Water vapour barrier performance of corn-zein coated polypropylene (PP) packaging films

The novel film structure of corn-zein coated on polypropylene (PP) synthetic film for packaging industry was developed to examine the feasibility of resulting coated films as an alternative water barrier performance for food packaging. The effects of coating formulation (solvent, corn-zein, plasticizer concentration and plasticizer type) on final properties of films were observed. Corn-zein is the most important protein of corn and has good film forming property. Composites structures of PP films coated with corn-zein were obtained through a simple solvent casting method. Polyethylene glycol (PEG) and glycerol (GLY) were used as plasticizer to increase film flexibility. Statistical analysis based on full factorial design was performed to observe coating formulation effects. The high water vapour barriers were obtained for films coated with coating formulation consisting of higher amounts of corn-zein plasticized by GLY. The lower glass transition temperatures (T _g) of films were obtained by plasticization of films and T _g decreased by increasing plasticizer content. The statistical analysis defined the key parameters of coating formulation that had major effects on the final properties of coated PP films as corn-zein, plasticizer concentration and plasticizer type. In conclusion, corn-zein coatings could have potential as an alternative to conventional synthetic polymers used in composite multilayer structures for food packaging applications.     

Bionanocomposites of Cassava Starch and Synthetic Clay

Starch-based biofilms containing synthetic Laponite clay and glycerol were prepared using a solvent casting technique. Electron microscopy images showed predominance of the exfoliated type of nanocomposite. Dynamic mechanical analysis revealed a larger influence of glycerol content on the polymer β relaxation and T _g than the clay content. Gas barrier properties were influenced by clay particles and plasticizer content. An increase of clay content led to lower gas permeability values. Although both glycerol and Laponite are hydrophilic, no significant changes were observed on the water sorption by starch films at different relative humidity values. Mechanical properties are kept similar after the inorganic filler incorporation.     

A comparative study of structure,thermal degradation,and combustion behavior of starch from different plant sources

The present study investigated the structure, degradation properties, and combustion behavior of starch from maize, sweet potato, lotus root, and tobacco. Compared with other plant starches, tobacco starch had the smallest size, the highest amylose content and the least crystallinity. Microscale combustion calorimetry (MCC) experiment demonstrated that sweet potato starch showed the maximum peak heat release rate value (888.0 W g^?1) while tobacco starch showed the minimum value (316.0 W g^?1) and thermogravimetric analysis coupled with Fourier transform infrared spectrometer (TG-FTIR) results showed tobacco starch had good char formability (residue mass: 15.6%) and released more incombustible gaseous products, such as H₂O and CO₂. These results suggest that the thermal properties of plant starches were mainly influenced by the structural features and amylose content, especially the amylose ratio, and tobacco starch was very promising for application in green flame-retardant material.     

Thermal analysis of the influence of water content on glass transitions

Starch is an important natural substance in which the water content has a significant influence on its structure and properties. In the present study, the effect of the water content on glass transition temperatures T _g and heat capacities C _p of wheat, maize and potato starches were investigated by high-sensitivity differential scanning calorimetry (temperature modulated TMDSC and conventional DSC). Thermal analysis measurements were performed on starch samples with different water contents. The exact water mass percentage of each sample was determined using the Karl-Fischer method. The obtained results show that the water content does influence the starch thermal properties in a systematic and measurable trend, the higher the water% the lower the glass transition temperature, and the higher the heat capacity jump during gelatinisation. At this stage possible interpretations of the results are just put forward and should be confirmed through complementary measurements.     

Thermal behaviors and characteristics of polylactide/poly(butylene succinate) blend films via reactive compatibilization and plasticization

