Effect of copper content on the pyrolysis process of organic components in waste printed circuit boards:Based on experimental and quantum chemical DFT simulations

In recent years,scientists have become increasingly concerned in recycling electronic trash,particularly waste printed circuit boards(WPCBs).Previous research has indicated that the presence of Cu impacts the pyrolysis of WPCBs.However,there may be errors in the experimental results,as printed circuit boards(PCBs)with copper and those without copper are produced differently.For this experiment,we blended copper powder with PCB nonmetallic resin powder in various ratios to create the samples.The apparent kinetics and pyrolysis properties of four resin powders with varying copper concentrations were compared using nonisothermal thermogravimetric analysis(TG)and thermal pyrolysis-gas chromatography mass spectrometry(Py-GC/MS).From the perspective of kinetics,the apparent activation energy of the resin powder in the pyrolysis reaction shows a rise(0.1<a<0.2)-stable(0.2<a<0.4)-accelerated increase(0.4<a<0.8)-decrease(0.8<a<0.9)process.After adding copper powder,the apparent activation energy changes more obviously when(0.2<a<0.4).In the early stage of the pyrolysis reaction(0.1<a<0.6),the apparent activation energy is reduced,but when a?0.8,it is much higher than that of the resin sample without copper.Additionally,it is discovered using thermogravimetric analysis and Py-GC/MS that copper shortens the temperature range of the primary pyrolysis reaction and prevents the creation of compounds containing bromine.This inhibition will raise the temperature at which compounds containing bromine first form,and it will keep rising as the copper level rises.The majority of the circuit board molecules have lower bond energies when copper is present,according to calculations performed using the Gaussian09 software,which promotes the pyrolysis reaction.

Distribution behavior of valuable elements in oxygen-enriched top-blown smelting process of waste printed circuit boards

Oxygen-enriched top-blown smelting is a promising technology for processing waste printed circuit boards(WPCBs).The distribution behavior of valuable elements in WPCBs during smelting was investigated by varying the oxygen-enriched concentration,oxygen volume,CaO/SiO_(2)(mass ratio),and Fe/SiO_(2)(mass ratio).The optimal operating conditions were obtained by implementing a one-factor-at-a-time method.X-ray diffractometer,scanning electron microscopy−energy dispersive spectrometer,and inductive coupled plasma-atomic emission spectroscopy methods were utilized to detect the chemical composition,occurrence state as well as elemental contents of alloy and slag.It is found that the elements of Cu,Sn and Ni are mainly accumulated in the alloy while Fe is mainly oxidized into the slag.The direct yields of Cu,Sn and Ni are 90.18%,85.32%and 81.10%under the optimal conditions of temperature 1250℃,oxygen-enriched concentration 30%,oxygen volume 24 L,CaO/SiO_(2) mass ratio 0.55,and Fe/SiO_(2) mass ratio 1.05.The results show that the valuable metals are mainly lost in the slag through mechanical entrainment.

Pyrolysis kinetics and TG-FTIR analysis of waste epoxy printed circuit boards

Thermal decomposition of waste epoxy PCBs was performed in different atmospheres （nitrogen, argon, air and vacuum） at a heating rate of 10 ℃/rain by DSC-TGA, and the pyrolysis characteristic was analyzed. The gases volatilized from the experiment were qualitatively analyzed by TG-FTIR. Kinetics study shows that pyrolysis reaction takes place between 300 and 400℃, and the activation energies are 256, 212 and 186.2 kJ/mol in nitrogen, argon and vacuum, respectively. There are two mass-loss processes in the decomposition under air atmosphere. In the first mass-loss process, the decomposition is the main reaction, and in the second process, the oxidation is the main reaction. The activation energy of the second mass-loss process is 99.6 kJ/mol by isothermal heat-treatments. TG-FTIR analysis shows carbon dioxide, carbon monoxide, hydrogen bromide, phenol and substituent phenol are given off during the pyrolysis of waste epoxy PCBs.

