AP-101 – Extractions of Binder from Powder Injected Metals Using Supercritical Fluids
Supercritical fluids and in particular supercritical carbon dioxide have shown to be a viable technology for a variety of extractions. While process conditions require high pressures, technological advances have now made it feasible to acquire such equipment for the undergraduate laboratory. One novel application we are currently investigating involves supercritical fluid extraction of organic binders from metal parts produced by powder injection molding (PIM). The initial proof-of-concept studies have been undertaken in our laboratory with bench top equipment manufactured by Supercritical Fluid Technologies, Inc.
AP-102 – Effect of Operating Conditions on Static/Dynamic Extraction of Peanut Oil Using Supercritical Carbon Dioxide
Supercritical fluid extraction was successfully used to extract peanut oil from peanuts at temperatures between 40 and 80 °C and pressures of 5000-7000 psi. Static/dynamic cycling was used with a 10 minute static soak time, followed by a 10 minute dynamic interval. The overall extraction time was held constant at 3 hours. Peanut oil yield was determined gravimetrically. The crossover phenomenon was observed with the crossover pressure occurring at 6000 psi. Above the crossover pressure, an isobaric increase in temperature has a positive effect on the extraction yield, while below the crossover pressure an increase in temperature resulted in a decrease in oil yield. Yields between static/dynamic cycling and continuous runs were comparable, suggesting CO2 usage could be reduced by half by static/dynamic cycling, creating a cost effective, greener process.
AP-103 – Solubilities of Substituted Phenols in Supercritical Fluid Carbon Dioxide
Substituted phenols are an important class of compounds having widespread use (germicides, disinfectants, ingredients in fuel, etc.). In this work, the solubilities of selected substituted phenols (2,5-dimethylphenol, 2,4,6-trimethylphenol,2,3,5-trimethylphenol, 4-phenylphenol, 4-tertbutylphenol) in binary (single solute + SCF CO2) and ternary (two solutes + SCF CO2) systems were investigated using a SFT Phase Monitor.
AP-104 – Positive-Tone Resist for Supercritical CO2 Processing
Carbon dioxide is widely recognized today as a “Green Chemistry” solvent. The unique physical and chemical properties of carbon dioxide in its supercritical state, namely the absence of surface tension, low viscosity, high diffusivity, and easily tunable solvent strength provide for utility in a variety of industrial and scientific applications. In the microelectronics fabrication industry this non-toxic, environmentally friendly solvent is being heavily investigated as an alternative agent for device cleaning, microelectromechanical systems (MEMS) drying, and lithographic processing. With the emerging advances in fabrication techniques and materials, microelectronic device features with dimensions below 100 nm are now possible to produce.
AP-105 – Economic Feasibility Study on the Supercritical Fluid Extraction of Edible Oils
Supercritical carbon dioxide extraction is currently used in several food and pharmaceutical manufacturing applications. Its “greener” nature makes it a desirable option when compared with traditional organic solvent extractions. The purpose of this work is to compare the cost of using supercritical CO2 to commercially extract peanut oil with that of the traditional hexane extraction process. Solubility values of peanut oil in supercritical CO2 were also obtained under different conditions of temperature and pressure.
AP-106 – Crystal Doping Aided by Rapid Expansion of Supercritical Solutions
The purpose of this study was to test the utility of rapid expansion of supercritical solution (RESS) based cocrystallizations in inducing polymorph conversion and crystal disruption of chlorpropamide (CPD). CPD crystals were recrystallized by the RESS process utilizing supercritical carbon dioxide as the solvent. The supercritical region investigated for solute extraction ranged from 45 to 100°C and 2000 to 8000 psi. Solute extraction was made possible by utilizing a SFT-150.
Chandra Vemavarapu 1,2, Matthew J. Mollan 1and Thomas E. Needham2
1Pharmaceutical Sciences, Pfizer Global R&D, Ann Arbor, MI 48105 2Applied Pharmaceutical Sciences, University of Rhode Island, Kingston, RI 02881
AAPS PharmSciTech 2002; 3 (4) article 29 (http://www.aapspharmsci.org)
AP-107 – Solubilities of Substituted Phenols in Supercritical Fluid Carbon Dioxide
Substituted phenols are an important class of compounds having widespread use (germicides, disinfectants, ingredients in fuel, etc.) There is little information in the literature regarding the solubilities of phenols in SCF CO2. Accurate and precise solubility data for the compounds of interest is essential for the design of any SCF-based process. In this work, the solubilities of selected substituted phenols (2,5-dimethylphenol, 2,4,6-trimethylphenol,2,3,5-trimethylphenol, 4-phenylphenol, 4-tertbutylphenol) in binary (single solute + SCF CO2) and ternary (two solutes + SCF CO2) systems were investigated using a SFT Phase Monitor.
AP-108 Study on Critical Points of Carbon Dioxide + Single and Multicomponent Solid Solute Systems
The phase behavior of solutes in SCF is an important aspect, which is often overlooked in the solubility determinations. Solid solutes when in contact with supercritical CO2 can exhibit complex phase behavior such as depression in melting point resulting in multiple phases, and therefore can considerably influence the determination of solid solubility. The purpose of this study is to research solubilities of aromatic carboxylic acids and substituted phenols in SCF- CO2 using the SFT phase monitor.
AP-109 – Design and process aspects of laboratory scale SCF particle formation systems
Consistent production of solid drug materials of desired particle and crystallographic morphologies under cGMP conditions is a frequent challenge to pharmaceutical researchers. The purpose of this article is therefore to provide the information and resources necessary for startup research involving particle formation using supercritical fluids. The importance of each stage of particle formation in tailoring the particle morphology is discussed in this article along with presenting various alternatives to perform these operations.
Chandra Vemavarapu a, b, ∗, Matthew J. Mollan a, Mayur Lodaya a, Thomas E. Needham b
a Pharmaceutical Sciences, Pfizer Global R&D, 2800 Plymouth Road, Ann Arbor, MI 48105, USA
b Applied Pharmaceutical Sciences, University of Rhode Island, Kingston, RI 02881
C. Vemavarapu et al. / International Journal of Pharmaceutics 292 (2005) 1–16
AP-110 – Low-Temperature Growth of Carbon Nanotubes from the Catalytic Decomposition of Carbon Tetrachloride
Of the variety of methods used to synthesize CNTs(carbon nanotubes), metalencapsulated dendrimers represent a particularly attractive catalyst for nanotube growth. For such nanocomposite growth, our synthetic strategy has been to find a method to control the size and distribution of the catalyst seed particle, as well as to develop a low-temperature, nonreactive means of carbon production, to best preserve the structure of temperature-sensitive dendrimers. As an initial step toward this goal, we present the use of supercritical carbon dioxide as a medium for the decomposition of CCl4 using iron-encapsulated polypropyleneimine (PPI) dendrimers as a catalyst for MWNT growth.
Jason K. Vohs, Jonathan J. Brege, Jeffery E. Raymond, Allan E. Brown, Geoffrey L. Williams,† and Bradley D. Fahlman*
Departments of Chemistry and Biology, Central Michigan UniVersity, Mount Pleasant, Michigan 48859
B J. AM. CHEM. SOC. PAGE EST: 1.9
AP-111 – Supercritical Fluid Facilitated Growth of Copper and Aluminum Oxide Nanoparticles
Within the last five years, there has been an explosion of research in supercritical fluids; more recent reports are now exploiting this medium for nanomaterials synthesis. An important goal for undergraduate curricula should be the constant upgrading of content to include the most leading-edge techniques. To this end, this Journal has published a few articles related to SCF technology for undergraduates. This article describes a module to introduce undergraduate inorganic chemistry students to an exciting area of nanotechnology that also incorporates SCFs, an environmentally-friendly alternative to organic solvents.
Geoffrey L. Williams
Department of Biology, Central Michigan University, Mount Pleasant, MI 48859
Jason K. Vohs, Jonathan J. Brege, and Bradley D. Fahlman*
Department of Chemistry, Central Michigan University, Mount Pleasant, MI 48859; *firstname.lastname@example.org
Journal of Chemical Education • Vol. 82 No. 5 May 2005 • www.JCE.DivCHED.org
AP-112 – Supercritical Carbon Dioxide Extraction of Mitragyna Speciosa
Mitragyna speciosa is a narcotic plant but with specific medicinal importance. The main components of the leaves of M. speciosa are indole alkaloids. Previous scientific researches have shown that the alkaloidal extracts possess very potent anti-inflammatory, analgesic and opioid properties. The three most abundant indoles are mitragynine, paynanthine and speciogynine – the first two of which appear to be unique to this species. All these compounds were obtained from classical organic solvent (diethyl acetate, dichloromethane or methanol) extraction. In this research programme, supercritical fluid extraction (SFE) of M. speciosa was performed. An optimal condition of supercritical fluid extraction was developed using an analytical-scale SFE system. The conventional extraction methods were conducted in parallel for comparison. CO2 extract of M.speciosa has never been studied yet and CO2 was chosen as the media of extraction because it is non-toxic and environmentally safe to prepare and use.
