Production of coloured glass-ceramics from incinerator ash using thermal plasma technology

Incineration is a major treatment process for municipal solid waste in Taiwan. It is estimated that over 1.5 Mt of incinerator ash are produced annually. This study proposes using thermal plasma technology to treat incinerator ash. Sintered glass-ceramics were produced using quenched vitrified slag with colouring agents added. The experimental results showed that the major crystalline phases developed in the sintered glass-ceramics were gehlenite and wollastonite, but many other secondary phases also appeared depending on the colouring agents added. The physical/mechanical properties, chemical resistance and toxicity characteristic leaching procedure of the coloured glass-ceramics were satisfactory. The glass-ceramic products obtained from incinerator ash treated with thermal plasma technology have great potential for building applications.     

Effect of thermal processing on the characteristics of incineration fly ash

This work investigated the possibilities of immobilizing incineration fly ash by applying different processing methods. Direct sintering of fly ash at 1050 degrees C produced material with increased resistance to leaching; however, the high content of halides prevented the achievement of appropriate strength. Fly ash melting and casting into metallic moulds resulted in the formation of glass with good chemical resistivity and mechanical properties, which were further improved by devitrification, and the formation of glass-ceramics. The most successful combination of strength and resistance to leaching was obtained by a process consisting of fly ash melting, by pouring the melt into water, then grinding, and sintering without additives at 850-950 degrees C. In this way, a material was produced that cannot only be landfilled as a stabilised and non-reactive waste in landfills for non-hazardous wastes, but can also be utilized as a valuable material for manufacturing useful products. This article provided valuable results for policy-makers in Slovenia, about the handling fly ash from incineration plants. Implications: Fly ash from an incineration plant was thermally treated using several processing routes. Ash-melting, by pouring the melt into water and sintering, produced glass-ceramics having an optimal combination of strength and resistance to leaching that can find applications as useful products. These results provide important data for policy makers in Slovenia regarding the building of incineration plants, and handling the solid-waste products, especially fly ash.     

On formation of CaO-Al(2)O(3)-SiO2 glass-ceramics by vitrification of incinerator fly ash

CaO-Al(2)O(3)-SiO(2) system glass ceramics of incinerator fly ash have been prepared by vitrification and then heat-treated in different conditions. The thermal molten process (TMP) was applied to heat treat vitrified samples at high temperatures whereas in the powder sintering process water-quenched vitrified samples were ground into powder and then sintered at high temperatures. Gehlenite was found present as the major phase in all treated samples. Treated samples in general exhibited good leachability characteristics as well as chemical durability, except in the HCl solution. Microstructure and physical properties varied with the treatment condition. Fine and relatively high dense structures with desirable properties were obtained for samples treated by the TMP. For both processes, higher temperature treatments caused crystal growth and thus poor properties were attained. Good physical and mechanical properties achieved at 900-950 degrees C in this study imply the treated samples have attractive potential for engineering applications.     

Heavy metal-rich wastes sequester in mineral phases through a glass-ceramic process

Certain sludges generated by industry are rich in contaminating elements and are a major environmental problem. In this study, we determine the ability of these contaminating elements to be incorporated into a glass-matrix and in various mineral phases after a crystallization process. The contaminating elements studied were obtained from sewage sludges (SS) and galvanic sludges (GS), our raw materials. The sludge samples were taken from urban wastewater treatment plant in Catalonia (NE Spain) with high levels of phosphorus oxide (P(2)O(5)). In silica glasses, P(2)O(5) acts as a network former. We determined the chemical composition of both the SS and GS, as well as their thermal behaviour by differential thermal analysis and thermal gravimetric analysis (DTA-TG) to obtain their melting curves. The vitreous transition temperature of the obtained glass was established by dilatometer technique at 725 degrees C. The DTA-TG curve of the glass obtained has an exothermal wide peak at 860 degrees C corresponding to crystallization of the two phases: a spinel phase and a phosphate phase. A second exothermal wide peak at 960 degrees C was attributed to the crystallization of aluminium pyroxene, anorthite and fluor-apatite, with two exothermal phenomena attributed to the evolution of these phases. An exothermal peak at 1100 degrees C was attributed to gehlenite crystallization. Scanning electron microscope observations and energy-dispersed X-ray spectroscopy microanalyses of glass-ceramic showed that the contaminating elements were concentrated in the spinel phases, which are the first phases to crystallize during the cooling of glass. Finally, the spinel structure permits the incorporation of all the contaminating elements into it.     

