UV‐radiation–induced preirradiation grafting of methyl methacrylate onto lignocellulose fiber in an aqueous medium and characterization

The preirradiation method of grafting has been established by ultraviolet radiation. Methyl methacrylate (MMA) was grafted onto jute fiber in an aqueous medium. The variation of graft weight with UV‐radiation time, monomer concentration, and reaction time was investigated. The conversion of monomer into homopolymer and graft copolymer was evaluated. The graft weight passes through a maximum value (～ 122%) with UV‐radiation time. The optimum value of the monomer concentration was evaluated for maximum degree of grafting. Graft copolymerization of MMA onto lignocellulose fiber significantly increases the elongation at break (～ 65%) compared to that of the “as‐received” sample. However, a linear decrease on breaking load was observed with the increase of graft weight. The estimation of degree of grafting was achieved using an IR technique by correlating band intensities with the degree of grafting. Considering the water‐absorption property, the grafted sample showed a maximum up to 61% decrease in hydrophilicity compared to that of the as‐received sample. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1667–1675, 2004     

Thermooxidative degradation of natural rubber/clay composite

The clay is treated with a reducing agent and an acid so as to obtain a clay containing various metal components with a variable‐valence state. Then, the clay is coprecipitated with natural rubber (NR) latex to prepare a vulcanized NR/clay composite. The degradation process of the NR/clay composite under hot air condition was studied dynamically by using a Fourier transform infrared spectrometer attaching an in situ sample cell and was also investigated using the TGA method. The test result obtained from the infrared spectrometry indicated that under low decomposition temperature, the decomposition products of the test samples mainly are ethylene, low molecular olefinic hydrocarbon, and carbonyl compounds. As the decomposition temperature rises, the low molecular olefinic hydrocarbon content decreases, the olefine with longer chain is formed, and a lot of alkane decomposition products are formed at the same time. When the content of the metal components with a variable‐valence state in clay such as Cu, Mn, Co, and Fe increases, the oxidation products containing the carbonyl group, the olefinic hydrocarbon, and CO₂ in the decomposition product of the test sample also increase. The TGA result clearly shows a shoulder peak that appears by the side of the main peak on the DTG curve of NR/clay composite. With the increase in the content of metal components with variable‐valence state in clay, the initial degradation temperature of the test sample (T₀), the degradation peak temperature (T_p1), and the final degradation temperature (T_f1) in first‐stage reaction, as well as the degradation peak temperature (T_p2) and the last final degradation temperature (T_f) in second‐stage reaction of all the test samples more or less shift to the direction of low temperature; besides, the activation energy (E) of the reaction of the test samples more or less decreases. This means that the metal components with variable‐valence state promote the oxidative degradation of the clay–rubber masterbatch. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3809–3815, 2006     

Lipid adsorption on commercial silica hydrogels from hexane and changes in triglyceride complexes with time

The structures of and lipid complexes with two commercial silica hydrogels (Trisyl and Sorbsil 40), which contain about 60% moisture, were examined by diffuse reflectance Fourier transform infrared spectroscopy. The spectra suggested that Trisyl contained less moisture than Sorbsil 40. However, the silanol groups of Sorbsil 40 were more active in adsorbing oleic acid, triglyceride, and phosphatidylcholine (PC) from hexane than those of Trisyl. Both adsorbents strongly bound PC through the PC carbonyl and phosphate groups. Lipid adsorption from hexane solution by Trisyl depended solely on trapped moisture, while Sorbsil 40 used moisture and silanol groups on the silica surface. Spectra of triglyceride-silica hydrogel complexes, obtained 24 and 72 h after obtaining the initial spectra, showed that Sorbsil 40 adsorption was by Van der Waals forces, but the triglyceride reoriented over time with an increase in hydrogen bonding. In contrast, Trisyl initially adosorbed triglyceride by hydrogen bonding which was stable for at least 72 h.     

