Effect of Cooling Rate on the Structural and Moisture Barrier Properties of High and Low Melting Point Fats

The effect of three cooling rates (rapid, intermediate and slow CR) on the moisture barrier properties and on the physical state of acetylated and high melting point hydrophobic self-supported moisture barriers has been investigated. The selected CR were representative of industrial processing conditions and the selected barrier materials of common effective GRAS substances (acetomonopalmitin, white beeswax, two commercial blends of beeswax and acetylated glycerides and a blend of palmitic/stearic acids). Variations of CR affected crystallisation kinetics, SFC in an extend depending on the fat chemical composition and degree of undercooling, crystal size and ratio of polymorphs present in the materials. It did not have major influence on the contact angles with water measured at the surface of the materials and on the mass–volume area properties of the material. The resultant effect on the macroscopic moisture barrier properties of the materials were evaluated using water vapour permeability (WVP) measurements. The CR had no significant effect on the WVP, except for one blend of acetylated fat and beeswax for which a slow CR may have favoured the healing of imperfections. The variations of WVP between all materials and CRs were mainly attributed to variation in materials polarity using multivariable analysis.     

低密度聚乙烯/超细煤粉复合材料的热反应性研究

选用神府主焦煤(SFC)作为原煤,通过行星球磨机制备超细煤粉,用氯化铁(FeCl3.6H2O)过渡金属盐对超细样品进行机械力化学固相改性,制备出活性煤粉,以不同配比与低密度聚乙烯(PE-LD)共混制备复合材料。利用差示扫描量热仪等分析测试手段,探讨了SFC、PE-LD以及PE-LD/SFC复合材料的热解反应性和热解动力学。结果表明,Kissiger法和Flynn-Wall-Ozawa法在热分析动力学允许的范围内,计算结果具有一致性;SFC在340～380℃时活化能为113kJ/mol,520～550℃时热解活化能为149kJ/mol;添加10%(质量分数,下同)和20%铁改性SFC的PE-LD/SFC复合材料,在低温区(120～135℃)的热解活化能分别为182.87、250.62kJ/mol;铁改性SFC含量为10%时,煤与PE-LD的反应性较好,两组分之间存在一定协同作用。     

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.     

基于二硫键的自修复水性聚氨酯的制备与性能研究

以芳香二硫化合物2,2'?二氨基二苯二硫醚（AD）为原料,制备了一种自愈性水性聚氨酯（WPU）材料。利用全反射傅里叶变换红外光谱仪、拉曼光谱仪、热失重分析仪、粒径分析仪、热台偏光显微镜和接触角仪对改性材料进行了结构表征与性能测试,探讨了聚氨酯材料的热稳定性、表面疏水性、自修复性能的变化。另外,通过拉伸测试,定量评价了材料的拉伸性能和自愈合效率。结果表明,AD成功引入到WPU分子链中;随着AD含量的增加,改性材料的热稳定性逐渐下降;表面疏水性提升,样品WPU?3的静态接触角达到了81.2 °;拉伸强度由WPU?0的1.1 MPa增至WPU?3的5.6 MPa;同时,在中等愈合温度（80 ℃）下,样品WPU?1加热3 h后可以使拉伸应变的愈合效率达到81 %左右。     

Influence of succinylation on the properties of cast films from red bean protein isolate at various plasticizer levels

The effects of succinylation at three anhydride levels (0.2, 0.4, and 0.6 g g⁻¹) on the properties of cast films from red bean protein isolate (RPI) at three glycerol levels of 0.2, 0.4, and 0.6 g g⁻¹ were investigated. The tested properties included tensile strength (TS) and elongation at break (EB), surface hydrophobicity, moisture content (MC), total soluble matter (TSM), water vapor transmission rate, and permeability (WVTR and WVP), permeability coefficient of oil (PO). The results showed that the succinylation greatly improved the mechanical properties (especially the EB), but decreased the surface hydrophobicity of cast films. The MC, TSM, WVTR, WVP, and PO were considerably increased by the succinylation. The size exclusion chromatography analysis indicated that the succinylation resulted in protein aggregation or association, and transformation of insoluble precipitates (initially present) to soluble protein components. The dependence of the influence of succinylation upon some selected properties on the plasticizer level suggests interactions between introduced anionic succinic moieties and the hydroxyl groups of the plasticizer. These results suggest that the succinylation treatment could be applied to modify the mechanical properties of legume proteins, especially in the case that requires excellent flexibility of cast films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of TAG composition on the solid fat content profile,microstructure, and hardness of model fat blends with identical saturated fatty acid content

