Synthesis and characterization of kraft lignin-based epoxy resins

Epoxidization is an interesting way to develop a new application of lignin and therefore to improve its application potential. In this work, kraft lignin-based epoxy resins were obtained by the epoxidization reaction, using the kraft lignin recovered directly from pulping liquor and modified by a methylolation reaction. The methylolated lignins were obtained by the reaction of original kraft lignin with formaldehyde and glyoxal, which is a less volatile and less toxic aldehyde. 1H-NMR spectroscopy showed that methylolated kraft lignin has more hydroxymethyl groups than glyoxalated kraft lignin. For the epoxidization reaction we studied the influence of the lignin:NaOH (w/w) ratio, temperature, and time of the reaction on the properties of the prepared epoxidized lignins. The structures of lignin-based epoxy resins were followed by epoxy index test and FTIR spectroscopy. Optimal conditions were obtained for lignin-based epoxy resin produced at lignin/NaOH = 1/3 at 70 ºC for 3h. Thermogravimetry analysis (TGA) revealed that the epoxidization enhances the thermal stability of lignins and may allow a wider temperature range for applications with lignin epoxy-PF blends

Characterization of alkaline lignins for use in penol-formaldehyde and epoxy resins

Besides polyurethanes and polyesters, phenolic and epoxy resins are the most prominent applications for technical lignins in thermosetting materials. To evaluate the potential application of lignin raw materials in phenol formaldehyde and epoxy resins, three types of alkaline lignins were characterized in terms of their structures and thermal properties. The lignin samples analyzed were kraft lignin (LIG-1), soda–rice straw lignin (LIG-2), and soda-wheat straw lignin (LIG-3). FTIR and 1H-NMR methods were used to determine their structure. Gel permeation chromatography (GPC) was used to determine the molecular weight distribution (MWD). Differential scanning calorimetry (DSC) was used to measure the glass transition temperature (Tg), and thermogravimetric analysis (TGA) to determine the thermal stability of lignin samples. Results showed that kraft lignin (LIG-1) has moderate hydroxyl-group content, is rich in G-type units, and has good thermal stability. These properties make it more suitable for direct use in phenol formaldehyde resins, and it is therefore a good raw material for this purpose. The alkaline soda-rice straw lignin (LIG-2) with a high hydroxyl-group content and excellent thermal stability is most suited to preparing lignin-based epoxy resin

FiltekTM Silorane and FiltekTM Supreme XT resins: tissue reaction after subcutaneous implantation in isogenic mice

The aim of this study was to evaluate the tissue compatibility of a silorane-based resin system (FiltekTM Silorane) and a methacrylatebased nanoparticle resin (FiltekTM Supreme XT) after implantation in the subcutaneous connective tissue of isogenic mice. One hundred and thirty five male isogenic BALB/c mice were randomly assigned to 12 experimental and 3 control groups, according to the implanted material and the experimental period of 7, 21 and 63 days. At the end of each period, the animals were killed and the tubes with the surrounding tissues were removed and processed for microscopic analysis. Samples were subjected to a descriptive and a semi-quantitative analyses using a 4-point scoring system (0-3) to evaluate the collagen fiber formation and inflammatory infiltrate. Data were statistically analyzed using the Kruskal Wallis test (a=0.05). The results showed that there was no significant difference between the experimental and control groups considering the three evaluation periods (p>0.05). The silorane-based and the methacrylate-based nanoparticle resins presented similar tissue response to that of the empty tube (control group) after subcutaneous implantation in isogenic mice.

A simple model to describe the thixotropic behavior of paints.

We propose a simple rheological model to describe the thixotropic behavior of paints, since the classical hysteresis area, which is usually used, is not enough to evaluate thixotropy. The model is based on the assumption that viscosity is a direct measure of the structural level of the paint. The model depends on two equations: the Cross-Carreau equation to describe the equilibrium viscosity and a second order kinetic equation to express the time dependence of viscosity. Two characteristic thixotropic times are differentiated: one for the net structure breakdown, which is defined as a power law function of shear rate, and an other for the net structure buildup, which is not dependent on the shear rate. The knowledge of both kinetic processes can be used to improve the quality and applicability of paints. Five representative commercial protective marine paints are tested. They are based on chlorinated rubber, acrylic, alkyd, vinyl, and epoxy resins. The temperature dependence of the rheological behavior is also studied with the temperature ranging from 5 ºC to 35 ºC. It is found that the paints exhibit both shear thinning and thixotropic behavior. The model fits satisfactorily the thixotropy of the studied paints. It is also able to predict the thixotropy dependence on temperature. Both viscosity and the degree of thixotropy increase as the temperature decreases.

