Effect of Plasticizers on the Moisture Migration Behavior of Low-Amylose Starch Films during Drying

We report the synergistic and competitive interactions between multiple plasticizers in plasticized low-amylose starch that result in either enhanced or reduced water migration fluxes and effective moisture diffusivities. The starch was plasticized using glycerol and xylitol either individually or in 1:1 combination. The water migration fluxes and moisture diffusivities were higher in xylitol plasticized films compared to the glycerol plasticized ones. For low plasticizer concentrations, the presence of both the plasticizers competitively reduced the effective moisture diffusivities and moisture migration fluxes due to antiplasticization. However, at higher plasticizer contents (at and above 15 wt%), the presence of multiple plasticizers enhanced the moisture migration fluxes and effective moisture diffusivities due to synergistic plasticization. The moisture migration fluxes and effective moisture diffusivities exhibited both moisture and plasticizer concentration dependence and the former was found to be stronger than the latter. These findings can be used for designing and controlling the vapor barrier properties of starch-based bioplastics during drying and formulation phase.     

Study on volume ratio and plasticizer screening of free coating membranes composed of ethyl cellulose and chitosan

The aim of this study was to optimize the formula of free blended coating membrane of ethyl cellulose (EC) and chitosan (CS), including their suitable ratio range and the best plasticizer used. The dry films were produced by a casting/solvent evaporation method, with different volume ratio of EC and CS solution plasticized by various plasticizers, respectively. The wet films were prepared by immersing dry films in pH 6.8 phosphate buffer saline (PBS) for 24 h. The promising ratio range of EC/CS was below 20/5 or 20/6 with various plasticizer, which was determined by comparing the viscosity of the blended solutions and the morphology of the blended films. The efficiency of plasticization was evaluated by measuring glass transition temperature (T_g). All the testing plasticizers have good compatibility with EC or CS and dibutyl phthalate (DBP) have the strongest efficiency inducing the lowest T_g (39.9°C) of the film. Mechanical properties were evaluated by the ratio of tensile strength (T) to elastic modulus (E). In the wet state, the films with DBP had the highest T/E value (1.2). The results of leaching of plasticizers also verified that DBP was the most stable plasticizer in the films. The release rates of tetramethylpyrazine phosphate (TMPP) through the pellets coated with the blended films of EC/CS (20 : 6 v/v) plasticized by various plasticizers showed that the more water‐soluble the plasticizer was, the more quickly TMPP dissolved from the coated pellets, which further indicated that the water‐insoluble plasticizers (such as DBP) could be more applicable to keep the sustained or controlled release property of the blended films in wet state. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1932–1939, 2006     

D‐isosorbide and 1,3‐propanediol as plasticizers for starch‐based films: Characterization and aging study

In the present work, D‐isosorbide and 1,3‐propanediol are proposed as alternative plasticizers obtained from renewable resources. Plasticized starch films were prepared by solvent casting method. The influence of using different “green” plasticizers in the final properties of starch‐based films was analyzed. Besides, the characterization of the films was also performed after storage time in order to evaluate the effect of the plasticizer on aging. UV‐spectrophotometry results showed better optical properties for both glycerol and D‐isosorbide films with higher transparency. The thermal and mechanical properties resulted influenced by the nature of the plasticizer. It was demonstrated that water vapor permeability was governed by the starch‐water interactions, whereas the oxygen permeability depended on the plasticizer's nature. The storage time affected the surface, mechanical, and thermal properties of the plasticized starch films. Atomic force microscopy results concluded that the topography of the films changed due to aging. The use of D‐isosorbide as plasticizer reduced the evolution of the mentioned properties and enhanced the reliability of the material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44793.     

