Mechanism of sulfate attack: A fresh look: Part 1: Summary of experimental results

This paper reports the results of an investigation on the effects of sodium and magnesium sulfate solutions on expansion and microstructure of different types of Portland cement mortars. The effects of using various sulfate concentrations and of using different temperatures are also reported. The results suggest that the expansion of mortars in sodium sulfate solution follows a two-stage process. In the initial stage, Stage 1, there is little expansion. This is followed by a sudden and rapid increase in the expansion in Stage 2. Microstructural studies suggest that the onset of expansion in Stage 2 corresponds to the appearance of cracks in the chemically unaltered interior of the mortar. Beyond this point, the expansion proceeds at an almost constant rate until the complete deterioration of the mortar specimen. In the case of magnesium sulfate attack, expansion occurs at a continually increasing rate. Microstructural studies suggest that a layer of brucite (magnesium hydroxide) on the surface forms almost immediately after the introduction of the specimens into the solution. The attack is then governed by the steady diffusion of sulfate ions across the brucite surface barrier. The ultimate failure of the specimen occurs as a result of the decalcification of the calcium silicate hydrate (C-S-H), and its conversion to magnesium silicate hydrate (M-S-H), after prolonged exposure to the solution. The effects of using various admixtures, and of changing the experimental variables such as the temperature and concentration of the solution, are also summarized in this paper. Models for the mechanism of the attack resulting from sodium and magnesium sulfate solutions will be presented in Part 2.     

Some problems involved in the water wash of neutralized vegetable oils

Summary An investigation of the removal of soap from neutralized vegetable oils by washing with water has shown that some oils are obtained practically soap-free after only one water wash whereas the soap in other oils cannot be removed even by repeated washing. Coconut, palm, and olive oils are easily washed whereas linseed and rapeseed oils are not. Peanut, sunflowerseed, soybean, and cottonseed oils are sometimes washable and sometimes not. With unwashable oils different methods for soap determination give inconsistent results because calcium and magnesium soaps, or other naturally-occurring compounds of these metals, are not determined to the same extent by these methods. Calcium and magnesium in the crude oils are probably combined with phosphatides or other lipids and remain to some extent in this state after neutralization. Calcium and magnesium present as soaps or as any other compound may be detected easily in crude, neutralized, and washed oils by the titration method of Wolff. Washability of neutralized oils may be improved in a number of ways; the most efficient is pre-treatment with concentrated phosphoric acid or re-refining with a mixture of sodium hydroxide and sodium carbonate. Either of these treatments can be applied in batch or continuous refining processes. To prevent contamination of washable oils with calcium and magnesium, soft water should be used for washing and in preparation of refining solutions.     

Investigations of pitting corrosion of magnesium by means of DEIS and acoustic emission

The paper presents methodology and results of electrochemical examination of magnesium in 0.1 M NaCl solution with different pH. The measurements were conducted under potentiodynamic conditions using Dynamic Electrochemical Impedance Spectroscopy (DEIS). Analysis of DEIS results was performed based on electrical equivalent circuit. As the result of analysis changes of separate parameters of the equivalent circuit vs. potential for different pH values of the environment were obtained. Simultaneously with DEIS measurements an investigation using acoustic emission was conducted. The results showed that for pH higher than 12.50 the properties of layers on the surface of magnesium change significantly. One can observe a stable passive state that has properties considerably different from those of the layers that form in solutions with lower alkalinity. In such conditions the beginning of pitting corrosion process can be unequivocally determined by the level of acoustic emission and the values of electrochemical parameters.     

碱式碳酸镁热解机理研究进展

本文论述了碱式碳酸镁的制备方法,系统的总结了碱式碳酸镁的应用以及分类,介绍了目前国内外对碱式碳酸镁热解机理的研究进展,提出了在不同条件下生成的碱式碳酸镁结晶水含量不同、晶形也不同,不同的条件下碱式碳酸镁的结晶水个数与晶形的确定有待于进一步研究。     

环保型镁合金酸洗液的研究

采用磷酸、硫酸取代铬酸,加入酸洗添加剂及缓蚀剂,研究了环保型镁合金酸洗液.分别研究了以磷酸和硫酸为主要成分的酸洗液对镁合金的酸洗效果,发现磷酸的酸洗效果要优于硫酸.对添加不同缓蚀剂的酸洗液酸洗效果进行分析,结果表明,六次甲基四胺作为缓蚀剂可以更好地保证试样的酸洗质量.运用正交试验优选酸洗液的最佳工艺配方.试验结果同时表明,酸度及缓蚀剂对镁合金材料的酸洗效果及表面质量有很大的影响,酸洗添加剂也可以提高酸洗的效果.     

