Mechanical and morphological characterization of starch/zein blends plasticized with glycerol

Blends of starch and zein plasticized with glycerol were prepared by melting in a batch mixer at 160°C. Glycerol was used as plasticizer in contents ranging from 20 to 40 wt % with respect to the starch/zein matrix. These blends were characterized by mechanical tests, dynamic mechanical analysis, and optical microscopy. In tensile tests, the Young's modulus and ultimate tensile strength increased with increasing zein content for all compositions, whereas elongation at break decreased sharply with increasing zein content up to 20%, and it remained nearly constant at higher contents of zein, which increased the stiffness of the blends. On the other hand, increase in the glycerol content caused a decrease in mechanical resistance of the blends. Storage modulus increased with increasing zein content and the tan δ curves showed that the blends exhibited two distinct glass transitions, one for each component, indicating a two‐phase system, confirming the morphological evidence of micrographs that displayed two separate phases. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4133–4139, 2006     

Structure and mechanical properties of soy protein materials plasticized by Thiodiglycol

Thiodiglycol (TDG) is a relatively nontoxic compound from organic wastes. By using TDG as a plasticizer with weights from 2.5 to 40%, we prepared soy protein isolate (SPI) films by a compression‐molding technique at 140°C and 15 MPa. The TDG‐plasticized films (SPI–TDG films) were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, dynamic mechanical thermal analysis, thermogravimetric analysis, optical transmittance, and water uptake experiments. The SPI–TDG film plasticized with 25% TDG exhibited good mechanical properties, such as a tensile strength and modulus of 20.3 and 582 MPa, respectively, whereas the SPI–glycerol film with 25% glycerol had a tensile strength and modulus of 16.2 and 436 MPa, respectively. The results from the thermogravimetric analysis and water uptake experiments indicated that the thermal stability and water resistance of the TDG‐plasticized SPI materials were higher than that of the glycerol‐plasticized one. The improvements in the mechanical properties, water resistance, and thermal stability of the SPI–TDG films could be attributed to the strong intermolecular hydrogen bonding between soy protein and TDG and the presence of fewer hydroxyl groups in TDG, as compared structurally with glycerol. This study provided a new plasticizer for the preparation of soy protein materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical properties and water vapor permeability of thin film from corn hull arabinoxylan

Isolated corn hull arabinoxylan was dissolved in water and provided a clear solution. Plasticizer (glycerol, propylene glycol, or sorbitol) was added to the arabinoxylan solution at 0–20 wt % (film dry weight), which was cast into stable films. Film thickness ranged from 22 to 32 μm. Mechanical properties, moisture content, and water vapor permeability (WVP) were studied for the arabinoxylan‐based films as a function of plasticizer concentration. Measured data for the corn hull arabinoxylan–based films were 13–18 wt % moisture content, 10–61 MPa tensile strength, 365–1320 MPa modulus, 6–12% elongation, and 0.23–0.43 × 10^?10 g m^?1 Pa^?1 s^?1 water vapor permeability. Plasticized arabinoxylan films produced in this study had lower WVPs than those of unplasticized films, which is likely attributable to the phenomenon known as antiplasticization. Scanning electron micrographs showed a homogeneous structure on film surfaces. Films containing sorbitol had the best moisture barrier properties. When grapes were coated with arabinoxylan and arabinoxylan/sorbitol films, weight loss rates of the fruit decreased by 18 and 41%, respectively, after 7 days. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2896–2902, 2004     

Mechanical properties of nanocomposites from sorbitol plasticized starch and tunicin whiskers