Efficient recovery of valuable metals from waste printed circuit boards by microwave pyrolysis

The recycling of waste printed circuit board(WPCBs) is of great significance for saving resources and protecting the environment. In this study, the WPCBs were pyrolyzed by microwave and the contained valuable metals Cu, Sn and Pb were recovered from the pyrolyzed WPCBs. The effect of pyrolysis temperature and time on the recovery efficiency of valuable metals was investigated. Additionally, the characterization for morphology and surface elemental distribution of pyrolysis residues was carried out to investigate the pyrolysis mechanism. The plastic fiber boards turned into black carbides, and they can be easily separated from the metals by manual. The results indicate that 91.2%, 96.1% and 94.4% of Cu, Sn and Pb can be recovered after microwave pyrolysis at 700 °C for 60 minutes. After pyrolysis, about 79.8%(mass)solid products, 11.9%(mass) oil and 8.3%(mass) gas were produced. These gas and oil can be used as fuel and raw materials of organic chemicals, respectively. This process provides an efficient and energy-saving technology for recovering valuable metals from WPCBs.

Recovery of Gold, Silver, Copper and Niobium from Printed Circuit Boards Using Leaching Column Technique

Nowadays, over 300 tons of Au are used in electronic equipment each year with other precious and strategic metals such as Ag, Pt, Pd, Cu, Nb, Ta, etc.. After the use-phase, the electronic devices become electronic waste （e-waste）; consequently it is important to consider e-waste as a secondary supply for the recovery of these metals. This paper presents the recovery ofAu, Ag, Cu and Nb from PCBs （printed circuit boards） of discarded computers using leaching column technique. The PCBs were crushed with a hammer mill until reaching a particle size between 3.33 mm to 0.43 mm, Then, it was leached with a sodium cyanide solution in a glass column using the following conditions： sodium cyanide concentration 4 g/L, flux 20 L/d kg PCBs day, pH between 10.5 to 11 and leaching time 15 days. Every day, after leaching, the pregnant solutions passed through a column with activated carbon to complete the closed loop system. The following recoveries were obtained： Au 46.6%, Ag 51.3%, Nb 47.2% and Cu 62.3%. A preliminary technical-economic study shows the feasibility to create a small-scale PCBs recycling plant. The initial investment is on the order of USS155,639, considering the recovered metals from the loaded carbon. The internal rate of return for a 10 years period IRR （internal rate of return） and NPV （net present value） estimated are 27% and US$105,926 respectively.

Metals Recovery from Fine Printed Circuit Boards Using Falcon SB Concentrator

Physical methods show great potential and advantages on comprehensive reutilization of waste printed circuit boards (PCBs) because of lower investment and operation cost, higher efficiency and environment friendliness. However, metals contained in fine fraction of PCBs cannot be recovered effectively by conventional equipments such as high tension electrostatic separator or shaking table. In the paper, this conundrum was resolved successfully with the enhanced Falcon SB concentrator. The separation mechanism of Falcon SB concentrator was analyzed and main factors affecting separation efficiency such as magnitude of rotation frequency of bowl, water counter pressure and slurry concentration of feed were studied and interaction of factors above also were investigated using Design-Expert software. Experiment results show that complete liberation degree and great difference of density between metals and nonmetals are suitable to recover metals from -74 μm PCBs using enhanced Falcon SB concentrator and 80.77 % integration efficiency can be achieved when slurry concentration of feed is 40 g/L with the water counter pressure of 0.01 MPa and rotation frequency of 50 Hz.

Fabrication of integrated resistors in printed circuit boards

In order to utilize integrated passive technology in printed circuit boards （PCBs）, manufacturing processing for integrated resistors by lamination method was investigated. Integrated resistors fabricated from Ohmega technologies in the experiment were 1 408 pieces per panel with four different patterns A, B, C and D and four resistance values of 25, 50, 75 and 100 fL Six panel per batch and four batches were performed totally. The testing was done for 960 pieces of integrated resistors randomly selected with the same size. The value distribution ranges and the relative standard deviation （RSD） show that the scatter degree of the resistance decreases with the resistor size increasing and/or with the resistance increasing. Patterns D with resistance of 75 and 100% for four patterns have the resistance value variances less than 10%. Patterns C and D with resistance of 100 Ω have the manufacturing tolerance less than 10%. The process capabilities are from about 0.6 to 1.6 for the designed testing patterns, which shows that the integrated resistors fabricated have the potential to be used in multilayer PCBs in the future.

