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Title: Surfactant-inhibited barium sulphate nanoparticles for use in drilling fluids
Author: Whyte, John Morrison
ISNI:       0000 0004 6353 2231
Awarding Body: University of Aberdeen
Current Institution: University of Aberdeen
Date of Award: 2016
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This project studied the production of barium sulphate nanoparticles through inhibition of crystal growth, during precipitation, by different surfactants. Barium sulphate is the pure form of the ore baryte, which due to its high density and softness, is the most commonly used additive used to increase the density of drilling fluids. A non-agglomerating, stable nano-scale dispersion of barium sulphate particles would have significant technical and commercial impact in the drilling fluids industry. This thesis tested the possibility of precipitating barium sulphate and restricting its crystal growth with inhibitors, creating nanoparticles. Six inhibitors were tested; dodecanoic acid, palmitic acid, stearic acid, adamantane carboxylic acid, methylnonanoic acid and a mixture of phosphate esters known commercially as Fazewet. Precipitated, inhibited barium sulphate was characterised using powder XRD, DRIFT FTIR and solid-state NMR (SSNMR). All inhibitors were shown to form single-phase, orthorhombic barium sulphate crystals proving that the inhibitors affect only the surfaces of precipitated crystals and do not enter the crystal lattice. FTIR allowed the relative adsorbed concentration of each inhibitor to be assessed. The results indicate that adsorbed inhibitor increases with increasing inhibitor concentrations but that their attachment is not proportional to the concentration. In most cases concentrations of 0.1mol l-1 of inhibitor were sufficient to saturate the crystal surface. SSNMR also agreed with this although the sample size was too small, due to equipment restrictions, to make definitive conclusions. Through the use of the Debye-Scherrer equation, the crystallite size was calculated and showed that at concentrations of 0.2mol l-1 all inhibitors other than palmitic acid produced nano-scale (< 100nm) crystallites. Further analysis showed that further reductions could be achieved through precipitation in an alkaline pH environment, with the application of mechanical shear and by using adding 50% v/v of ethanol. iv Laser diffraction particle size analysis showed that the dominant factor in reducing particle size distribution was inhibitor concentration. The volume-based PSD used by the laser diffraction system was considered to distort excessively the particle sizes present and so analysis switched to dynamic light scattering. DLS showed that dodecanoic acid, palmitic acid and stearic acid, despite forming nano-scale crystallites, could not produce a nano-scale dispersion of barium sulphate and as such were unsuitable for use in drilling fluids. Stable nano-scale dispersions were found to have been formed when inhibited with adamantane carboxylic acid, methylnonanoic acid and Fazewet. DLS also confirmed that dispersed particle size rather than simply crystallite size could be reduced with an alkaline pH and high mechanical shear. Concentration was still the dominant effect, however with the smallest particles sizes (ZAvg) being observed at concentrations of 0.6mol l-1. The particle sizes for the three modifiers were approaching that of the crystallite size, suggesting that some further reduction is possible, but large reductions are unlikely. All three inhibitors produced sub 100nm ZAvgs, with the smallest produced by methylnonanoic acid of 43nm. Spherical nanoparticles were observed through the use of ESEM and TEM. Due to equipment time restrictions only 0.2mol l-1 treatment levels could be examined, but ESEM showed apparent nanoparticle clusters, later confirmed using pixel count and SFDA methods. TEM analysis showed discrete particles as small as 3nm, indicating that the lower limit for achievable particle size may be lower than PSD measurements would suggest. The results indicate that adamantane carboxylic acid, methylnonanoic acid and Fazewet sufficiently inhibit crystal growth to be potential candidates for the production of barium sulphate nanoparticles. These three inhibitors produce a barium sulphate dispersion that is stable and nano-scale even after drying and redispersion.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Barium sulfate ; Drilling muds