A reinvestigation of the phase diagrams relative to some conjugated and non-conjugated bile salts in water has demonstrated the formation of lyotropic liquid crystalline phases, in contradiction with generally accepted statements. The phase behaviour is complex and the phase diagrams are unusual, compared to most surfactants and lipids. In particular, coexistence of liquid crystalline phases with crystals has been observed. The formation of liquid crystalline phases requires very long equilibration times and the thermal stability of the lyotropic phases is moderate. The observed structure is tentatively assumed to be of the reverse hexagonal type. Structural relations with currently accepted models for the organisation of bile salts into micelles and solid form have been found.
Conditional stability constants of coordination complexes comprising divalent transition metals, Cu2+, Ni2+, Zn2+, Co2+, and ethylenediaminetetraacetic acid (EDTA) were determined utilizing electrospray ionization mass spectrometry. The deviation of signal response of a reference complex was monitored at addition of a second metal ion. The conditional stability constant for the competing metal was then determined through solution equilibria equations. The method showed to be applicable to a system where Co2+ and Zn2+ competed for EDTA at pH 5. When Cu2+ and Ni2+ competed for EDTA, the equilibrium changed over time. This change was shown to be affected in rate and size by the type of organic solvent added. In this work, 30% of either methanol or acetonitrile was used. It was found that if calibration curves are prepared for both metal complexes in solution and the measurements are repeated with sufficient time space, any change in equilibrium of sample solutions will be discovered. Copyright © 2014 John Wiley & Sons, Ltd. Copyright © 2014 John Wiley & Sons, Ltd.
In this study, we present the binary phase diagrams for the aqueous systems of the alkyldecanoic salts racemic sodium 2-methyldecanoate and sodium (R)-2-methyldecanoate, respectively. Both systems form a micellar solution phase, as well as a normal hexagonal, a cubic, and a lamellar liquid crystalline phase. They also form a very narrow intermediate phase, situated between the hexagonal and cubic liquid crystalline phases. The methods used for characterization were crossed polaroids, polarizing optical microscope and 2H NMR quadrupolar splittings combined with SAXS studies. The cubic phase gave a well-resolved SAXS diffraction pattern, with eight peaks present, which establishes the bicontinuous cubic structure as Ia3d. A significant difference in these two phase diagrams, compared to those of unsubstituted alkanoates with the same chain length, is the very low Krafft boundary.
In this work, we continue our study of methyl -substituted surfactants and present the aqueous binary phase diagrams of racemic sodium 2-methyloctanoate, -nonanoate, and -dodecanoate, respectively. All systems have very low Krafft temperatures within the solution phase, between 1 and 4 degreesC. The phase sequences of the two shorter surfactants are very similar to those of the unsubstituted sodium octanoate, although with somewhat different range of existence for the phases formed. The sodium 2-methyldodecanoate system is different from the unsubstituted sodium dodecanoate system, as the former seems to lack a hexagonal phase. The surfactant systems were delineated using H-2 NMR splittings and crossed polarizers, and combined with SAXS for determination of phase structure.
The phase behavior over the entire concentration range for the system didodecyldimethylammonium bromide (DDAB)-sodium taurodeoxycholate (STDC)-water, at 25 degrees C, has been investigated, with emphasis on the DDAB-rich part. Polarizing microscopy, SAXS, H-2 NMR and H-1 self-diffusion NMR have been used in combination as probing techniques for phase behavior and microstructure. The system forms four major phases, all deriving from the respective binary surfactant systems. The two lamellar phases originating from the binary DDAB-water axis (D-I and D-II, at 3-30 and 83-91 wt.% DDAB, respectively) are only able to incorporate small amounts of STDC. The D-II phase solubilizes a comparatively higher amount of bile salt (up to ca. 6 wt.%), while the D, phase takes up less than 0.25 wt.%. From the STDC-water axis, a solution phase and a "hexagonal-like" liquid crystalline phase are derived, at 0-26 and 37-60 wt.% of STDC, respectively. Heterogeneous regions are also indicated on the basis of NMR and SAXS data. The most striking feature is the large extension of the isotropic solution phase, which originates from the water corner and curves toward the DDAB-rich side of the phase diagram. Even though at the upper limit of the solution phase the amount of water is reduced to 10 wt.%, the measured water and DDAB self-diffusion coefficients exclude the possibility of reverse-type structures.