Polylactide (PLA)/poly(butylene succinate) (PBS) blend films modified with a compatibilizer and a plasticizer were hot‐melted through a twin screw extruder and prepared by hydraulic press. Toluene diisocyanate (TDI) and polylactide‐grafted‐maleic anhydride (PLA‐g‐MA) were used as compatibilizers, while triethyl citrate and tricresyl phosphate acted as plasticizers. The effects of the type and content of compatibilizer and plasticizer on the mechanical characteristics, thermal properties, crystallization behavior, and phase morphology of the PLA/PBS blend films were investigated. Reactive compatibilization at increasing levels of TDI improved the compatibility of the PLA and PBS, affecting the toughness of the films. As evidenced by scanning electron microscope, the addition of TDI enhanced the interfacial adhesion of the blends, leading to the appearance of many elongated fibrils at the fracture surface. Furthermore, PLA/PBS blending with both TDI and PLA‐g‐MA led to an acceleration of the cold crystallization rate and an increment of the degree of crystallinity ( ). Toluene diisocyanate could be a more effective compatibilizer than PLA‐g‐MA for PLA/PBS blend films. The synergistic combination of compatibilizer and plasticizer brought a significant improvement in elongation at break and tensile‐impact toughness of the PLA/PBS blends, compared with neat PLA. Their failure mode changed from brittle to ductile due to the improved compatibility and molecular segment mobility of the PLA and PBS phases. Differential scanning calorimeter results revealed that the plasticizers triethyl citrate and tricresyl phosphate changed the thermal behavior of T_cc and T_m, affecting α′ and α crystal formations. However, these plasticizers only slightly improved the thermal stability of the films.     

Brazilian <Emphasis Type="Italic">Dioscoreaceas</Emphasis> starches

Determination of the characteristics of native starches is crucial in order to select their best application in various industrial fields. Thus, two different types of non-traditional native starches from the Dioscoreaceas species (Dioscorea sp. and Dioscorea piperifolia Humb. var. Wild) were studied regarding their thermal, structural and rheological properties. The results were contrasted with traditional commercial starch sources (potato, cassava and corn). From the thermogravimetric results (TG/DTG), D. piperifolia starch obtained the highest thermal stability of the samples, except for potato starch. Furthermore, using differential scanning calorimetry and viscoamylograph profiles (RVA), it was found that the Dioscoreaceas starches presented a higher onset (T _o) temperature and susceptibility to retrogradation. They also showed lower values in relation to relative crystallinity, which was calculated from their X-ray patterns and tendency to white (L*) colour. The shapes of the Discoreaceas starch granules were determined using electron microscopy; it was found that as the potato starch the Dioscoreaceas starches showed a wide range of particle size.     

Glass transition temperature of colloidal polystyrene dispersed in various liquids

Recently, there has been significant interest in measuring the glass transition temperature (T_g) of thin polymer films floated atop liquid substrates. However, such films still have intrinsically asymmetric interfaces, that is, a free surface and a liquid–polymer interface. In an effort to analyze the influence of different liquids on the T_g of confined polymers in which there is no interfacial asymmetry, a colloidal suspension of polystyrene (PS) nanoparticles (NPs) was employed. The T_gs of PS NPs suspended in either glycerol or an ionic liquid were characterized using differential scanning calorimetry. Nanoparticles suspended in an ionic liquid showed an invariance of T_g with confinement, that is, decreasing diameter. In contrast, nanoparticles suspended in glycerol showed a slight decrease in T_g with confinement. The dependence of NP T_g on the nature of the surrounding liquid exhibited a positive correlation with the interfacial energy of the liquid–PS interface and no correlation with interfacial softness, as measured by viscosity. A comparison of the results with thin films supported by liquid or solid substrates revealed a nontrivial interplay between interfacial softness and interfacial interactions on the T_g of confined PS. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1776–1783     

Structure of starches extracted from near isogenic wheat lines

Differential scanning calorimetry (DSC), acidic hydrolysis and different physico-chemical approaches were used to study thermodynamic and structural characteristics of starches from near-isogenic wheat lines to establish the effect of different combinations of active granule-bound starch synthase isoforms, taking part in amylose biosynthesis, on the structure and thermodynamic properties of starches. Obtained results suggest that the effect of different GBSS I combinations is realized through altered amylose localization within starch granules, reflecting in changes of melting temperature of crystalline lamellae (T _m) and rates of acidic hydrolysis. It has also been demonstrated that changes in T _m values for native wheat starches are determined by amylose content in amylopectin clusters.     