Surface-Enhanced Raman Scattering from Polyimide Model Compounds on Functionalized Metal Surfaces. Part II: Phthalic Anhydride/meta-Aminothiophenol/Silver

The interphase between a polyimide and a metal substrate was modeled by depositing phthalic anhydride (PA) onto a silver substrate pretreated with meta-aminothiophenol (m-ATP) and then curing in a mixture of acetic anhydride and pyridine or triethylamine. Surface-enhanced Raman scattering (SERS) and reflection-absorption infrared spectroscopy (RAIR) were used to determine the molecular structure of the interphase. It was found that m-ATP was adsorbed dissociatively onto silver substrates through the thiol groups. The tilt angle for m-ATP molecules adsorbed on silver substrates was determined using RAIR to be approximately 39°. However, there was no preferred rotational angle of the adsorbed APDS molecules about the molecular axes. When PA was deposited onto m-ATP pretreated silver substrates, anhydride groups of PA reacted with amino groups of m-ATP to form amic acids. When PA/m-ATP/Ag samples were chemically cured in acetic anhydride and pyridine or triethylamine, isoimide was the predominant product regardless of the use of pyridine or triethylamine as catalyst. These results were different from those obtained from PA/APDS/Au systems in which imide was the major product in the presence of triethylamine. These differences in the relative composition of cured products between two model systems were explained by the effect of substituents attached to APDS and m-ATP benzene rings.     

Mode of oleic acid adsorption on rice hull ash cristobalite

Fourier transform infrared spectroscopy was used to investigate the adsorption of oleic acid (OA) onto dry rice hull ash (RHA) silica. Adsorption partially occurred by surface hydrogen bonding of the carboxylic acid. There was also formation of carboxylate ions by reaction of OA with residual potassium oxide. These ions were strongly bound by the ash. Isopropanol inhibited OA adsorption by H-bonding and encouraged desorption of H-bonded OA, but without itself being significantly bound. RHA with 40% moisture also adsorbed a small amount of OA by H-bonding and reacted with OA to form and adsorb carboxylate ions.     

Miscibility behavior and coil overlap in ionic blends of phenylated polytriphenylene oxide and poly(methyl methacrylate)

Blends of sulfonated phenylated polytriphenylene oxide and poly(methyl methacrylate‐co‐4‐vinyl pyridine) were examined by dynamic mechanical, Fourier transform infrared, and NMR techniques. A high degree of miscibility was evident from a single drop in a plot of the storage modulus versus the temperature. The presence of ionic moieties due to proton transfer from sulfonic acid to 4‐vinyl pyridine was confirmed by both NMR and IR spectroscopy studies. The coils were found to be close to one another in dimethyl sulfoxide‐d₆ because the aromatic shielding effect of the phenyl rings of the phenylated polytriphenylene oxide units was observed from the upfield shift of most of the protons of poly(methyl methacrylate) in the NMR spectrum. However, the absence of cross peaks in the nuclear Overhauser and exchange spectroscopy experiments suggested that the intermolecular distance between the chains had to be larger than 4 Å. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 728–733, 2003     

Molecular orientation and relaxation in poly(butylene terephthalate)/polycarbonate blends

Rheo-optical Fourier-transform infrared (FTIR) spectroscopy is based on the simultaneous acquisition of stress-strain data and FTIR spectra on-line to the mechanical treatment of polymers and is frequently applied for the characterization of transient structural changes during deformation and stress-relaxation. In the present communication, this technique has been employed in order to investigate the distribution of molecular orientation and its relaxation in uniaxially drawn solution-cast films of semicrystalline partial miscible blends of poly(butylene terephthalate) (PBT) with polycarbonate (PC) containing 10, 30 and 50 wt% PC. The uniaxial deformation of these blend films having a PBT-crystallinity degree ranging from 31 to 12%, in unstretched blends, leads to a appreciable high segmental orientation for the crystalline PBT due to a structural transformation from lamellae to microfibrils. The formation of this fibrillar structure is attributed to non-reversibility of an extended phase with all-trans conformational sequence of the aliphatic segments of PBT, occurring during elongation. The rate of relaxation of this conformational transition, however, increases with increasing amorphous content in the blends. Also it is observed that even with increasing amorphous content in the PBT/PC blends the crystalline PBT shows significant orientation. In such cases, apart from the few lamellae which transform to microfibrils, it is suggested that a stress induced transformation of PBT chains in amorphous PBT-component to irreversible all-trans extended crystalline form also contributes to PBT crystalline orientation. In contrast with this high crystalline orientation, the amorphous PBT located in the interlamellar regions inside the PBT-spherulites show a lower orientation in blends as compared in pure PBT.On the other hand, an overall segmental orientation of PC chains in blends is of lower order which is attributed mainly to low stretching temperature compared to T_g of pure PC. The results are discussed in terms of the resulting spherulitic morphology and the temporary network formed by the elongated PBT and PC chains inside the interlamellar regions, in blends.     