利用粉煤灰制备镁橄榄石微晶玻璃的研究

为丰富微晶玻璃外观色泽,提高产品竞争力,利用氟硅酸盐在微晶玻璃制备中可作成核剂的特性,经过理论分析确定以粉煤灰提取有价成分后的含氟固体残渣为主要原料生产镁橄榄石微晶玻璃的配料。通过等温晶化制度对产品进行晶化处理;运用扫描电镜对产品的结晶过程进行观察;采用X射线衍射分析确定产品的主晶相,验证是否生成了该配料条件下的目标晶相。研究表明,晶化产物中生成了大量以镁橄榄石为主晶相的微晶体,且基础玻璃的熔融温度大为降低,该原料配比是成功的。     

PM10, PM2.5 and PM1.0—Emissions from industrial plants—Results from measurement programmes in Germany

Emission measurement programmes were carried out at industrial plants in several regions of Germany to determine the fine dust in the waste gases; the PM₁₀, PM_2.5 and PM_1.0 fractions were sampled using a cascade impactor technique. The installations tested included plants used for: combustion (brown coal, heavy fuel oil, wood), cement production, glass production, asphalt mixing, and processing plants for natural stones and sand, ceramics, metallurgy, chemical production, spray painting, wood processing/chip drying, poultry farming and waste treatment. In addition waste gas samples were taken from small-scale combustion units, like domestic stoves, firing lignite briquettes or wood.In total 303 individual measurement results were obtained during 106 different measurement campaigns. In the study it was found that in more than 70% of the individual emission measurement results from industrial plants and domestic stoves the PM₁₀ portion amounted to more than 90% and the PM_2.5 portion between 50% and 90% of the total PM (particulate matter) emission. For thermal industrial processes the PM_1.0 portion constituted between 20% and 60% of the total PM emission.Typical particle size distributions for different processes were presented as cumulative frequency distributions and as frequency distributions. The particle size distributions determined for the different plant types show interesting similarities and differences depending on whether the processes are thermal, mechanical, chemical or mixed. Consequently, for the groups of plant investigated, a major finding of this study has been that the particle size distribution is a characteristic of the industrial process. Attempts to correlate particle size distributions of different plants to different gas cleaning technologies did not lead to usable results.     

High infrared radiance glass-ceramics obtained from fly ash and titanium slag

A new glass–ceramic was synthesized by crystal growth from a homogenous glass obtained by melting a mixture of fly ash collected from a power plant in Hebei province of China, titanium slag collected from a titanium factory in Sichuan province of China, and MgCO₃ as an additive. According to the measurement results of differential thermal analysis, a thermal treatment of nucleating at 850 °C for 2 h and crystallizing at 985 °C for 1.5 h was used to obtain the crystallized glass. X-ray diffraction and scanning electron microscopy measurements showed that the main crystalline phase of this material was iron-ion substituted cordierite, (Mg,Fe)₂Al₄Si₅O₁₈, which is homogeneously dispersed within the parent glass matrix. The infrared radiance and thermal expansion coefficient of this material have been examined, and the results demonstrate that this glass–ceramic material has potential for application in a wide range of infrared heating and drying materials.     