Supergravity separation of Pb and Sn from waste printed circuit boards at different temperatures

Printed circuit boards（PCBs） contain many toxic substances as well as valuable metals, e.g., lead（Pb） and tin（Sn）. In this study, a novel technology, named supergravity, was used to separate different mass ratios of Pb and Sn from Pb–Sn alloys in PCBs. In a supergravity field, the liquid metal phase can permeate from solid particles. Hence, temperatures of 200, 280, and 400°C were chosen to separate Pb and Sn from PCBs. The results depicted that gravity coefficient only affected the recovery rates of Pb and Sn, whereas it had little effect on the mass ratios of Pb and Sn in the obtained alloys. With an increase in gravity coefficient, the recovery values of Pb and Sn in each step of the separation process increased. In the single-step separation process, the mass ratios of Pb and Sn in Pb–Sn alloys were 0.55, 0.40, and 0.64 at 200, 280, and 400°C, respectively. In the two-step separation process, the mass ratios were 0.12 and 0.55 at 280 and 400°C, respectively. Further, the mass ratio was observed to be 0.76 at 400°C in the three-step separation process. This process provides an innovative approach to the recycling mechanism of Pb and Sn from PCBs.

Distribution of heavy metals during pyrolysis of waste printed circuit boards

The volatilization behavior of Cu, Pb, Sn, Sb, Ni, Zn, Mn, Co, Cr, Cd during pyrolysis of waste printed circuit boards was investigated in a bench-scale fixed-bed pyrolysis system. It was found that volatility of heavy metals increases with operating temperature elevating, and bromine and vacuum have an obvious promoting effect on volatility of most of heavy metals. Over 99% weight of Cu and Ni are still remained in solid residue after pyrolysis, about 20% weight of Sb, Zn and Cd are transfered into liquid and gas during a pyrolysis process at 600 ℃, volatilization fractions of Pb, Sn, Mn, Co, Cr are less than 10% at the same conditions. The contents of heavy metals in liquid and gas products depend on not only volatility of metals, but also their initial contents in printed circuit boards, pyrolysis liquid and gas are primarily contaminated by Cu, Pb, Sn, Sb and Zn, their contents in liquid vary from 10^2 to 10^3 pg/mL, Mn, Co, Cr, Cd were detected only at very low level, less than 10 μg/mL.

Research on Selective Shredding of Wasted Printed Circuit Boards

Electronic scrap, especially wasted printed circuit boards (PCBs), is regarded as an environmental challenge. At present, the physical separation is thought to be the environmental friendly and economical method of treating and reutilizing electronic waste. An effective liberation of metals from non metallic components is a crucial step towards mechanical separation and recycling of wasted PCBs. In this paper, the selective shredding theory and mechanics characteristics of wasted PCBs were analyzed, and the shredded experiments of wasted PCBs by hammer mill were investigated. The result shows that the selective shredding exists in the wasted PCBs shredded process by hammer mill. The shredding velocity of non metallic components is far greater than that of metals in the wasted PCBs shredding, which makes the metals concentrate in the coarser fraction. And the impact force of hammer mill is superior to metal liberation from non metallic components, a satisfied metal liberation degree can be achieved in the wasted PCBs shredding by hammer mill.

Optimization of low-temperature alkaline smelting process of crushed metal enrichment originated from waste printed circuit boards

A novel low-temperature alkaline smelting process is proposed to convert and separate amphoteric metals in crushed metal enrichment originated from waste printed circuit boards. The central composite design was used to optimize the operating parameters,in which mass ratio of Na OH-to-CME, smelting temperature and smelting time were chosen as the variables, and the conversions of amphoteric metals tin, lead, aluminum and zinc were response parameters. Second-order polynomial models of high significance and3 D response surface plots were constructed to show the relationship between the responses and the variables. Optimum area of80%-85% Pb conversion and over 95% Sn conversion was obtained by the overlaid contours at mass ratio of Na OH-to-CME of4.5-5.0, smelting temperature of 653-723 K, smelting time of 90-120 min. The models were validated experimentally in the optimum area, and the results demonstrate that these models are reliable and accurate in predicting the smelting process.

Pyrolysis behaviour and combustion kinetics of waste printed circuit boards

The effective recycling of waste printed circuit boards(WPCBs)can conserve resources and reduce environmental pollution.This study explores the pyrolysis and combustion characteristics of WPCBs in various atmospheres through thermogravimetric and Gaussian fitting analyses.Furthermore,this study analyses the pyrolysis products and combustion processes of WPCBs through thermogravimetric and Fourier transform infrared analyses(TG-FTIR)and thermogravimetry-mass spectrometry(TG-MS).Results show that the pyrolysis and combustion processes of WPCBs do not constitute a single reaction,but rather an overlap of multiple reactions.The pyrolysis and combustion process of WPCBs is divided into multiple reactions by Gaussian peak fitting.The kinetic parameters of each reaction are obtained by the Coats-Redfern method.In an argon atmosphere,pyrolysis consists of the overlap of the preliminary pyrolysis of epoxy resin,pyrolysis of small organic molecules,and pyrolysis of brominated flame retardants.The thermal decomposition process in the O_(2) atmosphere is mainly divided into two reactions:brominated flame retardant combustion and epoxy combustion.This study provided the theoretical basis for pollution control,process optimization,and reactor design of WPCBs pyrolysis.