Effect of electrolyte additives on performance of plasma electrolytic oxidation films formed on magnesium alloy AZ91D

Various plasma electrolytic oxidation (PEO) films were prepared on magnesium alloy AZ91D in a silicate bath with different additives such as phosphate, fluoride and borate. Effects of the additives on chemical composition and corrosion resistance of the PEO films were examined by means of scanning electron microscopy (SEM), potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. The results showed that the PEO films obtained in solutions with both borate and fluoride had better corrosion resistance. In order to understand the corrosion mechanism of PEO films on magnesium alloy AZ91D, electronic property of the magnesium electrode with PEO films was studied by Mott-Schottky approach in a solution containing borate and chloride. The results indicated that magnesium electrodes with and without PEO films all exhibited n-type semiconducting property. However, in comparison with the magnesium electrode treated in solutions containing phosphate or borate, the electrode treated in solutions containing both borate and fluoride (M-film) had lower donor concentration and much negative flat band potential; therefore, the M-film had lower reactivity and higher corrosion resistance.     

Impact of osmotic agent on the transport of components using forward osmosis to separate ethanol from aqueous solutions

The separation of low molecular weight organic compounds such as the ethanol from aqueous solutions represents an important area to be investigated and increment the range of applications of forward osmosis. This investigation assesses the effects of using different draw solutes for ethanol separation from dilute aqueous solutions. The influence of glucose, sucrose, sodium chloride, and magnesium chloride was evaluated in terms of total permeate, reverse solute and ethanol fluxes. Inorganic solutes promoted higher total permeate and ethanol fluxes than the organic solutes (2.5 and 1.5 times higher in average, respectively) for the same molar concentration, while presenting only 1.1 times higher reverse solute fluxes. Despite the lower ethanol flux promoted by the organic draw solutes, these osmotic agents promoted higher concentration of ethanol in the total permeate flux, suggesting that they can also be alternatives for specific processes. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4499–4507, 2017     

镁粉的表面处理及应用

本文介绍了国外镁粉表面处理的不同方法 ,对不同的表面处理方法做了比较研究。详细叙述了镁粉在钢铁生产中降低 S等有害元素的应用 ,提出了一种镁粉的表面处理方法     

The crystallization of magnesium hydroxide

The thermodynamic association constant for the formation of the ion-pair MgOH⁺ in solutions of magnesium hydroxide has been studied by potentiometric and conductometric methods.The growth of magnesium hydroxide seed crystals in supersaturated solutions over a range of concentrations of magnesium and hydroxide ions and in the presence of phosphonate additives has been investigated by a precision conductance method. After a rapid initial surge of growth, an equation first order with respect to supersaturation can be used to explain the experimental data. A surface diffusion process is proposed as the controlling step in the crystallization process.     

The influence of hydrating agents on the hydration of industrial magnesium oxide

BACKGROUND: The influence of different hydrating agents on the pH of the hydrating solutions, rate of hydration of MgO to Mg(OH)₂ and product surface area was studied as a function of temperature of hydration. Hydrating agents used were aqueous solutions of ammonium chloride, magnesium acetate, magnesium nitrate, nitric acid, acetic acid, magnesium chloride, sodium acetate and hydrochloric acid and distilled water as control. These were chosen to determine either the effect of addition of a common ion, the effect of changing the solution pH or due to the presence of an acetate ion, found earlier to have a beneficial effect on the hydration of MgO. RESULTS: There was no significant difference in the hydration behaviour of the hydrating agents up to 50 °C, where less than 10% of magnesium hydroxide was formed. The amount of hydroxide increased at temperatures above 60 °C. When compared with the hydration in water, all the hydrating agents, with the exception of sodium acetate, showed a significant increase in the degree of hydration. Sodium acetate formed the lowest amount of magnesium hydroxide, ranging between 1.2 and 12.2% magnesium hydroxide. The largest percentage (56.7%) of magnesium hydroxide was formed from hydration in magnesium acetate. CONCLUSION: It seems that MgO hydration is a dissolution‐precipitation process controlled by the dissolution of MgO. The increased degree of hydration in magnesium acetate is possibly due to the presence of acetate and Mg²⁺ ions. Copyright © 2010 Society of Chemical Industry     

Formation and reactivity of oxides and basic salts. II. Radio-isotope studies of some calcareous materials

