Products of steel slags an opportunity to save natural resources

In Germany, and in the most industrial countries, the use of blast furnace and steel slags as an aggregate for civil engineering, for metallurgical use and as fertiliser has a very long tradition. Since the introduction of the basic oxygen steel making furnace (BOF) process and the electric arc furnace (EAF) process the German steel industry started extensive research on the development of fields of application for BOF and EAF slags. These investigations have been mainly performed by Forschungsgemeinschaft Eisenhüttenschlacken e. V. (FEhS), the Research Association for blast furnace and steel slags. Today steel slags are well characterised and long-term experienced materials mainly used as aggregates for road construction (e.g. asphaltic or unbound layers), as armour-stones for hydraulic engineering constructions (e.g. stabilisation of shores), and as fertiliser for agriculture purposes. These multifarious fields of application could only be achieved because the steelworks influence the quality of slags by a careful selection of raw materials and a suitable process route. Furthermore, subsequent procedures like a treatment of the liquid slag, an appropriate heat treatment and a suitable processing have been developed to ensure that the quality of steel slags is always adequate for the end use. Depending on the respective field of application, the suitability of steel slags has to be proven by determining the technical properties, as well as the environmental compatibility. For this reason test methods have been developed to evaluate the technical properties especially the volume stability and the environmental behaviour. To evaluate the volume stability a suitable test (steam test) has been developed and the results from laboratory tests were compared with the behaviour of steel slags under practical conditions, e.g. in a road. To determine the environmental behaviour leaching tests have been developed. In the meanwhile most of these test methods are drafted or already accepted as a CEN standard and are used for a continuous quality control. Usually the suitability of steel slags is stated by fulfilling the requirements of national and/or international standards and regulations. Based on these standards and regulations in Germany in 1998 about 97% of the produced steel slags have been used as aggregates for road construction (e.g. as surface layer, road base and sub base for high trafficked roads), ways, earthworks, and armourstones for hydraulic structures. Consistent to the successful long-term experience not only products of steel slags but also products of blast furnace slags have been eliminated from the European Waste Catalogue and the European Shipment of Waste Regulation of the European Community, as well as from the lists of OECD for transfrontier movements by the decision of the OECD-Council from 21 September, 1995.     

The use of waste basic oxygen furnace slag and hydrogen peroxide to degrade 4-chlorophenol

A new treatment method is developed to degrade 4-chlorophenol (4-cp) and its oxidation intermediates. The experimental results of this research demonstrate that 4-cp and its oxidation intermediates can be decomposed completely by basic oxygen furnace slag (BOF slag) with hydrogen peroxide (H₂O₂) in an acid solution. The factors that effect the treatment efficiency were studied including initial concentration of 4-cp, pH of the solution, concentration of H₂O₂ and amount of BOF slag. The BOF slags are final waste materials in the steel making process. The major components of BOF slag are CaO, SiO₂, Fe₂O₃, FeO, MgO and MnO. As the BOF slag in an acid solution, FeO and Fe₂O₃ can be dissociated to produce ferrous ion and ferric ion. Ferrous ion reacts with hydrogen peroxide to form “Fenton's reagent” which can produce hydroxyl radicals (OH^.). Hydroxyl radical possession of high oxidation ability can oxidize organic chemicals effectively. Results show that 100 mg/l of 4-cp is decomposed completely within 30 min by 438.7 g/l BOF slag with 8.2 mM hydrogen peroxide in pH=2.8±0.2 solution. The COD value of the solution is reduced from 290 to 90 mg/l. The factors studied which affect the 4-cp decomposition efficiency were the hydrogen peroxide concentration, BOF slag concentration, pH of the solution and initial concentration of 4-cp. Because large amounts of Fe₂O₃ and FeO are present in the BOF slag, the BOF slag not only has a high treatment efficiency, but also can be used repeatedly.     

