Studies on the structure and properties of thermoplastic starch/luffa fiber composites

Thermoplastic starch (TPS)/luffa fiber composites were prepared using compression molding. The luffa fiber contents ranged from 0 wt.% to 20 wt.%. The tensile strength of the TPS/luffa fiber composite with 10 wt.% of luffa fiber had a twofold increase compared to TPS. The temperature values of maximum weight loss of the TPS/luffa fiber composites were higher than for TPS. The water absorption of the TPS/luffa fiber composites decreased significantly when the luffa fiber contents increased. The strength of adhesion between the luffa fiber and the TPS matrix was clearly demonstrated by their compatibility presumably due to their similar chemical structures as shown by scanning electron microscope (SEM) micrographs and Fourier transform infrared (FTIR) spectra.     

热塑性淀粉/NCC纳米复合薄膜的制备及性能

先用硫酸水解微晶纤维素制得纳米纤维素晶体(NCC),再用溶液浇铸成膜法制得甘油塑化热塑性淀粉/NCC纳米复合薄膜,并考查NCC含量对纳米复合薄膜性能的影响.结果表明:当NCC含量小于9%时,拉伸强度和断裂伸长率均随NCC含量增加而增大,热稳定性也增强;当NCC含量增加到12%时,力学性能和热稳定性反而变差.添加不同含量NCC后,纳米复合薄膜的吸水率没有明显改变,透光率有所降低.     

Effect of jute and kapok fibers on properties of thermoplastic cassava starch composites

Since mechanical properties and water uptake of biodegradable thermoplastic cassava starch (TPCS) was still the main disadvantages for many applications. The TPCS matrix was, therefore, reinforced by two types of cellulosic fibers, i.e. jute or kapok fibers; classified as the low and high oil absorbency characteristics, respectively. The TPCS, plasticized by glycerol, was compounded by internal mixer and shaped by compression molding machine. It was found that water absorption of the TPCS/jute fiber and TPCS/kapok fiber composites was clearly reduced by the addition of the cellulosic fibers. Moreover, stress at maximum load and Young’s modulus of the composites increased significantly by the incorporation of both jute and kapok fibers. Thermal degradation temperature, determined from thermogravimetric analysis (TGA), of the TPCS matrix increased by the addition of jute fibers; however, thermal degradation temperature decreased by the addition of kapok fibers. Functional group analysis and morphology of the TPCS/jute fiber and TPCS/kapok fiber composites were also examined using Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) techniques.     

改性处理对热塑性聚合物基复合材料性能的影响

研究了冷却方式及改性处理对玻纤增强热塑性聚合物复合材料性能的影响.采用模压工艺制备复合材料,研究冷却方式、偶联剂处理及等离子改性处理对玻纤增强聚丙烯力学性能的影响,并通过DSC分析复合体系结晶性能的变化规律.结果表明:采用同加热板一起冷却的复合材料结晶性能较好,材料的拉伸性能最高;改性处理在一定程度上改善了材料的界面结...     

Studies on mechanical properties of wood fiber reinforced cross-linked starch composites made from enzymatically degraded allylglycidyl ether-modified starch

In a previous work we introduced a new family of thermoset composites of softwood fiber and allylglycidyl ether modified potato starch (AGE-starch with a degree of substitution of 1.3 and 2.3) prepared by hot pressing. To improve the processability of AGE-starch with a DS = 1.3 (LDS-3) and to increase hygromechanical properties, the LDS-3 matrix has now been partially degraded by α-amylase at 45 °C (pH 6) for 0.5, 6 and 18 h. The study shows that already a 30 min enzymatic hydrolysis has a marked effect on the modified starch molecular weight and its thermal properties. The new composites with enzyme hydrolyzed AGE-starch, generically named D-LDS-3, showed good fiber dispersion and excellent interface between the fiber and matrix as studied by SEM. Premixes of D-LDS-3 matrix and fiber showed improved processability. The water vapor absorption was evaluated at 43.2% and 82.2% RH and the stiffness and strength properties were measured. The water uptake was shown to be reduced. The strength of neat matrix D-LDS-3-6 at ambient 68% RH reached 63 MPa and Young’s modulus 3200 MPa and with 40 wt.% wood fiber reinforcement impressive 128 MPa and 4500 MPa, respectively.     