TAGs play an important role in determining the functional properties of fat‐based food products such as margarines, chocolate, and spreads. Nowadays, special attention is given to the role of the TAG structure and how it affects functional properties such as mouth feel, texture, and plasticity. Key to this research is the need to develop more healthy fats with a reduced level of trans and saturated fatty acids (SFAs), while maintaining the desired properties. In this study, fat blends with identical levels of SFA (50%) but differing in the ratio asymmetric/symmetric blends were evaluated by pulsed NMR and texturometry as a function of storage time and storage temperature. A higher trisaturated TAG content gave rise to a higher solid fat content (SFC) at higher temperature and a lower SFC at lower temperature for both palmitic and stearic based blends. On the other hand, the effect of symmetry on the SFC‐profile of the blends was only clear for the stearic based blends. At lower temperatures, the SFC of symmetric TAG based blend (blend SM) was markedly lower than that of asymmetric TAG based blend (blend iS). However, from 30°C onwards, the SFC of blend SM was clearly higher than that of blend iS. The microscopic analyses revealed a denser crystal network for a higher degree of trisaturated TAG and for symmetric stearic based blends. Moreover, some blends showed a clear evolution of the microstructure during storage with smaller crystals transforming into larger ones. Finally, texture analyses demonstrated the importance of the crystallization and storage temperature on the hardness of the blends.     

Improvement of water barrier properties of soybean protein isolate films by poly(3-hydroxybutyrate) thin coating

The aim of this work was to study the preparation of bilayer films formed by soy protein isolate (SPI) and polyhydroxybutyrate (PHB). This was done using the lowest possible concentration of PHB to improve the functionality of SPI films as food packaging or for agricultural uses, specially reducing their water vapor permeability (WVP). SPI films are environmentally friendly since they are biodegradable and come from renewable sources but they are brittle and have high water permeability. Even for the lowest concentration analyzed, PHB managed to form a homogeneous layer that successfully covered up the SPI film surface. All bilayers films showed a significant reduction of WVP of SPI films, and those with the highest PHB content showed the highest elastic Young's modulus and mechanical strength while maintaining a good elongation and low T_g value, similar to that of SPI. Despite of their hydrophobicity differences, a good adherence of both layers was achieved, which allowed to improve the mechanical and barrier properties of the SPI coated films with respect to films formed by both biopolymers separately. The combination of both SPI and PHB seems to be a good alternative to prepare a biodegradable material taking advantages of the best properties of each component.     

Enzymatic Interesterification of Palm Oil and Fractions: Monitoring the Degree of Interesterification using Different Methods

Interesterification is an important modification technique for fats and oils resulting in the redistribution of the fatty acids among the glycerol backbone and thus changing the physico-chemical properties of the modified fat. In this study palm oil, palm olein and soft palm mid fraction (PMF) were subjected to both enzymatic (batchwise) and chemical interesterification. The reaction products were characterized before, during and after interesterification by HPLC, pulsed NMR (p-NMR) and differential scanning calorimetry (DSC). Interesterification led to more uniform triacylglycerol (TAG) compositions with smaller differences in final physico-chemical properties between the studied substrates. The degree of interesterification was evaluated on the basis of TAG composition and solid fat content (SFC). Significant differences between both methods were observed. The degree of interesterification based on SFC is therefore a better tool to evaluate the rate constant of the reaction as the TAG composition method does not take into consideration the formation of positional isomers at the end of the enzymatic process.     

Another look at epoxy thermosets correlating structure with mechanical properties

All glassy epoxy polymers develop macroscopic properties at some degree of conversion. Our selected example, diglycidyl ether bisphenol‐A epoxy pre‐polymer, was cured with 3,3′‐diaminodiphenylsulfone at stoichiometric equivalents using a series of cure profiles to produce distinct variation in the degree of epoxy conversion and result in varying network and network connectivity. Activation energy of epoxy‐amine reaction in this selected system was ～61 kJ/mol. The calculated reaction energy barrier was found to vary with the extent of epoxy conversion and is attributed to multimechanistic reactions. Epoxy‐amine conversion was tracked in situ via near infrared spectroscopic analysis. A single cure condition (90°C) was selected for experiments focused on preferential linear chain growth and minimal branching and/or crosslinking. The physical properties for matrix materials from samples prepared to varying degrees of conversion were characterized and tested for fracture toughness, tensile, flexural, compression properties, molecular weight between crosslinks/crosslink density, and glass transition temperature(s). An empirical equation was also designed to predict molecular weight between crosslinks based on chemical connectivity and extent of reaction. POLYM. ENG. SCI., 54:1990–2004, 2014. © 2013 Society of Plastics Engineers     