Leaching assessment of road materials containing primary lead and zinc slags

Characterisation of the leaching behaviour of waste-containing materials is a crucial step in the environmental assessment for reuse scenarios. In our research we applied the multi-step European methodology ENV 12-920 to the leaching assessment of road materials containing metallurgical slag. A Zn slag from an imperial smelting furnace (ISF) and a Pb slag from a lead blast furnace (LBF) are investigated. The two slags contain up to 11.2 wt% of lead and 3.5 wt% of zinc and were introduced as a partial substitute for sand in two road materials, namely sand-cement and sand-bitumen. At the laboratory scale, a leaching assessment was performed first through batch equilibrium leaching tests. Second, the release rate of the contaminants was evaluated using saturated leaching tests on monolithic material. Third, laboratory tests were conducted on monolithic samples under intermittent wetting conditions. Pilot-scale tests were conducted for field testing of intermittent wetting conditions. The results show that the release of Pb and Zn from the materials in a saturated scenario was controlled by the pH of the leachates. For the intermittent wetting conditions, an additional factor, blocking of the pores by precipitation during the drying phase is proposed. Pilot-scale leaching behaviour only partially matched with the laboratory-scale test results: new mass transfer mechanisms and adapted laboratory leaching tests are discussed.     

Application of magnetic separation to steelmaking slags for reclamation

Integrated iron and steel plants generate large amounts of metallurgical slag, which usually contains some quantity of metals or mixtures of oxides that could be treated to be recycled in various applications. The conventional method for disposal of slags is dumping. However, it is possible to process the slags to be used in the production of metallic iron, or as an additive in cement making. In this study, a basic oxygen furnace (BOF) steelwork slag obtained from the Kardemir integrated iron and steel works, Karabuk, Turkey is used. A drum magnetic separator system with pre-engineered crucial processing parameters of drum revolution speed, drum radius, drum flesh thickness, and magnitude of the magnetic field applied is utilized, as these parameters have a competing influence on the results. Subsequently, the effects of slag grain size and the drum-blade gap are investigated in the separation efficiency of magnetic grains. It is found that collection of magnetic grains is improved by decreasing the grain size of slags and moreover, the collection of magnetic grains fraction is increased with an increase in the gap between the blades and drum.     

An overview of recovery of metals from slags

Various slags are produced as by-products in metallurgical processes or as residues in incineration processes. According to the origins and the characteristics, the main slags can be classified into three categories, namely ferrous slag, non-ferrous slag and incineration slag. This paper analysed and summarised the generation, characteristics and application of various slags, and discussed the potential effects of the slags on the environment. On this basis, a review of a number of methods for recovery of metals from the slags was made. It can be seen that a large amount of slags is produced each year. They usually contain a quantity of valuable metals except for blast furnace slag and they are actually a secondary resource of metals. By applying mineral processing technologies, such as crushing, grinding, magnetic separation, eddy current separation, flotation and so on, leaching or roasting, it is possible to recover metals such as Fe, Cr, Cu, Al, Pb, Zn, Co, Ni, Nb, Ta, Au, and Ag etc. from the slags. Recovery of metals from the slags and utilisation of the slags are important not only for saving metal resources, but also for protecting the environment.     

Steel slags in a landfill top cover – Experiences from a full-scale experiment

A full scale field study has been carried out in order to test and evaluate the use of slags from high-alloy steel production as the construction materials for a final cover of an old municipal landfill. Five test areas were built using different slag mixtures within the barrier layer (liner). The cover consisted of a foundation layer, a liner with a thickness of 0.7 m, a drainage layer of 0.3 m, a protection layer of 1.5 m and a vegetation layer of 0.25 m. The infiltration varied depending on the cover design used, mainly the liner recipe but also over time and was related to seasons and precipitation intensity. The test areas with liners composed of 50% electric arc furnace (EAF) slag and 50% cementitious ladle slag (LS) on a weight basis and with a proper consistence of the protection layer were found to meet the Swedish infiltration criteria of ?50 l (m² a)^?1 for final covers for landfills for non-hazardous waste: the cumulative infiltration rates to date were 44, 19 and 0.4 l (m² a)^?1 for A1, A4 and A5, respectively. Compared to the precipitation, the portion of leachate was always lower after the summer despite high precipitation from June to August. The main reason for this is evapotranspiration but also the fact that the time delay in the leachate formation following a precipitation event has a stronger effect during the shorter summer sampling periods than the long winter periods. Conventional techniques and equipment can be used but close cooperation between all involved partners is crucial in order to achieve the required performance of the cover. This includes planning, method and equipment testing and quality assurance.     

