Recycling of waste glasses into partially crystallized glass foams

Waste soda-lime glass, alone or mixed with wastes from the manufacturing of glass fibers, was successfully converted into partially crystallized glass foams by a particularly simple and economic processing, consisting of a direct heating of glass powders at temperatures from 900 to 1050 °C. The foaming operated by the oxidation of SiC, inserted as powder additive, was found to depend on a complex combination of processing temperature, soaking time, tendency of the investigated glasses toward devitrification, and amount of MnO₂, acting as oxidation promoter. Selected combinations led to foams with a good microstructural homogeneity and mechanical strength, suitable for application as aggregates in lightweight concrete.     

Fast sinter crystallisation of waste glasses

Abstract

Two glasses, belonging to the CaO–Al₂O₃–SiO₂ system and corresponding to the melting of mixtures of industrial wastes (recycled glasses, mining residues, ashes, asbestos containing cements, etc.), have been successfully converted into dense glass ceramics by sintering with concurrent crystallisation. The usage of fine glass powders (<37 μm) allowed very short sintering treatments, due to the enhanced nucleating activity of glass surfaces. In particular, dense glass ceramics could be produced by direct insertion of pressed glass powders in the furnace at the sintering temperature, followed by rapid cooling at room temperature after a 30 min holding time. The proposed approach evidences the feasibility of sintered glass ceramics by the fast and economic processes employed for traditional ceramics, with the advantage of superior mechanical properties (bending strength exceeding 100 MPa, Vickers' microhardness exceeding 6 GPa). Like in traditional ceramics, clay and water could be used for the shaping of pressed tiles, thus posing the conditions for massive industrial production.     

Integrated utilization of high alumina fly ash for synthesis of foam glass ceramic

Due to the numerous increase of the building energy consumption and huge volume of industrial wastes produced in China, the development of thermal insulation materials is quite needed. Herein, foam glass ceramic, a kind of thermal insulation materials, was fabricated by using solid wastes high alumina fly ash and waste glass as the main raw materials. First, in this study the proportion scheme of this research was designed by using Factsage 7.1 and the foaming agent was CaSO₄. Secondly, the decomposition of calcium sulfate and the influence of process parameters, namely the sintering temperature and the foaming agent additive amount, on the microstructure and mechanical properties of foam glass ceramic were investigated. The experimental results showed that when the proposed foam glass ceramic was sintered at between 1180 and 1220?°C, it exerted excellent macro and micro properties. The optimum parameters were 2% CaSO₄ addition and sintering temperature of 1200?°C, and the corresponding bulk density and compress strength values were 0.98?g/cm³ and 9.84?MPa, respectively. Overall these results indicated that the preparation of foam glass ceramic made up a promising strategy for recycling industrial waste into new kind of building insulation materials.     

Low temperature upcycling of vitreous byproduct of the MSW plasma processing into multifunctional porous glass-ceramics

Mixtures of glass residues, deriving from the plasma processing of municipal solid waste (‘Plasmastone’), and recycled glasses have been already converted into highly porous glass-ceramics by application of an inorganic gel casting technique (foaming, by intensive mechanical stirring, of alkali activated slurries) followed by sintering at 1000°C. The full potential of recycled glass, however, has not been disclosed yet. The present investigation, in fact, demonstrates that boro-alumino-silicate glass, from discarded pharmaceutical vials, may allow for sintering of cellular glass-ceramics at particularly low temperature, i.e. at 800°C. The full stabilisation of heavy metals from Plasmastone (already assessed for treatments at 1000°C) is not compromised, whereas the low processing temperatures favour the separation of magnetite, in turn imparting new functionalities (e.g. electromagnetic shielding) to waste-derived glass-ceramic foams.     