Weathering patinas on the medieval (S. XIV) stained glass windows of the Pedralbes Monastery (Barcelona, Spain)

Background, aim, and scope  The first step in the restoration of a medieval stained glass window is the evaluation of its degree of degradation. This implies the study of the chemical composition of the stained glass as well as the new mineral phases developed on its surface (patinas). Patinas are clearly related to glass composition, time, environmental conditions, microenvironments developed in local zones, bioactivity, physical and chemical factors, etc. This study was carried out on patinas developed in selected Na-rich stained glass of the Santa Maria de Pedralbes Monastery (Barcelona, Spain). The location of this monument in the city (about 5 km from the shoreline and close to the Collserola hill flank) helped to determine the environmental conditions in which patinas developed. The aim of our study was to characterize the patinas formed on the surface of the selected glass of this monastery in order to understand the role of the chemical composition of the original glass (Na-rich) as well as the environmental conditions in which they developed. Materials and methods  Powdered samples of two different color-type patinas (ochre-orange and brownish) were collected in the external and internal parts of the stained glass windows of the Prebystery and Chapter House of the Pedralbes Monastery by using a precision (odontological) drill. These patinas were subsequently analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Results  XRD analyses evidenced the presence of sulfates (gypsum and thenardite), calcite, Ca-oxalates (whewellite and weddellite), and quartz forming part of the patinas. Although these mineral phases can be found in both color-type patinas, whewellite and thenardite are more common in the ochre-orange patinas. The results obtained were validated by the FTIR measurements. It has been observed, when thenardite is present, that gypsum occurs as traces. Thenardite is in most of the cases associated with whewellite and mainly occurs in the internal parts of the glass. In contrast, weddellite is limited to the absence of thenardite and whewellite and to the external parts of the stained glass. Quartz is present in all the patinas independent of their location and color. Calcite also occurs in many samples. It appears in both color-type patinas and, in some cases, is associated to the presence of weddellite but not to whewellite and/or thenardite. Discussion  Glass composition together with environmental conditions and location of the patinas (internal or external parts of the stained glass window), as well as the provenance of the glass within the monastery, are the main factors that define the development of the new mineral phases. Moreover, the action of microorganisms, when present, can also strongly influence the development of some mineral phases. For example, the formation of calcite in the external parts of the stained glass (associated with the presence of oxalates) is related to the action of microorganisms. When calcite is formed in the internal parts of the glass and it is not associated with the presence of Ca-oxalates, an inorganic origin can be invoked. The presence of weddellite requires a very humid microenvironment with very little exposure to sunlight. In fact, this mineral phase has only been observed in the external parts of some glass located in the humid and shady side of the monastery. Whewellite (which only appears in the internal parts) needs a low degree of relative humidity. It has been observed that sulfur precipitating in basically one mineral phase (thenardite or gypsum) depends on the microenvironmental conditions of the moment and the glass composition. When thenardite occurs, it can be maintained that the original glass is of Na composition. The occurrence of quartz in all samples is interpreted as being due to the deposition of atmospheric particulate matter. The color of the patinas can be originated by different processes (presence of carotenes, organic pigmentation, atmospheric contamination, etc.). Conclusions  In the case of moderately weathered stained glass windows, the combination of XRD and FTIR techniques is very useful to obtain a fast preliminary evaluation of the degree of weathering of a stained glass window. The presence of specific mineral phases in the patina (e.g., thenardite) confirms the Na composition of the original stained glass. This is important since Na-rich glass underwent a lesser degree of weathering than K- or K-Ca-rich glass. However, their absence cannot preclude other possibilities. It has been extensively evidenced through time that environmental conditions play an important role on the formation of the different mineral phases which form part of the patinas. Recommendations and perspectives  The first step in the restoration of a stained glass window is the evaluation of the degree of deterioration of the glass. This evaluation includes a chemical analysis of the glass as well as a characterization of the patinas developed on their surfaces. The obtained results will be essential in order to define the best restoration practices to be followed.     

