Formulation of a self-emulsifying concentrate.
A small business wanted to reformulate a self-emulsifying pesticide concentrate for agro-chemical use without the aromatic solvents that its old formula was containing. They also had to change the emulsifiers which were no longer available in Venezuela. We reformulated a microemulsion with a “green” oil and surfactants which were obtainable in the local market. The company was able to adjust its line of products not only to the national environmental norms but to export specifications.

Formulation of a laminating oil.
A transnational company had stability problems with the lubricating/cooling emulsion it was using in aluminum lamination plants. An incorrect lamination was producing an unsteady slippage and a non-uniform thickness of the metal strip which was resulting in out-of-specification return of 10-20% of the band to the foundry. We carried out a diagnosis of the emulsion evolution during the process: the contact with hot slab produced water evaporation, hence a considerable change in water/oil ratio, as well as an increase in lipophilicity of the nonionic surfactant mixture. All these concomitant effects resulted in an emulsion inversion from O/W to W/O. At the extreme pressure prevailing between the rollers, the water drops become steel-like balls and do not enter the gap, which is then filled by lubricating oil. The company sent to our Laboratory a trainee for several months to get a good grasp of the formulation issues, before returning to fix the problem in 4 laminating plants worldwide.

Emulsion of refinery resídues.
A company was previously using orimulsion, an emulsified bitumen (extra heavy oil from the Orinoco belt) commercialized during the 1980’s and 1990’s by BITOR, a subsidiary of PDVSA, and had its power plant adapted to the combustion of such an emulsified fuel. When BITOR discontinued the commercialization of the product, the company wanted to substitute it by a “home-made” equivalent based on a refinery residual cut. Since each oil deserves the adjustment of the formulation to attain the proper emulsion properties, the know-how is paramount to attain a satisfactory formulation. We actually did it for this client, as well as for 5 others up to now. The combustion of an emulsion generally reduces the effluent problem when cmpared to the residue direct burning.

Emulsification of an extremely viscous resin. We had three similar projects, e. g. the manufature of waterborne paint (polyurethane with a client, alkyd polymer with another) and the preparation of a silicone putty (PDMS) with a third client.
Polymer resins used in paints are sometimes extremely viscous and can’t be emulsified easily and cheaply by conventional stirring methods. The best alternative to extreme high shear emulsification is to proceed by emulsion inversion, i.e. starting with a batch of resin to which some water is added with the proper emulsifier formulation, and submiting it to a long and slow motion stirring untill inversion takes place. In 20% of the cases the inversion, which is an instability phenomena difficult to control, failed to produce an O/W nanoemulsion, and instead resulted in a multiple w/O/W morpholgy which is not satisfactory for the applications. Our know-how accumulated over more than 10 years of research on the effect of formulation, composition and strirring protocol allowed us to recommend some process changes and the installation of control units to considerably reduce the out-of-specification occurrence.

Formulation of a well cleaner.
Petroleum porous media could become plugged by multiphasic systems like emulsions and suspensions, particularly by the deposition of a filter cake and the penetration of drilling fluids in the pores. The plugging is essentially due to capillary effects produced by the existence of several phases with a prevailing high interfacial tension. We have formulated microemulsions to be injected or formed in-situ, so that a single phase, which is easy to remove from the pores, is attained. This has allowed our client, a main transnational service company, to establish itself as the leader in the field with an innovative line of products. In some cases a well production has jumped from 500 to 10,000 Bbls/day.

Ajustment of a product to achieve customized properties.
Some complex formulas tend to exhibit unwanted behavior as time elapses such as precipitation or phase separation. This is a common situation when a formulation has to be changed to adapt it to the availablity of raw materials and functional substances. The elimination of the formation of a precipitate, or a phase separation or a color change is generally a matter of diagnosis to understand the reason of the undesirable behavior, e.g. a chemical reaction, an incompatibility between two substances or an inadequate stabilization of a dispersion. Once the source of the problem is determined, a reformulation has to be carried out to attain the same (or better) performance and property with other equivalent substances. We have solved this kind of problems in many instances, e g. a transparent shampoo which was becoming turbid and changing color, a liquid desinfectant which was producing a precipitate, a paint which was loosing its homogeneity, a salad dressing which was loosing its viscosity...

Use of wood pulping by-products.
The so-called “black liquors” from wood digestion processes (Kraft or other) contain lignin derivatives which are potential surfactants, with dispersant, foaming and emulsifying properties. We have realized fundamental studies, including the chemical modification of these susbtances to taylor their amphiphilic properties. We have carried out studies on how to adapt the lignin content of three pulping plants to the dispersant specifications set by a petroleum company to stabilize clay loaded drilling fluids. Other studies have shown that modified lignins exhibit appropriate properties as a polymeric surfactant.

Wettability adjustment.
We have used different kinds of materials to change the wettability according to the application. For instance lignite is an organic substance which could be considered as a unmature coal, and which is used to increase the viscosity of drilling fluids, provided it is well hydrophobated or hydrophilized depending of the type of mud. Transporting chains in beverage bottling plants have to be lubricated, generally not with lubricationg oil but thanks to the adsorption of cationic surfactants. Flying fine particles in mining facilities could be aggregated provided that their wettability and surface charge is adjusted with a proper adsorbant.

Formulation of special soaps/detergents.
Soaps and detergents with special purpose like desinfection or bactericide, used to clean street vendor stand, clinic or domestic issues.

Formulation to break emulsions (and foams).
In some cases the objective is to break emulsions to separate water from oil. The first step is generally a diagnosis on the stabilization mechanism, after which a formula may be elaborated to attain the breaking conditions. We have solved this kind of problems for many service companies selling dehydration and desalation additives to be adapted to a given crude oil or refinery cut. This is also the case when polyelectrolites and other flocculants of the undesirable materials (proteins, oils) are employed in waste water treatment plants. Our experts in such treamentt address not only the formulation problems, but also the associated process design, eventually using the up-to-date software, and pilot plant tests on micro, ultra and nanofiltration using the last membrane technology methods.

Formulation of a stable emulsion.
Conversely, the issue is sometimes to stabilize an emulsion. We have helped many industrial partners to tackle this kind of problem. It was the case of the manufacture of a parenteral emulsion whose drop size should not excess 1 micrometer, or the production of asphalt emulsions which has to be stable in the drum but must break quickly when it was put in contact with the granulated rocks that make up the asphaltic concrete “cold mix” for road pavement. Other cases dealt with a veterinary vaccine or cosmetic creams, or emulsified (waterborne) paints for which not only the stability is paramount but also the viscosity. The formation of stable nanoemulsions of triglyceride nutrients in fermentation processes (e. g. to make antibiotics) which involves foams, was a particularly delicate issue because the tiny oil drops could exhibit the typical antifoaming effect displayed by hydrophobe particles and thus alter the fermentation which requires the formation of some foam.

Characteriszation of petroleum production water.
The water produced by dehydration in petroleum industry contain oil and solids, and are often reinjected but they have to be treated, and before they have to be diagnosed : particles and drop sizes, densities of sedimented and suspended solids.