Competition between mono- and divalent ions in the association of counterions to the headgroups of amphiphiles was studied in one surfactant system with organic counterions (piperidine+/piperazine2+octanesulfonate) and one with inorganic counterions (Na+/Ca2+octyl sulfate). By conductivity and13C NMR chemical shift measurements the critical micelle concentration (CMC) was found to decrease drastically when small amounts of divalent counterions were present in the system. Self-diffusion coefficients of surfactant ions and organic counterions were measured in the micellar phase by the Fourier transform pulsed-gradient spin-echo (FT-PGSE) NMR method. The degree of counterion binding in the micellar system with piperidine+/piperazine2+counterions was obtained from FT-PGSE NMR measurements. It was observed that the divalent counterions were more strongly bound than the monovalent counterions. The experimental results were compared with theoretical Poisson–Boltzmann calculations. The cell model was used to study the electrostatic effects. Good agreement between electrostatic theory and experiment was observed; however, an attractive force exists between the monovalent piperidine counterions and the micelle, probably because of hydrophobic interactions.
Aqueous sodium hydroxide solutions are extensively used as solvents for lignin in kraft pulping. These are also appealing systems for cellulose dissolution due to their inexpensiveness, ease to recycle and low toxicity. Cellulose dissolution occurs in a narrow concentration region and at low temperatures. Dissolution is often incomplete but additives, such as zinc oxide or urea, have been found to significantly improve cellulose dissolution. In this work, lignin was explored as a possible beneficial additive for cellulose dissolution. Lignin was found to improve cellulose dissolution in cold alkali, extending the NaOH concentration range to lower values. The regenerated cellulose material from the NaOH-lignin solvents was found to have a lower crystallinity and crystallite size than the samples prepared in the neat NaOH and NaOH-urea solvents. Beneficial lignin-cellulose interactions in solution state appear to be preserved under coagulation and regeneration, reducing the tendency of crystallization of cellulose.
Emulsion stabilization by native cellulose has been mainly hampered because of its insolubility in water. Chemical modification is normally needed to obtain water-soluble cellulose derivatives. These modified celluloses have been widely used for a range of applications by the food, cosmetic, pharmaceutic, paint and construction industries. In most cases, the modified celluloses are used as rheology modifiers (thickeners) or as emulsifying agents. In the last decade, the structural features of cellulose have been revisited, with particular focus on its structural anisotropy (amphiphilicity) and the molecular interactions leading to its resistance to dissolution. The amphiphilic behavior of native cellulose is evidenced by its capacity to adsorb at the interface between oil and aqueous solvent solutions, thus being capable of stabilizing emulsions. In this overview, the fundamentals of emulsion formation and stabilization by biomolecules are briefly revisited before different aspects around the emerging role of cellulose as emulsion stabilizer are addressed in detail. Particular focus is given to systems stabilized by native cellulose, either molecularly-dissolved or not (Pickering-like effect).
With amphiphilic properties, cellulose molecules are expected to adsorb at the O/W interface and be capable of stabilizing emulsions. The effect of solvent quality on the formation and stability of cellulose-based O/W emulsions was evaluated in different alkaline systems: NaOH, NaOH-urea and tetrabutylammonium hydroxide (TBAH). The optimal solvency conditions for cellulose adsorption at the O/W interface were found for the alkaline solvent with an intermediate polarity (NaOH-urea), which is in line with the favorable conditions for adsorption of an amphiphilic polymer. A very good solvency (in TBAH) and the interfacial activity of the cation lead to lack of stability because of low cellulose adsorption. However, to achieve long-term stability and prevent oil separation in NaOH-urea systems, further reduction in cellulose's solvency was needed, which was achieved by a change in the pH of the emulsions, inducing the regeneration of cellulose at the surface of the oil droplets (in-situ regeneration).
Some aspects of the interfacial behavior of cellulose dissolved in an aqueous solvent were investigated. Cellulose was found to significantly decrease the interfacial tension (IFT) between paraffin oil and 85 wt% phosphoric acid aqueous solutions. This decrease was similar in magnitude to that displayed by non-ionic cellulose derivatives. Cellulose's interfacial activity indicated a significant amphiphilic character and that the interfacial activity of cellulose derivatives is not only related to the derivatization but inherent in the cellulose backbone. This finding suggests that cellulose would have the ability of stabilizing dispersions, like oil-in-water emulsions in a similar way as a large number of cellulose derivatives. In its molecularly dissolved state, cellulose proved to be able to stabilize emulsions of paraffin in the polar solvent on a short-term. However, long-term stability against drop-coalescence was possible to achieve by a slight change in the amphiphilicity of cellulose, effected by a slight increase in pH. These emulsions exhibited excellent stability against coalescence/oiling-off over a period of one year. Ageing of the cellulose solution before emulsification (resulting in molecular weight reduction) was found to favour the creation of smaller droplets.
