Synthesis and characterization of biodegradable polyethylene by graft copolymerization of starch using glucose–Ce(IV) redox system

Graft copolymerization of low‐density polyethylene (LDPE) onto starch was carried out with glucose–cerium(IV) redox initiator in an aqueous sulfuric acid medium under nitrogen atmosphere. The graft yield was influenced by various parameters like reaction time, temperature, and concentrations of acid, glucose, polyethylene (PE), starch, and initiator. A maximum graft yield of 85.66% was obtained at a temperature of 50°C and at higher concentration of starch. Effect of grafting on crystallinity, morphology, and thermal properties of modified PE has been evaluated using X‐ray diffraction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA/DTA). Biodegradability of starch‐grafted PE has been tested applying soil‐burial test. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3229–3239, 2006     

Formation of Nanocrystalline Calcia by the Decomposition of Calcite

Formation of nanocrystalline calcia from calcite has been studied in situ via transmission electron microscopy. The crystallographic transformation occurred via two mechanisms: the first is by distortion of the cleaved rhombohedron of calcite, formed by {104} planes in hexagonal coordinates, into a cube. This produced a microstructure of oriented, elongated nanocrystals of calcia with planar boundaries. In the second mechanism, the micrometer-sized parent calcite particles broke up into nano-sized grains as the decomposition began, leading to irregularly shaped, randomly oriented nanocrystals of calcia.     

Prediction of minimum velocity and minimum bed pressure drop for gas-solid fluidization in conical conduits

Experimental investigations have been carried out for spherical and non-spherical particles using beds comprised of single-sized particles and mixtures in the size and particle density ranges of 439 to 1524 μm and 1303 to 4948 kg/m³, respectively. Five conical fluidizers with varying apex angles of 8.86, 14.77, 19.60, 32.0 and 43.2 degrees were used. Experimental values of minimum velocity and bed pressure drop with air as the fluidizing medium have been compared with their respective values obtained from different models available in the literature. Deviations for each chosen model have been presented.     

Studies on chemical resistance of polyesters

Chlorendic anhydride based polyester ( I ,) tetrachlorophthalic anhydride based polyester ( II ), dibromoneopentyl glycol based polyester ( III ,) general purpose polyester ( IV ,) blend of dibromoneopentyl glycol based polyester with general purpose polyester ( V ,) chlorendic anhydride and dibromoneopentyl glycol based polyester ( VI ), and a blend of chlorendic anhydride based polyester and dibromoneopentyl glycol based polyester ( VII ) were prepared and their chemical resistance and moisture absorption studied in various reagents, acid, alkali, and water, at 25 and 65°C. It is found that the polyester ( III ) is the least affected in the presence of the acids. In 20% NaOH, there was a decrease in weight for all polyesters at both the temperatures compared to the control except the polyester ( VII ). Increase in weight of all the polyesters was observed during the absorption of moisture both at 25 and 65°C. The increase was higher at higher temperature. Polyester ( III ) thus shows the least absorption of moisture.     

Free convection heat transfer over a horizontal plate at low prandtl number

Boundary layer equations for free convection heat transfer along a semi-infinite horizontal plate are derived by giving more importance to the energy equation. The equations are obtained for low Prandtl number and two separate polynomials are used to approximate the temperature and velocity profiles in these regions. The rate of heat transfer is compared with the available analytical and numerical results based on conventional boundary layer equations.     

Thermal stability of PVC/chlororubber-20-graft polyblend–styrene–acrylonitrile blends. I

Thermal stability of PVC blends with chlororubber-20-graft polyblend-styrene-acrylonitrile [CR-20gp-SAN (2:1)] was studied by HCI evolution techniques and thermogravimetry under isothermal condition. The thermal stability of PVC/CR-20gp-SAN (2:1) blends has been compared with those of PVC/CR-20 and PVC/KM-365B blends. It has been observed that the thermal stability of modified PVC is less than that of unmodified PVC. The CR-20gp-SAN (2:1) modified PVC blends were found to be more stable than PVC/CR-20 blends but less stable than PVC/KM-365B blends. The rate of degradation in PVC blends were observed to be unaffected by the concentration of the modifiers, but the PVC/KM-365B blends were found to be degrading slower in comparison with PVC/CR-20 and PVC/CR-20gp-SAN (2:1) blends. The rate of degradation for PVC/CR-20 blends at lower concentrations (<10%) of modifiers is almost equal to that of PVC/CR-20-gp-SAN (2:1) blends, but more at higher concentrations of modifiers (>10%). The experimental results have been explained on the basis of the chemical nature of the modifiers and their miscibility with PVC.     