AP-113 – Evaluating biomass reactions with cosolvents/CO2 under subcritical and supercritical conditions
Cellulose and corn stover were subjected to a reaction with polar cosolvents (methanol and water)/CO2 at subcritical and supercritical conditions. Resulting products from a cellulose reaction at 300oC analyzed by GCMS consisted of a mixture of organic acids, sugars, and several other components. Examples of organic acids included acetic, hexanoic, heptanoic and malonic acids, whereas sugars were levoglucosan, D-Allose, and D-Galactose. Furthermore product samples from a corn stover reaction at 300°C suggested presence of ketones, aromatic hydrocarbons, and methyl esters. As evidenced by these results, reactions at high pressure are plausible although they are accompanied by a complex product composition, and an unreacted residue of cellulose and lignin.
AP-114 – Supercritical Carbon Dioxide Extraction of Catharanthus roseus
Catharantrus roseus is a well-known medicinal plant belonging to the family Apocynaceae. It is regarded as a rich source of pharmaceutically important indole alkaloids that are used as antitumor, hypotensive and antiarrhythmic agents. Among the indole alkaloids, vinblastine and vincristine are currently used to treat a wide variety of neoplasms and is recommended for treatment of Hodgkin’s disease, acute leukemia and choriocarcinoma, which is resistant to other types of therapy. The unique antitumor activities of these indole alkaloids have resulted in a great demand for vinblastine and vincristine as anticancer agents.
AP-115 – Toward the Direct Synthesis of Alane: Hydrogenation Studies of
Aluminum in Supercritical Fluid Media
Aluminum hydride (alane) has received a great deal of interest in recent years due its possible use as a hydrogen storage material. Alane contains 10.1 weight % hydrogen which meets the 2015 target set by the DOE of 9 weight % hydrogen. The decomposition of alane to its elements has no side reactions and has a decomposition enthalpy of 10 KJ/mol H2. Thermal decomposition begins above 60 °C, but is slow. Decomposition studies have shown an ideal temperature range of 130 – 150 °C but with added dopant of TiCl3 or LiH decomposition can be achieved at an acceptable rate at <100 °C. This, accompanied with recognition that rehydrogenation is realistic, makes alane a contender for use as an ideal hydrogen storage material.
AP-116 – Anxiolytic Activity of a SC CO2 Extract of Souroubea sympetala (Marcgraviaceae)
The purpose of this work was to develop an extraction technique to yield a betulinic acid-(BA) enriched extract of the traditional anti-anxiety plant Souroubea sympetala Gilg (Marcgraviaceae). Five extraction techniques were compared: supercritical carbon dioxide extraction (SCE), conventional solvent extraction with ethyl acetate (EtOAc), accelerated solvent extraction (ASE), ultrasonic assisted extraction (UAE) and soxhlet extraction (Sox). The EtOAc and SCE extraction methods resulted in BA-enriched extracts, with BA concentrations of 6.78  0.2 and 5.54  0.2 mg/g extract, respectively, as determined by HPLC-APCI-MS.The bioactivity of the BA-enriched extracts was compared in the elevated plus maze (EPM), a validated rodent anxiety behavior assay. Rats orally administered a 75 mg/kg dose of SCE extract exhibited anxiolysis as compared with vehicle controls, with a 50% increase in the percent time spent in the open arms, a 73% increase in unprotected head dips and a 42% decrease in percent time spent in the closed arms. No significant differences were observed between the SCE and EtOAc extracts for these measures, but the animals dosed with SCE extract had significantly more unprotected head dips than those dosed with the EtOAc extract. The SCE extract demonstrated a dose-response in the EPM, with a trend toward decreased anxiety at 25 mg/kg, and significant anxiolysis was only observed at 75 mg/kg dose. This study demonstrates that SCE can be used to generate a betulinic acid-enriched extract with significant anxiolysis in vivo. Further, the study provides a scientific basis for the ethnobotanical use of this traditional medicine and a promising lead for a natural health product to treat anxiety.
Martha Mullally,1† Kari Kramp,1,4† Chris Cayer,1,2 Ammar Saleem,1 Fida Ahmed,1 Calum McRae,3 John Baker,3 Andrew Goulah,4 Marco Otorola,5 Pablo Sanchez,5 Mario Garcia,5 Luis Poveda,5 Zul Merali,2 Tony Durst,1,6 Vance L. Trudeau7 and John Thor Arnason1*
1Centre for Research in Biopharmaceuticals and Biotechnology, Department of Biology, University of Ottawa, Ottawa, ON, Canada, K1N 6N5
2Institute of Mental Health Research, University of Ottawa, Ottawa, Ontario, Canada K1N 6N5
3Bioniche Life Sciences Inc., 231 Dundas Street East, Belleville, ON, Canada, K8N 1E2
4Loyalist College,Wallbridge-Loyalist Road, P.O. Box 4200, Belleville ON, Canada, K8N 5B9
5Universidad Nacional, Heredia, Costa Rica
6Department of Chemistry, University of Ottawa, Ottawa, ON, Canada, K1N 6N5
7Centre for Advanced Research in Environmental Genomics, Department of Biology, University of Ottawa, Ottawa, ON, Canada, K1N 6N5
PHYTOTHERAPY RESEARCH Phytother. Res. (2010) Published online inWiley InterScience (www.interscience.wiley.com) DOI: 10.1002/ptr.3246
AP-117 – Biodiesel Production – The Potential of Algal Lipids Extracted with scCO2
Supercritical carbon dioxide (scCO2) was used to extract components of interest from Scenedesmus dimorphus, a microalgae species, under varied algal harvesting and extraction conditions. Liquid chromatography-mass spectrometry (LC-MS) was used to quantify the concentration of fatty acid methyl esters (FAME) and the FAME profile of transesterified lipids, phospholipids and pigments extracted under varied supercritical temperatures and pressures. The scCO2 extraction results are compared with conventional solvent extraction to evaluate differences in the efficiency and nature of the extracted materials. Algae harvested by centrifugation (vs. lyophilization) demonstrated a similar extraction efficiency in scCO2, indicating potential energy benefits by avoiding conventional algal mass dehydration prior to extraction. Centrifuged algae and optimized extraction conditions (6000 psi; 100°C) resulted in comparable FAME yields to conventional processes, as well as increased selectivity, reflected in the decreased pigment, nitrogen and phospholipid contamination of the FAME. Cell pre-treatments—sonication, microwave, bead beating and lyophilization—showed an enhancement in extraction yield in both conventional solvent and scCO2 extraction, allowing for improved extraction efficiencies. This study suggests that scCO2, a green solvent, shows great potential for algal lipid extraction for the sustainable production of biodiesel.
Lindsay Soha and Julie Zimmerman*a,b
aYale University, Chemical and Environmental Engineering, 9 Hillhouse Ave., New Haven, CT, USA. E-mail: email@example.com; Fax: +1 203.432.9703; Tel: +1 203.432.4837
bYale University, School of Forestry and Environmental Studies, 195 Prospect St., New Haven, CT, USA
Green Chem., 2011, 13, 1422 www.rsc.org/greenchemDOI: 10.1039/c1gc15068e
AP-118 – Catalyst-free Biodiesel Reactions and Post Treatment Using Commercial Polymeric Resins
Biodiesel was synthesized under catalyst-free supercritical methanol reactions using a variety of oils at 250 to 325°C in a 1-liter high-pressure batch reactor. Multiple experiments were performed at 6 to 80 molar ratios of methanol to oil; product samples were then analyzed by titration, and a Gas Chromatograph which monitored conversion of triglyceride by measuring total glycerine. At 300°C and 27 molar ratios, 97% conversion was attained. Following the experiment samples were placed in separatory funnel and the crude biodiesel layer was treated further to remove free glycerine by centrifugation and also with an Amberlite BD10dry which was more effective.