Nanocomposite materials were obtained using sorbitol plasticized waxy maize starch as matrix and tunicin whiskers as the reinforcement. The effect of filler load (0–25 wt % whiskers) and the relative humidity levels (0–98%) on the mechanical behavior of the films are discussed for linear and nonlinear deformation. The performance of the films is explained, based on the morphology and structural behavior of the composite materials (Mathew and Dufresne, Biomacromolecules 2002, 3, 609). The nanocomposites exhibit good mechanical strength due to the strong interaction between tunicin whiskers, matrix, plasticizer (sorbitol), and water, and due to the ability of the cellulose filler to form a rigid three‐dimensional network. The evolution of T_g as a function of relative humidity level and filler load is studied in detail. A decrease in crystallinity of the amylopectin phase is observed at high filler loads, due to the resistance to chain rearrangement imposed by the whiskers. The mechanical strength increased proportionally with filler loads, showing an effective stress transfer from the matrix to the whiskers. An even distribution of whiskers (as determined by SEM) and plasticizer in the matrix contributes to the mechanical performance. The mechanical properties of the nanocomposites showed a strong dependence on relative humidity conditions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and mechanical properties of poly(vinyl alcohol) plasticized with glycerol

Thermomechanical behavior of membranes based on blends of poly(vinyl alcohol) (PVA) with different weight percentage (wt %) of glycerol has been studied. Solid‐state PVA/Glycerol polymer membranes were prepared by a solution casting method. The films were studied for thermal characteristics by differential scanning calorimetry (DSC) and thermogravimetric analysis and for the mechanical properties including hardness and modulus by nanoindentation method. The dispersion of glycerol within the polymer matrix was examined using scanning electron microscopy. Fourier transform infrared spectroscopy was used to confirm the formation of hydrogen bonding between the plasticizer and PVA in their blends and also to provide information on compatibility and physical interactions between the glycerol and PVA. It was found that the thermal properties particularly the melting point (T_m) for PVA blends exhibit a reduced value proportional to the glycerol content. The hardness and elastic modulus were also found to decrease with an increase in plasticizer content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Glycerol‐plasticized spirulina–poly(vinyl alcohol) films with improved mechanical performance

Spirulina–poly(vinyl alcohol) (PVA)–glycerol (SPG) films with improved mechanical performance, especially tensile strength (TS) and the elongation at break (EAB), are fabricated by a casting method. The integrity, color, solubility, microstructure, thermal properties, tensile strength, and compatibility of the SPG films are assessed. SPG films became smooth, homogeneous, and flexible after plasticizing with glycerol. The presence of PVA and hydrogen bonding of PVA with glycerol and spirulina protein improves the water resistance of SPG films by decreasing water absorption of spirulina protein and decreasing water diffusion through the films. The amount of carbonaceous residues decreases from 31% to 14% because of the co‐pyrolysis of spirulina, PVA, and glycerol. TS increases from 2.5 to 26 Mpa and modulus from 53 to 610 Mpa with increasing PVA content. Glycerol enhances film flexibility and EAB up to 50%. Spirulina can be composited with hydrophilic polymers to fabricate compatible, processable and thermally recyclable films with desirable mechanical performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44842.     

Mechanical properties of silk fibroin–microcrystalline cellulose composite films

Silk fibroin–microcrystalline cellulose (cellulose whisker) composite films with varied compositions were prepared by casting mixed aqueous solution/suspensions of the two components. Silk fibroin was dissolved in 10M LiSCN followed by dialysis; a cellulose whisker suspension was prepared by sulfuric acid hydrolysis of tunicate cellulose. Macroscopically homogeneous films were obtained at all mixing ratios. While the Young's modulus of the composite films showed a linear, additive dependence on the mixing ratio, the tensile strength and ultimate strain showed a maximum at a 70–80% cellulose content, reaching five times those of fibroin‐alone or cellulose‐alone films. At the same mixing ratio, infrared spectra of the composite films showed a shift of the amide I peak from 1654 to 1625 cm^?1, indicating the conformational change of fibroin from a random coil to a β structure (silk II) at the whisker–matrix interface. This change seems to be induced by contact of fibroin molecules with a highly ordered surface of cellulose whisker. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3425–3429, 2002     