An entropy-centric equilibrium cooperative theory for the melting behavior of nonideal triaclylglycerol mixtures

A new nonideal, equilibrium thermodynamics model was developed for the prediction of the solid fat content (SFC) of edible fats, which are mixtures of triaclylglycerols (TAGs). The SFC is the most dominant material structural parameter which influences macroscopic mechanical properties and functionality in foods, cosmetics and pharmaceutical incipients. By taking into consideration the entropy of mixing and the activity coefficient of a TAG in an effective solid medium, we calculate a freezing point depression. The new melting point is then nested into an equilibrium expression for the melting of that TAG in such effective solid medium. The model assumes that complex mixtures of TAGs consist of one solid phase in a specific polymorphic form and one liquid phase, obeying mass balances and the overall TAG composition determined experimentally. The SFC is then just the summation of the amount of solid TAG components in the mixture. Novel insights are gained from estimates of a cooperativity index for the melting of the different TAGs in the effective solid medium, while estimated solid-state activity coefficients speak to interactions of particular TAGs with the effective medium. The model was successfully fitted to eight different SFC-temperature profiles of complex fats and parameter estimates obtained and interpreted.     

Pulsed NMR Method for Solid Fat Content Determination in Tempering Fats Part II: Cocoa Butters and Equivalents in Blends with Milk Fat

Earlier, in part I of this paper, a method for Solid Fat Content (SFC) determination with pulsed NMR has been described for cocoa butters and cocoa butter equivalents. The present work (part II) is a continuation with these fats together with 10 to 30% milk fat. These fat blends need a modified pretreatment before NMR analysis. Crystallisation of the melted fat should be done at 0° C for 150 min and subsequent tempering performed at 19.0° C for 40 h. No other deviations from the earlier reported method have been carried out. Also SFC determination for chocolate has been described and used as a tool for the development of a proper NMR method, giving SFC on a pure fat blend more or less equal to SFC in corresponding milk chocolate. Different pretreatments (i.e. tempering temperatures) have given very different SFC results. A crystallographic understanding of these were achieved using X-ray, microscope and thermal analysis techniques. The chosen tempering temperature 19.0° C gave a single solid solution, which is essential in chocolate if the right properties of the fat are to be reached. Differences in SFC on pure fat blends by different tempering temperatures could, in the same way, be found in milk chocolates stored at corresponding temperatures. Storage temperature can, to a certain degree, be chosen in order to optimize and control the SFC (i.e. properties) in a chocolate product. The choice of initial temperature especially will strongly influence the SFC in chocolate and the crystal lattice remains virtually unaffected by changes in storage temperature.     

Influential Factors in the Synthesis of Polymethylhydrogenosiloxane Obtained via Cationic Ring-Opening Polymerization Using Synthetic Silica-Aluminates as Catalysts

In the ambit of the synthesis of silicon polymers and elastomers, there are a lot of variables that affect the final properties of the material, and consequently, their applications. In this work, we synthetized polymethylhydrogensiloxane using the ring opening polymerization (ROP) with 2,4,6,8-tetramethylcyclotetrasiloxane as monomer (D₄^H), a synthetic aluminosilicate like catalytic species and hexamethyldisiloxane as chain blocker. We made a set of experiments, in order to find the effect on the reaction yield, the absence of crosslinking, crosslinking degree and the mechanical properties of the final polymers. We found that the factor “chain blocker addition time” is significant for yield reaction and crosslinking degree of the elastomers, obtaining a greater crosslinking degree and reaction yield when is added at the beginning of the reaction. Also, using DSC measurements, we found an endothermal signal in 553 K corresponding to the elastomer’s chains rearrangement to dissipate the heat supplied. We obtained PMHS chains up to 24,270 g/mol indicating the ability of this kind of catalysts to achieve relatively high molecular weight chains.