AP-119 – Coprecipitation of Pharmaceutical Actives and Their Structurally Related Additives by the RESS Process
Coprecipitation of active pharmaceutical ingredients (API) with additives can provide the ability to add functionality to API’s at early stages of drug discovery and synthesis. It is with this objective that a number of drugs were recrystallized in the presence of structurally related additives. The rapid expansion of supercritical solution (RESS) process was evaluated to recrystallize the drug–additive mixtures. Results of RESS aided coprecipitation studies involving twelve drug–additive mixtures are reported in this manuscript. Characterization of these mixtures revealed a number of interesting phenomena. These include habit modification, solubility enhancement, particle size reduction, eutectic formation, reduction in crystallinity, amorphous conversion, hydrate formation, polymorph conversion and selective extraction. In viewing each of these phenomena from an application standpoint, this manuscript serves as proof of concept for altering the physicochemical and mechanical properties of API’s using supercritical fluid (SCF) coprecipitation. It was concluded from these studies that the rapid crystallization conditions offered by the SCF media alone does not provide the ability to consistently dope crystals. Competing mechanisms based on the relative solubility of drugs and additives in SCF media, as well as the selectivity of SCF solvents are to be taken into consideration while undertaking coprecipitations.
Chandra Vemavarapu a,b,⁎, Matthew J. Mollan b, Thomas E. Needham a
a Pharmaceutical Sciences, University of Rhode Island, Kingston, RI 02881, USA
b Pharmaceutical Sciences, Pfizer Global R&D, Ann Arbor, MI 48105, USA
C. Vemavarapu et al. / Powder Technology 189 (2009) 444–453
AP-120 – Extraction of Lignin from Sugar Cane Bagasse and Pinus Taeda Wood Chips using Ethanol–water Mixtures and Carbon Dioxide at High Pressures
The utilization of carbon dioxide under supercritical conditions in the delignification of wood has already been reported in the literature for several species of tree. In these studies organic solvents (acetic acid, ethanol, methanol, dioxane, etc.) were used as co-solvent and very high pressures (15–25MPa) were employed. Organosolv treatments of various woods have also been reported and have shown good results with ethanol–water mixtures, normally at volume ratios close to unit.
This article describes a study of the pulping of Pinus taeda wood chips and sugar cane bagasse, combining the use of ethanol–water mixtures and carbon dioxide at high pressures. Ethanol–water mixture was varied from 50 to 100% ethanol for sugar cane bagasse and from 30 to 100% ethanol for P. taeda wood chips, and the reaction times from 30 to 120 min and from 30 to 150 min for sugar cane bagasse and P. taeda wood chips, respectively. The effect of pressure and temperature on the yield and extent of delignification was studied, using a factorial experimental design, over the ranges 14.7–23.2MPa and 142–198 ◦C, respectively.
The obtained results indicate important differences from the organosolv process, which may be due to the presence of carbon dioxide and/or the high pressure employed in this work. The pulp yields and extent of delignification showed, as expected, a much greater influence of temperature than of pressure. The best results were obtained at 16.0MPa and 190 ◦C. Under these conditions the pulping yield and the residual Klason lignin content from P. taeda wood chips were 43.7 and 4.9%, respectively, and from sugar cane bagasse 32.7 and 8.7%, respectively. These data correspond to a delignification extent in the order of 93.1% for P. taeda wood chips and 88.4% for sugar cane bagasse. Higher pressures lead to similar pulp yields but higher residual lignin contents.
Daniel Pasquini a, Maria Teresa Borges Pimenta a, Luiz Henrique Ferreira b, Antonio Aprigio da Silva Curvelo a,∗
a Instituto de Quımica de Sao Carlos, Universidade de Sao Paulo, C.P. 780, 13560-970 Sao Carlos, S.P., Brazil
b Departamento de Quımica, Universidade Federal de Sao Carlos, C.P. 676, 13565-905 Sao Carlos, S.P., Brazil
D. Pasquini et al. / J. of Supercritical Fluids 36 (2005) 31–39
AP-121 – Room Temperature Aerobic Oxidation of Alcohols using CuBr2 with TEMPO and a Tetradentate Polymer Based Pyridyl-imine Ligand
A series of tetradentate pyridyl-imine terminated Schiff-base ligands has been investigated for their ability in the catalytic oxidation of alcohols when combined with copper bromide (CuBr2) and 2,2,6,6-tetramethylpiperidyl-1-oxy (TEMPO). Analogous bidentate ligands showed poorer catalytic activity and the ratio of Cu:ligand was of crucial importance in maintaining high yields. The polydimethylsiloxane (PDMS) derived pyridyl-imine terminated ligand combined with copper(II) ions affords an effective and selective catalyst for aerobic oxidations of primary and secondary alcohols under aqueous conditions. Preliminary mechanistic studies suggest that bimetallic complexes may be playing a role in the catalytic transformation.
AP-122 – Hetero-Polyaromatic Ring-Opening Reactions in scCO2
Production of cleaner fuels from increasingly low-grade feedstocks and non-edible biomass sources.
AP-123 – Efficient Aerobic Oxidation of Alcohols Using CuBr2 and a Series of α-w Pyridyl-imine Terminated Polydimethylsiloxane Ligands
From the point of view of Green Chemistry, polymer-based catalysts are very environmentally friendly. These catalysts can be used and recycled in green solvents such as liquid polymers and supercritical carbon dioxide. They can also be very selective.
In our recent studies, a series of α-w pyridyl-imine terminated polydimethylsiloxane ligands have been synthesized and characterized. It is interesting that these carbon dioxide miscible ligands form metallocyclic complexes when coordinated with copper(I) salt. Meanwhile, they provide perfect binding sites for copper (II) ions which then work as catalysts for more efficient aerobic oxidations of primary and secondary alcohols.
AP-124 – Solubility of Bio-sourced Feedstocks in ‘Green’ Solvents†
A group of 14 different bio-sourced, renewable feedstocks (homoserine, 1; glutamic acid, 2; aspartic acid, 3; 2,5-furandicarboxylic acid, 4; fumaric acid, 5; oxalacetic acid, 6; tartaric acid, 7; malic acid, 8; succinic acid, 9; levulinic acid, 10; g-hydroxybutyrolactone, 11; xylitol, 12; mannitol, 13; sorbitol, 14) have been examined for their solubility/miscibility in a variety of ‘green’ solvents, including water, supercritical carbon dioxide (scCO2), and ionic liquids. Two other bio-based compounds 5-hydroxymethylfurfural, 15, and D-xylose, 16, were studied in selected solvents. Trends in solubility have been assessed so that these data may be extrapolated to help predict solubilities of other related compounds. For example, 10, 11 and 15 all demonstrated appreciable solubility in scCO2, as they possess weak intermolecular interactions. The dicarboxylic acids studied (4–9) all proved soluble in modified scCO2 (by use of MeOH as a cosolvent). While the polyols (12–14) and 1 were insoluble in scCO2 but water of various pHs and ionic liquids proved adept at their dissolution. Some of the amino acids studied (2 and 3) were only soluble in water with an adjustment of pH.
Samantha M. Payne and Francesca M. Kerton*
Centre for Green Chemistry and Catalysis, Department of Chemistry, Memorial University of Newfoundland, St. John’s, Newfoundland and Labrador, Canada A1B 3X7. E-mail: firstname.lastname@example.org; Fax: +1 709 7373702; Tel: +1 709 7378089
Green Chem., 2010, 12, 1648–1653 DOI: 10.1039/c0gc00205d
AP-125 – SFE of Polyunsaturated Fatty Acids from Northern Shrimp (Pandalus borealis Kreyer) Processing By-products
This study investigated the potential of Northern shrimp (Pandelus borealis Kreyer) by-products as a source of omega-3 polyunsaturated fatty acids (x-3 PUFAs). The by-products (heads, shell and tail) of processing accounted for approximately 50–60% of the catch. Supercritical CO2 extraction (SFE) of the by-products at 35 MPa and 40 C generated a deep red oil, rich in x-3 PUFAs, specifically 7.8 ± 0.06% eicosapentaenoic acid (EPA) and 8.0 ± 0.07 % docosahexaenoic acid (DHA).
Virginie Treyvaud Amiguet a,1, Kari L. Kramp a,b,1, JinQin Maoa, Calum McRae b, Andrew Goulah b, Linda E. Kimpe a, Jules M. Blais a, John T. Arnason a,⇑
a University of Ottawa, Department of Biology, Centre for Advanced Research in Environmental Genomics, 30 Marie-Curie, Ottawa, ON, Canada K1N 6N5
b Loyalist College, BioSciences, 376 Wallbridge-Loyalist Road, P.O. Box 4200, Belleville, ON, Canada K8N 5B9
V. Treyvaud Amiguet et al. / Food Chemistry 130 (2012) 853–858
AP-126 – SFE OF MITRAGYNA SPECIOSA
Mitragyna speciosa is a narcotic plant but with specific medicinal importance. The main components of the leaves of M. speciosa are indole alkaloids. Previous scientific researches have shown that the alkaloidal extracts possess very potent anti-inflammatory, analgesic and opioid properties. The three most abundant indoles are mitragynine, paynanthine and speciogynine, the first two of which appear to be unique to this species. All these compounds were obtained from classical organic solvent (ethyl acetate, dichloromethane or methanol) extraction. CO2 extract of M. speciosa has never been studied yet. Hence, in this present investigation, supercritical fluid extraction (SFE) of M. speciosa was performed. Comparison of the TLC of SFE extracts with that of the ethyl acetate extract from this preliminary study shows no alkaloid was extracted out with 100% CO2. Alkaloids were only extracted with eluent system using ethanol as co-solvent and the optimal conditions was CO2-ethanol (80% EtOH), 40 °C and 5000psi. CO2 was chosen as the media of extraction because it is non-toxic and environmentally safe to prepare and use.