Aging properties and hydrophilicity of maize starch plasticized by hyperbranched poly(citrate glyceride)

Hyperbranched poly(citrate glyceride)s (HBPETs) as plasticizers were mixed with maize starch (S) via cooking and film formation. The structure, aging properties, and hydrophilicity of the plasticized starches were studied by means of Fourier transform infrared spectroscopy, X-ray diffraction, tension testing, contact angle testing, solubility measurements, moisture absorption, and water vapor permeability (WVP). Compared with a glycerol–S plasticized film, the HBPET–S composite films had better mechanical properties in terms of both strength and elongation at break, better aging resistance, less moisture absorption, less WVP, and more hydrophobicity on the film surface. The mechanisms behind the performances resulted from stronger and more stable H bonds between the abundant active end groups of HBPET and hydroxyls of starch and the high branching degree of the HBPETs; this was helpful for effectively inhibiting the recrystallization of starch. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46899.     

Efficiency of plasticization of PVC by higher-order di-alkyl phthalates and survey of mathematical models for prediction of polymer/diluent blend Tg's

Presently, a suitable theory to predict the T_g vs. composition relationship for a given polymer-plasticizer blend, based on detailed molecular structure and molecular energitics considerations, is not available. In particular, the plasticizer efficiency parameter, k, which is uniquely defined at low-to-moderate diluent concentrations, and is an essential variable in the Mauritz-Storey theory of the diffusion of large molecules in amorphous polymers in the rubbery state, must always be determined by experiment. In this work, k was determined by DSC for PVC that was plasticized over a range of concentrations with a number of higher branched and linear di-alkyl phthalates. The results will be used in our plasticizer diffusion theory as well as provide guidance in the future development of a general mathematical model for predicting k. It was seen that k decreased with increasing molecular weight for both the linear and branched phthalates. For a given molecular weight, the branched phthalates have higher k values than the linear structures. These results have been rationalized in terms of the additional free volume created by the inefficiency of packing polymer chains about these large penetrant molecules. The DSC scans also implied an increasing degree of microstructural heterogeneity with increasing plasticizer concentration. Finally, relationships between plasticizer diffusion coefficient in the rubbery state and the plasticized T_g were established for low-to-moderate diluent concentration for three of the plasticizers studied by utilizing experimental diffusion data from our earlier work on these systems.     

An Effective Moisture Diffusivity Model Deduced from Experiment and Numerical Solution of Mass Transfer Equations for a Shrinkable Drying Slab of Microalgae Spirulina

From experimental data, Spirulina effective moisture diffusivity was analytically estimated by considering two diffusion regions and the product shrinkage. Then, the moisture diffusivity was deduced from the numerical solutions of mass transfer equations by minimizing the difference between experimental and simulated drying curves and by taking into account the slab thickness variation. The range of moisture diffusivity used for simulations was estimated from minimal and maximal values of experimental effective diffusivities and calculation started with the mean value of experimental effective diffusivities. Identified effective diffusivities ranged from 1.79 × 10^?10 to 6.73 × 10^?10 m²/s. These diffusivities increased strongly with drying temperature and decreased slightly with moisture content. A suitable model correlating effective diffusivity, temperature, and moisture content was then established. Effective diffusivities given by this model were very close to experimental ones with a relative difference ranging from 0.5 to 24%.     

Effect of ketal group in castor oil acid-based plasticizer on the properties of poly(vinyl chloride)

Two castor oil acid esters containing a ketal or ketone group (KCL or CL), as alternative plasticizers for poly(vinyl chloride) (PVC), were prepared. The structures were confirmed by ¹H NMR and FTIR spectroscopies. The effects of the presence of a ketal or ketone group in these compounds on PVC plasticization were examined. The DMA and SEM results showed that both plasticizers were miscible with PVC and exhibited excellent plasticizing properties, compared to those of dioctyl phthalate (DOP). The PVC plasticized by KCL displayed a lower T_g value of 20.6 ° C, which was lower than that of PVC plasticized with DOP (22.3 ° C) and PVC plasticized with CL (40.5 ° C). Tensile tests indicated that PVC plasticized using KCL showed a 37% higher of elongation at break than PVC plasticized by CL and 30% higher than PVC plasticized by DOP. The plasticizing mechanism was also investigated. Moreover, exudation, volatility, and extraction tests, along with TGA indicated that the presence of ketal groups effectively improved the migration resistance of plasticizer and the thermal stability of PVC blends. Taken together, introducing ketal groups into plasticizer might be an effective strategy for improving its plasticizing efficiency.     