Cellulose laminates represent a remarkable convergence of natural materials and modern engineering, offering a wide range of versatile applications in sustainable packaging, construction, and advanced materials. In this study, novel all-cellulose laminates are developed using an environmentally friendly approach, where freshly regenerated cellulose II films are stacked without the need for solvents (for impregnation and/or partial dissolution), chemical modifications, or resins. The structural and mechanical properties of these all-cellulose laminates were thoroughly investigated. This simple and scalable procedure results in transparent laminates with exceptional mechanical properties comparable to or even superior to common plastics, with E-modulus higher than 9 GPa for a single layer and 7 GPa for the laminates. These laminates are malleable and can be easily patterned. Depending on the number of layers, they can be thin and flexible (with just one layer) or thick and rigid (with three layers). Laminates were also doped with 10 wt% undissolved fibers without compromising their characteristics. These innovative all-cellulose laminates present a robust, eco-friendly alternative to traditional synthetic materials, thus bridging the gap between environmental responsibility and high-performance functionality.
In this study, lightweight biobased foamed materials were successfully synthesized by the modification of renewable polysaccharides, such as starch and microcrystalline cellulose. Low-cost and nontoxic organic acids were utilized as catalysts in the first-step esterification reaction of the synthesis. The effects of different reaction conditions on the water absorbency and weight loss of freeze-casted polysaccharide–citrate–chitosan foams are discussed. Physical properties, such as pore-size distributions and compressive stress–strain curves, of the foams were determined. The characterization results show that the amide bonds formed between the carboxylic acid groups of polysaccharide–citrate and the amino groups of chitosan are crucial to the foamed material’s performance.
The isothermal ternary phase diagram for the 1-dodecylpyridinium bromide/dodecane/water system was determined at 40°C by 2H NMR and polarizing microscopy methods. Two liquid crystalline phases, a large cubic area and a normal hexagonal phase, and one isotropic normal micellar solution phase were characterized, and their ranges of existence were determined. The micelles were found to be probably small and spherical at lower concentrations of surfactant, and were found to grow at higher concentrations and on addition of oil. The two-phase areas, L1 + H1 and H1 + I, are both very narrow. The comparatively large cubic area, containing 43-63 wt% surfactant and 3-10 wt% dodecane, is probably consistent of more than one structure. SAXS experiments indicate two different structures built of discrete micellar aggregates.
The isothermal ternary phase diagram for the 1-dodecylpyridinium bromide (1-DPB)–water–dodecanol system was determined at 40°C, using2H NMR, polarizing microscopy, and SAXS methods. All of the phases were characterized, and their ranges of existence were determined. The surfactant is easy to dissolve in water, yielding a normal micellar solution phase. After the normal micellar phase, on the binary surfactant–water axis, a normal hexagonal liquid crystalline phase is found at higher surfactant concentrations. On addition of dodecanol, four more phases are formed, i.e. a cubic, a lamellar, and a reverse hexagonal phase, followed by a reverse micellar solution phase. The lamellar liquid crystalline phase dominates the ternary phase diagram. The structures of the liquid crystalline phases were further examined using SAXS measurements, and the results are discussed in terms of the critical packing parameter, cpp, and electrostatic forces. The SAXS experiments show a pronounced swelling of the rods in the hexagonal phase, from 28.5 to 33 Å on addition of dodecanol, whereas the cylindrical aqueous core of the reverse hexagonal phase has a diameter of 18–21 Å, depending on sample composition. The average bilayer thickness of the lamellar phase is about 24 Å.
The binary phase equilibria for the system sodium taurodeoxycholate-water have been studied. The system forms a liquid crystalline phase in addition to the previously known isotropic solution phase at 22 °C. 2H (water) NMR quadrupole splitting, SAXS data in combination with the polarizing microscopic texture observed for the liquid crystal indicate that the liquid crystalline phase consists of a hexagonal-type aggregate structure. A metastable liquid crystal, probably with lamellar-type structure, also appears to exist prior to the formation of the stable hexagonal phase. A micellar growth is measured with the NMR self-diffusion method for the isotropic solution phase. Electrical conductance experiments are used to determine the liquid crystal-solution thermal transition.