     

Contribution of amino acid substitutions at two different interior positions to the conformational stability of human lysozyme

To elucidate correlative relationships between structural changeand thermodynamic stability in proteins, a series of mutanthuman lysozymes modified at two buried positions (Ile56 andIle59) were examined. Their thermodynamic parameters of denaturationand crystal structures were studied by calorimetry and X-raycrystallography. The mutants at positions 56 and 59 exhibiteddifferent responses to a series of amino acid substitutions.The changes in stability due to substitutions showed a linearcorrelation with changes in hydrophobicity of substituted residues,having different slopes at each mutation site. However, thestability of each mutant was found to be represented by a uniqueequation involving physical properties calculated from mutantstructures. By fitting present and previous stability data formutant human lysozymes substituted at various positions to theequation, the magnitudes of the hydrophobicity of a carbon atomand the hydrophobicity of nitrogen and neutral oxygen atomswere found to be 0.178 and –0.013 kJ/mol.Ų, respectively.It was also found that the contribution of a hydrogen bond witha length of 3.0 Å to protein stability was 5.1 kJ/moland the entropy loss of newly introduction of a water moleculeswas 7.8 kJ/mol.     

Edible starch sodium octenyl succinate film formation and its physical properties

Edible starch sodium octenyl succinate (SSOS) films, with or without glycerol as plasticizer, were prepared by solution‐casting method. The effect of SSOS concentration, degree of substitution (DS) of octenyl group, as well as glycerol content, on the properties of SSOS films was studied including tensile strength, water vapor permeability (WVP), and oil permeability (OP). The results indicated that the tensile strength of SSOS film was up to 39.4 ± 1.9 MPa when the concentration of SSOS was 0.05 g/mL and DS was 0.05. The increase of glycerol content resulted in a decrease of film tensile strength. WVP of SSOS films was relatively low. Meanwhile, study in OP showed that SSOS films were oilproof. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Potential of Pinhão husk (Araucaria angustifolia) as a structural reinforcement agent in the properties of edible films of Pinhão flour and gelatin

In this study, the use of Pinhão husk as a source of reinforcement material for development of edible films, where the Pinhão seed flour and bovine gelatin were used as matrices for the films. Mechanical properties, water vapor permeability, solubility and opacity, microstructure, and thermal degradation characterized the films produced. The films presented homogeneous and cohesive structures. Pinhão husk content positively affected film properties by increasing tensile strength (TS) and decreasing water vapor permeability (WVP), with Pinhão flour film formulations (5.0% Pinhão flour, 1.2% glycerol, and 0.4% Pinhão husk) and gelatin (5.0% gelatin, 2.0% glycerol, and 0.4% Pinhão husk) those that presented the best results (5.06 MPa for TS and 0.14 g.mm/kPa.h.m² for WVP) and (3.88 MPa for TS and 0.28 g.mm/kPa.h.m² for WVP), respectively The thermal degradation study revealed that the films are stable at temperatures below 150°C, losing only free water and volatile compounds of low molecular weight. Pinhão husk can reinforce films, making them suitable as biodegradable and edible packaging materials for eco-friendly food products. This contributes to the circular economy, preserves biodiversity, and reduces plastic waste, offering promising sustainable packaging solutions.     

Study on ketalization reaction of polyvinylalcohol by ketones. III. Reaction between polyvinylalcohol and methyl ethyl ketone and behavior of polyvinylketal in water

Ketalization reaction of polyvinylalcohol (PVA) by methyl ethyl ketone (MEK), dimethyl-sulfoxide (DMSO) as solvent, under the presence of acidic catalyst, in homogeneous system was carried out, and the synthesis of polyvinylketal with any ketalization degree was successfully performed. The reaction mechanism of PVA with MEK is identical with that with acetone: for both cases, the equilibrium constant is ca. 0.07 at 40°C and the heat of reaction is 7.5 kcal/mol. Films prepared from the polyvinylketal were soaked in water and degree of swell, solubility, and hydrolysis of films were measured. The reaction of film with water, in acidic side, easily proceeds, and at first the film swells; then, as deketalization reaction proceeds, the film dissolves in water. With polyvinylketal of the ketalization degree of above 15 mol %, dissolution time is controlled by both ketalization degree and pH of water, which reveals that deketalization reaction proceed proportionally to proton concentration at 37°C. On the other hand, in the neutral condition where hydrolysis does not proceed at all, polyvinylketal of ketalization degree of 10–40 mol % dissolves in water at 0°C. The polyvinylketal obtained by MEK is more stable in water than that from acetone since MEK has hydrophobicity.     