Diffuse reflectance fourier transform infrared spectroscopy of phospholipid adsorption onto silicic acid

Diffuse reflectance Fourier transform infrared spectroscopy was used to study the mode of adsorption of phosphatidylcholine (PC) in hexane onto silicic acid (SA). PC adsorption was mainly through the charged phosphate group with minimal binding through the ester carbonyl. When the SA surface with adsorbed PC is washed with hexane, containing a small concentration of isopropanol, the desorbed PC is recovered without structural change, i.e., there is no evidence of PC hydrolysis in the adsorption process. Adsorbent misture probably promotes PC adsorption due to the increased availability of surface water hydroxyl groups for interaction with the PC phosphate groups. Isopropanol promoted PC binding by destabilizing PC reverse miscelles in solution, thus promoting its adsorption.     

Mullite for Structural, Electronic, and Optical Applications

Mullite (3Al₂O₃·2SiO₂) is becoming increasingly important in electronic, optical, and high-temperature structural applications. This paper reviews the current state of mullite-related research at a fundamental level, within the framework of phase equilibria, crystal structure, synthesis, processing, and properties. Phase equilibria are discussed in terms of the problems associated with the nucleation kinetics of mullite and the large variations observed in the solid-solution range. The incongruent melting behavior of mullite is now widely accepted. Large variations in the solid solubility from 58 to 76 mol% alumina are related to the ordering/disordering of oxygen vacancies and are strongly coupled with the method of synthesis used to form mullite. Similarly, reaction sequences which lead to the formation of mullite upon heating depend on the spatial scale at which the components are mixed. Mixing at the atomic level is useful for low-temperature (<1000°C) synthesis of mullite but not for low-temperature sintering. In contrast, precursors that are segregated are better suited for low-temperature (1250° to 1500°C) densification through viscous deformation. Flexural strength and creep resistance at elevated temperatures are significantly affected by the presence of glassy boundary inclusions; in the absence of glassy inclusions, polycrystalline mullite retains >90% of its room-temperature strength to 1500°C and displays very high creep resistance. Because of its low dielectric constant, mullite has now emerged as a substrate material in high-performance packaging applications. Interest in optical applications mainly centers on its applicability as a window material within the mid-infrared range.     

Fatty acid composition of spanish shortenings with special emphasis on <Emphasis Type="Italic">trans</Emphasis> unsaturation content as determined by fourier transform infrared spectroscopy and gas chromatography

A Fourier transform infrared spectroscopic procedure was used to analyze 34 edible fats (22 shortenings and 12 vegetable margarines) as neat fats (IR_NF) to determine their total trans fatty acid (TFA) content. The sloping baseline was corrected with a reference spectrum based on a nonprocessed olive oil. The calibration was done using seven partially hydrogenated fats with an individual TFA content previously determined by the combination of gas chromatography (GC) with argentation thin-layer chromatography. Taking into account the different absorptivities of various trans isomers, different correction factors were calculated using the calibration standards (0.83 and 1.71 for single trans bonds in both diethylene and triethylene and for trans, trans-diethylene fatty acids, respectively) and applied to calculate the total TFA of samples. Moreover, the samples were converted to their methyl esters and reanalyzed following the same procedure (IR_FAME). Differences in TFA content of fats were not found when a t-test was used to compare the results obtained by IR_NF vs. either IR_FAME or GC, suggesting that IR of neat fats could be used, thus avoiding the need to prepare sample solutions in organic solvents and to prepare fatty acid methyl esters. The mean TFA content (determined by IR_NF) of a representative group of Spanish shortenings (22 samples) that varied widely in terms of fat sources, processes, and purposes (bakery, sandwiches, ice cream, coatings, chocolate coverings) was 6.55±11.40%, although more than 54% contained <3% of TFA. Fatty acid composition of shortenings by direct GC using a 100-m polar cyanopolysiloxane capillary column indicated that the mean trans-18∶2 isomer content was 0.58%, ranging from 0.9 to 3.4%. Small amounts of trans-18∶3 isomers (<0.3%) were observed in 18 of the 22 shortenings studied; the maximal value was <2%. The mean value of the fraction saturated+TFA of shortenings was high (59.95±12.73%), including two values higher than 83%.