低密度聚苯乙烯仿木线材挤出发泡研究

结合聚苯乙烯（PS）化学自由挤出发泡工艺,探讨了合成级新料与再生原料树脂的特性对发泡效果和发泡制品冲击性能的影响;比较了放热型改性AC发泡剂、吸热型改性NaHCO3放热吸热复合发泡剂对再生料PS发泡制品的密度、泡孔结构、气孔均匀度的影响;探究了不同发泡剂对发泡制品芯层泡孔结构的影响。结果表明,发泡剂含量为1 %时,采用AC发泡剂和复合发泡剂的发泡制品的密度分别为0.47 g/cm3和0.39 g/cm3。     

Design and synthesis of foam glasses from recycled materials

Recycling has emerged as an environmental key point due to the diminishing of natural resources and the generation of ever-increasing amounts of industrial solid wastes. Glass wastes are among the materials that attract great interest in the recycling concept. This work presents the results of foams production from four series of compositions. The first series comprises powders of a sodium-calcium-silicate sheet glass cullet as the main component, an alkali-earth aluminosilicate glass as an additive, and a reagent grade silicon carbide (SiC) powder as gassing agent. In the second series, the glass cullet was used in combination with fly ashes (FLA) as main components, while SiC waste from abrasive paper served as foaming agent. In the third and fourth series, carbonates (calcite and dolomite) were used for foaming powder mixtures composed of sheet glass cullet and FLA, and powdered cathode ray tube panel glasses, respectively. All the processing parameters, including the main components, the nature and content of foaming agents are shown to play a crucial role on the foaming ability and final properties of the glass foams.     

Suppressing the effect of cullet composition on the formation and properties of foamed glass

The process of foaming glass is very dependent on the chemical composition of the glass. In this study we used a foaming-agent/oxidizing-agent couple and a crystallization inhibitor to foam cullets of flat, container and CRT-panel glass. Foamed glass with a density of 110–120?kg?m^–3, a thermal conductivity of 50–52?mW?m^–1 K^–1 and a homogeneous pore structure was obtained from a mixture of panel glass, 0.33?wt% carbon and 4.45?wt% Fe₂O₃. We also showed that it is possible to fabricate foamed glass with the same density or pore structure as mentioned above by adding up to 50?wt% container cullet or 70?wt% flat glass to the mixture. In the foamed samples with a low content of panel glass, crystals form, resulting in an increased open porosity, density and inhomogeneous pore structure. The crystallization can, however, be inhibited by adding calcium phosphate, so enabling the preparation of high-quality foamed glass from flat glass or flat/container-glass mixture. The pore gas is predominantly CO₂ and the pressure inside the pores is 0.36–0.47?bar. The reduced effect of the composition on the foaming process suggests that there is a great potential for stabilizing the production of foamed glass and ensuring the product's quality.     

Recycling of inorganic waste in monolithic and cellular glass‐based materials for structural and functional applications

The stabilization of inorganic waste of various nature and origin, in glasses, has been a key strategy for environmental protection for the last decades. When properly formulated, glasses may retain many inorganic contaminants permanently, but it must be acknowledged that some criticism remains, mainly concerning costs and energy use. As a consequence, the sustainability of vitrification largely relies on the conversion of waste glasses into new, usable and marketable glass‐based materials, in the form of monolithic and cellular glass‐ceramics. The effective conversion in turn depends on the simultaneous control of both starting materials and manufacturing processes. While silica‐rich waste favours the obtainment of glass, iron‐rich wastes affect the functionalities, influencing the porosity in cellular glass‐based materials as well as catalytic, magnetic, optical and electrical properties. Engineered formulations may lead to important reductions of processing times and temperatures, in the transformation of waste‐derived glasses into glass‐ceramics, or even bring interesting shortcuts. Direct sintering of wastes, combined with recycled glasses, as an example, has been proven as a valid low‐cost alternative for glass‐ceramic manufacturing, for wastes with limited hazardousness. The present paper is aimed at providing an up‐to‐date overview of the correlation between formulations, manufacturing technologies and properties of most recent waste‐derived, glass‐based materials. © 2016 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Fly ash-based geopolymers containing added silicate waste. A review

This review summarizes different types of industrial wastes such as biomass ash, red mud, recycled glass and heavy metals waste, in their application for geopolymer production. These wastes, which are currently abundant and urgent to dispose of, cannot be used alone in the geopolymer process because they do not provide a suitable SiO₂/Al₂O₃ molar ratio for this technology. For this reason, these by-products are commonly used in addition to other aluminosilicate sources such as fly ash or metakaolin. Important parameters which affect the properties and performance of fly ash based geopolymers with addition of a variety of wastes are discussed based on a comprehensive literature review.     

