Intercalation of fatty acids into layered double hydroxides

Surfactant-mediated intercalation of aliphatic fatty acids into a commercial,layered double hydroxide (LDH) with the approximate composition of [Mg0.689Al0.311(OH2)] (CO3)0.1569nH2O was explored. The reactions were conducted at elevated temperatures with the LDH powder suspended in a fatty acid oil-water emulsion. The acidic fatty acid, e.g. stearic acid, reacts with the basic carbonate anions from LDH-CO3. In the process, CO2 is released as a gas and the fatty acids are intercalated as a bilayer. A high concentration of anionic or non-ionic surfactants, i.e. sodium dodecylsulphate or Tween 60, facilitates the intercalation process by emulsifying the molten fatty acids and dispersing the LDH particles. The presence of carboxylate anions in the interlayer region was confirmed by the carboxylate absorption peaks observed in the region 1700–1000 cm-1 on Fouriertransform infrared spectroscopy (FT-IR). Several bands were observed, i.e. ionised and non-ionised. An increase in the d-spacing of the d003 plane of the brucite-like LDH layers was observed on X-ray diffraction (XRD) analysis of all the LDH intercalates. The d-spacing increased linearly with the length of the carboxylic acid chain. Sharp reflection peaks were obtained on XRD, showing the high crystallinity of the LDH intercalates. The thermal decomposition of these materials was explored on thermogravimetric or differential thermogravimetric analysis (TGA/DTA) and temperature-scanned XRD. The mole ratio of Mg to Al was obtained by XRF and the morphology by scanning electron microscopy (SEM). The present method works well with long-chain aliphatic fatty acids at temperatures above or at the melting point of the desired acid. Temperature proved to be the most important parameter to control during the preparation process, i.e. at low temperatures incomplete reactions were obtained. The method is convenient, economical and environmentally friendly. It employs the readily available carbonate form of LDH as a starting reagent, water is used as medium rather than organic solvents, there are no high-temperature calcinations, and an inert atmosphere is not required. CopyrightDissertation (MSc)--University of Pretoria, 2008.Chemistryunrestricte

Thermal analysis and FTIR studies of volatile corrosion inhibitor model systems

Model compounds simulating amine–carboxylic acid-based volatile corrosion inhibitors were characterized by thermogravimetric analysis and Fourier transform infrared spectroscopy. These systems are usually employed as equimolar mixtures to protect ferrous metals against atmospheric corrosion. The key finding of this study was that the vapors released by such equimolar mixtures initially contain almost free amine only. After prolonged vaporization a steady-state azeotrope-like composition is approached. It contains excess carboxylic acid and features impaired corrosion inhibition efficiency according to the Skinner test. In part, this behavior can be attributed to the mismatch in the volatilities of the amine and carboxylic acid constituents.http://www.elsevier.com/locate/corscihb2013ai201

TGA-FTIR study of the vapors released by triethylamine-acetic acid mixtures

Proprietary mixtures of amines and carboxylic acids are used as volatile corrosion inhibitors (VCIs) for the protection of iron and steel components against atmospheric corrosion. This study was focused on the nature of the vapors they release. VCI model compounds comprising mixtures of triethylamine and acetic acid were studied using thermogravimetric analysis coupled with Fourier-transform infrared spectroscopy (TGA–FTIR) at 50 ◦C. As vaporization progressed, the composition of the remaining liquid and the emitted vapor converged to a fixed amine content of ca. 27 mol%. This was just above the composition expected for the 1:3 amine to carboxylic acid complex. Mixtures close to this composition also featured the lowest volatility.The National Metrology Institute of South Africa (NMISA), the Institutional Research Development Programme (IRDP) of the National Research Foundation of South Africa, and Xyris Technology CC.http://www.elsevier.com/locate/tcaai201

Degradation of insecticides used for indoor spraying in malaria control and possible solutions