Nanopartícul·les core-shell estabilitzades en polímer amb propietats calítiques i bactericides medioambientalment segure

Aquest projecte de doctorat és un treball interdisciplinari adreçat a l’obtenció de nous nanocompòsits (NCs) funcionals sintetitzats a partir de materials polimèrics bescanviadors d’ions que són modificats amb nanopartícules metàl•liques (NPMs) de diferent composició. Els materials desenvolupats s’avaluen en funció de dues possibles aplicacions: 1) com a catalitzadors de reaccions orgàniques d’interès actual (NCs basats en pal•ladi) i, 2) la seva dedicació a aplicacions bactericides en el tractament d’aigües domèstiques o industrials (NCs basats en plata). El desenvolupament de nanomaterials és de gran interès a l’actualitat donades les seves especials propietats, l’aprofitament de les quals és la força impulsora per a la fabricació de nous NCs. Les nanopartícules metàl•liques estabilitzades en polímer (Polymer Stabilized Metal Nanoparticles, PSNPM) s’han preparat mitjançant la tècnica in-situ de síntesi intermatricial (Inter-matrix synthesis, IMS) que consisteix en la càrrega seqüencial dels grups funcionals de les matrius polimèriques amb ions metàl•lics, i la seva posterior reducció química dins de la matriu polimèrica de bescanvi iònic. L’estabilització en matrius polimèriques evita l’agregació entre elles (self-aggreagtion), un dels principals problemes coneguts de les NPs. Pel desenvolupament d’aquesta metodologia, s’han emprat diferents tipus de matrius polimèriques de bescanvi iònic: membrana Sulfonated PolyEtherEtherKetone, SPEEK, així com fibres sintètiques basades en polypropilè amb diferents tipus de grups funcionals, que ens permeten el seu ús com a filtres en la desinfecció de solucions aquoses o com a material catalitzador. Durant el projecte s’ha anat avançant en l’optimització del material nanocomposite final per a les aplicacions d’interès, en quant activitat i funcionalitat de les nanopartícules i estabilitat del nanocomposite. Així, s’ha optimitzat la síntesi de NPs estabilitzades en resines de bescanvi iònic, realitzant un screening de diferents tipus de resines i la seva avaluació en aplicacions industrials d’interès.

Unconventional magnetic behavior of iron-oxide nanoparticles in polymeric matrices

We report the results of magnetization and 57Fe Mössbauer spectroscopy measurements performed in the temperature range 5-300 K on composites containing iron¿oxide nanoparticles encased in polystyrene type resins. After carrying out a suitable field treatment in order to decouple the particles from the matrix, a fraction of the particles freely rotate in response to an applied magnetic field

Five years of sleep apnea treatment with a mandibular advancement device. Side effects and technical complications

Objective: To determine the variation in prevalence of temporomandibular disorders (TMD), other side effects, and technical complications during 5 years of sleep apnea treatment with a mandibular advancement device. Materials and Methods: Forty patients diagnosed with obstructive sleep apnea received an adjustable appliance at 70% of the maximum protrusion. The protrusion was then progressively increased. TMD (diagnosed according to the Research Diagnostic Criteria for TMD), overjet, overbite, occlusal contacts, subjective side effects, and technical complications were recorded before and a mean of 14, 21, and 58 months after treatment and analyzed by the Wilcoxon test (P Less-than .05). Results: Fifteen patients still used the oral appliance at the 5-year follow-up, and no significant variation in TMD prevalence was observed. Subjective side effects were common, and a significant reduction was found in overjet, overbite, and in the number of occlusal contacts. Furthermore, the patients made a mean of 2.5 unscheduled dental visits per year and a mean of 0.8 appliance repairs/relines per year by a dental technician. The most frequent unscheduled visits were needed during the first year and were a result of acrylic breakage on the lateral telescopic attachment, poor retention, and other adjustments to improve comfort. Conclusions: Five-year oral appliance treatment does not affect TMD prevalence but is associated with permanent occlusal changes in most sleep apnea patients during the first 2 years. Patients seek several unscheduled visits, mainly because of technical complications.