Recycling of poly(ethylene terephthalate) into closed‐cell foams

The increase of the elongational viscosity of recycled poly(ethylene terephthalate) (PET) is investigated with the aim of producing closed‐cell foams by means of a cost‐effective reactive extrusion technique. A recycled PET grade containing controlled contamination levels of polyvinyl chloride (PVC) and poylethylene (PE) is selected, and compared with virgin bottle‐grade PET as a reference. Reactive processing with a tetrafunctional epoxy additive induces randomly branched molecules with a lower degree of branching in recycled PET than in virgin PET, as shown by a molecular structure analysis. The corresponding increase in elongational viscosity is related to foaming experiments performed using supercritical CO₂ in a pressurized vessel. Observations of foam microstructures reveal that modified virgin PET forms closed‐cell structures under a large variety of foaming conditions, as opposed to unmodified virgin and recycled PET, which collapse as a result of insufficient elongational resistance. Closed‐cell foams are also obtained using modified recycled PET, providing that the temperature at which the pressure is released is lowered to 260°. Recycling of PET into closed‐cell foams is thus achieved, although the processing window is slightly reduced compared to virgin PET.     

Production of alumino-borosilicate foamed glass body from waste LCD glass

A foaming process for waste LCD glass is presented, in which waste LCD glass is recycled to produce alumino-borosilicate foamed glass, which can eventually be used as a heat-insulating material, a light-weight aggregate for civil engineering applications, or a carrier for sewage treatment. The effects on waste LCD glass foaming of a variety of carbon foaming agents, metal salt foaming agents, and bonding agents are examined, as well as other factors such as chemical composition, foaming temperature, and grain size of the raw materials from the waste LCD glass. After examining all the variables that influence the foaming process, it was confirmed that the waste LCD glass is suitable as a raw material for producing alumino-borosilicate foamed glass. The alumino-borosilicate foamed glass has excellent physical properties, with density less than 0.14 g/cm³, heat conductivity less than 0.054 W/(mK) @20 °C, bending strength more than 35 N/cm², compressive strength more than 39 N/cm² and a coefficient of linear thermal expansion less than 4.5 × 10^?6 m/m °C. This clearly shows that the lightweight alumino-borosilicate foamed glass could be useful for various applications.     

Gas-releasing reactions in foam-glass formation using carbon and MnxOy as the foaming agents

The gas-releasing reaction is the most important process in the preparation of foam glass. In this paper we investigated the gas-releasing reactions by means of thermogravimetry coupled with mass spectrometry. We used carbon (activated charcoal and carbon black) and/or manganese oxides (MnO₂, Mn₂O₃, and Mn₃O₄) as the foaming additives. We show that manganese oxides have different functions in the foaming process. The thermal decomposition of MnO₂ below the sintering temperature has a negative impact on the foaming process as it shifts the foaming to higher temperatures, increases the mass-loss rate, leading to open pores, and burns out the carbon. When foaming in an oxidizing atmosphere, the carbon is burnt out by the oxygen from the atmosphere. Instead, Mn₂O₃ can be used as the foaming agent in an oxidizing atmosphere. In the oxygen-free atmosphere, Mn₃O₄ can be used as the oxidizing agent, supporting the oxidation of carbon and the foaming process. The redox equilibrium of manganese (Mn²⁺/Mn³⁺), influenced by the oxygen partial pressure in the pores and physically dissolved oxygen in the glass, shows the strongest influence on the foaming process. The CO/CO₂ ratio in the evolved gases depends on the carbon source and the temperature.     