AP-127 – Solubilities of CO and H2 in Neat and CO2-Expanded Hydroformylation Reaction
Accurate knowledge of the phase equilibria of CO2-expanded hydroformylation reaction mixtures is essential to rational process design and development. Vapor-liquid equilibria of the following systems were measured in a variable-volume view cell at temperatures ranging from (313.15 to 353.15) K and pressures up to 9 MPa: CO + 1-octene, CO2 + 1-octene, CO + 1-octene + CO2, CO + nonanal, CO2 + nonanal, CO + nonanal + CO2, H2 + 1-octene, H2 + 1-octene + CO2, H2 + nonanal, and H2 + nonanal + CO2. The measured solubilities of CO and H2 in the liquid phases were consistent with literature values. The presence of CO2 was found to enhance the solubilities of both CO and H2 in the liquid phase. The enhancement factor is up to 1.54 for carbon monoxide and 1.82 for hydrogen. The Peng-Robinson equation of state (PR EoS) with van der Waals mixing rules and binary interaction parameters modeled the VLE data adequately, with much better fits for the 1-octene systems compared to the more polar nonanal systems.
Zhuanzhuan Xie, William K. Snavely, Aaron M. Scurto, and Bala Subramaniam*
Center for Environmentally Beneficial Catalysis, Department of Chemical & Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045-7609
Journal of Chemical & Engineering Data, Vol. 54, No. 5, 2009
AP-128 – Solubility of Bio-Sourced Feedstocks in ‘Green’ Solvents
A group of 14 different bio-sourced, renewable feedstocks have been examined for their solubility/miscibility in a variety of ‘green’ solvents, and trends in solubility have been assessed so that the data may be extrapolated to help predict solubilities of other related compounds. This information could provide valuable insight into the workability of a host of new, green reactions using these compounds, opening the door to a realm of more environmentally friendly syntheses.
AP-129 – Identification of Phospholipids,Fatty Acids in Oils and Their Oxidation Products Using SFE, MALDI and ESI-MS
The ability to sensitively detect and analyze large molecules and their reaction products is important for the analysis of biological materials, including medical samples, plants and foods. Such analyses present special challenges in terms of the need to selectively extract the compound or class of compounds in order to separate them from the complex mixture found in biological samples. In addition, conventional techniques for separating and identifying relatively small molecules are not applicable to high molecular weight materials where the volatility is low and they are often viscous liquids or solids at room temperature.
AP-130 – Synthesis of Biodiesel from Edible, Non-edible and Waste Cooking Oils Via Supercritical Methyl Acetate Transesterification
The use of methyl acetate instead of methanol for supercritical synthesis of glycerol-free biodiesel from vegetable oils is a new process and its study is very limited in the literature. In this work, it has been tested for the first time on three edible and non-edible oils with different fatty acid composition. The process was also applied to waste oil with higher free fatty acid (FFA) content. The results demonstrate that the oil composition does not significantly influence the biodiesel yield.
The influence of temperature, pressure and molar ratio of reactants was studied. All the oils achieved complete conversion after 50 min at 345 C, 20 MPa with methyl acetate:oil molar ratio equal to 42:1. The obtained data also allowed calculating the apparent rate coefficients and activation energies.
Eventually, some new information on the process was obtained. Thermal degradation of triacetin, which substitutes glycerol as the by-product of the transesterification reaction, was observed. Some indicative experiments were performed to understand the role of the acetic acid produced by FFA esterification.
Pasquale Campanelli, Mauro Banchero *, Luigi Manna
Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Corso Duca degli Abruzzi, 24, 10129 Torino, Italy
P. Campanelli et al. / Fuel 89 (2010) 3675–3682
AP-131 – Aqueous Extraction of Oil and Protein from Soybeans with Subcritical Water
Aqueous extraction using subcritical water is an environmentally friendly alternative to extracting oil and protein from oilseeds with flammable organic solvents. The effects of solids-to-liquid ratio (1:3.3–1:11.7), temperature (66–234 _C), and extraction time (13–47 min) were evaluated on the extraction of oil and protein from soybean flakes and from extruded soybeans flakes with subcritical water. A central composite design (23) with three center points and six axial points was used. Subcritical water extractions were carried out in a 1-L high-pressure batch reactor with constant stirring (300 rpm) at 0.03–3.86 MPa. In general, oil extraction was greater for extruded soybean flakes than with soybean flakes. More complete oil extraction for extruded soybean flakes was achieved at around 150 _C and extraction was not affected by solids-to-liquid ratios over the range tested, while oil extraction from soybean flakes was more complete at 66 _C and low solids-toliquid ratio (1:11.7). Protein extraction yields from flakes were generally greater than from extruded flakes. Protein extraction yields from extruded flakes increased as temperature increased and solids-to-liquid ratio decreased, while greater protein extraction yields from soybean flakes were achieved when using low temperatures and low solidsto- liquid ratio.
S. C. Ndlela • J. M. L. N. de Moura •
N. K. Olson • L. A. Johnson
S. C. Ndlela • N. K. Olson, Iowa Energy Center-BECON, Nevada, IA 50201, USA
J. M. L. N. de Moura • L. A. Johnson (&), Center for Crops Utilization Research, Iowa State University, 1041 Food Sciences Building, Ames, IA 50011-1061, USA e-mail: email@example.com
J. M. L. N. de Moura • L. A. Johnson, Department of Food Science and Human Nutrition, Iowa State University, Ames, IA 50011-1061, USA
J Am Oil Chem Soc DOI 10.1007/s11746-011-1993-7
AP-132 – Green Application of Flame Retardant Cotton Fabric Using Supercritical CO2
To increase cotton’s consumption by inventing products and processes that demonstrate preferred use of cotton over competing fibers in needed and emerging applications involving plastics, textiles, and composites.
AP-133 – One-Pot Algal Biodiesel Production in Supercritical Carbon Dioxide
To advance the realization of algae as a feedstock for biodiesel, process technologies and closed-loop biomass use must be optimized. Life-cycle analysis (LCA) of the biodiesel production process highlights the potential significant impact of improvements in the extraction of algal lipids and conversion into biodiesel. Further, a single-step lipid extraction and transesterification process was shown to have the highest energy rewards. This work investigates the potential for using scCO2 for the extraction and conversion process. scCO2 is shown to be an effective and selective solvent for extracting triglycerides from algal biomass. This work also explores the fundamental science necessary to achieve a one-pot approach that both extracts and transesterifies lipid from algae using supercritical carbon dioxide/methanol (scCO2/MeOH) and heterogeneous catalysts. A variety of basic and acidic heterogeneous catalysts have been surveyed for their effectiveness at transesterification of triglyceride (TG) to fatty acid methyl esters (FAME). Further the enhanced solubility of FAME over reaction intermediates, TG, and glycerol, is likely to provide a driving force for reaction. This research offers the foundations for a simple one-pot system wherein biodiesel can be directly, selectively, and sustainably produced from algae for further application in an algae biorefinery.
AP-134 – Chemical Conversion of Biomass under Subcritical-Supercritical – Solvent Conditions using a Pilot Scale Flow Reactor
The first phase of this project evaluated the reaction pathways for biomass feedstock in the presence of various cosolvents including acetone, methanol, CO2, and water using a 1 liter (di: 7.6cm, l: 23.1cm) high pressure batch reactor. Additionally, the effect of temperature on the extent of the reaction was assessed at 200 to 350 oC. In both instances biomass conversion rates compared to the starting material ranged from 70 to 90 %, with the remaining portion being the unreacted fraction and lignin. The resulting products consisted of complex chemical fractions: organic acids, organic ester derivatives, sugars, sugar-alcohols, thermal degradation products and more. Although the impact of using various cosolvents was noticeable at lower temperatures, at higher temperatures the extent thermal degradation products increased due to longer heating times to reach the target temperature (2 to 8 hrs.). Despite the challenges with longer residence time when using the batch reactor, results from this study gave an important understanding of the reaction behavior and interaction of the solvent and biomass.