Early stage of weathering of medieval-like potash–lime model glass: evaluation of key factors

Purpose  

Throughout history, a consequent part of the medieval stained glass windows have been lost, mostly because of deliberate or accidental mechanic destruction during war or revolution, but, in some cases, did not withstand the test of time simply because of their low durability. Indeed, the glasses that remain nowadays are for many in a poor state of conservation and are heavily deteriorated. Under general exposure conditions, stained glass windows undergo different kinds of weathering processes that modify their optical properties, chemistry, and structure: congruent dissolution, leaching, and particle deposition (the combination of those two leading together to the formation of neocrystallisations and eventually crusts). Previous research has studied the weathering forms and the mechanisms from which they are originated, some others identified the main environmental parameters responsible for the deterioration and highlighted that both intrinsic (glass composition) and extrinsic (environmental parameters) factors influence glass degradation. Nevertheless, a clear quantification of the impact of the different deterioration extrinsic factors has not been performed.     

Combined glassification of EAF dust and incinerator fly ash

Stainless steelmaking dust contains large amount of heavy metals, such as Cr and Ni. If these hazardous materials are not treated properly, they will cause detrimental secondary contamination. Preliminary study on recycling stainless steelmaking dust employed the thermal molten technology. Glass-ceramics were formed by combination stainless steel dust and incinerator fly ash with the ratio of 1:9. The major phases were Augite, Akermanite, and Donathite. It was found that the glass-ceramics shows the best characteristic at 900 degrees C after 5 h of heat treatment. This product can be used as building materials or refractory materials.     

Comparison of the particle size distribution of heavy-duty diesel exhaust using a dilution tailpipe sampler and an in-plume sampler during on-road operation

Originally constructed to develop gaseous emission factors for heavy-duty diesel trucks, the U.S. Environmental Protection Agency's (EPA) On-Road Diesel Emissions Characterization Facility has been modified to incorporate particle measurement instrumentation. An electrical low-pressure impactor designed to continuously measure and record size distribution data was used to monitor the particle size distribution of heavy-duty diesel truck exhaust. For this study, which involved a high-mileage (900,000 mi) truck running at full load, samples were collected by two different methods. One sample was obtained directly from the exhaust stack using an adaptation of the University of Minnesota's air-ejector-based mini-dilution sampler. The second sample was pulled from the plume just above the enclosed trailer, at a point approximately 11 m from the exhaust discharge. Typical dilution ratios of about 300:1 were obtained for both the dilution and plume sampling systems. Hundreds of particle size distributions were obtained at each sampling location. These were compared both selectively and cumulatively to evaluate the performance of the dilution system in simulating real-world exhaust plumes. The data show that, in its current residence-time configuration, the dilution system imposes a statistically significant bias toward smaller particles, with substantially more nanoparticles being collected than from the plume sample.     

Comparison of the Particle Size Distribution of Heavy-Duty Diesel Exhaust Using a Dilution Tailpipe Sampler and an In-Plume Sampler during On-Road Operation

ABSTRACT

Originally constructed to develop gaseous emission factors for heavy-duty diesel trucks, the U.S. Environmental Protection Agency's (EPA) On-Road Diesel Emissions Characterization Facility has been modified to incorporate particle measurement instrumentation. An electrical low-pressure impactor designed to continuously measure and record size distribution data was used to monitor the particle size distribution of heavy-duty diesel truck exhaust. For this study, which involved a high-mileage (900,000 mi) truck running at full load, samples were collected by two different methods. One sample was obtained directly from the exhaust stack using an adaptation of the University of Minnesota's air-ejector-based mini-dilution sampler. The second sample was pulled from the plume just above the enclosed trailer, at a point ~11 m from the exhaust discharge. Typical dilution ratios of about 300:1 were obtained for both the dilution and plume sampling systems. Hundreds of particle size distributions were obtained at each sampling location. These were compared both selectively and cumulatively to evaluate the performance of the dilution system in simulating real-world exhaust plumes. The data show that, in its current residence-time configuration, the dilution system imposes a statistically significant bias toward smaller particles, with substantially more nanoparticles being collected than from the plume sample.     