The phase behavior and phase structure of catanionic surfactant mixtures of DoTAC (dodecyltrimethylammonium chloride) and SN (sodium nonanoate) with water are studied by combined 2H NMR, SAXS, and microscopy techniques at 40 °C. The system forms a large isotropic micellar solution phase with excess water. As the concentration of total surfactant is increased, the solution phase coexists with different liquid crystalline phasesa lamellar phase at equimolar ratio of the two surfactants and hexagonal phases with excess DoTAC and excess SN. The lamellar and hexagonal liquid crystalline phases formed by the binary DoTAC system extensively swell with water on adding the anionic surfactant, and the swelling is more dramatic for the lamellar phase which extends to an equimolar ratio of the two surfactants. The mesophase of the short alkyl chain is incapable of solubilizing any substantial amounts of the long chain DoTAC molecules. SAXS data shows a decrease in bilayer thickness and an unchanged average area per polar group on adding SN into the lamellar phase. For the DoTAC-rich hexagonal phase, the diameter of the cylinder remains unchanged and the average area per polar headgroup is decreased in catanionic mixtures. The 2H NMR quadrupolar splitting values in the hexagonal liquid crystalline phase indicate that the polar headgroups are less extensively hydrated in catanionic mixtures compared to the hydration of the headgroups in the single surfactant systems. The 2H splitting value in the lamellar phase first decreases, going through a zero splitting value, and then the splitting increases again on a continuous decreasing of the total surfactant concentrations. Alkyl chain asymmetry is found to play a dominant role in the formation and stability of aggregates in catanionic surfactant mixtures.
We report a facile in situ synthesis of spherical copper nanoparticles (NPs) templated by a gelled cellulose II matrix under alkaline aqueous reaction conditions. In under 20 min, the hybrid material could be obtained in a one-pot reaction. Field-emission scanning electron microscopy (FE-SEM) revealed that the polycrystalline NPs of 200–500 nm were well distributed in the regenerated cellulose matrix. The average Cu crystallite size was of the order of 20 nm, as estimated from both X-ray diffraction (XRD) and FE-SEM. XRD data also indicated that the composite contained up to approximately 20% Cu2O. In suspensions containing the hybrid material, growth of Escerichia coli and Staphylococcus aureus strains was inhibited by 80% and 95%, respectively, after 72 h. The synthesis procedure offers a general approach to designing various low-cost hybrid materials of almost any shape, and the concept could be extended to utilization areas such as catalysis, functional textiles, and food packaging as well as to electronic applications.
BACKGROUND
The electrochemical recovery of copper from DTPA and C12-DTPA (a surface-active derivative of DTPA) complex solutions was investigated in a membrane flow cell. Electrolysis time, solution flow rate, applied current density, and solution pH were evaluated.
RESULTS
The chelating surfactant C12-DTPA can promote the kinetics of copper electrodeposition more than DTPA depending on the experimental conditions. At a current density of 30 A m–2, a solution flow rate of 0.6 L min–1, and pH 10 after 180 min treatment, the copper recovery and current efficiency were 50% and 43.3%, respectively, in the Cu(II)-DTPA system and about 65% and 53.6%, respectively, in the Cu(II)-C12-DTPA system. The differences in the amount of recovery could be explained in terms of differences in the diffusion of copper complexes with DTPA and C12-DTPA to the cathode, as well as their solution behavior and pH-dependent conditional stability constants (log10 K’CuDTPA3-).
CONCLUSION
Electrochemical methods could be effectively combined with foam flotation for the chelating surfactant C12-DTPA, to recover copper and C12-DTPA. This makes the overall treatment more sustainable, and can be helpful in complying with the increasingly stringent environmental regulations
The electrochemical recovery of copper and chelating agent from their complex solution using a membrane flow cell was investigated. The parameters electrolysis time, solution pH, current density, and temperature were investigated.
Electrochemical investigation indicated that chelating ligands can be recovered by the electrodeposition of copper ions on the cathode. For copper and EDTA recovery, the results indicated that recovery efficiency was affected by time, current density, and temperature. The recovery process was not influenced by pH in the range studied (pH 8–12), which can be explained by the low variation in the conditional stability constant, i.e. Δlog10 K' ≤ 0.7, over the pH range. However, when NTA, EDTA, and DTPA were compared, the results indicated that the recovery efficiency decreased as the conditional stability constant of the chelating agent–Cu(II) complex increased. The maximum current efficiency of copper and EDTA recovery after 5 h of treatment was approximately 85%, whereas the recovery was 80% of the initial concentration (0.05 mol L−1) at a current density of 1 A dm−2, temperature of 333 K, and pH of 10.
Relatively high recovery efficiency makes the process fairly sustainable and hinders the discharge of copper ions and chelating ligands as pollutants into the environment.