Nb–Si–N纳米复合薄膜中界面的结构与力学性能

为了考察Nb–Si–N纳米复合薄膜中的界面结构形式,采用基于密度泛函理论(DFT)的第一性原理方法,计算了单个Si原子在NbN晶体中固溶结构形式,以及Nb–Si–N中由Si原子形成的界面结构形式,并分别考察NbN、Nb–Si–N固溶结构及其界面结构形式的力学性能。计算结果表明:单个Si原子在NbN晶体中可以实现间隙固溶或置换固溶;Nb–Si–N中存在置换型界面与间隙型界面两类结构形式;Nb–Si–N固溶结构及其界面结构形式的弹性常数、体模量和剪切模量均低于NbN晶体的力学性能;较NbN的弹性模量各向异性有明显差异不同,置换型与间隙型界面的弹性模量各向异性并不十分突出,但是置换型与间隙型界面的弹性模量的最大值下降非常明显。     

聚乙烯/矿物粉复合降解薄膜的机械性能及光降解性能

用2%钛酸酯偶联剂对滑石粉、膨润土粉粒进行表面改性,通过双螺杆挤出机将改性滑石粉和膨润土分别与聚乙烯树脂(PE)得填充母料,其中无机填料占80%;以不同比例的填充母料与PE混和,采用吹塑法制备了单一填充母料(含滑石粉或膨润土)和混和填充母料(既有滑石粉又有膨润土)的PE/矿物粉复合薄膜。研究了填充母料对PE复合薄膜的机械性能和光降解性的影响,实验结果表明:两种母料都具有较好的成膜性,对薄膜产生一定的增强减韧作用;另外,在填充母料用量一样的情况下,滑石粉母料填充薄膜的力学性能高于膨润土的,而目单一母料填充薄膜的力学性能优于混和母料填充薄膜的力学性能。在自然光照和紫外光照实验中,PE/矿物粉复合薄膜的机械性能下降和红外光谱的变化显示了滑石粉和膨润土能够极大的促进PE薄膜的降解。     

Films made from poly(vinyl alcohol‐co‐ethylene) and soluble biopolymers isolated from municipal biowaste

Blends were obtained from poly(vinyl alcohol‐co‐ethylene) and water‐soluble biopolymers isolated from the alkaline hydrolysate of two materials sampled from an urban waste treatment plant: that is, an anaerobic fermentation digestate and a compost. The digestate biopolymers contained more lipophilic and aliphatic C and less acidic functional groups than the compost biopolymers. Evidence was obtained for a condensation reaction occurring between the biopolymers and the synthetic polymer. The thermal, rheological, and mechanical properties of the blends were studied. Films containing a low concentration (ca. 6–7%) of biopolymers exhibited up to three times higher yield strength than the neat synthetic polymer. The films' properties were found to be dependent on the concentration and nature of the biopolymers. The results offer a scope for investigating biopolymers sourced from other biowastes and for a better understanding of the reasons for the observed effects and exploiting their full potential for modifying or replacing synthetic polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41359.     

Mechanical and Optical Properties of Polyamide 6/Clay Nanocomposite Cast Films: Influence of the Degree of Exfoliation

PA6 nanocomposite films with different nanoclay dispersion degrees are prepared by melt compounding and cast extrusion. The dispersion of the MMT platelets (homogeneity and degree of exfoliation) is evaluated qualitatively by TEM and quantitatively by rheology and NMR; it ranges from microcomposites to highly exfoliated nanocomposites. Compared to neat PA6, the optical properties (clarity, gloss, haze) are worse for the microcomposites and better for the nanocomposites. The mechanical properties depend strongly on the exfoliation level. Better exfoliation leads to higher stiffness. The strain at break decreases compared to neat PA6 films even in the case of highly exfoliated nanocomposites films. At low MMT content, the microcomposite has a higher ductility than well exfoliated nanocomposites films.