Glass transition temperature of polymer nanocomposites: Prediction from the continuous‐multilayer model

The continuous‐multilayer model introduced in our previous study for the T_g behavior of thin films is adapted to nanocomposite systems. T_g enhancement in both thin films and nanocomposites with attractive interfacial interactions can be explained by the same model. Various shapes of nanoparticles are proposed to rationalize the adaptation of the one‐dimensional model for the T_g behavior of thin film to three‐dimensional system such as nanocomposite. The tendency of predicted T_g enhancements in poly(methyl methacrylate) and P2VP nanocomposites with silica particles are qualitatively fit to experimental data in literatures. For the further quantitative fitting, the model is partially modified with the consideration for other factors affecting T_g deviation in nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2281–2287, 2009     

Structural and hydration studies of waxy and mealy potato starch cultivars by deuterium,carbon-13 CP-MAS/MASS NMR,and electron microscopy

Proton and deuterium pulsed Nuclear Magnetic Resonance (NMR) techniques were employed to investigate the hydration properties of raw and cooked (steamed, oven baked and microwave baked) waxy (LaSoda and Pontiac) and mealy (Russet Burbank and Norchip) potato cultivars and starches. Three water components (T_2Q internal, T_2A medium and T_2B long component) were resolved in potato cultivars and starches. The first water component T_2Q is assigned to the anisotropically bound water within the potato starch granule structure. The T_2A corresponds to trapped water, whereas, the T_2B-long component is assigned to the average between weakly bound and free water populations. The anisotropically bound water (T_2Q internal) in potato cultivars and starches does not seem to be in fast chemical exchange with free and weakly bound water populations. Well defined powder patterns with a residual deuterium quadrupole splitting of about 1 kHz were observed at 22°C for raw potato cultivars and starches (17%, w/w). The quadrupole splitting, however, disappeared after cooking as a result of heat induced structural changes, and only rapidly, isotropically reorienting water remained. The T_2A and T_2B values were also significantly affected by the cooking method. The T_2B values of cooked potatoes were shorter than those of raw potatoes. Heat induced structural changes were reflected in the shorter T_2B value of the cooked and crushed potatoes. Lower average ¹H NMR transverse relaxation rates were observed in cooked waxy (LaSoda) in comparison with those of other potatoes.     

A novel temperature‐step method to determine the glass transition temperature of ultrathin polymer films by liquid dewetting

A novel temperature‐step experimental method that extends the Bodiguel‐Fretigny liquid dewetting method of investigating polymer thin films is described and results presented from an investigation of thickness effects on the glass transition temperature (T_g) of ultrathin polystyrene (PS) films. Unlike most other methods of thin film investigation, this procedure promises a rapid screening tool to determine the overall profile of T_g versus film thickness for ultrathin polymer films using a limited number of samples. Similar to our prior observations and other literature data, with this new method obvious T_g depression was observed for PS thin films dewetting on both glycerol and an ionic liquid. The results for PS dewetting on the two different liquids are similar indicating only modest effects of the substrate on the T_g‐film thickness relationship. In both instances, the T_g depression is somewhat less than for similar PSs supported on silicon substrates reported in the literature. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1343–1349     

Phase Diagram of Gelatin Plasticized by Water and Glycerol

Summary: Gelatin is widely used in capsules manufacturing. Most of the capsules in pharmaceutical applications are hard capsules made out of concentrated solutions of gelatin, where water has been progressively removed during the drying process. More recently soft capsules found an increasing interest in pharmaceutical and cosmetic applications where they are filled and sealed with a liquid substance. In order to keep the shells of capsules flexible after drying at room temperature, plasticizer is added to the gelatin aqueous solutions. We present in this paper a systematic investigation of gelatin films, equilibrated under a range of relative humidity (RH). The films contain glycerol as plasticizer P or only water and gelatin, (G). In order to analyze the role of the plasticizer, we fixed various P/G ratios and measured the water retention versus RH. Films were characterized by DSC (Mettler Toledo DSC823). Glass transition temperature T_g, melting temperature T_m and enthalpy associated with helix-coil transition were determined. The role of water and glycerol was examined in relation with the large variations of these transition temperatures with film composition. Non equilibrium effects are also discussed, in particular concerning the glass transition temperature, the relaxation effects and the water repartition between amorphous coils and helical structure. In conclusion, we propose a unique phase diagram of the gelatin films with any proportion of water and glycerol.     

Comparison of the fragility index of different eudragit polymers determined by activation enthalpies

The present study aimed to apply fragility index (m) of polymers in the determination of the optimal amount of plasticizer in polymer films. The fragility index of different Eudragit polymers (RS, RL, EPO) was assessed by differential scanning calorimerty (DSC), applying the Arrhenius connection (logq–1/T _g). The fragility of Eudragit EPO films proved to be the highest, while in the case of RS and RL, the increase of the alkyl-chain length caused the increase of fragility. Studying the effect of plasticizer (triethyl citrate, TEC) on the m value of Eudragit RL and RS films, a near linear reduction of the fragility index could be observed between 5–30% TEC concentration, but above 30%, this value leveled out to constant.     

