the Directive 2002/95/EC of the European Parliament and of the Council of 27
January 2003 on the restriction of the use of certain hazardous substances in electrical and
electronic equipment (the “RoHS Directive”). Toshiba Semiconductor Company uses a variety
of alternatives depending on the product, country/region of manufacture, cost, materials
availability, and thermal environment of the product. Six primary alternatives selected by
Toshiba Semiconductor Company include tin-silver (SnAg), tin-silvercopper (SnAgCu), nickel-
palladium-gold, (NiPdAu), gold (Au), silver (Ag) and tin-copper (SnCu), among others. In
March 2011 Toshiba released a PC that is 100% PVC and BFR-free, the Tecra A11-EV1, on the
US market. Other models that have a PVC-free main body and have no BFRs in the case and all
plastic parts weighing 10g or more are the Portege R600,R700, R830, the Libretto W100 and the
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Tecra R840/850.
Toshiba has a commitment to phase out PVC, BFRs, antimony and compounds, beryllium and
compounds and phthalates by FY2015 from all its consumer products, if alternatives are
available. Previously, Toshiba had a commitment to phase out PVC and BFRs from all its
products – not only from their notebook PCs and mobiles - with a timeline of FY 2009; although
it now has a PVC/BFR free PC it did not meet this commitment for all products. Toshiba also
had a commitment to replace phthalates, beryllium and compounds and antimony and
compounds by 2012 in all its consumer electronic products, if alternatives are available.
Acer
Acer makes progress on releasing New BVR/PVC free products. Acer has informed Greenpeace
that the majority of its products will be PVC/BFR free in the near future. Acer has adopted a
timeline of 2012 for the phase out of all phthalates, beryllium and compounds and antimony and
compounds in all new products. Certain phthalates are to be phased out by 2011, along with PVC
and all phthalates by 2012. Acer needs to bring products to market that are free of these
substances.
HP
By July 2007, all PVC and BFRs were restricted from the external case plastics in HP branded
products. In 2013, all of HP’s notebook products and 60% of our desktop computer products
were low-halogen. When technically feasible, we will continue to phase out brominated flame
retardants (BFRs), polyvinyl chloride (PVC), and phthalates to meet market demands and
customer expectations. Unfortunately, it was not practical for HP or the industry as a whole to
make these material transitions in all the many types of products at this time. However HP
believes restriction under RoHS legislation may be possible in 2016, provided that some critical
issues can be overcome or addressed by specific exemptions.
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HP is taking a proactive approach to evaluating materials in its products to assess environmental,
health or safety risks. HP strives to replace legally permitted materials when scientific data have
established a potential health or environmental risk and lower risk, commercially and technically
viable alternatives are available. At HP the evaluation of alternative materials is a continuous
process.
Apple
Mac and MacBook now ship with PVC-free power cords. All Apple products are now free of
BFRs and other “harmful toxins” such as PVC and phthalates, with the exception of power cords
which are undergoing certification in regions outside of those mentioned above. Products are
also mercury-free and have arsenic-free glass. Apple planned to completely eliminate the use of
PVC and brominated flame retardants in its products by the end of 2008 – and were the first
Company to achieve this goal for PCs. Apple plans to eliminate all forms of chlorine and
bromine, not just those in PVC and flame retardants. However, antimony is not mentioned and
Beryllium is no longer referred to.
Dell
Dell has BFR/CFR/PVC-free standard offerings of all Latitude notebook and XPS 13 Ultrabook
products, and is continually adding others. Dell provides a list of 19 whole product systems that
are PVC/BFR free. All removable media storage devices, memory and hard disk drives became
BFR/CFR/PVC-free in 2011. Dell made a commitment that by the end of 2011, all newly
introduced Dell personal computing products will be BFR/CFR/PVC-free, as acceptable
alternatives are identified. However, it no longer commits to removing these substances from all
products (just computing ones) as per its previous commitment, and the timeline is unreasonable.
Dell states that: “while we have not yet fully achieved our goal of making all newly introduced
Dell personal computing products BFR- and PVC-free, we have reduced these materials across
all our consumer products and many can be configured to be BFR and PVC-free”. Dell has
completed its phase out of arsenic and mercury. Before 2006, Dell had already restricted PVC and
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BFRs in plastic parts. That year, the company began to focus on phasing out remaining substances in
components such as motherboards and cables.
Hewlett Packard (HP)
Hewlett Packard (HP) takes the silver medal in this ranking, coming second only to Indian
electronics company, Wipro. But the company’s environmental affairs manager, Hans
Wendschlag, says HP’s commitment to greener products is largely due to factors other than the
Greenpeace campaign. “Ecolabels and public procurement specifications have been the main
drivers behind green commitments in the IT industry,” he says.
Conclusions
Today, there are considerably more electronic products that are free from hazardous chemicals
than there were in 2006. This is the result of both legislation and intense campaigning from
environmental and consumer organizations, which have put the electronics industry under
pressure to phase out certain chemicals.
Clearly most of the RoHS substances are hazardous but the choice of substitutes needs to be
carefully considered as some will be better and some may be worse. Lead-free solders, based on
tin and silver, are clearly less toxic to humans than lead but silver has a considerable
environmental impact, for example, silver is toxic to some aquatic organisms, and cyanide is
used in silver refining and has caused serious environmental harm as well as deaths of workers
from cyanide poisoning.
Replacement of BFRs (PBB and PBDE) needs to be carefully considered. Clearly flame-
retardants save many thousands of lives and so should be used but the uncontrolled burning of all
types of plastics, with or without brominated flame retardants, emit toxic and carcinogenic
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 37
substances and so is inadvisable. So when material change is considered as a method for e waste
management, it is found that
• No exact or drop-in replacement
• Several alternative materials have been recommended for each of the banned materials
• There is not yet much field data available for the new materials
• Most of the cases, the alternative materials are costly and inferior in performance
• More Research & Development is needed in near future
Unless the European Parliament, NGOs, and manufacturers driving for broadly restricting more
substances via RoHS can justify and demonstrate that any replacement substances chosen will
have better environmental performance (as well as being functionally appropriate and
economical) than those they are replacing, they should reconsider adding more substances for
restriction to the RoHS recast and certainly narrow the scope of the proposed restrictions.
Suggested Solutions for E Waste Management
1. It’s better to prevent waste than to treat or clean up waste afterwards.
2. Design synthetic methods to use and generate substances that minimize toxicity to human
health and the environment.
3. Design chemical products to affect their desired function while minimizing their toxicity.
4. Minimize the use of auxiliary substances wherever possible make them innocuous when
used.
5. Use renewable raw material or feedstock rather whenever practicable.
6. Minimize or avoid unnecessary derivatization if possible, which requires additional
reagents and generate waste.
7. Catalytic reagents are superior to stoichiometric reagents.
NO.F.MRP/12th Plan/14-15/KLCA025 Dated 10/12/2014Page 38
8. Design chemical products so they break down into innocuous products that do not persist
in the environment.
9. Develop analytical methodologies needed to allow for real-time, in-process monitoring
and control prior to the formation of hazardous substances.
10. Choose substances and the form of a substance used in a chemical process to minimize
the potential for chemical accidents, including releases, explosions, and fires.
11. Safe recycling of existing e-waste
12. Strict implementation of RoHS regulations
13. Personal realization and discipline in using emerging materials and devices
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