Poly(citrate glyceride): a hyperbranched polyester for starch plasticization

Hyperbranched polyesters (HBPETs), terminated with either hydroxyl or carboxyl groups, were prepared from citric acid and glycerol in simple one‐step syntheses. The HBPET structure and degree of branching were investigated using Fourier transform infrared and ¹H NMR spectroscopies and gel permeation chromatography. The HBPET plasticizers were combined with a maize starch via cooking and film formation. The mechanical, thermal, paste and structural properties of the plasticized starch composites were studied in detail using differential scanning calorimetry, thermogravimetric analysis, rapid viscosity analysis and X‐ray diffraction. The HBPETs reduced the pasting viscosity but slightly increased the pasting temperature of the starch. The smaller breakdown and setback values of the plasticized starch pastes relative to those of native starch suggested weaker retrogradation. Compared with glycerol/starch plasticized films, HBPET/starch composite films had lower crystallinity, lower glass transition temperature and better mechanical and thermal properties. The properties of the plasticized starch samples strongly depended on the terminal groups and the molecular weight of the HBPET plasticizers. © 2017 Society of Chemical Industry     

Epoxidation of modified natural plasticizer obtained from rice fatty acids and application on polyvinylchloride films

In recent years, much research effort has been driven to develop alternative plasticizers for medical and commodity plastic materials. In this study, a modified natural plasticizer, synthesized by esterification of rice fatty acids, was modified by epoxidation with peroxy acid generated in situ. Two natural epoxidized plasticizers were obtained, using peracetic acid (NP‐Ac) and peroctanoic acid (NP‐Oc) as reagent. PVC films after addition of these natural epoxidized plasticizers presented fairly good incorporation and plasticizing performance, as demonstrated by results of mechanical properties, T_g values (as shown by DSC), optical microscopy, exudation, and migration tests, FTIR and X‐ray diffraction obtained for plasticized PVC films. NP‐Ac plasticizer presented enhanced plasticizing performance compared with NP‐Oc, probably due to a higher epoxidation degree obtained in the reaction with peracetic acid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and properties of thermoplastic pea starch using N,N‐bis(2‐hydroxyethyl)formamide as the plasticizer

N,N‐bis(2‐hydroxyethyl)formamide (BHF) was synthesized efficiently and used as a new plasticizer for pea starch to prepare thermoplastic starch (TPS). The hydrogen bond interaction between BHF and pea starch was proven by Fourier‐transform infrared (FT‐IR) spectroscopy. As detected by scanning electron microscope (SEM), pea starch granules were completely disrupted, and the homogeneous materials were obtained. The crystallinity of pea starch and BHF‐plasticized thermoplastic pea starch (BTPS) was characterized by X‐ray diffraction (XRD). Rheological properties of TPS were analyzed. The water resistance of BTPS was better than that of glycerol‐plasticized thermoplastic pea starch (GTPS). At RH 33%, the tensile strength of BTPS was higher than that of GTPS for TPS containing 30% plasticizer. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Identification of Effective Diffusivities in Anisotropic Material of Pine Wood during Drying with Superheated Steam

Simulation of 3D drying of anisotropic solids requires knowledge of the diffusivities of moisture in all three directions. These are seldom available in the range of temperatures and moisture contents of interest. This article presents methodology for identification of axial and radial diffusivities in wood in superheated steam drying and the results for wood of Pinus silvestris at a steam temperature 160°C and atmospheric pressure. Axial diffusivity (along fibers) was 5.76 times higher than radial diffusivity.     