Polymeric multilayers capsules constructed using the layer-by-layer (LbL) technique are interesting candidates for the purposes of storage, encapsulation and release in a wide range of biomedical applications. In the current study, cellulose-based nanocapsules were produced via the LbL technique. In this procedure, alternating deposition of the two biocompatible polymers anionic cellulose, carboxymethylcellulose (CMC), and cationic cellulose, quaternized hydroxyethylcellulose ethoxylate (QHECE), on a cationic vesicular template made of didodecyldimethylammonium bromide (DDAB), was performed. The obtained nanocapsules, were characterized by dynamic light scattering (DLS), ⇣ potential measurements, and field-emission scanning electron microscopy (FE-SEM). DLS measurements revealed that the size of the spheres is about hundreds of nanometer with polydispersity index (PDI) values between 0.2 and 0.3, indicating a relatively homogeneous size distribution. In addition, FESEM characterization also indicated the shape and size of obtained material. The surface charge analysis of the nanocapsules by ⇣ potential measurements indicated the presence of electrostatically stabilized nanoparticles. The values of diameter, PDI and surface charge for cationic vesicles coated by CMC were 204 nm, 0.26 and –38 mV, respectively. After deposition of QHECE, the diameter, PDI, and surface charge were about 265 nm, 0.36 and +32.5 mV, respectively. Figure 1 shows FE-SEM images of cellulose nanoparticles fabricated via LbL deposition of polyelectrolyte layers. As seen in the microscopy images, the shape of the core-shell particles are not fully spherical which could be due to drying e↵ects of the sample before FE-SEM characterization. The construction of cellulose nanocontainers by using an alternating deposition of oppositely charged biobased polyelectrolytes on vesicles o↵ers several advantages such as simplicity, reproducibility, biocompatibility, low-cost, mild reaction conditions, and high controllability over the thickness and composition of the shell.
In this study, Cu and Cu2O nanoparticles (NPs) were synthesized through chemical reduction of soluble copper-chelating ligand complexes using formaldehyde as a reducing agent. The influence of various chelating ligands, such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and a surface-active derivative of DTPA (C12-DTPA), as well as surfactants (i.e., hexadecyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium chloride (DoTAC), sodium dodecyl sulfate (SDS), and dimethyldodecylamine-N-oxide (DDAO)), on morphology and the composition of produced NPs was investigated. In the absence of surfactants, spherical copper particles with polycrystalline structure could be obtained. X-ray diffraction (XRD) analysis revealed that, in the presence of EDTA, the synthesized NPs are mainly composed of Cu with a crystallite size on the order of 35 nm, while with DTPA and C12-DTPA, Cu2O is also present in the NPs as a minority phase. The addition of ionic surfactants to the copper–EDTA complex solution before reduction resulted in smaller spherical particles, mainly composed of Cu. However, when DDAO was added, pure Cu2O nano-octahedrons were formed, as verified by high-resolution scanning electron microscopy (HR-SEM) and XRD. Furthermore, a hybrid material could be successfully prepared by mixing the octahedral Cu2O NPs with cellulose dissolved in a LiOH/urea solvent system, followed by spin-coating on silica wafers. It is expected that this simple and scalable route to prepare hybrid materials could be applied to a variety of possible applications.
Chelating agents, molecules that very strongly coordinates certain metal ions, are used industrially as well as in consumer products to minimize disturbances and increase performance of reactions and applications. The widely used sequestering agents, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) belong to this branch of readily water-soluble compounds. When these chemical structures also have hydrophobic parts, they are prone to adsorb at air-water interfaces and to self-assemble. Such bifunctional molecules can be called chelating surfactants and will have more extended utilization prospects than common chelating agents or ordinary ionic surfactants. The present review attempts to highlight the fundamental behavior of chelating surfactants in solution and at interfaces, and their very specific interactions with metal ions. Methods to recover chelating surfactants from metal chelates are also described. Moreover, utilization of chelating surfactants in applications for metal removal in environmental engineering and mineral processing, as well as for metal control in the fields of biology, chemistry and physics, is exemplified and discussed.
Ion flotation was studied for the removal of cadmium, zinc, and strontium ions from aqueous solutions at pH 5–9 in a customized flotation cell, using an aminopolycarboxylic chelating surfactant, 2-dodecyldiethylenetriamine pentaacetic acid (C12-DTPA) in combination with two foaming agents: dodecyltrimethylammonium chloride (DoTAC) and dimethyldodecylamine-N-oxide (DDAO). The results from experiments showed that both Zn2+ and Cd2+ could be removed via ion flotation to 100% at pH 5, and Sr2+ could be removed via ion flotation to 60%–70% at pH 7–9. The removal of metal ions from the flotation cell was seen to vary with pH, but this was not exclusively related to the magnitudes of the formed metal ion-chelating surfactant conditional stability constants. The removal was also dependent on the foam properties of the samples that were found to vary over the investigated pH interval. The outcome of the investigation points to the chelating surfactant C12-DTPA having excellent chelating properties for all of the studied ions above pH 7. In combination with correctly chosen foaming agents, the optimized surfactant system could be expected to provide very efficient remediation of waters polluted with metal ions via ion flotation.
