Girma Biresaw

Utilization of agricultural biomass in the production of the biopolymer schizophyllan

Schizophyllan is a homoglucan produced by the fungus Schizophyllum commune, with a β-1,3-linked backbone and β-1,6-linked side chains of single glucose units at every other residue. Schizophyllan is commercially produced for pharmaceutical and cosmetics uses. However, the unique physical properties of schizophyllan suggest that it may have biomaterials applications. Schizophyllan is conventionally produced by submerged culture fermentation using glucose as a carbon source. This study demonstrates for the first time the efficient utilization of agricultural biomass substrates, particularly distiller’s dried grains with solubles, for schizophyllan production. Sugar composition analysis, NMR, and permethylation linkage analysis confirmed that the recovered product was schizophyllan. Schizophyllan produced from agricultural residues was of a high molecular weight and exhibited solution viscosity properties similar to those of commercially produced material. Utilization of biomass substrates could reduce the cost of schizophyllan production and provide a new value-added bioproduct for integrated biorefineries of the future.

Simplified process for preparation of schizophyllan solutions for biomaterial applications.

ABSTRACT Schizophyllan is a biopolymer commercially produced for pharmaceutical and cosmetics uses. However, schizophyllan also has potential biomaterial applications. Schizophyllan is conventionally produced from glucose and recovered by diafiltration and ultrafiltration to produce a highly purified product. Here we demonstrate a simplified process for preparation of schizophyllan solutions for biomaterial applications. Schizophyllan was produced in 1.5-L bioreactors from distiller’s dried grains with solubles (DDGS), an abundant coproduct of dry grind fuel ethanol production. Downstream processing eliminated filtration and concentration steps, providing solutions containing 4.2 ± 0.3 g schizophyllan/L. Solutions contained high-molecular-weight schizophyllan and exhibited viscosity properties similar to those of commercial schizophyllan. Schizophyllan solutions showed promise as a component of biolubricants in friction and wear tests and by dynamic surface and interfacial tension measurements.

Tribological Properties of Limonene Bisphosphonates

Abstract Limonene was chemically modified by reacting it with dialkyl phosphites of varying alkyl structures under inert atmosphere in the presence of free radical initiators. The reaction gave a mixture of mono- and di-adduct products and was optimized to produce only the di-adduct product limonene bisphosphonate by forcing both limonene double bonds to react completely. The product mixture was carefully characterized using a combination of gas chromatography–mass spectroscopy, infrared spectroscopy, and nuclear magnetic resonance spectroscopy (1H, 13C, 31P). The bisphosphonates were investigated for their physical and tribological properties. The alkyl bisphosphonates displayed density and viscosity that was a function of the alkyl structure (methyl, ethyl, n-butyl) and much higher than the values for the unreacted limonene. They also displayed improved oxidation stability but lower viscosity index and solubility in polyalphaolefin (PAO6) and high-oleic sunflower oil (HOSuO) base oils. Tribological characterization of the neat modified oils on a four-ball tribometer showed improved extreme-pressure weld point by all three di-adducts and improved anti-wear coefficient of friction (COF) and wear scar diameter (WSD) by the n-butyl di-adduct only. The limonene bisphosphonates also displayed improved COF and WSD as additives in PAO6 and HOSuO base oils at low concentrations. The effects of chemical modifications on physical and tribological properties can be explained in terms of increased polarity of the modified products, insertion of heavy atoms (from PO3) into the limonene structure, and complete absence of unsaturation in the modified products.

Chemical, Physical and Tribological Investigation of Polymercaptanized Soybean Oil

Polymercaptanized soybean oil (PMSO) was investigated for its chemical, physical and tribological properties relative to soybean oil (SO) and also as a potential multi-functional lubricant additive in high oleic sunflower oil (HOSuO). Analytical investigations showed that PMSO is obtained by conversion of 76% of double bonds in SO into thiol (–SH) and sulfide (R–S–R′) groups. PMSO product mixture comprised 70% monomer and 30% oligomers, versus 99.6 and 0.4%, respectively, for SO. Relative to SO, PMSO displayed higher density, viscosity and oxidation stability; similar cold flow properties; and lower viscosity index. PMSO displayed good solubility in HOSuO (>10% w/w), but poor solubility in polyalpha olefin-6 (<1% w/w). Investigation of PMSO as a lubricant additive in HOSuO showed that it had multi-functional properties. Thus, blending of PMSO in HOSuO resulted in improved oxidation stability; improved friction and wear in 4-ball anti-wear tests; improved extreme pressure (EP) properties in 4-ball EP tests; and no effect on cold flow properties.