     

Optical properties of plasticized polycarbonate

Optical properties of polycarbonate plasticized by pentaerythritol tris(1,1,2,3,3,3‐hexafluoropropyl) ether (HFP), diheptadecyl‐o‐phthalate and pentaerythrityl tetrabenzoate (TBP) have been determined at wavelengths from 300 to 700 nm. X‐ray diffraction analysis, which was used to examine the polymer structure, showed that all the plasticized systems were amorphous. HFP and, especially, TBP impeded crystallization of the polymer. Plasticized polycarbonate films remained transparent over long periods of time even if they were heated at a temperature higher than the polymer glass transition temperature. © 2003 Society of Chemical Industry     

Experimental Observations of Substrate Fracture Caused by Residually Stressed Films

Model systems for studying thin-film cracking consisting of thin plates of alumina and soda-lime glass were diffusion bonded to silica substrates at high temperature. Upon slow cooling, substrate fracture was induced by residual stresses from the thermal and elastic mismatch of the film and substrate. In particular, multiple substrate cracks formed parallel to the interface. The observed crack paths closely followed predictions based on a zero mode II stress intensity. Crack depths were found to be strongly dependent on the relative substrate thickness and the Young's modulus ratio.     

Kinetics and crystal structure of isothermal crystallization of poly(lactic acid) plasticized with triphenyl phosphate

In this article, the spherulitic growth rate of neat and plasticized poly(lactic acid) (PLA) with triphenyl phosphate (TPP) was measured and analyzed in the temperature range of 104–142°C by polarizing optical microscopy. Neat PLA had the maximum value of 0.28 μm/s at 132°C, whereas plasticized PLA had higher value than that of neat PLA, but the temperature corresponding to the maximum value was shifted toward lower one with increasing TPP content. The isothermal crystallization kinetics of neat and plasticized PLA was also analyzed by differential scanning calorimetry and described by the Avrami equation. The results showed for neat PLA and its blends with various TPP contents, the average value of Avrami exponents n were close to around 2.5 at two crystallization temperatures of 113 and 128°C, the crystallization rate constant k was decreased, and the half‐life crystallization time t_1/2 was increased with TPP content. For neat PLA and its blend with 15 wt % TPP content, the average value of n was 2.0 and 2.3, respectively, the value of k was decreased, and the value of t_1/2 was increased with crystallization temperature (T_c). Further investigation into crystallization activation energy ΔE_a of neat PLA and its blend with 15 wt % TPP showed that ΔE_a of plasticized PLA was increased compared to neat PLA. It was verified by wide‐angle X‐ray diffraction that neat PLA and its blends containing various TPP contents crystallized isothermally in the temperature range of 113–128°C all form the α‐form crystal. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Viscoelastic properties of plasticized PVC reinforced with cellulose whiskers

New nanocomposites are processed with a plasticized poly(vinyl chloride) matrix reinforced by cellulose whiskers whose characteristics are a high aspect ratio and a large interface area. Dynamic mechanical analysis performed on samples reinforced with a filler fraction of up to 12.4 vol % gives the viscoelastic properties of the composite above and below its glass transition temperature. Different theoretical predictions are proposed to describe this behavior, but none of them is found wholly satisfactory for describing the reinforcing effect of these fillers. A model based on the Halpin–Kardos equation, with the assumption of an immobilized phase around the whiskers, is developed to account for significant decrease in the modulus drop, on passing above the glass transition temperature. The small discrepancy between this model and the experimental modulus measured in the rubber plateau is discussed as a possible effect of a percolating whisker network whose crosslinks are assured by chains adsorbed onto the whisker surface. Swelling experiments support this hypothesis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1797–1808, 1999     

Dielectric and electromechanical studies of plasticized poly(vinyl chloride) fabricated from plastisol