The spreading of single styrene-acrylic latex particles on silicon oxide surfaces was studied using atomic force microscopy (AFM). Three latexes with different glass transition temperature (Tg) were used and the effects of temperature, time and preparation method were investigated. Particle sizes and shape were measured with AFM and the contact angles were calculated. The observed rate for the spreading of latex particles was low and it took several days before the particles reached steady state, even at temperatures well above their Tg. The experimental particle spreading results deviated with two orders of magnitude from predictions using the WLF equation for polymer diffusion. The deviation could be attributed to polymer-surface interactions that slowed down the particle spreading. The work of adhesion was calculated using two models. The results from using the regular Young-Dupré equation and a modified version of this equation that also included the mechanical properties (E-modulus and Poisson�s ratio) of the latexes, were compared. For soft latex particles the results from the two models agreed well and were of the order of 75 J/m2, but for glassy latexes the Young-Dupré equation underestimated the work of adhesion.
In this study, the effect of different alcohols and esters as a coagulation medium in the regeneration of cellulose dissolved in an aqueous LiOH-urea-based solvent was thoroughly investigated using various methods such as solid state NMR, X-ray diffraction, water contact angle, oxygen gas permeability, mechanical testing, and scanning electron microscopy. It was observed that several material properties of the regenerated cellulose films follow trends that correlate to the degree of cellulose II crystallinity, which is determined to be set by the miscibility of the coagulant medium (nonsolvent) and the aqueous alkali cellulose solvent rather than the nonsolvents’ polarity. This article provides an insight, thus creating a possibility to carefully tune and control the cellulose material properties when tailor-made for different applications.
Rice straw, a waste agriculture material grown and harvested in Willows, CA, was used,is a raw material in the production of thin medium- and high-density fiberboards (MDFs and HDFs). The rice straw was cleaned, size-reduced, and soaked in water before being refined. Defibration was performed in it pressurized pilot-plant single-disk refiner, OHP 20". The fiber production capacity reached a level of 63 kg/h. and the proper fiber quality for MDF/HDF production was established. Analysis of the produced fiber showed an average fiber length of approximately 0.9 mm, in average fiber width of 31 mu m, a shive weight of below 24%, and a dust content of less than 30%. Production of fiberboards was performed by addition of 3%, 4%, and 5% methylene diphenyl diisocyanate (MDI). The flexural properties, internal bond strength, and thickness swelling of the produced fiberboards were evaluated according to ASTM methods. The finished fiberboards based on rice straw and MDI resin showed excellent properties. The internal bond (IB) reached levels of 2.6 MPa, and the modulus of rupture (MOR) and modulus of elasticity (MOE) showed levels comparable to those of wood-based fiberboards and were acceptable according to the requirements or medium-density fiberboard (MDF) for interior applications (American National Standards Institute, ANSI A208.2-2002). The water-repelling properties of the 3-min rice-straw fiberboards were encouraging; the thickness swelling, (TS) was in the range of 15-30%. Two different methods to avoid adhesion between the press plates and the resinated fiber material during hot pressing were investigated: protective paper sheets were placed between the fiber mat and press plates, or a press-release agent was sprayed oil steel plates that were then placed ill the press before pressing Satisfactory results were obtained with both methods, and no adhesion was observed between the fiberboard and the steel plates. The method of using press-release agent during pressing had no notable negative effects oil the fiberboard properties.
Wheat straw was used as raw material in the production of fibreboards. The size-reduced straw was pretreated with steam, hot water and sulphuric acid before the defibration process to loosen its physical structure and reduce the pH. No synthetic binder was added. Adhesive bonding between fibres was initiated by activation of the fibre surfaces by an oxidative treatment during the defibration process. Fenton’s reagent (ferrous chloride and hydrogen peroxide) was added. Two different levels of hydrogen peroxide (H2O2), 2.5% or 4.0% were used. The resulting fibres were characterized in terms of fibre length distribution, shive content, pH and pH-buffering capacity. The properties of finished fibreboards were compared with medium-density fibreboard (MDF) with density above 800 kg/m3 produced from straw and melamine modified UF resin. The modulus of rupture (MOR), modulus of elasticity (MOE) and internal bond (IB) were lower than those of conventional manufactured wheat straw fibreboards but close to the requirements of the MDF standard (EN 622-5: 2006). The water absorption properties for the H2O2 activated straw fibreboards were relatively high, but were reduced by 25% with the addition of CaCl2 into the defibrator system as a water-repelling agent. Increased levels of hydrogen peroxide improved the mechanical and physical properties of the straw fibreboard.