Note: The Use of Triallyl Cyanurate in Bonding PVC Plastisols to Steel

The use of diallyl phthalate as the basis for a non-extractable plasticizer for poly(vinylchloride) (PVC) is well-known. Used in conjunction with a primary plasticizer and a polymerization initiator, a plastisol coating for steel can be formulated which is oil or grease tolerant and can also be used for bonding some structural steel parts if the area is relatively large compared with the load to be applied. Defrayne and Twiss¹ describe the bonding of automobile hood assemblies by vinyl plastisol adhesives and Schneberger² emphasizes their use in the automobile industry though neither article gives the formulations employed. Commercial formulations giving pull-off strengths of the order of 1 to 4 MN. m^-2 always incorporate a proportion of a phenolformaldehyde resin or even an epoxy, but sound-deadening and other coatings of steel do not necessarily need this reinforcement. Phillips and Longworth³ particularly studied the use of diallylphthalate (DAP) as a polymerizable plasticizer and the consequent improvement in adhesion to mild steel. Sherlock⁴ used a simple formulation without additives when investigating the effect of surface cleaning and conversion coatings (oxides and phosphates). It was suggested that, as outlined below, improved adhesion would be expected if a small proportion of triallyl cyanurate (TAC) were added to the polymerizable plasticizer. This paper shows this expectation to be achieved although the proportion of the more expensive TAC needed for substantial increase in bond strength is greater than was hoped.     

Reactivity,chemical structure,and molecular mobility of urea–formaldehyde adhesives synthesized under different conditions using FTIR and solid‐state 13C CP/MAS NMR spectroscopy

This study was conducted to investigate the effects of reaction pH condition and hardener type on the reactivity, chemical structure, and molecular mobility of urea–formaldehyde (UF) resins. Three different reaction pH conditions, such as alkaline (7.5), weak acid (4.5), and strong acid (1.0), were used to synthesize UF resins, which were cured by adding four different hardeners (ammonium chloride, ammonium sulfate, ammonium citrate, and zinc nitrate) to measure gel time as the reactivity. FTIR and ¹³C‐NMR spectroscopies were used to study the chemical structure of the resin prepared under three different reaction pH conditions. The gel time of UF resins decreased with an increase in the amount of ammonium chloride, ammonium sulfate, and ammonium citrate added in the resins, whereas the gel time increased when zinc nitrate was added. Both FTIR and ¹³C‐NMR spectroscopies showed that the strong reaction pH condition produced uronic structures in UF resin, whereas both alkaline and weak‐acid conditions produced quite similar chemical species in the resins. The proton rotating‐frame spin–lattice relaxation time (T_1ρH) decreased with a decrease in the reaction pH of UF resin. This result indicates that the molecular mobility of UF resin increases with a decrease in the reaction pH used during its synthesis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2677–2687, 2003     

Microstructure determination and thermal studies of n‐acryloylcarbazole/vinyl acetate copolymers

Copolymers of N‐acryloylcarbazole (A) and vinyl acetate (V) were synthesized by bulk polymerization using benzoyl peroxide (BPO) as free‐radical initiator at 65°C in different in‐feed ratios. The composition of the copolymer was determined by ¹H‐NMR spectrum. The comonomer reactivity ratios, determined by Kelen–Tudos (KT) and nonlinear error‐in‐variables (EVM) methods, were r_A= 16.75 ± 1.38, r_V = 0.015 ± 0.002, and r_A = 16.36, r_V = 0.015, respectively. Complete spectral assignments of the ¹H and ¹³C{¹H} NMR spectra of the copolymers were done by the help of distortionless enhancement by polarization transfer (DEPT) and two‐dimensional NMR techniques such as heteronuclear single quantum coherence (HSQC) and total correlation spectroscopy (TOCSY). The methine and methylene carbon resonances were found to be compositional as well as configurational sensitive. The signals obtained were broad pertaining to the restricted rotation of bulky carbazole group. The thermal stability and glass‐transition temperatures (T_g) of the copolymers were found to be dependant on polymer composition and characteristic of rotational rigidity of the polymer chain. Variation in the values of T_g with the copolymer composition was found to be in good agreement with theoretical values obtained from Johnston and Barton equations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2720–2733, 2007     

An electrochemical impedance spectroscopy and scanning electron microscopy study of the influence of positive plate compression on the electrochemical behaviour of lead-acid batteries

This study has developed an electrochemical impedance spectroscopy (EIS) method for the in situ investigation of the influence of positive plate compression on the electrochemical behaviour of lead-acid batteries during charge/discharge cycling. The EIS data for a fully charged and fully discharged battery are internally consistent with the expected kinetics of a battery in the opposite states of charge, and demonstrate that EIS measurements may be recorded with a high level of reproducibility. Furthermore, this study has necessitated the development of a special cell incorporating horizontally orientated battery plates that can be subjected to elevated pressure through the stacking of lead bricks on top of the cell, as well as a physically robust reference electrode system that can withstand the application of pressure. For this purpose, a platinum-wire pseudo-reference electrode has been developed, and has been shown to exhibit sufficient electrode stability over the period of an EIS recording, enabling the measurement of reproducible and meaningful EIS data. Additionally, the influence of positive plate compression on the behaviour of the lead-acid battery has been investigated by using scanning electron microscopy (SEM). Clearly, the experimental data show that plate compression enhances significantly the kinetics and concomitant performance of the lead-acid battery, and this is related to the enhanced reactivity of the active material, as rationalized by using the agglomeration-of-spheres (AOS) model.