Two-step micro cellular foaming of amorphous polymers in supercritical CO2

Microcellular foaming of amorphous rigid polymers, polymethylmethacrylate (PMMA) and polystyrene (PS) was studied in supercritical CO₂ (ScCO₂) in the presence of several types of additives, such as triblock (styrene-co-butadiene-co-methylmethacrylate, SBM and methylmethacrylate-co-butylacrylate-co-methylmethacrylate, MAM) terpolymers. This work is focused in the two-step foaming process, in which the sample is previously saturated under ScCO₂ being expanded in a second step out of the CO₂ vessel (e.g. in a hot oil bath) where foaming is initiated by the change of temperature near or above the glass transition temperature of the glass/polymer glassy system. Samples were saturated under high pressures of CO₂ (300 bar), at room temperature, for 16 h, followed by a quenching at a high depressurization rate (150 bar/min). In the last step, foaming was carried out at different temperatures (from 80 °C to 140 °C) and different foaming times (from 10 s to 120 s). It was found that cellular structures were controlled selecting either the additive type or the foaming conditions. Cell sizes are ranging from 0.3 μm to 300 μm, and densities from 0.50 g/cm³ to 1 g/cm³ depending on the polymers considered.     

The use of egg shells to produce Cathode Ray Tube (CRT) glass foams

Cleaned Cathode Ray Tube (CRT) (panel and funnel) waste glasses produced from dismantling TV and PC colour kinescopes were used to prepare glass foams by a simple and economic processing route, consisting of a direct heating of glass powders at relatively low temperatures (600–800 °C). This study reports on the feasibility of producing glass foams using waste egg shells as an alternative calcium carbonate-based (95 wt%) foaming agent derived from food industry. The foaming process was found to depend on a combination of composition, processing temperature and mixture of raw materials (glass wastes). Hot stage microscopy (HSM), X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize foams and evaluate the foaming ability and the sintering process. The experimental compositions allowed producing well sintered glass foams with suitable properties for some functional applications with environmental benefits such as: (1) reduced energy consumption because of the low heat treatment temperatures used; and (2) materials produced exclusively from residues.     

Study of the cellular structure heterogeneity and anisotropy of polypropylene and polypropylene nanocomposite foams

This article presents the analysis of the processing parameters influence on the foaming behavior and cellular structure of PP‐montmorillonite foams. Polypropylene nanocomposites containing 5.0 phr of an organically‐modified montmorillonite (MMT) were initially melt‐compounded in a twin‐screw extruder with azodicarbonamide (ADC) and later foamed using a one‐step compression‐molding process. The cellular structure and morphology of the foams was assessed using both scanning and transmission electron microscopies. A time‐dependant double‐effect was observed during foaming: (1) first of all, the melt strength of the polymer, too high for shorter times, not allowing full cell growth, and too low for high foaming times due to thermal oxidation; (2) and polymer degradation, clearly observed for very high foaming times, directly affecting polymer's melt resistance. Comparatively, PP‐MMT foams exhibited a broader foaming time processing window, a more isometric type of cellular structure and decreased open‐cell contents, indicating an effective nucleation and cell wall stabilization induced by the exfoliated MMT particles. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

回收聚乙烯的交联发泡及其产品性能研究

介绍了以3种回收低密度聚乙烯（PE）为原材料,热膨胀微球为发泡剂,运用模压法加工成型制备得到的交联发泡聚乙烯板材。通过差示扫描量热仪、扫描电子显微镜、摆锤式冲击试验机和电子万能试验机等对所制备交联发泡聚乙烯产品的热学性能、形貌、抗冲击性能和抗拉伸性能进行了表征和分析。结果表明,聚乙烯回收料经加工后,熔点及分子量均有所提升,这归因于过氧化二异丙苯（DCP）的交联作用;交联后形成的网络结构有利于泡孔的稳定,3种回收料交联发泡后均得到了独立分布的泡孔;拉伸强度和冲击强度最高可达9.7 N/mm²和21.5 kJ/m²;氧化诱导时间为7.3 min;此发泡材料可望用于生产浮漂和浮力球等各类型水上产品。     

Foaming behavior of microcellular foam polypropylene/modified nano calcium carbonate composites