To have better control of the reaction extent at pilot scale, a flow reactor was assembled. The system consisted of a 250 ml/min slurry pump with reactor chamber that is 212 cm longer by 3 cm diameter, a maximum system working pressure up to 69 Mpa, electrical heating jackets and a condenser. Biomass slurry of 5 to 10% was fed into the reactor at varying temperatures from 200 to 350 oC and at residence times of 5 to 30 minutes. Analysis results from the flow reactor study will be main focus for this discussion.
AP-135 – Extraction of oil from chia seeds with supercritical CO2
Chia (Salvia Hispanic, L.) is a crop that was used as food, medicine and paints by the Aztec Indians in Mexico before 1492, andnowhas a promissory future in several countries. Chia seeds oil is rich in polyunsaturated fatty acids, particularly omega-3 linolenic acid (54–67%) and omega-6 linoleic acid (12–21%) which pose great benefits for human and animal health. The oil extraction from Chia seeds using supercritical CO2 seems to be a good alternative because it operates at low temperature with good mass-transfer rates and with no solvent residual in the final product. The objective of this work is to evaluate the extraction yield of oil from chia seeds and the concentration of omega-3 and omega-6 acids using supercritical extraction with CO2 at three pressures: 136, 272, and 408 bar, and three temperatures: 40, 60, and 80◦C.
Jose Antonio Rocha Uribea,∗ , Jorge Ivan Novelo Pereza , Henry Castillo Kauila , Gabriel Rosado Rubioa , Carlos Guillermo Alcocerb
a FIQ, Universidad Autónoma de Yucatán, Periferico Norte km 33.5, C. P. 97203, Mérida, Yucatán, Mexico
b Oleox Industries S. A. de C.V. Anillo Periferico T.C. 13917 Int. 7 Col. Cholul, C. P. 97300, Merida, Yucatan, Mexico
J.A.R. Uribe et al. / J. of Supercritical Fluids 56 (2011) 174–178
AP-136 – Extraction and Characterization of Oil from Thevetia Peruviana Using Supercritical CO2
Thevetia peruviana is an always green tree that grows well at adverse conditions and it is well adapted to Yucatan weather. Its kernal contains more than 60% of oil. Because the toxicity of the plat the oil is non edible and then a good candidate for biofuel production. In this study it is reported the results of supercritical extraction of oil from Thevetia peruviana kernals. The yield obtained 70% is higher than that obtained using solvent extraction 62% with petroleum ether, 60% with n-hexane, and to 40% using mechanical extraction.
AP-137 – Extraction and characterization of oil from Moringa oleifera using supercritical CO2 and traditional solvents
Looking for a good raw material for biodiesel at the Mexican-Yucatan peninsula, the study present data on the extraction of oil from Moringa oleifera kernals. Solvent extraction with n-hexane and ethanol, and supercritical extraction with CO2 are presented and compared with reported data. For supercritical extraction pressures of 200 to 400 bar and temperatures of 40 and 60⁰C were tested. Analysis with Gas Chromatography reveals that the main fatty acids are Oleic acid (69%), Palmitic acid (10%), and stearic acid (8%).
AP-138 – Cannabis Extraction by Supercritical Carbon Dioxide – Selection and Preparation of Feed Stock
Carbon Dioxide (CO2) extraction of cannabis is becoming more prevalent as the extract market grows with the spread of medical and recreational legalization. However, due to the historically underground nature of working with the substance, little true scientific experimentation and process development has occurred; even less has been published. Those new to the field have limited guidance.
The following is a compilation of the process learnings regarding feedstock selection and preparation that Supercritical Fluid Technologies (SFT) customers’ companies currently working in the CO2 cannabis extraction field, have shared with us. Due to the proprietary nature of each company’s specific process, the material here will be presented in a generic way that is applicable to the majority of processors.
AP-139 – Extraction of Rare Earth Elements from their Oxides using Organophosphorus Reagent Complexes with HNO3 and H20 in SC CO2
Abstract: Direct extraction of metals from solids with complexing agents in supercritical CO2 (SC-CO2) has recently attracted interests in separation, purification, recovery, and analysis of metals. In the present study, the static/dynamic extraction of rare earth elements (Nd, Ce) from their oxides (Nd2O3, CeO2) with organophosphorus complexes with HNO3 and H2O in SC-CO2 was investigated. The static extraction efficiency of Nd from Nd2O3 with the tri-n-butylphosphate (TBP)-HNO3 complex could reach 95%under optimized experimental conditions. However, the static extraction efficiency of Nd from Nd2O3 with the trilkyl phosphine oxide (TRPO)-HNO3 complex was less than 10%, and
the static extraction efficiency of Ce from CeO2 with the TBP-HNO3 complex was less than 1%. The dynamic extraction efficiency of Nd from Nd2O3 with the TBP-HNO3 complex could reach more than 97%. Effects of parameters were evaluated on the extraction efficiency to ascertain the optimum conditions. This study illustrated the extraction process using the TBP-HNO3 complex in SC-CO2 would be feasible for
separation, purification, recovery, and analysis of some rare earth elements from various oxide mixtures.
DUANWuhua (段五华), CAO Pijia (曹丕佳), ZHU Yongjun (朱永贝睿)
(Institute of Nuclear andNew Energy Technology, Tsinghua University,Beijing 102201, China)
Received 31May 2009; revised 7 September 2009
AP-140 – Cannabis Extraction by Supercritical Carbon Dioxide – Effects of Extraction Parameters
Carbon Dioxide (CO2) extraction of cannabis is becoming more prevalent as the extract market grows with the spread of medical and recreational legalization. However, due to the historically underground nature of working with the substance, little true scientific experimentation and process development has occurred; even less has been published. Those new to the field have limited guidance.
The following is a compilation of the process learnings regarding selection of extraction parameters that Supercritical Fluid Technologies (SFT) customers’ companies who are currently working in the CO2 cannabis extraction field have shared with us. Due to the proprietary nature of each company’s specific process, the material here will be presented in a generic way that is applicable to the majority of processors.
AP-141 – Cannabis Extraction by Supercritical Carbon Dioxide – Dewatering
All Cannabis feedstock contains water, even that which is properly dried and cured. Removing this water from the extract after processing raises the cannabinoid concentration of the extract, prevents it from spattering when consumed directly though vaping or in a rig, presents a cleaner taste to the consumer, and enables a more attractive appearance.
CO2 processing creates extract that will be laden with dry ice. Depending on the equipment and processing conditions the extract will need to be de-gassed and/or heated prior to dewatering.
AP – 142 – Extraction of anthocyanins from haskap berry pulp
Extraction of anthocyanins from haskap berry pulp using supercritical carbon dioxide: Influence of co-solvent composition and pretreatment
Guangling Jiao, Azadeh Kermanshahi pour∗
Biorefining and Remediation Laboratory, Department of Process Engineering and Applied Science, Dalhousie University, PO, 15000, Halifax, Nova Scotia, B3H 4R2,
Extracts rich in anthocyanin compounds were obtained from haskap berry pulp paste using supercritical carbon dioxide (scCO2) and water as co-solvent. The extraction conditions including pressure, temperature, and amount of water were further optimized by Box-Behnken design. The highest total anthocyanins (TA) yield of 52.7% was
achieved at 45 MPa, 65 °C, 5.4 g water to 3.2 g berry pulp paste, 15 min static and 20 min dynamic time. Different combinations of water and ethanol as co-solvent did not significantly affect the TA yield. Furthermore, similar anthocyanin extraction yields were obtained in the case of the pulp paste and rehydrated freeze-dried berry pulp powder, which indicates that freeze drying pretreatment is not required prior to scCO2 extraction.
Compared with conventional extraction, the use of scCO2 and water as co-solvent offered higher anthocyanin extraction efficiency (52.7% versus 38.3%) with improved antioxidant activity (89.8% versus 72.2%).
AP-143 – Naturally Occuring and related Synthetic Cannabinoids and their Potential Therapeutic Applications
Ahmed M. Galal1,*, Desmond Slade1, Waseem Gul1,5, Abir T. El-Alfy2, Daneel Ferreira1,3 and Mahmoud A. Elsohly1,4,5
Abstract: Naturally occurring cannabinoids (phytocannabinoids) are biosynthetically related terpenophenolic compounds uniquely produced by the highly variable plant, Cannabis sativa L. Natural and synthetic cannabinoids have been extensively studied since the discovery that the psychotropic effects of cannabis are mainly due to ! 9-THC. However,
cannabinoids exert pharmacological actions on other biological systemssuch as the cardiovascular, immune and endocrine systems. Most of these effects have been attributed to the ability of these compounds to interact with the cannabinoid CB1 and CB2 receptors. The FDA approval of Marinol®, a product containing synthetic ” 9-THC (dronabinol), in 1985 for the control of nausea and vomiting in cancer patients receiving chemotherapy, and in 1992 as an appetite stimulant for AIDS patients, has further intensified the research interest in these compounds. This article reviews patents (2003-2007) that describe methods for isolation of cannabinoids from cannabis, chemical and chromatographic methods for their purification, synthesis, and potential therapeutic applications of these compounds.