Vacuum pyrolysis characteristics of waste epoxy printed circuit boards

Vacuum pyrolysis was employed to dispose scrap brominated epoxy printed circuit boards (PCBs).Pyrolysis characteristics of waste PCBs under normal pressure and vacuum were investigated in this paper.A detailed study on the analysis of the elemental composition of PCBs and the pyrolysis products was performed.The thermal decomposition kinetics was measured by a thermogravimetric (TG) analyzer.The activation energy of pyrolysis under nitrogen atmosphere and vacuum were 193 kJ/mol to 206 kJ/mol and 145 kJ/mol to 165 kJ/mol,respectively.The composition of materials was analyzed by elemental analyzer.The pyrolysis products were analyzed by GC (gas chromatograph),GC-MS (chromatography and mass spectrometry) and FT-IR (Fourier transform infrared spectroscopy).Vacuum helped to increase the yield of pyrolysis oil.The liquid yield of PCBs pyrolysis at 15 kPa and normal pressure were 31.3% and 23.5%,respectively.The main components in pyrolysis oils were phenol,isopropyl-phenol,and their brominated substitution.

Defect Detection in Printed Circuit Boards with Pre-Trained Feature Extraction Methodology with Convolution Neural Networks

Printed Circuit Boards(PCBs)are very important for proper functioning of any electronic device.PCBs are installed in almost all the electronic device and their functionality is dependent on the perfection of PCBs.If PCBs do not function properly then the whole electric machine might fail.So,keeping this in mind researchers are working in this field to develop error free PCBs.Initially these PCBs were examined by the human beings manually,but the human error did not give good results as sometime defected PCBs were categorized as non-defective.So,researchers and experts transformed this manual traditional examination to automated systems.Further to this research image processing and computer vision came into actions where the computer vision experts applied image processing techniques to extract the defects.But,this also did not yield good results.So,to further explore this area Machine Learning and Artificial Intelligence Techniques were applied.In this studywe have appliedDeep Neural Networks to detect the defects in the PCBS.PretrainedVGG16and Inception networkswere applied to extract the relevant features.DeepPCB dataset was used in this study,it has 1500 pairs of both defected and non-defected images.Image pre-processing and data augmentation techniques were applied to increase the training set.Convolution neural networks were applied to classify the test data.The results were compared with state-of-the art technique and it proved that the proposed methodology outperformed it.Performance evaluation metrics were applied to evaluate the proposed methodology.Precision 94.11%,Recall 89.23%,F-Measure 91.91%,and Accuracy 92.67%.

Products Made from Nonmetallic Materials Reclaimed from Waste Printed Circuit Boards

Printed circuit boards （PCBs） are in all electronic equipment, so with the sharp increase of electronic waste, the recovery of PCB components has become a critical research field. This paper presents a study of the reclaimation and reuse of nonmetallic materials recovered from waste PCBs. Mechanical processes, such as crushing, milling, and separation, were used to process waste PCBs. Nonmetallic materials in the PCBs were separated using density-based separation with separation rates in excess of 95%. The recovered nonmetals were used to make models, construction materials, composite boards, sewer grates, and amusement park boats. The PCB nonmetal products have better mechanical characteristics and durability than traditional materials and fillers. The flexural strength of the PCB nonmetallic material composite boards is 30% greater than that of standard products. Products derived from PCB waste processing have been brought into industrial production. The study shows that PCB nonmetals can be reused in profitable and environmentally friendly ways.

Preparation of pure SnO_2 powders from tin slag of printed circuit boards waste

The recycling method and principle of SnO2 from the tin slag of printed circuit boards（PCB） waste were investigated. In this study, pure SnO2 powders were obtained through a multi-step process including ball-milling, roasting, dissolving, precipitating, and pickling. The total recovery rate of tin can be up to 91 %. The SnO2 powders obtained is the single phase, and the content of SnO2 is up to 99.9 %. However, the SnO2 particles are easier to agglomerate during the precipitation process. The agglomerate SnO2 particles are about 7.778 lm in mean particle size（D50）. This preparation method presents a viable alternative for the tin slag recycling. The tin is not only recycled, but also reused directly to prepare pure SnO2 powders.