Identification and Measurement of Intermolecular Interaction in Polyester/Polystyrene Blends by FTIR-Photoacoustic Spectrometry

Fourier transform infrared photoacoustic spectrometry was used to reveal and identify n–π type intermolecular interaction formed in plastic comprising binary blends of polystyrene and a biodegradable polymer, either polylactic acid, polycaprolactone or poly(tetramethyleneadipate-co-terephthalate). This was the first reported direct and definitive experimental evidence of n–π type bond formation in thermoplastic blends of these polyesters with polystyrene. Also, an infrared method was devised that permits quantitative measurement of the degree of interaction between the two polymers at various concentrations in the blends. The method employs spectral deconvolution by least squares curve fitting of the polymer carbonyl band into its underlying peaks. In a new algorithm the method compares deconvoluted Gaussian/Lorentzian peaks of the polymer blends with deconvoluted peaks in the neat polymers and computes both the magnitude and direction of change in the n–π bond formation with change in polymer concentration. The results indicated that the degree of interaction was dependent on the type and concentration of the biodegradable polymer in the blend. These findings are supported by differential scanning calorimetry and thermogravimetric analyses. Unlike conventional spectral deconvolution methods, this technique with its new algorithm approximates infrared absorptivities of all the underlying peaks, and is thus a superior method that should be applicable to multicomponent polymer blends in general.

CHAPTER 4:Thiol-ene and H-Phosphonate-ene Reactions for Lipid Modification

This chapter is a short introduction to the thiol-ene reaction and includes the thiol-ene reaction as a click chemistry reaction, radical chain reactions, basic mechanisms and kinetics, the use of the thiol-ene reaction for the synthesis of novel bio-based materials (polymers, lubricants and coatings), addition of H-phosphonates to double bonds, some reaction information and bio-based products, and possible applications of the products (lubricants, plasticizers and anti-microbial agents).

Physical Characteristics of Tetrahydroxy and Acylated Derivatives of Jojoba Liquid Wax in Lubricant Applications

Jojoba liquid wax is a mixture of esters of long-chain fatty acids and fatty alcohols mainly C38:2–C46:2. The oil exhibits excellent emolliency on the skin and, therefore, is a component in many personal care cosmetic formulations. The virgin oil is a component of the seed of the jojoba (Simmondsia chinensis) plant which occurs naturally in the Sonora Desert in the United States and northwestern Mexico as well as in the northeastern Sahara desert. The seed contains 50–60% oil by dry weight. The plant has been introduced into Australia, Argentina, and Israel for commercial production of the jojoba oil. As a natural lubricant, we are seeking to explore its potential as a renewable industrial lubricant additive. Thus, we have chemically modified the carbon-carbon double bonds in the oil structure in order to improve its already good resistance to air oxidation so as to enhance its utility as well as its shelf life in nonpersonal care applications. To achieve this goal, we have hydroxylated its –C=C– bonds. Acylation of the resulting hydroxyl moieties has generated short-chain vicinal acyl substituents on the oil which keep the wax liquid, improving its cold flow properties and also protecting it from auto-oxidation and rancidity.

Adsorption Behavior of Heat Modified Soybean Oil via Boundary Lubrication Coefficient of Friction Measurements

The frictional behaviors of soybean oil and heat modified soybean oils with different Gardner scale viscosities as additives in hexadecane have been examined in a boundary lubrication test regime (steel contacts) using Langmuir adsorption model. The free energy of adsorption (ΔGads ) of various heat modified soybean oils were compared with unmodified soybean oil. It was observed, that relative distribution of unsaturation in the molecule, average molecular weight and thus viscosity can affect adsorption on the metal surface. Heat modified soybean oils consistently have a lower ΔGads values compared to unmodified soybean oil. Lower ΔGads corresponds to stronger adsorption on the metal surface. The heat modification thus provides oils with stronger adsorption and higher viscosities, good for use in industrial lubricant formulations. This information can be used to design suitable lubricant molecules that will have optimum structure for effective metal adsorption as well as exhibit excellent boundary lubrication properties.© 2008 ASME

Film-Forming Properties of Estolides

Estolides are biobased materials obtained from synthesis of ingredients derived from agricultural products. They are oligoesters obtained by the reaction of fatty acids and/or methyl esters with a double bond. By varying the chemistries of the starting materials and the reaction conditions, estolides of varying chemical structures, and physical properties are obtained. Estolides have been found to have suitable properties for some lubrication applications. However, the effect of estolide chemical/physical characterstics on its tribological properties have yet to be understood. In this work, the effect of estolide physical/chemical variability on its film-forming properties is examined.Copyright