AP-144 – Cannabidiol from inflorescences of Cannabis sativa L.: Green extraction and purification processes
AP-144 – Cannabidiol from inflorescences of Cannabis sativa L.: Green extraction and purification processes..
Cannabidiol from inflorescences of Cannabis sativa L.: Green extraction and purification processes
Stefania Marzoratia,*, Danilo Friscioneb, Enrico Picchib, Luisella Verottaa
a Università degli Studi di Milano, Department of Environmental Science and Policy, Via Celoria 2, 20133 Milano, Italy
b Alfatech S.p.A., Via Angelo Scarsellini 97, 16149 Genova, Italy
This work investigates an extraction and purification downstream process able to provide cannabidiol (CBD) enriched products starting from inflorescences of Cannabis sativa L. Even though the legislation concerning nonpsychoactive Cannabis derivatives is still an open issue, the interest in this compound is justified worldwide by the scientifically demonstrated health beneficial effects of CBD for the treatment of many disorders. For these reasons, the interest in CBD-based formulations, for the sake of readiness for the future market demands, is quite high. Despite the fact that the recent literature is highly addressed to the topic of cannabinoids and their related biological activities, there is still a general lack in strategic proposals aiming at recovering and purifying specifically CBD through scalable processes.
In this work, preliminary studies were addressed to convert the main product of the plant metabolism, cannabidiolic acid, to CBD by heat-treatment-induced decarboxylation of the dried biomass. Then, a “green strategy”, supercritical CO2 extraction, enabled to yield a 50 % w/w CBD-enriched oil, avoiding any use of toxic organic solvents. Yields and compositions of methanolic extraction and supercritical CO2 were compared. Results confirmed the enhanced selectivity of supercritical CO2. A winterization process, followed by flash chromatography, successfully removed waxes and the psychotropic fraction, providing an almost 80 % w/w CBD-enriched final product.
AP-145 – Carotenoids, chlorophylls and phycocyanin from Spirulina: supercritical CO2 and water extraction methods for added value products cascade
aDepartment of Environmental Science and Policy, Università degli Studi di Milano, via Celoria 2, 20133 Milano, Italy
bAlgaria srl, via Tucidide 61, 20133 Milano, Italy
In the last decade, the cyanobacterium Spirulina has gained a high commercial interest as a food supplement, mainly due to its high protein content as well as high amounts of pigments, such as carotenoids, chlorophylls and phycocyanins. In particular, phycocyanin has been widely considered as a precious food-dye because of its protein-based structure and the rare intense-blue color. Different strategies were developed for the isolation and purification of phycocyanin. The main drawback of such processes is that carotenoids and chlorophylls are generally wasted together with the residual biomass. In this study, a different approach is proposed, suggesting an integrated pigment extraction chain. The body of the strategy involves two consecutive steps of the supercritical-CO2 extraction of carotenoids and chlorophylls, before phycocianin extraction. The total carotenoid, chlorophyll a and chlorophyll b contents in the extracts were equal to 3.5 ± 0.2 mg g−1, 5.7 ± 0.2 mg g−1 and 3.4 ± 0.3 mg g−1, respectively (by dry Spirulina weight). The biomass residue, exhausted in terms of carotenoids and chlorophylls, was then extracted in water to yield phycocyanin. Consecutive steps were developed in order to ehance the phycocyanin purity, including electrocoagulation, dialysis and protein salting-out. These processes yielded 250 mg g−1 of phycocyanin (by dry Spirulina weight). A potentially scalable strategy to obtain the blue pigment with high purity (A620/A280 = 2.2) was developed. The practical application of the extracted blue phycocyanin pigment as a cotton-based tissue colorant was also experimented.
AP-147 PMMA-sepiolite nanocomposites as new promising materials for the production of nanocellular polymers
Victoria Bernardo⁎, Judith Martín-de León, Ester Laguna-Gutiérrez, Miguel Ángel Rodríguez-Pérez
Cellular Materials Laboratory (CellMat), Condensed Matter Physics Department, University of Valladolid, Campus Miguel Delibes, Paseo de Belén n7, 47011 Valladolid, Spain
In this work, a new system based on poly(methyl methacrylate) (PMMA) sepiolite nanocomposites that allow producing nanocellular polymers by using the gas dissolution foaming technique is described. Nanocomposites with different nanoparticle types and contents have been produced by extrusion. From these blends, cellular materials have been fabricated using the so-called gas dissolution foaming method. An extensive study of the effect of the processing parameters (saturation pressure and foaming temperature) on the cellular materials produced has been performed. Results showed that among the three sepiolites used, only those modified with a quaternary ammonium salt are suitable for being used as nucleating agents in PMMA. With these nanoparticles bimodal cellular polymers, with micro and nanometric cells, have been produced. Cell sizes in the range of 300–500 nm and cell densities of the order of 1013–1014 nuclei/cm3 have been obtained in the nanocellular region. A foaming temperature of 80 °C and a wide range of saturation pressures (between 10 and 30 MPa) and low particle contents (between 0.5 and 1.5 wt%) allow obtaining these materials. Furthermore, it has been found that cell size in the nanometric population can be controlled by means of the particles content; a reduction in the cell size is obtained when the particles content increases. Finally, results indicate that an increase in the foaming temperature leads to cellular nanocomposites with lower relative densities (below 0.21) and larger cell sizes (above 450 nm).
AP-146: Easy-way production of highly transparent nanocellular polymers films
J. Martín-de Le´on a,*, M. Jim´enez a, J.L. Pura d, V. Bernardo b, M.A. Rodriguez-P´erez a,c
a Cellular Materials Laboratory (CellMat), Condensed Matter Physics Department, University of Valladolid, Valladolid, 47011, Spain
b CellMat Technologies S.L. Paseo de Belen 9A, 47011, Valladolid, Spain
c BioEcoUVA Research Institute on Bioeconomy, University of Valladolid, Spain
d Gds Optronlab, Condensed Matter Physics Department, Universidad de Valladolid, 47011, Spain
The key parameters and production route for the easy production of highly transparent nanocellular films based on polymethylmethacrylate (PMMA) with thickness below 1 mm are herein described. The use of the gas dissolution foaming process (CO2 as physical blowing agent) with saturation pressures of 40
and 50 MPa, a saturation temperature of 0 ◦C and a saturation time of 2.5 h together with an adequate approach to foam the samples leads to the production of directly transparent nanocellular PMMA with relative densities in the range of 0.47–0.80 and cell sizes in the internal part of the film ranging 23–29 nm.
The produced materials present maximum transparency of 61% for a thickness of 0.5 mm without any postprocessing, a value comparable to the one previously obtained in the literature for nanocellular PMMA produced using a long-lasting process that included additional time-consuming post-processing of the samples. The produced cellular materials have been in-deep characterized, and the influence of several key parameters such as the solid skin thickness, transition region, and cellular structure on the final optical transmittance has been studied.
AP-148 – Understanding the role of MAM molecular weight in the production of PMMA/MAM nanocellular polymers
Victoria Bernardoa,∗, Judith Martin-de Leona, Ester Laguna-Gutierreza, Tiziano Catelanib, Javier Pintob, Athanassia Athanassioub, Miguel Angel Rodriguez-Pereza
a Cellular Materials Laboratory (CellMat), Condensed Matter Physics Department, University of Valladolid, Valladolid, Spain
b Nanophysics, Istituto Italiano di Tecnologia (IIT), Genova, Italy
Nanostructured polymer blends with CO2-philic domains can be used to produce nanocellular materials with controlled nucleation. It is well known that this nanostructuration can be induced by the addition of a block copolymer poly(methyl methacrylate)-poly(butyl acrylate)-poly(methyl methacrylate) (MAM) to a poly(methyl methacrylate) (PMMA) matrix. However, the effect of the block copolymer molecular weight on the production of nanocellular materials is still unknown. In this work, this effect is analysed by using three types of MAM triblock copolymers with different molecular weights, and a fixed blend ratio of 90 wt% PMMA and 10 wt% of MAM. Blends were produced by extrusion. As a result of the extrusion process, a non-equilibrium nanostructuration takes place in the blends, and the micelle density increases as MAM molecular weight increases. Micelle formation is proposed to occur as result of two mechanisms: dispersion, controlled by the extrusion parameters and the relative viscosities of the polymers, and self-assembly of MAM molecules in the dispersed domains. On the other hand, in the nanocellular materials produced with these blends, cell size decreases from 200 to 120 nm as MAM molecular weight increases. Cell growth is suggested to be controlled by the intermicelle distance and limited by the cell wall thickness. Furthermore, a theoretical explanation of the mechanisms underlying the limited expansion of PMMA/MAM systems is proposed and discussed.