Wheat straw was investigated as a raw material for manufacturing of medium density fibreboard (MDF) in a fully equipped pilot-plant. Commercial urea melamine formaldehyde (UMF) and a mixture of UMF-resin and urea melamine phenol formaldehyde (UMPF) adhesives were used as binders in manufacturing of high performance MDF. The study evaluated the quality of MDF produced of straw (i.e., SMDF). Different qualities of wheat straw and different resin contents (14–17%) were used. Moreover, the SMDF was produced at different thicknesses of 9 and 16 mm and densities of 750–1000 kg/m3. The properties of the resulting SMDF were evaluated by analysing mechanical and water absorption (anti-swelling) properties as a function of density. Internal bond (IB), modulus of rupture (MOR), modulus of elasticity (MOE), thickness swelling (TS), and water absorption (WABS) were the properties analysed. SMDF-panels produced with densities above 780 kg/m3 and resin contents above 14% met the requirements for wood-based MDF standard EN 622-5:1997.
Wheat straw was used to produce medium-density fiberboard (MDF). The chemical and physical characteristics of fractionated size-reduced wheat straw were investigated. The pH, pH-buffering capacity, ash, and silicon content increased as wheat straw particle size decreased. Ash of the finest straw, <0.2 mm, had high ash (15%) and silicon (18%) contents. The outer and inner parts of size-reduced straw were analyzed using scanning electron microscopy (SEM). The SEM micrographs revealed a complex ultrastructure containing a notable portion of thin-walled cells approximately 1 mu m thick. Pressurized defibration of size-reduced wheat straw produced lignocellulosic fibers nearly 1.0 mm long combined with approximately 24% of small particles and dust. The high water uptake of straw-based MDF was significantly reduced using melamine-modified urea-formaldehyde (UF) resin and removing wheat straw particles and dust by screening. UF resin was added at levels of 12.5%, 13.1%, and 14%. In terms of water resistance, 12-mm-thick straw MDF displayed thickness swelling below 10%, acceptable according to the EN 622-5 MDF standards. It was concluded that manufacturing wheat straw MDF entails straw size reduction (hammer-milling), removing small particles and dust, and adding melamine-modified UF resin to attain necessary MDF quality standards.
Production of fiber composite materials such as Medium Density Fiberboard (MDF) and particleboard (PB) is in general based on wood as a raw material. However, cereal straws and other annual agriculture waste materials have regained an interest as a potential raw material for production of MDF. The cereal straws are among the most common lignocellulosic materials that are easily accessible, non-expensive and renewable. The aim of this investigation was to produce high performance MDF based on wheat straw and urea formaldehyde (UF) resin. The usage of UF-resin for wheat straw MDF-panels has so far resulted in acceptable strength properties but poor moisture resistance and thickness swelling (TS). Application of melamine modified UF-resin for wood based MDF has improved the moisture resistance of produced MDF panels. In this investigation two commercial melamine modified UF-resins were used as binders (adhesives) in the production of wheat straw MDF. Hammer milled wheat straw was treated with water and sulfuric acid (0.6 %) before refining. The reason was to improve the curing, conditions of the UF-resins by a reduction of the pH and the pH-buffering capacity of refined wheat straw fiber. Refining of wheat straw was performed at slightly lower pressure and retention time compared with refining of wood material. However, a lot of fines and dust (wheat straw fibers < 0.5 mm) were generated during refining. A hi-h resin content of the melamine modified UF-resin was necessary (15 %) to compensate for the high ratio of wheat straw fines and dust. Final panel properties of wheat straw MDF could meet the requirements of the MDF standard (EN 622-5:1997), including the TS. Strength properties as internal bond (IB) and modulus of rupture (MOR) were increased as a function of density. Thickness swelling was reduced as a function of density. The usage of wheat straw as a raw material in combination with a melamine modified UF-resin, as an adhesive, is a possible route for manufacturing of high performance Medium Density Fiberboard.