Rates of calcium exchange between solid and solution in the ageing of hydrated lime and of calcium carbonate samples have been determined using calcium-45 radio-isotope. After a comparatively rapid calcium uptake of about 1 molecular layer at the hydrated lime surface, the exchange rate diminishes as the ions need to diffuse more deeply into the hydrated lime structure. Results for calcium carbonate samples of widely different specific surfaces are compatible with very slow ageing in water. Rates of gypsum precipitation from radioactive calcium chloride and nitrate solutions have been compared in neutral and acidic media and in the presence of albumen. Lower gypsum saturation ratios are established ultimately in neutral rather than acidic media, particularly in solutions containing no salts other than gypsum. Solid hydrated lime reacts rapidly with dilute sulphuric acid, aluminium and magnesium sulpnates, magnesium chloride or sea-water, releasing calcium ions into solution. The radioactivities of the solutions decrease subsequently as gypsum separates out or calcium ions are adsorbed by the finely-divided magnesium hydroxide precipitated. At higher magnesium salt concentrations, the calcium-45 radioactivity does not initially increase so sharply. This is ascribed to basic salt formation preventing all of the lime from going quickly into solution.     

On the kinetics of magnesia hydration in magnesium acetate solutions

High‐quality magnesium hydroxide powders can be produced by hydrating slow‐reacting magnesia in dilute magnesium acetate solutions. The kinetics of this process are very crucial for process design and control, and for the production of a powder with desirable particle morphology. In this work, industrial heavily‐burned magnesia powders were hydrated in 0.01–0.1 mol dm⁻³ magnesium acetate solutions at temperatures ranging between 333 and 363 K. Examination of the magnesium hydroxide produced and the analysis of the kinetic data suggest that the hydration of heavily burned magnesia in magnesium acetate solutions is a dissolution–precipitation process controlled by the dissolution of magnesia particles. The activation energy was estimated to be 60 kJ mol⁻¹, while the reaction order with respect to acetate concentration was found to be about one. © 1999 Society of Chemical Industry     

Durability of geopolymer materials in sodium and magnesium sulfate solutions

This paper presents an investigation into the durability of geopolymer materials manufactured using class F fly ash and alkaline activators when exposed to a sulfate environment. Three tests were used to determine resistance of geopolymer materials. The tests involved immersions for a period of 5 months into 5% solutions of sodium sulfate and magnesium sulfate, and a solution of 5% sodium sulfate+5% magnesium sulfate. The evolution of weight, compressive strength, products of degradation and microstructural changes were studied.In the sodium sulfate solution, significant fluctuations of strength occurred with strength reduction 18% in the 8FASS material prepared with sodium silicate and 65% in the 8FAK material prepared with a mixture of sodium hydroxide and potassium hydroxide as activators, while 4% strength increase was measured in the 8FA specimens activated by sodium hydroxide. In the magnesium sulfate solution, 12% and 35% strength increase was measured in the 8FA and 8FAK specimens, respectively; and 24% strength decline was measured in the 8FASS samples. The most significant deterioration was observed in the sodium sulfate solution and it appeared to be connected to migration of alkalies into solution. In the magnesium sulfate solution, migration of alkalies into the solution and diffusion of magnesium and calcium to the subsurface areas was observed in the specimens prepared using sodium silicate and a mixture of sodium and potassium hydroxides as activators. The least strength changes were found in the solution of 5% sodium sulfate+5% magnesium sulfate. The material prepared using sodium hydroxide had the best performance, which was attributed to its stable cross-linked aluminosilicate polymer structure.     

Modeling the effects of solution temperature and concentration during sulfate attack on cement mortars

Simple chemistry-based empirical models have been developed to assess the role of temperature and concentration of the sulfate solution in the process of expansion of cement mortars that are subjected to external sulfate attack. ASTM Type I PC mortars, prepared according to ASTM C-109, were immersed in sodium and magnesium sulfate solutions at five different concentrations and four different temperatures. For both solutions, the trends in the measured expansion suggested the use of a simple rate law to analyze the effect of concentration. For the effect of temperature, an Arrhenius relationship was developed to determine the activation energy required to initiate expansion in sodium sulfate solution. Regression-based statistical models were found to be sufficient to explain the effect of temperature of magnesium sulfate solution on the expansion. Implications of using these models for developing potential test methods, as well as to enable interpretation of data from nonstandard test methods, are discussed.     

Gelcasting of alumina suspension using gellan gum as gelling agent

As one of the excellent colloidal ceramic forming methods for fabricating complex shaped ceramic components, gelcasting has been extensively investigated in the past two decades. In this article, a novel nontoxic system for gelcasting of ceramics was investigated using gellan gum as gelling agent. The rheological and gelling properties of gellan gum solutions with different types of cations and different concentrations of divalent magnesium ions were studied. Influences of concentration of gellan gum and solid loading of alumina suspension on the rheological properties and gelling properties of alumina suspension were investigated. The rheological properties of concentrated alumina suspension mixing with gellan gum and magnesium chloride were evaluated. Dense ceramics prepared by gellan gum gelation showed homogeneous microstructure and good mechanical properties.     