A new process was used to prepare microcellular foams with supercritical carbon dioxide as the physical foaming agent in a batch. The foaming temperature range of the new process was about five times broader than that of the conventional one. Characterization of the cellular structure of the original polypropylene (PP) and PP/nano‐CaCO₃ (nanocomposites) foams was conducted to reveal the effects of the blend composition and processing conditions. The results show that the cellular structure of the PP foams was more sensitive to the foaming temperature and saturation pressure variations than that of the nanocomposite foams. Uniform cells of PP foams are achieved only at a temperature of 154°C. Also, the low pressure of 20 MPa led to very small cells and a low cell density. The competition between the cell growth and cell nucleation played important role in the foam density and was directly related to the foaming temperature. Decreasing the infiltration temperature depressed the initial foaming temperature, and this resulted in significantly larger cells and a lower cell density. A short foaming time led to a skin–core structure; this indicated that a decrease in the cell size was found from skin to core, but the skin–core structure gradually disappeared with increasing foaming time. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of the glass–calcium carbonate mixture's characteristics on the foaming process and the properties of the foam glass

We prepared foam glasses from cathode-ray-tube panel glass and CaCO₃ as a foaming agent. We investigated the influences of powder preparation, CaCO₃ concentration and foaming temperature and time on the density, porosity and homogeneity of the foam glasses. The results show that the decomposition kinetics of CaCO₃ has a strong influence on the foaming process. The decomposition temperature can be modified by varying the milling time of the glass–CaCO₃ mixture and thus for a specific CaCO₃ concentration an optimum milling time exists, at which a minimum in density and a homogeneous closed porosity are obtained. Under the optimum preparation conditions the samples exhibit a density of 260 kg/m³. The thermal conductivity of the foam glass was measured to be 50–53 mW/(m K). The observed dependence of the foaming process on the decomposition kinetics of the foaming agent can be applied as a universal rule for foaming processes based on thermal decomposition.     

Open-celled microcellular foaming and the formation of cellular structure by a theoretical pattern in polystyrene

An open-celled structure was produced using polystyrene and supercritical carbon dioxide in a novel batch process. The required processing conditions to achieve open-celled structures were predicted by a theoretical model and confirmed by the experimental data. The theoretical model predicts that at least a saturation pressure of 130 bar and a foaming time between 9 and 58 s are required for this system to produce an open-celled structure. The foaming temperature range has been selected to be higher than the polymer glass transition temperature yet not higher than a temperature limit where the gas starts leaving the system. The experimental results in the batch foaming process verified the model substantially. The SEM pictures showed the presence of pores between the cells, and the mercury porosimetry test results verified the overall open-celled structure. Experimental results also showed that by increasing the saturation pressure and the foaming temperature, there was a drop in the time required for open-celled structure formation. At saturation pressure of 130 bar, foaming temperature of 150 °C and a foaming time of 60 s, open-celled microcellular polystyrene foams were obtained using supercritical CO₂ in the batch process. Based on the results, a schematic diagram, depicting the process of foam structure formation from nucleation to bubble coalescence and gas escape from polymer, was proposed. Theoretical calculations showed that by increasing foaming time, cell size was increased and cell density was reduced and the experimental results verified this prediction.     

Cell structure and impact properties of foamed polystyrene in constrained conditions using supercritical carbon dioxide

To obtain cellular with small cell diameter, to control cell structure and to improve impact strength of foaming materials, the quick-heating method was applied for foaming polystyrene (PS) using supercritical CO₂ (Sc-CO₂) as physical blowing agent. Then, changes of cell structure and impact strength in microcellular foamed PS materials under constrained conditions were studied. The effects of foaming processing parameters, such as foaming temperature, saturation pressure and foaming time on the cell structure and impact strength of foamed PS in the constrained conditions were studied. The results showed that the Sc-CO₂ solubility and nucleation density in the constrained conditions were not influenced compared with those under free foaming conditions. However, cells in constrained foaming process are mostly circular and independent with thick cell walls; the phenomenon of cell coalescence and collapse was effectively eliminated under constrained conditions. In addition, cell diameters in constrained foaming process decrease with increase in foaming temperature and increase with increase in the foaming time. Compared with that in free foaming conditions, the cell growth was restrained dramatically under constrained conditions which resulted in smaller cell diameter. Moreover, higher impact strength could be obtained for foamed PS as foaming time was prolonged, foaming temperature was increased or saturation pressure was enhanced.