Copper recovery from waste printed circuit boards concentrated metal scraps by electrolysis

Copper recovery is the core of waste printed circuit boards （WPCBs） treatment. In this study, we proposed a feasible and efficient way to recover copper from WPCBs concentrated metal scraps by direct electrolysis and thctors that affect copper recovery rate and purity, mainly CuSO4.5H2O concentration, NaCI concentration, H2SO4 concentration and current density, were discussed in detail. The results indicated that copper recovery rate increased first with the increase ofCuSO4- 5H2O, NaCI, H2SO4 and current density and then decreased with further increasing these conditions. NaCI, H2SO4 and current density also showed a similar impact on copper purity, which also increased first and then decreased. Copper purity increased with the increase of CuSO4.5H2O. When the concentration of CuSO4-5H2O NaCI and H2oSO4 was respectively 90, 40 and 118 g/L and current density was 80 mA/cm-, copper recovery rate and purity was up to 97.32% and 99.86%, respectively. Thus, electrolysis proposes a feasible and prospective approach for waste printed circuit boards recycle, even for e-waste, though more researches are needed for industrial application.

Non-toxic, high selectivity process for the extraction of precious metals from waste printed circuit boards

The work presented here focused on the extraction of gold (Au), silver (Ag) and palladium (Pd) from electronic waste using a solution of ammonium thiosulfate. Thiosulfate was used as a valid alternative to cyanide for precious metal extractions, due to its non-toxicity and high selectivity. The interactions between sodium thiosulfate, total ammonia/ammonium, precious metal concentrations and the particle size of the waste printed circuit boards (WPCBs) were studied by the response surface methodology (RSM) and the principal component analysis (PCA) to maximize precious metal mobilization. Au extraction reached a high efficiency with a granulometry of less than 0.25 mm, but the consumption of reagents was high. On the other hand, Ag extraction depended neither on thiosulfate/ammonia concentration nor granulometry of WPCBs and it showed efficiency of 90% also with the biggest particle size (0.50 < Ø < 1.00 mm). Pd extraction, similarly to Au, showed the best efficiency with the smallest and the medium WPCB sizes, but required less reagents compared to Au. The results showed that precious metal leaching is a complex process (mainly for Au, which requires more severe conditions in order to achieve high extraction efficiencies) correlated with reagent concentrations, precious metal concentrations and WPCB particle sizes. These results have great potentiality, suggesting the possibility of a more selective recovery of precious metals based on the different granulometry of the WPCBs. Furthermore, the high extraction efficiencies obtained for all the metals bode well in the perspective of large-scale applications.

Self-catalytic pyrolysis thermodynamics of waste printed circuit boards with co-existing metals

Waste printed circuit boards(WPCBs)are generated increasingly recent years with the rapid replacement of electric and electronic products.Pyrolysis is considered to be a potential environmentally-friendly technology for recovering organic and metal resources from WPCBs.Thermogravimetric analysis and kinetic analysis of WPCBs were carried out in this study.It showed that the co-existing metals(Cu,Fe,Ni)in WPCBs have positive self-catalytic influence during the pyrolysis process.To illustrate their catalytic effects,the apparent activation energy was calculated by differential model.Contributions of different reactions during catalytic pyrolysis process was studied and the mechanism function was obtained byŠesták-Berggren model.The results showed that Cu,Fe,Ni can promote the reaction progress and reduce the apparent activation energy.Among the three metals,Ni plays better catalytic role than Cu,then Fe.This work provides theoretical base for understanding the three metals’catalytic influence during the pyrolysis of non-metal powders in WPCBs.

Crushing performance and resource characteristicof printed circuit board scrap

The crushing performance of printed circuit board (PCB) was studied on several crushers. The results show that PCB is a material which is difficult to crush. The crushing performance of PCB with disk crusher, especially vibration grinding, which has cut or impact action, excels that of jaw crusher or roller crusher. The PCB scrap is worthwhile to recycle using variety of modern characterization methods. When compared with natural resources, this material stream remains a rich precious metal and nonferrous metals. In PCB scrap, metals account for 47% of the total material composition, in which there exists 19.66% copper, 11.47% iron, 3.93% lead, 300 g/t gold and 510 kg/t silver, etc. In addition, the PCB scrap contains 27% of plastics and 26% of refractory oxides.