Kinetics of steel slag leaching: Batch tests and modeling

Reusing steel slag as an aggregate for road construction requires to characterize the leaching kinetics and metal releases. In this study, basic oxygen furnace (BOF) steel slag were subjected to batch leaching tests at liquid to solid ratios (L/S) of 10 and 100 over 30 days; the leachate chemistry being regularly sampled in time. A geochemical model of the steel slag is developed and validated from experimental data, particularly the evolution with leaching of mineralogical composition of the slag and trace element speciation. Kinetics is necessary for modeling the primary phase leaching, whereas a simple thermodynamic equilibrium approach can be used for secondary phase precipitation. The proposed model simulates the kinetically-controlled dissolution (hydrolysis) of primary phases, the precipitation of secondary phases (C-S-H, hydroxide and spinel), the pH and redox conditions, and the progressive release of major elements as well as the metals Cr and V. Modeling indicates that the dilution effect of the L/S ratio is often coupled to solubility-controlled processes, which are sensitive to both the pH and the redox potential. A sensitivity analysis of kinetic uncertainties on the modeling of element releases is performed.     

Metallic-phase lead in slag of municipal solid waste incineration ash and leaching characteristics

Metallic phases in slags and their influence on the leaching characteristics were investigated. The proportions of metallic phase in four slags were 0.028%, 0.24%, 1.87%, and 3.05% by weight. The lead content was 10–248 mg/kg in bulk slag after metal removal, while in the metallic phase it was 579–7390 mg/kg. Lead concentrations in the metallic phase were more than ten times higher than in slags after metal removal. Lead was distributed in the metallic phase at 2.0%, 8.3%, 10.3%, and 47.4%. The concentrations of all metallic elements in metallic phases were much higher than in bulk slag. Iron, copper, and nickel had accumulated in magnetic metals, while aluminum and zinc were found in nonmagnetic metals. As regards chromium, manganese, lead, and tin, the proportion of metallic phases depended on the slag samples. By removing metallic phases, both water and pH 4 leachable lead decreased. The basic principles of melting residues containing lead are the separation of lead as a metal in reductive melting, and the containment of lead ions into uniform glassy particles in oxidization melting. Melting slag can be seen to contribute to environmental preservation by facilitating the recycling of materials through the separation of metals from melting slag. Received: February 21, 2000 / Accepted: July 27, 2000     

Recycling of Malaysia’s electric arc furnace (EAF) slag waste into heavy-duty green ceramic tile

Recently, various solid wastes from industry such as glass waste, fly ash, sewage sludge and slag have been recycled into various value-added products such as ceramic tile. The conventional solutions of dumping the wastes in landfills or incineration, including in Malaysia are getting obsolete as the annual huge amount of the solid wastes would boost-up disposal cost and may cause permanent damage to the flora and fauna. This recent waste recycling approach is much better and greener as it can resolve problems associated with over-limit storage of industrial wastes and reduce exploration of natural resources for ceramic tile to continuously sustain the nature. Therefore, in this project, an attempt was made to recycle electric arc furnace (EAF) slag waste, obtained from Malaysia’s steel making industry, into ceramic tile via conventional powder compaction method. The research work was divided into two stages. The first stage was to evaluate the suitability of EAF slag in ceramic tile by varying weight percentage of EAF slag (40 wt.%, 50 wt.% and 60 wt.%) and ball clay (40 wt.%, 50 wt.% and 60 wt.%), with no addition of silica and potash feldspar. In the second stage, the weight percentage of EAF slag was fixed at 40 wt.% and the percentage of ball clay (30 wt.% and 40 wt.%), feldspar (10 wt.% and 20 wt.%) and silica (10 wt.% and 20 wt.%) added was varied accordingly. Results obtained show that as weight percentage of EAF slag increased up to 60 wt.%, the percentage of apparent porosity and water absorption also rose, with a reduction in tile flexural strength and increased porosity. On the other hand, limiting the weight percentage of EAF slag to 40 wt.% while increasing the weight percentage of ball clay led to a higher total percentage of anorthite and wollastonite minerals, resulting in higher flexural strength. It was found that introduction of silica and feldspar further improved the flexural strength due to optimization of densification process. The highest flexural strength, lowest apparent porosity and water absorption of EAF slag based tile was attained at the composition of 40 wt.% EAF slag – 30 wt.% ball clay – 10 wt.% feldspar – 20 wt.% silica. The properties of ceramic tile made with EAF slag waste (up to 40 wt.%), especially flexural strength are comparable to those of commercial ceramic tile and are, therefore, suitable as high flexural strength and heavy-duty green ceramic floor tile. Continuous development is currently underway to improve the properties of tile so that this recycling approach could be one of the potential effective, efficient and sustainable solutions in sustaining our nature.     