BACKGROUND: The insecticide dichloro-diphenyl-trichloroethane (DDT) is widely used in indoor residual spraying (IRS) for malaria control owing to its longer residual efficacy in the field compared to other World Health Organization (WHO) alternatives. Suitable stabilization to render these alternative insecticides longer lasting could provide a less controversial and more acceptable and effective alternative insecticide formulations than DDT. METHODS: This study sought to investigate the reasons behind the often reported longer lasting behaviour of DDT by exposing all the WHO approved insecticides to high temperature, high humidity and ultra-violet light. Interactions between the insecticides and some mineral powders in the presence of an aqueous medium were also tested. Simple insecticidal paints were made using slurries of these mineral powders whilst some insecticides were dispersed into a conventional acrylic paint binder. These formulations were then spray painted on neat and manure coated mud plaques, representative of the material typically used in rural mud houses, at twice the upper limit of the WHO recommended dosage range. DDT was applied directly onto mud plaques at four times the WHO recommended concentration and on manure plaques at twice WHO recommended concentration. All plaques were subjected to accelerated ageing conditions of 40°C and a relative humidity of 90%. RESULTS: The pyrethroids insecticides outperformed the carbamates and DDT in the accelerated ageing tests. Thus UV exposure, high temperature oxidation and high humidity per se were ruled out as the main causes of failure of the alternative insecticides. Gas chromatography (GC) spectrograms showed that phosphogypsum stabilised the insecticides the most against alkaline degradation (i.e., hydrolysis). Bioassay testing showed that the period of efficacy of some of these formulations was comparable to that of DDT when sprayed on mud surfaces or cattle manure coated surfaces. CONCLUSIONS: Bioassay experiments indicated that incorporating insecticides into a conventional paint binder or adsorbing them onto phosphogypsum can provide for extended effective life spans that compare favourably with DDT’s performance under accelerated ageing conditions. Best results were obtained with propoxur in standard acrylic emulsion paint. Similarly, insecticides adsorbed on phosphogypsum and sprayed on cattle manure coated surfaces provided superior lifespans compared with DDT sprayed directly on a similar surface.The Bill & Melinda Gates Foundation through the Grand Challenges Exploration Initiative.http://www.malariajournal.com

Degradation of insecticides used for indoor spraying in malaria control and possible solutions

BACKGROUND: The insecticide dichloro-diphenyl-trichloroethane (DDT) is widely used in indoor residual spraying (IRS) for malaria control owing to its longer residual efficacy in the field compared to other World Health Organization (WHO) alternatives. Suitable stabilization to render these alternative insecticides longer lasting could provide a less controversial and more acceptable and effective alternative insecticide formulations than DDT. METHODS: This study sought to investigate the reasons behind the often reported longer lasting behaviour of DDT by exposing all the WHO approved insecticides to high temperature, high humidity and ultra-violet light. Interactions between the insecticides and some mineral powders in the presence of an aqueous medium were also tested. Simple insecticidal paints were made using slurries of these mineral powders whilst some insecticides were dispersed into a conventional acrylic paint binder. These formulations were then spray painted on neat and manure coated mud plaques, representative of the material typically used in rural mud houses, at twice the upper limit of the WHO recommended dosage range. DDT was applied directly onto mud plaques at four times the WHO recommended concentration and on manure plaques at twice WHO recommended concentration. All plaques were subjected to accelerated ageing conditions of 40°C and a relative humidity of 90%. RESULTS: The pyrethroids insecticides outperformed the carbamates and DDT in the accelerated ageing tests. Thus UV exposure, high temperature oxidation and high humidity per se were ruled out as the main causes of failure of the alternative insecticides. Gas chromatography (GC) spectrograms showed that phosphogypsum stabilised the insecticides the most against alkaline degradation (i.e., hydrolysis). Bioassay testing showed that the period of efficacy of some of these formulations was comparable to that of DDT when sprayed on mud surfaces or cattle manure coated surfaces. CONCLUSIONS: Bioassay experiments indicated that incorporating insecticides into a conventional paint binder or adsorbing them onto phosphogypsum can provide for extended effective life spans that compare favourably with DDT’s performance under accelerated ageing conditions. Best results were obtained with propoxur in standard acrylic emulsion paint. Similarly, insecticides adsorbed on phosphogypsum and sprayed on cattle manure coated surfaces provided superior lifespans compared with DDT sprayed directly on a similar surface.The Bill & Melinda Gates Foundation through the Grand Challenges Exploration Initiative.http://www.malariajournal.com

TGA-FTIR study of the vapours released by volatile corrosion inhibitor model systems

