M. Ikram-Ul-Haq

Generation of copper rich metallic phases from waste printed circuit boards

The rapid consumption and obsolescence of electronics have resulted in e-waste being one of the fastest growing waste streams worldwide. Printed circuit boards (PCBs) are among the most complex e-waste, containing significant quantities of hazardous and toxic materials leading to high levels of pollution if landfilled or processed inappropriately. However, PCBs are also an important resource of metals including copper, tin, lead and precious metals; their recycling is appealing especially as the concentration of these metals in PCBs is considerably higher than in their ores. This article is focused on a novel approach to recover copper rich phases from waste PCBs. Crushed PCBs were heat treated at 1150°C under argon gas flowing at 1L/min into a horizontal tube furnace. Samples were placed into an alumina crucible and positioned in the cold zone of the furnace for 5 min to avoid thermal shock, and then pushed into the hot zone, with specimens exposed to high temperatures for 10 and 20 min. After treatment, residues were pulled back to the cold zone and kept there for 5 min to avoid thermal cracking and re-oxidation. This process resulted in the generation of a metallic phase in the form of droplets and a carbonaceous residue. The metallic phase was formed of copper-rich red droplets and tin-rich white droplets along with the presence of several precious metals. The carbonaceous residue was found to consist of slag and ∼30% carbon. The process conditions led to the segregation of hazardous lead and tin clusters in the metallic phase. The heat treatment temperature was chosen to be above the melting point of copper; molten copper helped to concentrate metallic constituents and their separation from the carbonaceous residue and the slag. Inert atmosphere prevented the re-oxidation of metals and the loss of carbon in the gaseous fraction. Recycling e-waste is expected to lead to enhanced metal recovery, conserving natural resources and providing an environmentally sustainable solution to the management of waste products.

High temperature investigations on optimising the recovery of copper from waste printed circuit boards

High temperature pyrolysis investigations were carried out on waste printed circuit boards (PCBs) in the temperature range 800-1000°C under inert conditions, with an aim to determine optimal operating conditions for the recovery of copper. Pyrolysis residues were characterized using ICP-OES analysis, SEM/EDS and XRD investigations. Copper foils were successfully recovered after pyrolysis at 800°C for 10-20 min; the levels of Pb and Sn present were found to be quite low and these were generally present near the foil edges. The relative proportions of Pb and Sn became progressively higher at longer heating times due to enhanced diffusion of these molten metals in solid copper. While a similar behaviour was observed at 900°C, the pyrolysis at 1000°C resulted in copper forming Cu-Sn-Pb alloys; copper foils could no longer be recovered. Optimal conditions were identified for the direct recovery of copper from waste PCBs with minimal processing. This approach is expected to make significant contributions towards enhancing material recovery, process efficiency and the environmental sustainability of recycling e-waste. Pyrolysis at lower temperatures, short heating times, coupled with reductions in process steps are expected to significantly reduce energy consumption and pollution associated with the handling and processing of waste PCBs.

A novel approach for reducing toxic emissions during high temperature processing of electronic waste

A novel approach is presented to capture some of the potentially toxic elements (PTEs), other particulates and emissions during the heat treatment of e-waste using alumina adsorbents. Waste PCBs from mobile phones were mechanically crushed to sizes less than 1mm; their thermal degradation was investigated using thermo-gravimetric analysis. Observed weight loss was attributed to the degradation of polymers and the vaporization of organic constituents and volatile metals. The sample assembly containing PCB powder and adsorbent was heat treated at 600°C for times ranging between 10 and 30min with air, nitrogen and argon as carrier gases. Weight gains up to ∼17% were recorded in the adsorbent thereby indicating the capture of significant amounts of particulates. The highest level of adsorption was observed in N2 atmosphere for small particle sizes of alumina. SEM/EDS results on the adsorbent indicated the presence of Cu, Pb, Si, Mg and C. These studies were supplemented with ICP-OES analysis to determine the extent of various species captured as a function of operating parameters. This innovative, low-cost approach has the potential for utilization in the informal sector and/or developing countries, and could play a significant role in reducing toxic emissions from e-waste processing towards environmentally safe limits.

Environmental Impact of Processing Electronic Waste – Key Issues and Challenges

Extensive utilization of electric and electronic equipment in a wide range of applications has resulted in the generation of huge volumes of electronic waste (e-waste) globally. Highly complex e-waste can contain metals, polymers and ceramics along with several hazardous and toxic constituents. There are presently no standard approaches for han‐ dling, dismantling, and the processing of e-waste to recover valuable resources. Inappro‐ priate and unsafe practices produce additional hazardous compounds and highly toxic emissions as well. This chapter presents an overview of the environmental impact of proc‐ essing e-waste with specific focus on toxic elements present initially in a variety of e-waste as well as hazardous compounds generated during e-waste processing. Hazardous constit‐ uents/ and contaminants were classified in three categories: primary contaminants, secon‐ dary contaminants, and tertiary contaminants. Primary contaminants represent hazardous substances present initially within various types of e-waste; these include heavy metals such as lead, mercury, nickel and cadmium, flame retardants presents in polymers etc. Sec‐ ondary contaminants such as spent acids, volatile/toxic compounds, PAHs are the byproducts or waste residues produced after inappropriate processing of e-waste and the tertiary contaminants include leftover reagents or compounds used during processing. A detailed report is presented on the environmental impact of processing e-waste and the detrimental impact on soil contamination, vegetation degradation, water and air quality along with implications for human health. Challenges and opportunities associated with appropriate e-waste management are also discussed.