国内电炉钢发展现状与应用前景

通过电炉铜与转炉铜能耗对比,突显了电炉钢的节能与环保优势,同时介绍了国内外电炉钢应用现状。随着社会工业化的发展所带来的钢铁积蓄量的增加,以及电炉钢技术的不断完善和发展,加之迎合国家低碳经济政策的实施,国内电炉钢发展具有广阔前景。     

Sb release characteristics of the solid waste produced in antimony mining smelting process

Sb release characteristics of blast furnace slag, mining waste rock and tailing sand were investigated in static immersion and dynamic leaching test. These three kinds of waste samples were collected from the antimony mine in Lengshuijiang, China, produced in mining smelting process. Effects of solid/liquid ratio, sample size and pH of leaching solution on Sb release characteristics were inspected based on the analysis of scanning electron microscope, pH and EC of leachate. The optimal parameters for Sb leaching of each sample were analyzed. For blast furnace slag and mining waste rock, Sb release contents increased along with the decline of solid/liquid ratio. The maximum accumulative release contents were 42.13, 34.26 mg/kg at the solid/liquid ratio of 1:20. While Sb release content for tailing sand decreased first and then increased with the reduction of solid/liquid ratio. When the solid/liquid ratio was 1:5, the accumulative Sb release content reached the most (24.30 mg/kg). Sb release content of mining waste rock increased with the drop of leaching solution pH, with the highest accumulative release content of 26.01 mg/kg at pH 2.0. Sb release contents of blast furnace slag and tailing sand showed positive correlation with the variation of leaching solution pH. The maximum accumulative release contents of these two samples were 215.91 and 147.83 mg/kg, respectively, when leaching solution pH was 7.0. In summary, Sb release capacity of the three samples in descending order was tailing sand, blast furnace slag and mining waste rock. pH and EC of the leachate in dynamic test varied independently with the initial pH of leaching solution while showing close relationship with mineral hydrolysis in the waste.     

Recovery of copper and cobalt from ancient slag.

About 2.5 million tonnes of copper smelter slag are available in Küre, northern part of Turkey. This slag contains large amounts of metallic values such as copper and cobalt. A representative slag sample containing 0.98% Cu, 0.49% Co and 51.47% Fe was used in the experimental studies. Two different methods, direct acid leaching and acid baking followed by hot water leaching were used for recovering Cu and Co from the slag. The effects of leaching time, temperature and acid concentration on Cu- and Co-dissolving efficiencies were investigated in the direct acid leaching tests. The optimum leaching conditions were found to be a leaching time of 2 h, acid concentration of 120 g L(-1), and temperature of 60 degrees C. Under these conditions, 78% Cu and 90% Co were extracted. In the acid baking + hot water leaching tests, 74% Co was dissolved after 1 h of roasting at 200 degrees C using a 3:1 acid:slag ratio, whereas the Cu-dissolving efficiency was 79% and the total slag weight loss was approximately 50%.     

Technical and environmental long-term properties of industrial residues--summary of field and laboratory investigations

In Sweden, use of industrial residues is still hindered by concern for their long-term properties. A three-year research project was therefore initiated aiming to (1) identify the crucial processes of ageing related to the usefulness of residues in roads; (2) investigate the consequences of these processes for technical and environmental properties of the residues, and (3) propose a method for accelerated ageing to predict the long-term properties. This paper gives an overview of the project methodology, a summary of the test results and references to papers where further details are given.The project, running through 2006-2008, compared naturally aged samples of two residues used as sub-bases in existing asphalt paved roads with samples of fresh residues from producers’ piles. Steel slag of electric arc furnace (EAF) type and municipal solid waste incinerator (MSWI) bottom ash were chosen. The samples were thoroughly characterised in order to identify which ageing processes had been crucial.The results showed that:

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Bottom ash from the pavement edge was more aged than bottom ash from the road centre. However, no difference in pH was found, instead the differences were caused by differences in water exposure.