Bond strength of orthodontic brackets using different light and self-curing cements

The purpose of the study was to evaluate the shear bond strength of stainless steel orthodontic brackets directly bonded to extracted human premolar teeth. Fifty teeth were randomly divided into ¿ve groups: (1) System One (chemically cured composite resin), (2) Light Bond (light-cured composite resin), (3) Vivaglass Cem (self-curing glass ionomer cement), (4) Fuji Ortho LC (light-cured glass ionomer cement) used after 37% orthophosphoric acid¿etching of enamel (5) Fuji Ortho LC without orthophosphoric acid¿etching. The brackets were placed on the buccal and lingual surfaces of each tooth, and the specimens were stored in distilled water (24 hours) at 378C and thermocycled. Teeth were mounted on acrylic block frames, and brackets were debonded using an Instron machine. Shear bond strength values at fracture (Nw)were recorded. ANOVA and Student-Newman-Keuls multiple comparison tests were performed (P , .05). Bonding failure site was recorded by stereomicroscope and analyzed by Chi-square test, selected specimens of each group were observed by scanning electron microscope. System One attained the highest bond strength. Light Bond and Fuji Ortho LC, when using an acid-etching technique, obtained bond strengths that were within the range of estimated bond strength values for successful clinical bonding. Fuji Ortho LC and Vivaglass Cem left an almost clean enamel surface after debracketing.

Prevalence of complications after the oral rehabilitation with implant-supported hybrid prostheses

Objectives: Assess the main problems referred by the patients and observed by the professionals after the bucodental rehabilitation with an implant-supported hybrid prothesis. Patients and Methods: A retrospective study was carried out in which there were 43 patients included who were visited in the Department of Oral Surgery and Orofacial Implantology of University of Barcelona Dental School for one year. An oral rehabilitation with an implant-supported hybrid prosthesis was made to those patients. The following variables were registered: age, gender, number of inserted implants, type of implant and principal problems produced by the hybrid prosthesis. Results: The rehabilitation with an implant supported hybrid prosthesis was only performed in 43 of 116 cases treated in one year (January, 2006 to January, 2007). They were 26 men and 17 women of ages between 37 and 74 years, being the rate age of 56,5 years. The main complication recorded was the mucositis, associated frequently with a difficulty to carry a correct oral hygiene and to an overextention of the tail of resin of the prosthesis. Other observed problems were the peri-implantitis, the break of the acrylic teeth and the loss of some of the prosthetic screws. Conclusions: The most frequent complication after the laying of an implant supported hybrid prosthesis was the mucositis, associated mainly with a prosthetic tail too long and to the consequent difficulty of carrying a correct oral hygiene. In spite of the high prevalence of observed complications, most of them were mild and resolved on subsequent visits.

Equilibrium of the simultaneous etherification ofisobutene and isoamylenes with ethanol inliquid-phase

The simultaneous etherification of isobutene and isoamylenes with ethanol has been studied using macroreticu-lar acid ion-exchange resins as catalyst. Most of the experiments were carried out over Amberlyst-35. In addition,Amberlyst-15 and Purolite CT-275 were also tested. Chemical equilibrium of four chemical reactions was studied:ethyl tert-butyl ether formation, tert-amyl ethyl ether formation from isoamylenes (2-methyl-1-butene and 2-methyl-2-butene) and isomerization reaction between both isoamylenes. Equilibrium data were obtained in a batchwisestirred tank reactor operated at 2.0 MPa and within the temperature range from 323 to 353 K. Experimental molarstandard enthalpy and entropy changes of reaction were determined for each reaction. From these data, the molarenthalpy change of formation of ethyl tert-butyl ether and tert-amyl ethyl ether were estimated. Besides, the chemical equilibrium between both diisobutene dimers, 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene, wasevaluated. A good agreement between thermodynamic results for the simultaneous etherification carried out in thiswork and those obtained for the isolated ethyl tert-butyl ether and tert-amyl ethyl ether systems was obtained.