Comparison of sorbitol and glycerol as plasticizers for thermoplastic starch in TPS/PLA blends

This article investigates the structure and properties of thermoplastic starch/PLA blends where the TPS phase is plasticized by sorbitol, glycerol, and glycerol/sorbitol mixtures. The blends were prepared using a twin‐screw extruder where starch gelatinization, water removal, and dispersion of TPS into a PLA matrix were carried out sequentially. The plasticizers were added to starch in the first stage of the extruder to allow complete starch gelatinization. The PLA was added at mid‐extruder and thoroughly mixed with the TPS. The plasticizer concentration was varied from 30 to 42% and the TPS content was varied from 27 to 60% on a weight basis. In all investigated blends, the PLA formed the continuous phase and the TPS was the dispersed phase. The viscosity, blend morphology, tensile mechanical properties as well as the thermal properties of the materials were measured. It was found that the glycerol/sorbitol ratio has an important effect on the blend properties. Finer blend morphologies, higher tensile strength and modulus but lower crystallization rate were found for the sorbitol plasticized blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PLGA with less than 1 month of half-life time: Tensile properties in dry and wet states and hydrolytic degradation

In this study, the degradation mechanism and tensile properties of plasticized poly(D,L-lactide-co-glycolide) (PLGA) are evaluated. Purasorb PDLG 5010 is first extruded into rods with or without plasticizers, i.e, D,L-lactide or aspirin. Then, the hydrolytic degradation of such rods is studied in phosphate buffer solution. A very fast hydrolytic degradation (half-life time lower than 1 month) that is enhanced by the presence of plasticizer occurs through a heterogeneous mechanism and leads to the formation of hollow rods. The mechanical properties of these rods are studied in dry and wet states. Finally, water diffusivity in plasticized (or not) PLGA is estimated.     

Urea and formamide as a mixed plasticizer for thermoplastic starch

Mixtures of urea and formamide were tested as plasticizers for thermoplastic starch (TPS). The hydrogen bonding interactions between urea/formamide and starch were investigated by using Fourier‐transform infrared spectroscopy (FT‐IR). The thermal stability, mechanical properties and starch retrogradation behavior were also studied by thermogravimetric analysis (TGA), tensile testing and X‐ray diffraction (XRD), respectively. TPS plasticized by urea (20 wt%) and formamide (10 wt%) showed better thermal stability and water resistance than conventional TPS plasticized by glycerol. Moreover, the tensile stress, strain and energy at break, respectively, reached 4.83 MPa, 104.6 % and 2.17 N m after storing in an atmosphere of relative humidity (RH) of 33 % for one week. At the same time, this mixed plasticizer could effectively restrain the retrogradation of starch. Copyright © 2004 Society of Chemical Industry     

Plasticizer migration from plasticized into unplasticized poly(vinyl chloride)

There exist important industrial applications, such as hoses or plastic windows, dealing with closely combining plasticized and rigid poly(vinyl chloride). Nevertheless, migration of plasticizer causes severe variation of the mechanical performance of the end-products. This work comprises an effort to investigate and understand these phenomena, also as an extension of previous work of ours in migration to liquid environments. The common system plasticized PVC/dioctylphthalate/unplasticized PVC was studied under two-sided diffusion conditions, i.e., from a thin sheet of plasticized sheet. The whole assembly was placed between two glass plates and then was held in an oven at 64°C to simulate accelerated test conditions. Some pressure was also applied to ensure perfect contact between the plastic sheets. Three different levels of initial plasticizer concentration (48, 66, and 100 phr) have been considered for a period of about five months, until equilibrium was reached. During this period the migration process was monitored by weight changes. Plots of M_t/M_∞ vs. t^½, where M_∞ the amount migrated at equilibrium and M_t the amount lost at time t, resulted in evident linear relationship. Therefore, it was proved that the Fick's law approximation for short times can be used to describe the migration kinetics for this solid/solid system. On the other hand, macroscopic observations revealed that no plasticizer was accumulated at the interface, i.e. all plasticizer leaving the plasticized sheet entered the rigid ones. Finally, it seems that the controlling stage is the diffusion inside plasticized PVC while possible annealing of the plasticized polymer structure cannot be excluded.     