Wheat straw was used as raw material in production of medium density fibreboard (MDF) and high-density fibreboard (HDF). The straw fibreboard process was performed without addition of synthetic binders. Adhesive bonding between fibers was initiated by activation of the fibre surfaces by an oxidative pre-treatment in the defibration process. Hydrogen peroxide was added into the blowline to get a fast and effective process. Adhesive bonding between the activated fibres were later formed when pressing. The fiber quality and pH and pH buffering capacity was analysed at different hydrogen peroxide loadings. The effects of mechanical and physical properties of the non-resin wheat straw MDF/HDF were evaluated. Mechanical bending properties, Modulus of Rupture (MOR), Modulus of Elasticity (MOE), and Internal Bond (IB) were generally lower than conventional wood-based MDF/HDF but close to the requirements of the MDF-standard. Modulus of Elongation (MOE) was surprisingly high and exceeded the levels in the MDF-standard. Moreover, the thickness swelling of the non-resin wheat straw MDF was high but was reduced by the addition of a hydrophobic agent (metallic ion). Increased level of hydrogen peroxide improved the panel properties and the usage of the hydrophobic agent reduced the thickness swelling.
Wheat straw waste materials were processed in a fully equipped pilot-scale MDF-process. Hammermilled wheat straw was used as a raw material in combination with a commercial melamine modified Urea Formaldehyde (UF) resin. Approximately 15 wt % of the wheat straw particles smaller than 0.7 mm was removed in a sifting operation. Medium density fiberboard was produced in the range of 790 to 860 kg/m3 average densities and at a resin content of 12.5, 13.1 and 14 wt %. The panels produced were approved according to the European Standard for MDF (EN 622-5:1997). Four different wheat straw fractions were investigated and sifted at 1.0 mm, 0.6 mm and 0.2 mm screen hole diameter, including the fine particles less than 0.2 mm. The ash content of the four wheat straw fractions varied between 7 wt % and 15 wt %. The maximum level of ash (15 wt %) was observed for the finest particle fraction based on materials less than 0.2 mm. The silicone (Si) content in corresponding ash samples of the sifted wheat straw was analysed by Energy Dispersive X-ray analysis, EDX. The silicone content increased from 18 % to 24 % at a reduced particle size. Moreover, the pH-buffering capacity of the four wheat straw fractions was reduced as the particle size of the specific fractions was increased.
The micellisation in binary mixed surfactant systems of a chelating surfactant and a foaming agent has been studied by surface tension measurements in order to calculate the interaction parameter (beta). 2-dodecyldiethylenetriamine pentaacetic acid, 4-C(12)-DTPA, is an amphoteric chelating surfactant applicable for removing disturbing metal ions from industrial processes, or for heavy metal decontamination of soil or leachate. 4-C(12)-DTPA contains multiple donor atoms and forms very stable coordination complexes with metal ions. The metal complexes can easily be recovered from water by flotation, if the foaming is enhanced by a foaming agent with strong interactions to the chelating surfactant. Two foaming agents were examined, one cationic and one anionic. As expected, strong interactions were found between the negatively charged 4-C(12)-DTPA and the cationic dodecyltrimethylammonium chloride, DTAC. The influence of metal ion chelation, as well as pH, on the interaction parameter was also investigated.
In this investigation a new type of recoverable complexing agent (chelating surfactant) has been compared with a conventional complexing agent; diethylenetriamine pentaacetic acid (DTPA), in the metal ion sequestering of thermomechanical pulps (TMP) to be hydrogen peroxide bleached. After different degrees of washing of the pulps, bleaching experiments at different total alkali charges were performed with and without sodium silicate additions, and the ISO brightness of hand-made sheets was measured. The residual hydrogen peroxide in the bleaching liquor was also determined. No significant difference in either the brightness development or the residual hydrogen peroxide content could be detected between the pulps treated with equivalent molar ratios of the different complexing agents. Furthermore, the recovery of the chelating surfactant-manganese complexes from laboratory made white water by froth flotation was also studied. Two different foaming agents; sodium dodecyl sulphonate (SDS) and dimethyldodecylamine oxide (DDAO), were tested in the froth generation. After an addition of 160 ppm of DDAO, more than 80% of the manganese chelates could be recovered in the foam, containing 3% of the initial water mass.
In this investigation a new type of recoverable complexing agent (chelating surfactant) has been compared with a conventional complexing agent (DTPA) in the metal ion management of thermomechanical pulps (TMP) to be hydrogen peroxide bleached. After different degrees of washing of the pulps, bleaching experiments at different total alkali charges were performed with and without sodium silicate additions, and the ISO brightness of hand-made sheets was measured. The residual hydrogen peroxide in the bleaching liquor was also determined. No significant difference in either the brightness development or the residual hydrogen peroxide content could be detected between the pulps treated with equivalent molar ratios of the different complexing agents. Furthermore, the recovery of the surfactant-manganese complexes from laboratory made white water by foam flotation was also studied. Two different foaming agents, SDS and DDAO, were tested. After an addition of 160 ppm of the latter surfactant, about 80% of the manganese chelates could be recovered in the foam, containing 3% of the initial water mass.