The effects of composition and processing variables on the properties of thermoplastic polyaniline blends and composites

Pure polyaniline (PANI) has a high electrical conductivity and can be made soluble and thermoplastic, but it still lacks adequate mechanical properties for large-scale commercial use and therefore, it has been blended with other polymers such as poly(methyl methacrylate) (PMMA). In the work described in this paper, the scaled up synthesis of conductive polyaniline by an oxidative chemical method under controlled pH and temperature has been optimised. Re-doping of deprotonated insulating base with excess of the mono-functional organic acids such as p-toluenesulfonic (TSA) or dodecylbenzenesulfonic (DBSA) in aqueous media was successful. A wide range of techniques including TGA, GPC, EA, FTIR, XRD and SEM were employed for the characterisation of PANI powders and blends. Compositions of PANI-HCI, TSA or DBSA and thermoplastic matrix PMMA with or without a plasticiser were melt-processed by compression moulding for 3 min at 210°C to produce plaques. The effectiveness of four different phenolic plasticisers was compared and hydroquinone was found to produce the blends with the highest conductivities. A few preliminary injection-moulded plaques were made and their conductivities were compared with those of the compression-moulded samples.     

Thermal properties of thermoplastic starch/synthetic polymer blends with potential biomedical applicability

Previous studies shown that thermoplastic blends of corn starch with some biodegradable synthetic polymers (poly(-caprolactone), cellulose acetate, poly(lactic acid) and ethylene-vinyl alcohol copolymer) have good potential to be used in a series of biomedical applications. In this work the thermal behavior of these structurally complex materials is investigated by differential scanning calorimetry (DSC) and by thermogravimetric analysis (TGA). In addition, Fourier-transform infrared (FTIR) spectroscopy was used to investigate the chemical interactions between the different components. The endothermic gelatinization process (or water evaporation) observed by DSC in starch is also observed in the blends. Special attention was paid to the structural relaxation that can occur in the blends with poly(lactic acid) at body temperature that may change the physical properties of the material during its application as a biomaterial. At least three degradation mechanisms were identified in the blends by means of using TGA, being assigned to the mass loss due to the plasticizer leaching, and to the degradation of the starch and the synthetic polymer fractions. The non-isothermal kinetics of the decomposition processes was analyzed using two different integral methods. The analysis included the calculation of the activation energy of the correspondent reactions.     

Improving the mechanical properties of thermoplastic starch/poly(vinyl alcohol)/clay nanocomposites

Thermoplastic starch/poly(vinyl alcohol) (PVOH)/clay nanocomposites, exhibiting the intercalated and exfoliated structures, were prepared via melt extrusion method. The effects of clay cation, water, PVOH and clay contents on clay intercalation and mechanical properties of nanocomposites were investigated. The experiments were carried out according to the Taguchi experimental design method. Montmorillonite (MMT) with three types of cation or modifier (Na⁺, alkyl ammonium ion, and citric acid) was examined. The prepared nanocomposites with modified montmorillonite indicated a mechanical improvement in the properties in comparison with pristine MMT. It was also observed that increases in tensile strength and modulus would be attained for nanocomposite samples with 10%, 5% and 4% (by weight) of water, PVOH and clay loading, respectively. The clay intercalation was examined by X-ray diffraction (XRD) patterns. The chemical structure and morphology of the optimum sample was also probed by FTIR spectroscopy and transmission electron microscopy (TEM).     

New biocomposites based on thermoplastic starch and bacterial cellulose

Bacterial cellulose, produced by Acetobacter Xylinum, was used as reinforcement in composite materials with a starch thermoplastic matrix. The composites were prepared in a single step with cornstarch by adding glycerol/water as the plasticizer and bacterial cellulose (1% and 5% w/w) as the reinforcing agent. Vegetable cellulose was also tested as reinforcement for comparison purposes. These materials were characterized by different techniques, namely TGA, XRD, DMA, tensile tests, SEM and water sorption assays. All composites showed good dispersion of the fibers and a strong adhesion between the fibers and the matrix. The composites prepared with bacterial cellulose displayed better mechanical properties than those with vegetable cellulose fibers. The Young modulus increased by 30 and 17 fold (with 5% fibers), while the elongation at break was reduced from 144% to 24% and 48% with increasing fiber content, respectively for composites with bacterial and vegetable cellulose.     