Recycling polymeric waste from electronic and automotive sectors into value added products

The environmentally sustainable disposal and recycling of ever increasing volumes of electronic waste has become a global waste management issue. The addition of up to 25% polymeric waste PCBs (printed circuit boards) as fillers in polypropylene (PP) composites was partially successful: while the tensile modulus, flexural strength and flexural modulus of composites were enhanced, the tensile and impact strengths were found to decrease. As a lowering of impact strength can significantly limit the application of PP based composites, it is necessary to incorporate impact modifying polymers such as rubbery particles in the mix. We report on a novel investigation on the simultaneous utilization of electronic and automotive rubber waste as fillers in PP composites. These composites were prepared by using 25 wt.% polymeric PCB powder, up to 9% of ethylene propylene rubber (EPR), and PP: balance. The influence of EPR on the structural, thermal, mechanical and rheological properties of PP/PCB/ EPR composites was investigated. While the addition of EPR caused the nucleation of the β crystalline phase of PP, the onset temperature for thermal degradation was found to decrease by 8%. The tensile modulus and strength decreased by 16% and 19%, respectively; and the elongation at break increased by ~71%. The impact strength showed a maximum increase of ~18% at 7 wt.%–9 wt.% EPR content. Various rheological properties were found to be well within the range of processing limits. This novel eco-friendly approach could help utilize significant amounts of polymeric electronic and automotive waste for fabricating valuable polymer composites.

Formation of carbyne-like materials during low temperature pyrolysis of lignocellulosic biomass: A natural resource of linear sp carbons

The exploration, understanding and potential applications of ‘Carbyne’, the one-dimensional sp allotrope of carbon, have been severely limited due to its extreme reactivity and a tendency for highly exothermic cross-linking. Due to ill-defined materials, limited characterization and a lack of compelling definitive evidence, even the existence of linear carbons has been questioned. We report a first-ever investigation on the formation of carbyne-like materials during low temperature pyrolysis of biobased lignin, a natural bioresource. The presence of carbyne was confirmed by detecting acetylenic –C≡C– bonds in lignin chars using NMR, Raman and FTIR spectroscopies. The crystallographic structure of this phase was determined as hexagonal: a = 6.052 Å, c = 6.96 Å from x-ray diffraction results. HRSEM images on lignin chars showed that the carbyne phase was present as nanoscale flakes/fibers (~10 nm thick) dispersed in an organic matrix and showed no sign of overlapping or physical contact. These nanostructures did not show any tendency towards cross-linking, but preferred to branch out instead. Overcoming key issues/challenges associated with their formation and stability, this study presents a novel approach for producing a stable condensed phase of sp-bonded linear carbons from a low-cost, naturally abundant, and renewable bioresource.

Influence of Wettability and Reactivity on Refractory Degradation – Interactions of Molten Iron and Slags with Steelmaking Refractories at 1550°C

Refractories, materials that can withstand high temperatures, play an important role in the iron and steel sector which alone accounts for ~70% of total refractories pro‐ duced. In this chapter, detailed wettability and interfacial phenomena investiga‐ tions on alumina-carbon and zirconia-carbon refractories at steelmaking temperatures. The wettability between refractory substrates and molten iron/slags was investigated at 1550°C using the sessile drop approach in a horizontal tube fur‐ nace equipped with a CCD camera. Detailed experimental results were obtained on alumina-carbon/molten iron system at high temperatures. Alumina is known to be non-wetting to molten iron while carbon can be easily wetted. Observed contact an‐ gles were found to depend strongly on the substrate composition and contact time. While the refractory substrates containing 50 and 60% carbon were found to be nonwetting to molten iron, the substrates containing higher amounts of C (≥ 70%) were found to become increasingly wetting. Molten iron droplets were seen to spread on these substrates. The wettability of zirconia-carbon and alumina-carbon (C: 10-20 wt %) with two steelmaking slags (Slag 1: MnO: 50%, SiO2: 25%, Al2O3:25%, and Slag 2: MnO: 40%, SiO2:60%) was investigated at 1550°C. The wettability with Slag 1 was found to be‐ come poorer with increasing carbon content in the refractory; however a complete wetting was observed after 20 minutes of contact. Slag 2 showed a better wettability with higher carbon refractories. The extent of gasification of ZrO2 – C system was found to be 9 times higher than the Al2O3 – C system. At ~5 minutes of contact, the slag appeared to get lifted away from the substrate leading to a slowing down of slag penetration. The maximum height of the gaseous gap decreased with increas‐ ing carbon in the substrate [880μm, 630μm & 440μm respectively for 20%, 15% & 10% carbon in the substrate]. The formation of the gaseous gap between slag 1 and the substrate was attributed to poor wetting and gas pressure. Slag 2 did not exhibit the formation of a gaseous gap due to lower contact angles between the slag and refractory. Alumina – carbon showed higher contact values but no gas gap forma‐

Interfacial Reactions between Alumina and Carbon Refractories and Molten Iron at 1,823 K

Abstract High temperature interactions of alumina–carbon refractories with molten iron were investigated at 1,823 K in argon atmosphere. These studies were specifically focussed on the decomposition of alumina in the simultaneous presence of carbon and iron, and associated refractory degradation. Refractory mixtures were prepared by blending 90 wt% alumina with 10 wt% synthetic graphite; 5–15 wt% iron powder was then mixed with the refractory mixture. Using phenol formaldehyde as a binder, pellets were prepared from various blends; these were heat treated at 1,823 K for 30 min in Ar atmosphere. The presence of molten iron significantly enhanced the decomposition of alumina resulting in an enhanced refractory degradation as well as the formation of a new reactant product. This product was identified as a Fe–Al intermetallic phase from SEM/EDS (scanning electron microscopy/energy-dispersive spectroscopy) and x-ray microdiffraction investigations.