AP-149 – Low-density PMMA/MAM nanocellular polymenrs using low MAM contents: Production and characterization
Victoria Bernardoa,∗, Judith Martin-de Leona, Javier Pintob, Tiziano Catelanic, Athanassia Athanassioub, Miguel Angel Rodriguez-Pereza
a Cellular Materials Laboratory (CellMat), Condensed Matter Physics Department, University of Valladolid, Campus Miguel Delibes, Paseo de Belén nº7, 47011, Valladolid, Spain
b Smart Materials, Istituto Italiano di Tecnologia, Via Morego 30, 16163, Genova, Italy
c Electron Microscopy Facility, Istituto Italiano di Tecnologia, Via Morego 30, 16163, Genova, Italy
Low-density nanocellular polymers are required to take advantage of the full potential of these materials as high efficient thermal insulators. However, their production is still a challenging task. One promising approach is the use of nanostructured polymer blends of poly(methyl methacrylate) (PMMA) and a block copolymer poly(methyl methacrylate)-poly(butyl acrylate)-poly(methyl methacrylate) (MAM), which are useful for promoting nucleation but seem to present a severe drawback, as apparently avoid low relative densities. In this work, new strategies to overcome this limitation and produce low-density nanocellular materials based on these blends are investigated. First, the effect of very low amounts of the MAM copolymer is analysed. It is detected that nanostructuration can be prevented using low copolymer contents, but nucleation is still enhanced as a result of the copolymer molecules with high CO2 affinity dispersed in the matrix, so nanocellular polymers are obtained using very low percentages of the copolymer. Second, the influence of the foaming temperature is studied. Results show that for systems in which there is not a clear nanostructuration, cells can grow more freely and smaller relative densities can be achieved. For these studies, blends of PMMA with MAM with copolymer contents from 10 wt% and as low as 0.1 wt% are used. For the first time, the production strategies proposed in this work have allowed obtaining low density (relative density 0.23) nanocellular polymers based on PMMA/MAM blends.
AP-150 – Production and characterization of nanocellular polyphenylsulfone foams
V. Bernardo n, J.Martín-deLeón,M.A.Rodríguez-Pérez Cellular MaterialsLaboratory(CellMat),CondensedMatterPhysicsDepartment,UniversityofValladolid,CampusMigue Delibes,PaseodeBelénno. 7,47011 Valladolid, Spain
Nanocellular foams have been produced by means of a gas dissolution process using polyphenylsulfone
(PPSU) as matrix polymer. Cell sizes in the range 20–30 nm and cell nucleation densities higher than
1015 cm3 have been achieved for materials with relative densities in the range 0.65–0.75. The influence
of both saturation pressure and foaming temperature has been studied. On the one hand, it has been
proved that there is a large influence of the amount of gas (CO2) absorbed in the final cellular structure,
in fact it has been found a critical CO2 uptake between 9% and 9.5% at which the cell sizes evolve from the micro to the nanoscale. On the other hand, it has been found that there is a wide range of foaming
parameters(foaming time and foaming temperature) in which nanocellular foams can be produced.
AP-151 – Anisotrophy in nanocellular polymers promoted by the addition of needle-like sepiolites
Victoria Bernardo,* Judith Martin-de Leon and Miguel Angel Rodriguez-Perez
This work presents a new strategy for obtaining nanocellular materials with high anisotropy ratios by means of the addition of needle-like nanoparticles. Nanocellular polymers are of great interest due to their outstanding properties,whereas anisotropic structures allowthe realization of improved thermal and mechanical properties in certain directions.Nanocomposites based on poly(methyl methacrylate) (PMMA)with nanometric sepiolites are generated by extrusion. Fromthe extruded filaments, cellular materials are produced using a two-step gas dissolution foaming method. The effect of adding various types and contents of sepiolites is investigated. As a result of the extrusion process, the needle-like sepiolites are aligned in the machine direction in the solid nanocomposites. Regarding the cellular materials, the addition of sepiolites allows one to obtain anisotropic nanocellular polymers with cell sizes of 150 to 420nm and cell nucleation densities of 1013–1014 nuclei cm−3 and presenting anisotropy ratios ranging from 1.38 to 2.15, the extrusion direction being the direction of the anisotropy. To explain the appearance of anisotropy, a mechanism based on cell coalescence is proposed and discussed. In addition, it is shown that it is possible to control the anisotropy ratio of the PMMA/sepiolite nanocellular polymers by changing the amount of well-dispersed sepiolites in the solid nanocomposites
AP-152 – Supercritical Fluid Extraction of Rare Earth Elements from Nickel Metal Hydride Battery
Yuxiang Yao,† Nina F. Farac,† and Gisele Azimi*,†,‡
†Laboratory for Strategic Materials, Department of Chemical Engineering and Applied Chemistry, 200 College Street, Toronto,
Ontario M5S 3E5, Canada
‡Department of Materials Science and Engineering, University of Toronto, 184 College Street, Toronto, Ontario M5S 3E4, Canada
ABSTRACT: Today’s world relies upon critical green technologies that are made of elements with unique properties irreplaceable by other materials. Such elements are classified under strategic materials; examples include rare earth elements that are in increasingly high demand but facing supply uncertainty and near zero recycling. For tackling the sustainability challenges associated with rare earth elements supply, new strategies have been initiated to mine these elements from secondary sources. Waste electrical and electronic equipment contain considerable amounts of rare earth elements; however, the current level of their recycling is less than 1%. Current recycling practices use either pyrometallurgy, which is energy intensive, or hydrometallurgy that rely on large volumes of acids and organic solvents, generating large volumes of environmentally unsafe residues. This study put emphasis on developing an innovative and sustainable process for the urban mining of rare earth elements from waste electrical and electronic equipment, in particular, a nickel metal hydride battery. The developed process relies on supercritical fluid extraction utilizing CO2 as the solvent, which is inert, safe, and abundant. This process is very efficient in the sense that it is safe, runs at low temperature, and does not produce hazardous waste while recovering ∼90% of rare earth elements. Furthermore, we propose a mechanism for the supercritical fluid extraction of rare earth elements, where we considered a trivalent rare earth element state bonded with three tri-n-butyl phosphate molecules and three nitrates model for the extracted rare earth tri-n butyl phosphate complex. The supercritical fluid extraction process has the double advantage of waste valorization without utilizing hazardous reagents, thus minimizing the negative impacts of process tailings.
KEYWORDS: Rare earth elements, Supercritical fluid extraction, Recycling, Urban mining, Waste electrical and electronic equipment, Nickel metal hydride battery
AP-153 – Highly anisotropic nanocellular polymers based on tri-phasic blends of PMMA with two nucleating agents
Victoria Bernardo a,⇑, Judith Martin-de Leon a, Miguel Angel Rodriguez-Perez a,b
a Cellular Materials Laboratory (CellMat), Condensed Matter Physics Department, University of Valladolid, Valladolid, Spain
b Instituto BIOECOUVA, Universidad de Valladolid, Valladolid, Spain
One strategy to produce nanocellular polymers is the use of nucleating species to promote nucleation. Whereas two-phase systems are widely studied, tri-phasic blends with two nucleating agents are uncommonly investigated. In this work, nanocellular polymers are obtained using tri-phasic blends of polymethylmethacrylate (PMMA) with two nucleating agents: needle-like sepiolites and a polymethylmethacrylate-polybutylacrylate-polymethylmethacrylate (MAM) block copolymer. Blends of PMMA with different concentrations of MAM and a fixed amount of sepiolites are produced by extrusion. Results show that at low MAM contents (1 wt%), the nucleation is a combination of the action of the two additives, but the addition of sepiolites induces the appearance of anisotropic structures. Meanwhile, at high MAM concentrations (10 wt%), MAM nanostructuration controls the nucleation and sepiolites increase the anisotropy. The alignment of the MAM micelles and the sepiolites in the extrusion direction promotes coalescence in this direction, leading to highly anisotropic nanocellular structures. Mean cell sizes of 100–300 nm and an average anisotropy ratio of 2.77 are obtained thanks to the combined effect of MAM and sepiolites.