Proprietary mixtures of amines and carboxylic acids are used as volatile corrosion inhibitors (VCIs) for the protection of steel and iron components against atmospheric corrosion during storage and transportation. Interactions between amines and carboxylic acids have been comprehensively reported in the literature. However, little is known about the nature of the vapours these mixtures emit. The present study focused on the development of the evolved gas analysis method which will help in the characterisation of the vapours released by VCIs. In the method, the evaporation of various amine-carboxylic acid binary mixtures was monitored by thermogravimetric analysis (TGA). The nature and the composition of the released vapours was followed by Fourier transform infrared (FTIR) spectroscopy. Mixtures consisting of triethylamine (TEA) and acetic acid were studied as a model compound using TGA-FTIR at 50 °C to validate the TGA-FTIR method. As vaporisation progressed, the composition of the remaining liquid and the emitted vapour converged to a fixed amine content of ca. 27 mol %. This is just above the composition expected for the 1:3 amine: carboxylic acid complex. Mixtures close to this composition also featured the lowest volatility. TGA-FTIR proved to be a convenient method for studying the evaporation of TEA-acetic acid mixtures, and the nature and composition of the released vapours. Amine addition leads to the dissociation of carboxylic acid dimers in favour salt formation. The formation of an ion pair between the amine and carboxylic acid was confirmed by the FTIR spectra of the liquid phase. The resulting amine-carboxylic acid mixtures showed a slow mass loss rate on TGA when compared with the pure amines and pure carboxylic acids. This indicated that the mixtures have low volatility, hence low vapour pressure compared with the pure components. The low vapour pressure of the mixtures was confirmed by the calculated gas permeability values. These values were much higher for the pure amines and the pure carboxylic acids. However, they dropped significantly on amine addition. The strong amine-carboxylic acid interaction is responsible for the suppressed volatility of the mixtures. No interaction is observed between amine and carboxylic acid molecules in the vapour phase at 230 °C. The method developed was applied to characterise the model compounds simulating the amine-carboxylic acid-based volatile corrosion inhibitors. These model systems contained the primary, secondary and tertiary amines (hexylamine, morpholine and triethylamine), as well as carboxylic acids with different chain lengths (acetic, propanoic, hexanoic and octanoic). These systems are usually employed as equimolar mixtures to protect ferrous metals against atmospheric corrosion. The key finding of the study was that the vapours released by such equimolar mixtures initially contain almost exclusively free amine. After prolonged vaporisation, a steady-state “azeotrope”-like composition is approached. It contains excess acid and features impaired corrosion-inhibition efficiencies according to the Skinner test. In part, this behaviour can be attributed to the mismatch between the volatilities of the amine and carboxylic acid constituents.Thesis (PhD)--University of Pretoria, 2013.gm2013Chemical Engineeringunrestricte

A critical assessment of the methods for intercalating anionic surfactants in layered double hydroxides

Anionic surfactant intercalated layered double hydroxides (LDH) of high purity are easily prepared via direct coprecipitation and also by the ion exchange method provided that the precursor contains a monovalent anion, e.g., LDH–Cl or LDH–NO3. However, LDH–CO3 is an attractive starting material as it is commercially available in bulk form owing to large-scale applications as a PVC stabilizer and acid scavenger in polyolefins. Thus, intercalation of dodecyl sulfate and dodecylbenzenesulfonate into a commercial (LDH) with approximate composition [Mg0.654Al0.346(OH)2](CO3)0.173 • 0.5H2O] was explored. Direct ion exchange is difficult as the carbonate is held tenaciously. In the regeneration method it is removed by thermal treatment and the surfactant form obtained by reaction with the layered double hydroxide that forms in aqueous medium. Unfortunately the resulting products are impure, poorly crystallized and only partial intercalation is achieved. Better results were obtained using water-soluble organic acids, e.g., acetic, butyric, or hexanoic acid, to aid decarbonation of LDH–CO3. Intercalation proceeded at ambient temperatures with the precursor powder suspended in an aqueous dispersion of the anionic surfactant. The carboxylic acids are believed to assist intercalation by facilitating the elimination of the carbonate ions present in the anionic clay galleries

Mn2Al-LDH- and Co2Al-LDH-stearate as photodegradants for LDPE film

The layered double hydroxides (LDH) Mn2Al-LDH-stearate and Co2Al-LDH-stearate were prepared by a surfactant-assisted intercalation of the corresponding precursor LDH-CO3 forms. These compounds were evaluated as potential photodegradant additives in low density polyethylene films with a thickness of ca. 40 mm. They were incorporated into blown polyethylene films via a 10% masterbatch. The films were subjected to accelerated ageing in a QUV weatherometer. The machine was fitted with A320 lamps and operated on a dry cycle at 63 C and an irradiance of 0.67 W/m2. It was found that 100 h of QUV exposure was sufficient to cause mechanical embrittlement of films containing as little as 0.1% of either active additive.Financial support for this research, from the Institutional Research Development Programme (IRDP), the South African Cooperation Fund for Scientific and Technological Developments (NEPAD) and the THRIP program of the Department of Trade and Industry and the National Research Foundation of South Africa, Evergreen (Pty) Ltd as well as Xyris Technology CC, is gratefully acknowledged

Thermal properties of lauric- and stearic acid intercalated layered double hydroxides

A commercial layered double hydroxide (LDH) with nominal composition [Mg0.689A10.311(OH)2](CO3)0.156.zH2O was intercalated with lauric and stearic acid using a surfactant-assisted method. X-ray diffraction, thermal analysis and infrared spectroscopy confirmed that bilayer-intercalated compounds were formed and that the surfactant (sodium dodecyl sulfate) was not co-intercalated. These compounds shows interesting thermal behavior with two phase transformations observed at elevated temperatures. At temperatures that are significantly higher than the melting points of the corresponding free acids, the alkyl chains assume a disordered liquid-like state within the clay galleries. However, at even higher temperatures the materials become completely amorphous like true melts