热塑性淀粉塑料吸水性研究

采用增塑剂和热剪切方法制备热塑性淀粉塑料(TPS),在一定相对湿度环境下,测定不同配方TPS试样的含水量,研究了增塑剂种类(甘油和甲酰胺)与用量、直链淀粉用量和聚乳酸用量对TPS吸水性的影响。并对含水量随时间的变化曲线与Peleg模型曲线拟合分析,证明了Peleg模型在描述热塑性淀粉吸水过程的有效性和可靠性。     

Morphological studies on roll extruded,plasticized composites

A study of the morphologies of polymer/carbon black composites, plasticized with small molecule organics, is presented. Four different plasticizers and three different polymers were used. In all cases, the plasticizers depress the T_g of the polymers. Whereas in some cases the organic small molecule was found to be molecularly dispersed in the polymer matrix, phase separation occurred in other cases beyond a certain composition. In the latter instances, the excess plasticizer formed crystalline aggregates and a depression of the melting point of the plasticizer was observed. The samples were prepared by a process similar to roll extrusion, which causes biaxial orientation of the crystalline aggregates.     

Modeling the Rehydration Process of Dried Tomato

Rehydration of air-dried tomatoes was investigated at four temperatures (25, 40, 60, and 80°C). To describe the rehydration kinetics, two empirical models, Peleg and Weibull, were considered. The empirical models described the rehydration process properly. The equilibrium moisture content decreased as rehydration temperature increased, whereas the kinetic constants of the Peleg and Weibull models, k ₁ and β, respectively, increased with increasing temperature. This influence was described in terms of an Arrhenius relationship. The Peleg constant k ₂ was also found to be a function of temperature, increasing as temperature increased, whereas the Weibull shape parameter α decreased with increasing temperature. In addition, a mathematical model based on one-dimensional, steady-state, fully developed capillary flow of water with negligible inertia effects within the air-dried tomato was developed. This model was found to adequately describe the rehydration behavior of dried tomatoes.     

Influence of plasticizer with different functional groups on thermoplastic starch

Retrogradation of amorphous thermoplastic starch (TPS) films obtained by compression molding of spray dried modified potato starch was investigated. The aim was to investigate the influence of plasticizers with similar molecular weight but different functionality, i.e., isoleucine, asparagine and malic acid, on the properties of plasticized powder and TPS films. Combinations of malic acid with glycerol, urea, and maltodextrin were also evaluated. Except for isoleucine formulated starch, all samples were obtained as amorphous powders and films. Malic acid was identified as a strong antiretrogradation agent as it inhibited recrystallization of starch over the full range of humidity levels. Malic acid was also found to inhibit the retrogradation of formulations containing urea, glycerol and maltodextrin. The converse of the strong inhibition implied strong moisture absorption and high strain at break values, and low tensile strengths. Malic acid was also identified as a potential crosslinking agent to control swelling of starch‐based products. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42012.     

Films of chitosan and N‐carboxymethylchitosan. Part II: effect of plasticizers on their physiochemical properties

Chitosan (Ch) and N‐carboxymethylchitosan (N‐CMCh) films were prepared by the casting method at concentrations of 1% and 2% of polymer, with or without plasticizer: polyethylene glycol (PEG‐400) and glycerol (G), at 15% (w/w). The influence of composition on mechanical properties, water vapour transmission rate (WVTR), water saturation, and aqueous dissolution of the films was analysed. The thermal stability of the mixture (polymer:plasticizer, 1:1) was evaluated by thermogravimetric analysis (TGA). In general, all the properties were affected by the plasticizers. The plasticized films showed lower strength and a higher percentage of elongation (%E), in the following order: G > PEG‐400 > unplasticized film. The total WVTR increased with Ch concentration, with a different WVTR profile for Ch and N‐CMCh. While the PEG‐400 addition did not significantly modify the WVTR profile of films, the glycerol enhanced the transport of water vapour through both polymers. The plasticizer addition increased the time of water film saturation, in the following order: G > PEG‐400 > unplasticized film; this was more pronounced in the N‐CMCh films, probably due to the formation of hydrogen bonds. The solubility of the films was also affected by their composition. Copyright © 2006 Society of Chemical Industry