Studies on the properties and characteristics of starch-LDPE blend films using cross-linked, glycerol modified, cross-linked and glycerol modified starch

Corn starch was modified by cross-linking with epichlorohydrin and plasticizer glycerol. X-ray diffraction studies showed that relative crystallinity of the native and cross-linked starch were similar and were not affected by cross-linking. Different films were prepared by blending corn starch, cross-linked starch or glycerol modified starch in LDPE. The mechanical properties of the films were studied for tensile strength, elongation, melt flow index, and burst strength. The properties of the blend films were compared with LDPE films. It was observed that with the blending of 7.5% native starch, there was a decrease in tensile strength, elongation and melt flow index but burst strength increased. The tensile strength, elongation and melt flow index of the films containing cross-linked starch was considerably higher than those containing native starch but the burst strength showed a reverse trend. For native starch and cross-linked starch modified with glycerol, the elongation and melt flow index of the films increased but burst strength decreased. Surface scanning of the blend films were done by scanning electron microscope. Film containing cross-linked starch/glycerol modified starch in the blend was observed to be smoother than the native starch blend films.     

Characterization of Biodegradable Nanocomposite Films Prepared with Glutelin from Jatropha curcas L. by Response Surface Methodology and Infrared Spectroscopy

The water vapor permeability (WVP) and hardness of biodegradable nanocomposite films based on glutelin from Jatropha curcas L. were determined and the results were analyzed by response surface methodology (RSM). The effects of independent variables constituted by the plasticizer (glycerol), nanofiller (cloisite), and pH on the physical parameters were evaluated. The regression models obtained for each physical property adequately described the measurements used in the experimental design, with regression coefficients of 0.9513 and 0.9421 for WVP and hardness. The regression coefficients show that pH has the most significant effect on the WVP, whereas the cloisite content has the largest influence on the hardness of the nanocomposite film. Fourier transform infrared spectroscopy provided confirmation of the results obtained by RSM. Corroboration that the gluteline structure is in a similar form as the WVP and primarily influenced by pH was obtained using conventional and second derivative infrared spectra. However, the hardness of the film primarily depends on the cloisite content. This methodology may be useful for the design and elaboration of nanocomposite films based on J. curcas L. with specific barrier and mechanical properties.     

Preparation and properties of carboxyl-functional mixed esters of hydrolyzed starch

Mixed esters of hydrolyzed starch represent a new class of chemically modified natural polymers demonstrating a broad range of properties. Members of this class of polymers have both neutral aliphatic ester side chains and carboxyl-functional half-ester side chains. Use of hydrolyzed starch as the backbone polymer results in products that are considerably lower in molecular weight than whole starch derivatives, but which are still polymeric in character. Synthesis proceeds smoothly in pyridine using anhydrides as acylating agents and the pure solid mixed ester products are isolated by precipitation in water. Measurement of degree of substitution (D.S.) by NMR or hydrolysis characterizes the chemical composition of the polymers. The actual D.S. achieved in the synthesis depends upon the competition between starch and residual water for anhydrides, which can be quantitatively evaluated by monitoring the acid content of the reaction mixture. The T_g and T_s of starch mixed esters vary with both D. S. and length of the aliphatic ester side chain. As the composition changes from acetate—phthalate to butyrate—phthalate a T_g range of greater than 100°C is observed. Hydrolyzed starch mixed esters are hydrophobic and organic-soluble, but may be readily solubilized in aqueous base through the half-ester groups. Solutions show surface activity which varies according to the type and extent of substitution.     