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Steel slag from the pavement edge showed traces of carbonation and leaching processes, whereas slag from the road centre was identical to fresh slag.

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Water exposure to the subbase materials after ten years in an asphalt paved road was calculated to less than 0.1-0.5 litres per kg.

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Ageing reactions in steel slag and MSWI bottom ash, ready for use, were too small to be verified by laboratory measurement of deformation properties under loaded conditions.

An accelerated ageing test for steel slag was set up to achieve the carbonation (decrease in pH) and leaching that was observed in the pavement edge material.An accelerated ageing test for bottom ash was set up to achieve the pozzolan reactions that were observed in SEM analyses of in situ specimens.It is recommended to use uncrushed particles when properties of aged material are studied, in order to preserve the original particle surfaces.     

Use of Pb blast furnace slag as a partial substitute for fine aggregate in cement mortar

The technical properties of cement mortars containing natural fine aggregate that is replaced by lead blast furnace slag at 25 and 35% level were assessed at fixed water-to-cement (W/C) ratio and at fixed flow table value. The leachabilities of some toxic elements from the cement mortars were also assessed to test the environmental suitability of the slag for use in preparation of cement mortar. At fixed W/C ratio, the strength of the mortar decreased with increase of the slag content. On the other hand, at fixed consistency, strength increased with increasing slag content in the mortar composition. The concentrations of some toxic elements in the leachates collected from the mortars containing slag were slightly higher than for the control mortar, but the concentrations in the leachates remained within the regulatory limits for recycling in construction applications. For most elements, leaching from a mortar containing 35% of slag was similar to that from a mortar containing 25% of slag. Therefore, 35% of natural sand can be beneficially replaced with Pb slag to produce cement mortar without affecting the mechanical and leaching properties studied in this work.     

Physicochemical properties of slags produced at various amounts of iron addition in lead smelting

In the process of lead production from lead-bearing materials generated in copper metallurgy, a large amount of hazardous waste in the form of slag is produced. To assess the effect of the slag on the environment, its physicochemical properties were determined. In this study, the following methods were used: wavelength dispersive X-ray fluorescence (WD XRF), X-ray diffraction (XRD), and Bunte-Baum-Reerink method to determine softening and melting points, as well as viscosity examination and leaching tests. The measurements were performed on the slag produced with two different amounts of iron addition to the lead smelting process. The resulting slags, an oxide rich phase slag and a sulfide rich phase slag have different compositions and physicochemical properties. It was found that the increase in iron addition causes an increase in the softening melting point of the oxide rich phase slag by about 100 °C, and a twofold increase in the viscosity of both slag phases. The increase in iron addition also results in the decrease in As leachability and increase in Zn, Fe, and Cu leachability from the slags. Slag produced with increased iron addition has a greater impact on the environment.

     

Recycling municipal incinerator fly- and scrubber-ash into fused slag for the substantial replacement of cement in cement-mortars

Fly- and scrubber-ash (weight ratio of approximately 1:3) from municipal solid waste incinerators (MSWI) are a major land-fill disposal problem due to their leaching of heavy metals. We uniformly mixed both types of ash with optimal amounts of waste glass frit, which was then melted into a glassy slag. The glassy slag was then pulverized to a particle size smaller than 38 μm for use as a cement substitute (20–40% of total cement) and blended with sand and cement to produce slag-blended cement-mortar (SCM) specimens. The toxicity characteristics of the leaching procedure tests on the pulverized slag samples revealed that the amount of leached heavy metals was far below regulatory thresholds. The compressive strength of the 28-day cured SCM specimens was comparable to that of ordinary Portland cement mortars, while the compressive strength of specimens cured for 60 or 90 days were 3–11% greater. The observed enhanced strength is achieved by Pozzolanic reaction. Preliminary evaluation shows that the combination of MSWI fly- and scrubber-ash with waste glass yields a cost effective and environmentally friendly cement replacement in cement-mortars.     