Poly(vinyl chloride) (PVC) plastisol is used in many industrial applications and is considered an electrically inactive material. To explore the potential of plastisol as an electroactive material, the dielectric properties, space charge distribution, mechanical properties, internal structure and electromechanical behavior of plasticized PVC (PVC gel) prepared from plastisol by heating were investigated. The gel exhibited a large dielectric constant at low frequencies (1–1000 Hz), an asymmetric charge distribution and excellent mechanical properties. Various DC electric fields were applied to the gel placed parallel between two electrodes and the electrostatic adhesive force to the anode was measured. The results of small‐ and wide‐angle X‐ray scattering suggested that the electromechanical properties of the gel originated from the characteristics of the physical crosslinking distance (ca 20 nm) of PVC in the gel structure. Considering the dielectric properties, space charge density and adhesion force to the anode, PVC gels prepared from plastisol using the heating method have potential for use as electroactive materials. © 2013 Society of Chemical Industry     

Ageing of soft thermoplastic starch with high glycerol content

In this study, a soft and thermoplastic starch with an improved ageing‐resistant property was prepared by melt blending method for a biodegradable biomaterial. The glycerol content varies from 30 to 60 wt %. The aging temperature and humidity of the glycerol‐plasticized thermoplastic starch (GTPS) was 37°C and 50 ± 5 RH %, respectively. The retrogradation was characterized by X‐ray diffraction (XRD), dynamic mechanical thermal analysis (DMTA), Fourier transform infrared (FTIR), and the stress‐strain mechanical properties. The XRD results suggest that high content of glycerol promotes the formation of single helix structure of V‐type, but inhibits double helix structure of B‐type. Changing of the tan δ, storage modules (E′), and the glass transition temperatures as a function of glycerol content and ageing time was detected by DMTA. FTIR result shows that the shifting speed of the peak of hydroxyl group stretching fell as the glycerol content increased. The glycerol content has no obvious effect on the mechanical properties when it is high enough. Results from all characterizations demonstrate that the ageing speed is closely relative to the plasticizers content. The higher content of glycerol possesses an obviously inhibitory effect on the ageing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 574–586, 2007     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003     

Structure–Property–Process Relationship for Blown Films of Bimodal HDPE and Its LLDPE Blend

Blown films of bimodal‐high‐density polyethylene (HDPE) (BPE) and its blend containing 40 wt% of linear low‐density polyethylene (LLDPE) are prepared in various neck‐heights (NHs). The crystal structures of both films are investigated in detail using small‐angle X‐ray scattering and wide‐angle x‐ray diffraction techniques. The results show that the blending of LLDPE notably modifies the crystal structure of BPE, including crystal density (ρ_c), crystallite size of the 110 plane (〈L₁₁₀〉), thickness of the lamellar crystal (L_c), and grain widths of the lamellae. The relationships between NH, crystal structure, and the resistance of dart‐drop impact (DDI) are investigated for both BPE and BPE/LLDPE films. The results indicate that the reorientation of lamellae might be a primary factor responsible for the DDI property. However, large values of ρ_c, L_c, and 〈L₁₁₀〉 are required for the film to achieve high DDI.     

Dynamic mechanical and thermal properties of plasticized poly(lactic acid)

The blends of low molecular weight triacetin (TAC) and oligomeric poly(1,3‐butylene glycol adipate) (PBGA) were used as multiple plasticizers to lubricate poly(lactic acid) (PLA) in this study. The thermal and mechanical properties of plasticized polymers were investigated by means of dynamic mechanical analysis and differential scanning calorimetry. Atomic force microscopy (AFM) was used to analyze the morphologies of the blends. Multiple plasticizers were effective in lowering the glass transition temperature (T_g) and the melting temperature (T_m) of PLA. Moreover, crystallinity of PLA increased with increasing the content of multiple plasticizers. Tensile strength of the blends decreased following the increasing of the plasticizers, but increased in elongation at break. AFM topographic images showed that the multiple plasticizers dispersed between interfibrillar regions. Moreover, the fibrillar crystallite formed the quasicrosslinkings, which is another cause for the increase in elongation at break. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1583–1590, 2006