AP-154 – Overcoming the Challenge of Producing Large and Flat Nanocellular Polymers: A Study with PMMA
Judith Martín-de Leon,* Victoria Bernardo, Paula Cimavilla-Román, Saul Perez-
Tamarit, and Miguel Angel Rodríguez-Perez
Although nanocellular polymers are interesting materials with improved properties in comparison with conventional or microcellular polymers, the production of large and flat parts of those materials is still challenging. Herein, gas dissolution foaming process is used to produce large and flat nanocellular polymethylmethacrylate samples. In order to do that, the foaming step is performed in a hot press. The methodology is optimized to produce flat samples with dimensions of 1001006mm3, relative densities in the range 0.25–0.55 and cell sizes around 250 nm. Additionally, foaming parameters are modified to study their influence on the final cellular structure, and the materials produced in this paper are compared with samples produced by using a most conventional approach in which foaming step is conducted in a thermal bath. Results obtained show that an increment in the foaming temperature leads to a reduction in relative density and an increase of cell nucleation density. Moreover, differences in the final cellular structure for materials produced by both foaming routes are studied, proving that although there exist some differences, the mechanisms governing the nucleation and growing are the same in both processes, leading to the production of homogeneous materials with very similar cellular structures.
AP-155 – The influence of cell size on the mechanical properties of nanocellular PMMA
Judith Martín-de Leóna,∗, Frederik Van Loockb, Victoria Bernardoa, Norman A. Fleckb,
Miguel Ángel Rodríguez-Péreza
a Cellular Materials Laboratory (CellMat), Condensed Matter Physics Department, University of Valladolid, Valladolid, Spain
b Engineering Department, University of Cambridge, Trumpington Street, CB2 1PZ, Cambridge, United Kingdom
A B S T R A C T
Solid-state foaming experiments are conducted on three grades of polymethyl methacrylate (PMMA). Nanocellular PMMA foams are manufactured with an average cell size ranging from 20 nm to 84 nm and a relative density between 0.37 and 0.5. For benchmarking purposes, additional microcellular PMMA foams with an average cell size close to 1 μm and relative density close to that of the nanocellular foams are manufactured. Uniaxial compression tests and single edge notch bend tests are conducted on the PMMA foams. The measured Young’s modulus and yield strength of the PMMA foams are independent of cell size whereas the fracture toughness of the PMMA foam increases with decreasing average cell size from the micron range to the nanometer range.
Ap-156 – Transparent nanocellular PMMA: Characterization and modeling of the optical properties
Judith Martín-de Leóna,∗, Jose Luis Purab, Victoria Bernardoa, Miguel Ángel Rodríguez-Péreza
a Cellular Materials Laboratory (CellMat), Condensed Matter Physics Department, Universidad de Valladolid, 47011, Spain
b Gds Optronlab, Condensed Matter Physics Department, Universidad de Valladolid, 47011, Spain
ABSTRACT: In this work, the optical properties of transparent nanocellular polymethylmethacrylate (PMMA) have been studied, experimental and theoretically. Transmittance measurements of samples presenting different cell sizes (14, 24, 39 and 225 nm) and a constant relative density of around 0.45 have been carried out obtaining values as high as 0.94 for the sample with the smaller cell size and a thickness of 0.05 mm. In addition, the light absorption coefficient has been measured as a function of cell size and wavelength. It has been found that the transmittance has a strong dependence with the wavelength, presenting these transparent materials Rayleigh scattering. On the other hand, the transmission of visible light through these nanocellular materials has been modelled for the first time. The developed model reproduces with good accuracy the trends observed in the experimental results and provides remarkable insights into the physics mechanisms controlling the optical behavior of these materials.
AP-157 – Low Density Nanocellular Polymers Based on PMMA Produced by Gas Dissolution Foaming: Fabrication and Cellular Structure Characterization
Judith Martín-de León *, Victoria Bernardo and Miguel Ángel Rodríguez-Pérez
Cellular Laboratory (CellMat), Universidad de Valladolid, Valladolid 47011, Spain; firstname.lastname@example.org (V.B.); email@example.com (M.Á.R.-P.) Correspondence: firstname.lastname@example.org; Tel.: +34-983-184-035
Academic Editor: Michael D. Guiver
Received: 13 May 2016; Accepted: 11 July 2016; Published: 18 July 2016
Abstract: This paper describes the processing conditions needed to produce low density nanocellular
polymers based on polymethylmethacrylate (PMMA) with relative densities between 0.45 and 0.25,
cell sizes between 200 and 250 nm and cell densities higher than 1014 cells/cm3. To produce these
nanocellular polymers, the foaming parameters of the gas dissolution foaming technique using CO2
as blowing agent have been optimized. Taking into account previous works, the amount of CO2
uptake was maintained constant (31% by weight) for all the materials. Foaming parameters were
modified between 40 C and 110 C for the foaming temperature and from 1 to 5 min for the foaming
time. Foaming temperatures in the range of 80 to 100 C and foaming times of 2 min allow for
production of nanocellular polymers with relative densities as low as 0.25. Cellular structure has
been studied in-depth to obtain the processing-cellular structure relationship. In addition, it has
been proved that the glass transition temperature depends on the cellular structure. This effect is
associated with a confinement of the polymer in the cell walls, and is one of the key reasons for the
improved properties of nanocellular polymers.
Keywords: nanocellular polymer; nanocellular foam; gas dissolution foaming; confinement; PMMA
AP-158 – Key Production Parameters to Obtain Transparent Nanocellular PMMA
Judith Martín-de León,* Victoria Bernardo, and Miguel Ángel Rodríguez-Pérez
Transparent nanocellular polymethylmethacrylate (PMMA) with relative density around 0.4 is produced for the first time by using the gas dissolution foaming technique. The processing conditions and the typical characteristics of the cellular structure needed to manufacture this novel material are discovered. It is proved that low saturation temperatures (−32 °C) combined with high saturation pressures (6, 10, 20 MPa) allow increasing the solubility of PMMA up to values not reached before. In particular, the highest CO2 uptake ever reported for PMMA, (i.e., 48 wt%) is found for a saturation pressure of 20 MPa and a saturation temperature of −32 °C. Due to these processing conditions, cell nucleation densities of 1016 nuclei cm−3 and cell sizes clearly below 50 nm are achieved. The nanocellular polymers obtained, with cell sizes ten times smaller than the wavelength of visible light and very homogeneous cellular structures, show a significant transparency.
AP-159 – Two-Stage Depressurization in Gas Dissolution Foaming: The Production of Nanocellular Materials Free of Defects
Judith Martín-de León,* Victoria Bernardo, and Miguel Ángel Rodríguez-Pérez
ABSTRACT: Nanocellular polymethylmethacrylate (PMMA) is produced through a newly proposed method, a two-stage depressurization in the gas dissolution foaming process. This method modifies the depressurization step and allows controlling the pressure during cell growth, avoiding this way, the appearance of micrometric defects in the produced cellular materials. Three grades of PMMA, as well as different production parameters, are tested in order to study their influence on the final materials. Moreover, cellular structures are compared with those obtained with a one-stage depressurization process. Additionally, this work analyzes the foaming mechanisms taking place during the production of nanocellular materials.
AP-160: Transformation under pressure: Discovery of a novel crystalline form of anthelmintic drug Praziquantel using high-pressure supercritical carbon dioxide
Lauren MacEachern a,b, Azadeh Kermanshahi-pour a,*, Mahmoud Mirmehrabi b,*
a Biorefining and Remediation Laboratory, Department of Process Engineering and Applied Science, Dalhousie University, 1360 Barrington Street, Halifax, Nova Scotia B3J 1Z1, Canada
b Solid State Pharma Inc., 1489 Hollis Street, Suite 300, Halifax, Nova Scotia B3J 3M5, Canada
A B S T R A C T
Supercritical carbon dioxide (CO2) has been used as a processing technique to control polymorphism of pharmaceuticals. However, there are fewer reports of novel polymorphs being discovered by supercritical CO2 processing. As supercritical crystallization methods gain attention for potential in pharmaceutical processing, they may become a critical screening tool for discovery of new polymorphs. In this work, a case study is presented for a novel crystalline form of the anthelmintic drug, Praziquantel, found through supercritical CO2 processing. The novel form of Praziquantel was characterized by chromatography, nuclear magnetic resonance and infrared spectroscopy, X-ray powder diffraction, thermal analysis, and scanning electron microscopy. Furthermore, the novel form exhibited 13–20% improved solubility compared to commercial Form A between pH 1.6 and 7.5 and was physically stable under stressed conditions (40 ◦C and 75% relative humidity) for 7.5 weeks. Overall, this work showed that supercritical CO2 processing is a valuable tool to screen for novel, and possibly viable polymorphs of pharmaceutical compounds with improved properties.