Efficiency of a blast furnace slag cement for immobilizing simulated borate radioactive liquid waste

The efficiency of a blast furnace slag cement (Spanish CEM III/B) for immobilizing simulated radioactive borate liquid waste [containing H3BO3, NaCl, Na2SO4 and Na(OH)] has been evaluated by means of a leaching attack in de-mineralized water at the temperature of 40 degrees C over 180 days. The leaching was carried out according to the ANSI/ANS-16.1-1986 test. Moreover, changes of the matrix microstructure were characterized through porosity and pore-size distribution analysis carried out by mercury intrusion porosimetry (MIP), X-ray diffraction (XRD) and thermal analysis (TG). The results were compared with those obtained from a calcium aluminate cement matrix, previously published.     

Reprocessing of metallurgical slag into materials for the building industry

Several methods of reprocessing metallurgical (blast furnace) slag into materials for the building industry, based on melting aggregates with submerged combustion, were developed and tested. The first method involves melting hot slag with some additives directly in a slag ladle with a submerged gas-air burner, with the objective of producing stabilized slag or glass-ceramic. The second method involves direct draining of melted slag from a ladle into the slag receiver, with subsequent control of the slag draining into the converter where special charging materials are added to the melt, with the objective of producing glass-ceramic. A third method involves melting cold slag with some additives inside a melting converter with submerged gas-air burners, with the objective of producing glass-ceramic fillers for use in road construction. Specific to the melting process is the use of a gas-air mixture with direct combustion inside the melt. This feature provides melt bubbling to help achieve maximum heat transfer from combustion products to the melt, improve mixing (and therefore homogeneity of the melt), and increases the rate of chemical reactions. The experimental data for different aspects of the proposed methods are presented. The reprocessed blast-furnace slag in the form of granules can be used as fillers for concretes, asphalts, and as additives in the production of cement, bricks and other building materials. As well, reprocessed blast-furnace slag can be poured into forms for the production of glass-ceramic tiles.     

Reuse of residues arising from lead batteries recycle: a feasibility study

The performance of products arising from the stabilization/solidification of slags from lead batteries recycle into a Portland cement matrix has been evaluated not only in order to get a stabilized waste to be disposed of according to the current legislation, but also to obtain a recyclable material, with both economic and environmental benefits. Under this respect a detailed characterization of raw slags has been performed and different slag-cement samples have been prepared by varying the slag content. The parameters related to the cementation process have been evaluated and a series of tests on the final waste forms have been carried out, aimed at assessing both mechanical performance and leaching behaviour. In spite of the acceptable values for flexural, compressive and tensile strength, however, the high release of lead from the solidification products seems to be a limiting factor for a reusable material. While explanations of such phenomenon are given (high alkalinity of Portland cement; early "doping" of cementitious components by lead in the amorphous state), the main conclusion of the research work is that further efforts should be addressed to the adoption of a different or a modified incorporation matrix.     

Effect of MgO and CaO/SiO2 on the immobilization of chromium in synthetic slags

This work investigated the chemical and mineralogical properties of CaO–SiO₂–Cr₂O₃–CaF₂–MgO slags. Synthetic slags were prepared and the effect of the slag basicity (mass ratio CaO/SiO₂) and MgO contents on the stability of the mineralogical species formed was analyzed. The morphology and composition of the slags were analyzed by X-ray powder diffraction (XRD) and scanning electron microscope-energy dispersive spectroscopy (SEM–EDS), whilst their chemical stability was evaluated by leaching with an aqueous acetic acid solution. It was found that in slags with CaO/SiO₂?=?1, the main Cr-compound was MgCr₂O₄ spinel, which forms octahedron crystals. Small amounts of CaCr₂O₄ and CaCrO₄ were also observed. It was found that with increasing the slag basicity from 1 to 2 the compounds MgCr₂O₄ and CaCr₂O₄ were formed together with the Cr(V)-containing compound complex Ca₅(CrO₄)₃F which forms hexagonal crystals. The results showed that the highest Cr concentration levels in the leaching liquors corresponded to slags with CaO/SiO₂?=?2, probably owing to the formation of CaCrO₄ and Ca₅(CrO₄)₃F, whilst the lowest chromium concentration levels corresponded to MgO-based slags owing to the stable binding of chromium in spinel with MgO. Additionally, potential–pH diagrams for the Ca–Cr–H₂O and Mg–Cr–H₂O systems at 25?°C were calculated.