Hydrolysis behaviour of crosslinked poly(ester anhydride) networks prepared from functionalised poly(ε-caprolactone) precursors

Biodegradable poly(ester anhydride) networks based on functionalised poly(ε-caprolactone) precursors with different hydrophobicities, molecular weights and architectures were synthesised. Networks that were prepared from the star-shaped precursors clearly showed higher gel contents and crosslinking densities than the networks that were prepared from the linear precursors. Functionalising with different alkenylsuccinic anhydrides and/or varying the molecular weight of the precursor, the thermal properties, surface hydrophobicity and erosion of the crosslinked networks were widely tailored. The dissolution behaviour of the networks changed dramatically as the molecular weight of the precursor increased from 2000 to 4000 g/mol or the alkenyl chain of the alkenylsuccinic anhydride increased from 8 to 18 carbons. The networks that were prepared from the lower molecular weight precursors, without an alkenyl chain or with an 8 carbon alkenyl chain, lost their mass in a few days, whereas the networks that were prepared from higher molecular weight precursors or contained a hydrophobic 18 carbon alkenyl chain did not show any mass loss over a period of 8 weeks.     

Surface hydrophilization of electrospun PLGA micro-/nano-fibers by blending with Pluronic F-108

Poly(lactide-co-glycolide) (PLGA) has been widely explored as scaffolds in tissue engineering. However, its hydrophobicity can adversely affect events such as protein adsorption and downstream cell adhesion in tissue engineering applications. Although surface modification techniques (high energy radiation/chemical treatment) to modify the hydrophobicity of PLGA can be useful at the macroscopic scale, their usefulness for micro-/nano-meter scale objects can be limited due to adverse affects on physical properties. Therefore, in this study we report the surface hydrophilization of electrospun micro-/nano-fiber meshes of PLGA (85:15) by blending with small quantities (0.5-2%) of a non-ionic surfactant Pluronic^® F-108 (PF-108). The blended fiber meshes showed a decrease in surface contact angle when compared to pure PLGA fiber meshes demonstrating an improvement in surface hydrophilicity due to blending. This was corroborated by XPS analysis that demonstrated surface enrichment of PF-108. Thermal and mechanical studies demonstrated that blending with small quantities of PF-108 do not compromise the bulk properties of PLGA. Therefore these studies demonstrated the feasibility of hydrophilization of electrospun PLGA micro-/nano-fibers, without compromising the bulk properties (thermal and mechanical) of native PLGA.     

Influence of forming method of blending versus casting layer-by-layer on structural properties and packing performances of casein-gelatin composite edible film under different appending proportion

In order to obtain casein edible films with great packing performance, gelatin as the reinforcing additive with different ratios were loaded via two methods including layer- by- layer and blending. A comparative study on structure properties between double layers and blending films made from casein and gelatin was obtained by scanning electron microscopy and Fourier transform infrared spectroscopy. The difference between the films' packing characters were conducted by water vapor permeability (WVP), optical property, and mechanical properties (including tensile strength (TS) and elongation (EAB)). The results showed that the degree of films roughness increased and the structural stability decreased as the increase of gelatin additive ratio in both double layers and blending films. Thickness and WVP both displayed a trend of increasing first then decreasing at the dividing of gelatin instead of casein in 50%. Importantly, WVP values in double layers film with a largest value of 6.95 gm⁻¹Pa⁻¹s⁻¹ was higher than blending films, observably (P < 0.05). Additionally, TS in blending film was increased by 23.44% than double layers film under the gelatin additive proportion of 70%, and EAB value in double layers film was larger by 207.65% than blending film under the gelatin additive proportion of 10%.     

Correlation of Rheological and Microstructural Properties in a Model Lipid System

Model systems having different microstructures and rheological properties were obtained by controlled crystallization from a mixture of high-melting and low-melting lipids. Based on analysis of confocal scanning light microscopic images, the microstructural characteristics of the systems were quantified by use of different approaches including microstructure density, Euler characteristic, nearest-neighbor analysis, fractal dimension of microstructure interface, and fractal dimension by the particle-counting method (PCM). The solid-fat content (SFC) of semisolid lipid samples was measured by nuclear magnetic resonance (NMR) spectroscopy and rheological properties were analyzed by compressive penetration tests with a texture analyzer. As expected, SFC had a major impact on rheological properties, but lipid crystalline microstructure also had significant effects. Correlation analysis showed that rheological properties were highly correlated with the various quantitative microstructural parameters, with the exception of the fractal dimension by the PCM. Empirical models adequately correlated rheological properties with SFC and microstructure density. Compression modulus increased by a factor of about ten as SFC increased from 0.28 to 0.51. However, for systems with the same SFC, compression modulus was dependent on microstructure. At low SFC compression modulus increased by about a factor of seven over the range of microstructures formed, whereas at higher SFC compression modulus only increased by a factor of about two.