Retention of Heavy Metals and Their Separation on Silica Gel Modified with Calconecarboxylic Acid

Abstract

Sorption of 35 metal ions on silica gel impregnated with a mixture of Aliquat 336 and calconecarboxylic acid was investigated. It was found that the complexation of metals is relatively rapid, and the relative capacity of the sorbent is different for various metals and increases with pH. Only alkali metals are not retained on the sorbent, and alkaline earth metals are retained from solutions of pH > 4, contrary to other metal ions. The retained metals can be eluted from the sorbent with dilute solutions of hydrochloric or perchloric acid without elution of the chelating reagent The sorbent was used for the preconcentration of trace amounts of heavy metals from aqueous solutions in the presence of macro-amounts of sodium, potassium, calcium, and magnesium as well as for the separation of some metal ion mixtures by extraction chromatography.     

乙酸镁改性对凹凸棒黏土微结构和黏度的影响

选用不同浓度乙酸镁对凹凸棒黏土进行改性处理,采用FT-IR、XRD和SEM进行了结构表征,测定了改性前后凹凸棒黏土的比表面积、组成和Zeta电位,考察了乙酸镁浓度对凹凸棒黏土在自来水和饱和氯化钠盐水中黏度的影响.结果表明,在乙酸镁浓度为10％时,改性凹凸棒黏土表现出最高的黏度,乙酸镁与棒晶间的离子交换作用是黏度提高的主要因素.     

Structural dependence of chemical durability in modified aluminoborate glasses

Alkali and alkaline earth aluminoborate glasses feature high resistance to cracking under sharp contact loading compared to other oxide glasses. However, due to the high content of hygroscopic B₂O₃, it is expected that applications of these glasses could be hindered by poor chemical durability in aqueous solutions. Indeed, the compositional and structural dependence of their dissolution kinetics remains unexplored. In this work, we correlate the dissolution rates of aluminoborate glasses in acidic, neutral, and basic solutions with the structural changes induced by varying the aluminum-to-boron ratio. In detail, we investigate a total of seventeen magnesium, lithium, and sodium aluminoborate glasses with fixed modifier content of 25 mol%. We show that the structural changes induced by alumina depend on the network modifier. We also demonstrate a correlation between the chemical durability at various pH values and the structural changes in Mg-, Li- and Na-aluminoborate glasses. The substitution of alumina by boron oxide leads to a general decrease in chemical corrosion in neutral and acidic solutions. The lowest dissolution rate value is observed in Mg-aluminoborate glasses, as a consequence of the intermediate character of magnesium which can increase the network cross-linking. For basic solutions, the chemical durability is almost constant for the different amount of alumina in the three series, likely because B₂O₃ is susceptible to nucleophilic attack, which is favored in high-OH⁻ solutions.     

Physical and Adsorptive Characterization of Precipitated Magnesium Silicate from Rice Hull Ash Silica

Precipitation of magnesium silicate from sodium silicate and MgCl₂ and MgSO₄ solutions was investigated at four different reactant feed rates and two temperatures (25 °C and 50 °C). Sodium silicate solutions were produced from rice hull ash silica. The final product was characterized by scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis/differential thermal analysis, crystal size distribution, and filtration rate measurements. Physical characteristics of the studied magnesium silicates were determined by the Brauner‐Emmett‐Teller method and their adsorption capacities were compared to commercial magnesium silicate (Florisil). The adsorption was spontaneous and endothermic. The best fit of the kinetic results was achieved by a pseudo‐second‐order equation. The equilibrium data were found to be well represented by the Freundlich isotherm equation.     

Study of the behaviour of magnesium stearate with different specific surface areas on the surface of particles during mixing

The behaviour of two types of magnesium stearate with different specific surface areas on granule particles was examined. The magnesium stearate concentration was measured with an energy-dispersive X-ray fluorescence analyser. Different measurement procedures were used to investigate the properties of the two types of magnesium stearate when using different blending times and rotation speeds. Correlations were found between the specific surface area of the magnesium stearate, the blending time, the rotation speed and the specific surface free energy of the excipients. If magnesium stearate has a high specific surface area it shows higher adhesion work and is able to create a very thin homogeneous layer on the surface of the particles. Magnesium concentration was detected with the energy-dispersive X-ray fluorescence analyser. Based on the X-ray investigation the optimum blending time and rotation speed can be determined.