On the Minimum Efficiency and the Most Penetrating Particle Size for Fibrous Filters

Equations for predicting the minimum efficiency and most penetrating particle size for fibrous filters have been derived by considering the diffusion and interception mechanisms. The results show that the most penetrating particle size decreases with increasing filtration velocity and with increasing fiber volume fraction, and increases with increasing filter fiber size. The corresponding equation for minimum efficiency has also been derived showing the dependence on filtration velocity, fiber volume fraction, and fiber size. These results have been compared with experimental data and satisfactory agreement has been obtained.     

A High-Volume Sampler for the Determination of Particle Size Distributions in Ambient Air

A size selective particle sampler has been developed for continuous sampling of the urban aerosol over periods ranging from hours to weeks, providing relatively large sample weights. The system, which is now operating in New York City, uses a parallel array of two-stage samplers. The cyclones used as the first stage collectors have 50% particle retention at 3.5,2.5,1.5 and 0.5 µm aerodynamic diameter, respectively. Undersize particles which pass through the cyclones are captured on glass fiber filters. Equal intake velocities are assured by using flow equalizers on the inlets to the cyclones. Accurate control of the flow through the cyclones is obtained by the use of an integrated circuit pressure transducer in conjunction with a specially designed feedback control circuit. The collection efficiencies of the cyclone were calibrated using monodisperse ferric oxide test aerosols tagged with Tc-99m. Mass balances of the par-ticulates collected on the cyclones and filters are obtained for the five sampling stages. Preliminary results show the distributions of the total suspended particulates in New York City to be bimodal. The distributions of lead, copper, and manganese with particle size are also discussed.     

Photocatalytic activity of TiO2 films grown on different substrates

Titanium dioxide films were prepared on glass, indium-tin oxide (ITO) glass and p-type monocrystalline silicon and studied for the photocatalytic degradation of rhodamine B in an aqueous medium. Raman, AFM, and XPS spectroscopic investigations of these films indicated that microstructure of titanium oxide films were greatly affected by the substrate materials. Rutile was confirmed to be easily formed on the surface of ITO glass, and TiO2 tended to grow as closely packed particles that were elongated strips with an average size of 20 nm, and had lovely contrast with the perfectly round particles grown on p-type monocrystalline silicon. Charge transfer between the film and silicon substrate was verified by surface photovoltage spectra. This may be the real reason why the films grown on ITO glass and silicon substrates exhibit higher photocatalytic reactivity than the film on glass substrate. Moreover, the different surface properties also seem to be responsible for the different activity.     

利用废CRT屏玻璃为原料制备泡沫玻璃

以废阴极射线管(CRT)屏玻璃为主要原料,碳黑为起泡剂,采用粉末烧结法制备了低密度保温泡沫玻璃。通过扫描电镜(SEM)、导热系数测定仪等分析手段,研究了起泡剂的用量、发泡温度和发泡时间对泡沫玻璃泡径、密度、热学性能以及机械力学性能的影响。结果表明,在相同烧制工艺条件下,随起泡剂掺加量增加,烧制所得的泡沫玻璃密度成"V"型变化;当其掺加量为0.20%时,泡沫玻璃在密度、孔径分布以及力学性能上均达到最佳。随着发泡温度的提高和发泡时间的延长,密度会逐渐减小,泡沫玻璃的气泡会逐渐增大,以致产生连通现象。当发泡温度为820℃、发泡时间为30min时烧制的泡沫玻璃密度为0.180 g/cm3,导热系数为0.0695 W/(m.K)。     

电选法回收利用废印刷线路板

废印刷线路板含有多种有价值的物质,随意丢弃或处理处置方法不当既污染环境,又造成资源流失。采用剪切式破碎和电力分选技术对废印刷线路板的机械分离进行了研究。结果表明,电选法可以实现废印刷线路板中金属和玻璃纤维、树脂的分离;在实验的粒径范围内(-14+20目到-120+200目分为5个粒径级别),金属主要集中在-20+120目粒级范围内,且该粒级范围分选效果最好。     