Contention postorthodontique avec attelle rigide en résine

Nous avons fait un examen clinique de 30 cas de contention postorthodontique avec attelle rigide en résine, de canine à canine sur les deux maxillaires. On décrit la fabrication de l'attelle, sa mise en place, les incidents possibles ou les problèmes cliniques apparus (mauvaise adhérence, gingivite ...) et les aspects psychologiques ou subjectifs du patient

Equilibrium of the simultaneous etherification ofisobutene and isoamylenes with ethanol inliquid-phase

The simultaneous etherification of isobutene and isoamylenes with ethanol has been studied using macroreticu-lar acid ion-exchange resins as catalyst. Most of the experiments were carried out over Amberlyst-35. In addition,Amberlyst-15 and Purolite CT-275 were also tested. Chemical equilibrium of four chemical reactions was studied:ethyl tert-butyl ether formation, tert-amyl ethyl ether formation from isoamylenes (2-methyl-1-butene and 2-methyl-2-butene) and isomerization reaction between both isoamylenes. Equilibrium data were obtained in a batchwisestirred tank reactor operated at 2.0 MPa and within the temperature range from 323 to 353 K. Experimental molarstandard enthalpy and entropy changes of reaction were determined for each reaction. From these data, the molarenthalpy change of formation of ethyl tert-butyl ether and tert-amyl ethyl ether were estimated. Besides, the chemical equilibrium between both diisobutene dimers, 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene, wasevaluated. A good agreement between thermodynamic results for the simultaneous etherification carried out in thiswork and those obtained for the isolated ethyl tert-butyl ether and tert-amyl ethyl ether systems was obtained.

Azolium-based systems: application of an anion exchange resin (A- form) method and 1H NMR analysis of the charged-assisted (CH)+·anion hydrogen bonds

The counteranion exchange of quaternary 1,2,3-triazolium salts was examined using a simple method that permitted halide ions to be swap for a variety of anions using an anion exchange resin (A¯ form). The method was applied to 1,2,3-triazolium-based ionic liquids and the iodideto- anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Additionally, an anion exchange resin (N3¯ form) was used to obtain the benzyl azide from benzyl halide under mild reaction. Likewise, following a similar protocol, bis(azidomethyl)arenes were also synthesized in excellent yields. The results of a proton NMR spectroscopic study of simple azolium-based ion pairs are discussed, with attention focused on the significance of the charged-assisted (CH)+···anion hydrogen bonds of simple azolium systems such as 1-butyl-3-methylimidazolium and 1-benzyl-3-methyl-1,2,3-triazolium salts.

Azolium-based systems: application of an anion exchange resin (A- form) method and 1H NMR analysis of the charged-assisted (CH)+·anion hydrogen bonds

The counteranion exchange of quaternary 1,2,3-triazolium salts was examined using a simple method that permitted halide ions to be swap for a variety of anions using an anion exchange resin (A¯ form). The method was applied to 1,2,3-triazolium-based ionic liquids and the iodideto- anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Additionally, an anion exchange resin (N3¯ form) was used to obtain the benzyl azide from benzyl halide under mild reaction. Likewise, following a similar protocol, bis(azidomethyl)arenes were also synthesized in excellent yields. The results of a proton NMR spectroscopic study of simple azolium-based ion pairs are discussed, with attention focused on the significance of the charged-assisted (CH)+···anion hydrogen bonds of simple azolium systems such as 1-butyl-3-methylimidazolium and 1-benzyl-3-methyl-1,2,3-triazolium salts.

Azolium-based systems: application of an anion exchange resin (A- form) method and 1H NMR analysis of the charged-assisted (CH)+·anion hydrogen bonds

The counteranion exchange of quaternary 1,2,3-triazolium salts was examined using a simple method that permitted halide ions to be swap for a variety of anions using an anion exchange resin (A¯ form). The method was applied to 1,2,3-triazolium-based ionic liquids and the iodideto- anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Additionally, an anion exchange resin (N3¯ form) was used to obtain the benzyl azide from benzyl halide under mild reaction. Likewise, following a similar protocol, bis(azidomethyl)arenes were also synthesized in excellent yields. The results of a proton NMR spectroscopic study of simple azolium-based ion pairs are discussed, with attention focused on the significance of the charged-assisted (CH)+···anion hydrogen bonds of simple azolium systems such as 1-butyl-3-methylimidazolium and 1-benzyl-3-methyl-1,2,3-triazolium salts.