Compatibility of cross-linked polymers with plasticizers by glass transition temperature measurement and swelling tests

To elucidate the compatibility of polymer and plasticizer components of binders a study of polymer–plasticizer interactions by differential scanning calorimetry (DSC) and swelling tests was conducted. The glass transition temperatures (T_g's) of mixtures of polymers and plasticizers, both cured and uncured, were determined with a DSC technique. Results with the PEG polymer systems were complicated by the partial crystallization of the polymer from the polymer/plasticizer mixtures. The PGA polymer system did not exhibit this behavior. However, the T_g's of cured PGA with various plasticizer mixtures made complicated departures from linearity (plots of T_g versus weight fraction of plasticizer) that indicated polymer–plasticizer interaction. By using least-squares analysis of data plotted by the equation Values of the interaction parameter K were determined for cured PGA in various plasticizer systems. These K values are in good agreement with the molecular flexibility of the plasticizers based on their molecular structure. The results of swelling tests are discussed to elucidate further the nature of the interaction of these polymers with plasticizers. Calculated polymer-plasticizer interaction values (χ) from the swelling tests correlated with the solubility parameter (δ) for a given class of polymer (polyether, polyester) and plasticizer (nitrate ester, ether-type). The efficiency of a plasticizer in reducing the T_g of a polymer (below the linearly interpolated value) was found not to be related to the swelling behavior of the polymer in the plasticizer.     

Preparation of novel antimicrobial-modified starch and its adsorption on cellulose fibers: Part I. Optimization of synthetic conditions and antimicrobial activities

Antimicrobial-modified starch was synthesized by covalently bonding guanidine polymer (PHGH) with potato starch via coupling reaction. Orthogonal tests were applied to optimize the reaction conditions. The coupling efficiency could reach 90.21% at the optimal conditions: temperature, 70 °C; time, 2 h; PHGH/starch, 120 wt.%; GDE/starch, 8 wt.%; pH, 11. PHGH modified starches exhibited high antimicrobial activities against both E. coli and S. aureus. Shaking flask method was more suitable for current non-released modified starches than diffusion method to evaluate the antimicrobial activities. In the presence of 1.0 wt.% PHGH in wood fibers, the growth inhibition reached almost 100%. The AFM results also demonstrated that the antimicrobial mechanism of PHGH was to destroy the membrane of the cells.     

Effect of Plasticizer Type and Concentration on Dynamic Mechanical Properties of Sugar Palm Starch–Based Films

In the quest for biodegradable and environmentally friendly packaging materials, starch-based films have been considered as a potential alternative to address ecological problems that emerged from the use of nonbiodegradable petroleum-based plastics. Thus, this article presents a new biopolymer (sugar palm starch) for the preparation of biodegradable packaging films using the solution-casting technique. The effects of different plasticizer types (glycerol [G], sorbitol [S], and glycerol-sorbitol [GS] combination) with varying concentrations (0, 15, 30, and 45, w/w %) on the dynamic mechanical properties of sugar palm starch (SPS) films were evaluated. It was observed that the storage (E′) and loss modulus (E″) of the plasticized SPS films decrease as plasticizer concentration increases from 15 to 45%. S-plasticized films showed higher storage modulus (1000 MPa) than G (880 MPa) and GS (920 MPa) plasticized films, irrespective of plasticizer concentration.     

Effect of nanoscale confinement on the glass transition temperature of free-standing polymer films: Novel,self-referencing fluorescence method

The effect of nanoscale confinement on the glass transition temperature, T_g, of freely standing polystyrene (PS) films was determined using the temperature dependence of a fluorescence intensity ratio associated with pyrene dye labeled to the polymer. The ratio of the intensity of the third fluorescence peak to that of the first fluorescence peak in 1-pyrenylmethyl methacrylate-labeled PS (MApyrene-labeled PS) decreased with decreasing temperature, and the intersection of the linear temperature dependences in the rubbery and glassy states yielded the measurement of T_g. The sensitivity of this method to T_g was also shown in bulk, supported PS and poly(isobutyl methacrylate) films. With free-standing PS films, a strong effect of confinement on T_g was evident at thicknesses less than 80–90 nm. For MApyrene-labeled PS with M_n = 701 kg mol⁻¹, a 41-nm-thick film exhibited a 47 K reduction in T_g relative to bulk PS. A strong molecular weight dependence of the T_g-confinement effect was also observed, with a 65-nm-thick free-standing film exhibiting a reduction in T_g relative to bulk PS of 19 K with M_n = 701 kg mol⁻¹ and 31 K with M_n = 1460 kg mol⁻¹. The data are in reasonable agreement with results of Forrest, Dalnoki-Veress, and Dutcher who performed the seminal studies on T_g-confinement effects in free-standing PS films. The utility of self-referencing fluorescence for novel studies of confinement effects in free-standing films is discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2754–2764, 2008