Mitigating environmental impact of waste glass materials: review of the existing reclamation options and future outlook

The environmental impact of waste glass (WG) is one of the major challenges crippling sustainable waste management and mitigation. Reclamation of recycled materials from waste glass remains a tedious task amidst complex technological approaches. The challenge as seen in the global containment measures increase the proportion of waste glass and minimize the existing capacity of landfill space. In many works, findings have shown how best to minimize the impact of waste glass as evidenced in their inclusion as building materials such as cement, mortars, concretes and blocks. The concept of this paper is to appraise previous studies carried out on the use of waste glass as key contributing factor in structural building. The scope of this paper will be broaden to include various successes recorded in the evolution of concrete mixtures containing different proportion of recycle glass. Part of the setbacks noted in the inclusion of these recycled materials as matrix, filler or fibre are also reported in this paper. Also discussed is the durability of glass materials in varying conglomerate involving cement in reinforcement of building and structures. Thermal insulating properties of recycled glass are also considered in this work where considerable energy is saved due to their low thermal conductivity. Based on the analysis of various studies and other factors considered in this paper, it is established that recycled glass materials can be accommodated in structural buildings, while continuous research is necessary to adapt waste glass to high pH value of Portland cement.

     

Preparation of glass-ceramics from molten steel slag using liquid-liquid mixing method

A novel approach to prepare glass-ceramics from molten steel slag (MSS) was proposed. In laboratory, the water-quenched steel slag was melted at 1350 °C to simulate the MSS. A mixture of additive powders in wt.% (55 quartz powder, 5 Na₂O, 16 emery powder, 15 CaO, 8 MgO, 1 TiO₂) were melted into liquid at 1350 °C separately. Then the MSS and the molten additives were mixed homogeneously in order to obtain parent glass melt. The proportion of MSS in the melt was 50 wt.%. The melt was subsequently cast, annealed, heat-treated and transformed into glass-ceramics. Their microstructure and crystallization behavior were analyzed. The samples exhibited excellent properties and displayed bulk crystallization. The major crystallized phase was diopside ((Fe_0.35Al_0.20Mg_0.44)Ca_0.96(Fe_0.08Si_0.70Al_0.20)₂O_6.12), which was uniformly distributed in the microstructure. The novel approach may help iron and steel industry achieve zero disposal of steel slag with utilization of the heat energy of the MSS.     

Application of reutilization technology to calcium fluoride sludge from semiconductor manufacturers

Glass ceramics were prepared from mixtures of wastes generated from refining of waste glass and semiconductor industrial wastewater sludge. The aim is then indeed to study the possible use and effects of integrating calcium fluoride (CaF2) as present in semiconductor wastewater sludge in the silica (glass) melts. CaF2 sludge was blended with a conditioner according to characteristics of the target. Calcium oxide-silicon dioxide-aluminum oxide system glass ceramics have relatively high melting points. Addition of CaF2 sludge to fluxes can significantly reduce the melting point and hence improve the kinetics of the reactions. CaF2 sludge and waste glass were co-melted in various ratios to elucidate their interactions at various heating temperatures. The results indicate that the lowest melting temperature was 1163 degrees C, obtained for the CaF2 sludge-waste glass mixture at a ratio 6:4 (wt:wt), which is significantly lower than that of CaF2 sludge (1378 degrees C). The benefits of using melting to dispose of sludge are the reduction of waste and the fixation of heavy metals. Heat treatment was used to convert the obtained glass into glass ceramics. Heavy metal leaching tests revealed that melting conditions lowered the heavy metal concentrations in the leachate to an order of magnitude lower than that in the sludge. Consequently, industrial sludge can be safely used as a fine aggregate material for a potentially wide range of construction applications.