Injectable hydrogel wound dressing based on strontium ion cross-linked starch

Severe skin wounds cause great problems and sufferings to patients. In this study, an injectable wound dressing based on strontium ion cross-linked starch hydrogel (SSH) was developed and evaluated. The good inject-ability of SSH made it easy to be delivered onto the wound surface. The good tissue adhesiveness of SSH ensured a firm protection of the wound. Besides, SSH supported the proliferation of NIH/3T3 fibroblasts and facilitated the migration of human umbilical vein endothelial cells (HUVECs). Importantly, SSH exhibited strong antibacterial effects on Staphylococcus aureus (S. aureus), which could prevent wound infection. These results demonstrate that SSH is a promising wound dressing material for promoting wound healing.     

Effects of glycerin and glycerol monostearate on performance of thermoplastic starch

The effects of glycerin and glycerol monostearate (GMS) on a variety of properties of anhydrous wheat starch are explored by means of DSC, TGA, as well as mechanical, rheological and moisture sorption assessment. It is found that, as glycerin content (GC) increases, both melting point and degradation temperature decrease, and the range of the processing window extends. Melt viscosity of the glycerin-plasticized starch depends on shear rate following power law, exponentially on GC, and on temperature in Arrhenius type. Increasing GC leads to a linear increment of the equilibrium moisture sorption, which, however, can be depressed significantly by incorporating a small amount of GMS. Moreover, the presence of 2% GMS in the formulations can efficiently reduce the melt viscosity and enhance its temperature sensitivity while has insignificant effect on the non-Newtonian behaviour and mechanical properties.     

Effect of carrageenan on properties of biodegradable thermoplastic cassava starch/low-density polyethylene composites reinforced by cotton fibers

Applications of biodegradable thermoplastic starch (TPS) have been restricted due to its poor mechanical properties, limited processability and high water uptake. In order to improve properties and processability, thermoplastic cassava starch (TPCS) was compounded with low-density polyethylene (LDPE). The TPCS/LDPE blend was, then, modified by a natural gelling agent, i.e. carrageenan and natural fibers, i.e. cotton fibers. All composites were compounded and processed using an internal mixer and an injection molding machine, respectively. It was found that stress at maximum load and Young’s modulus of the TPCS/LDPE composites significantly increased by the addition of the carrageenan and/or the cotton fibers. The highest mechanical properties were obtained from the TPCS/LDPE composites modified by both the carrageenan and the cotton fibers. Percentage water absorption of all of the TPCS/LDPE composites was found to be similar. All modified composites were also degraded easier than the non-modified one. Furthermore, all the composites were analyzed using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Scanning electron microscopy (SEM).     

Effect of heat treatment of starch on the properties of the starch hydrogels

Development of hydrogels prepared by crosslinking of corn starch and polyvinyl alcohol with glutaraldehyde was attempted. The membranes were characterized by FTIR spectroscopy and XRD. The mechanical properties of the hydrogels were characterized by tensile tests. Diffusion studies of salicylic acid and gatifloxacin through the membranes were also evaluated. FTIR spectroscopy indicated absence of carbonyl group absorption band of glutaraldehyde and presence of hydroxyl group in the hydrogel membranes. XRD studies indicated that the crystallinity of the membranes was mainly due to PVA. The membranes had sufficient strength to be used for biomedical applications. Diffusion studies indicated diffusion of both anionic and cationic drugs through the hydrogel membranes.     

Natural fiber-reinforced thermoplastic starch composites obtained by melt processing

Thermoplastic starch (TPS) from industrial non-modified corn starch was obtained and reinforced with natural strands. The influence of the reinforcement on physical–chemical properties of the composites obtained by melt processing has been analyzed. For this purpose, composites reinforced with different amounts of either sisal or hemp strands have been prepared and evaluated in terms of crystallinity, water sorption, thermal and mechanical properties. The results showed that the incorporation of sisal or hemp strands caused an increase in the glass transition temperature (T_g) of the TPS as determined by DMTA. The reinforcement also increased the stiffness of the material, as reflected in both the storage modulus and the Young’s modulus. Intrinsic mechanical properties of the reinforcing fibers showed a lower effect on the final mechanical properties of the materials than their homogeneity and distribution within the matrix. Additionally, the addition of a natural latex plasticizer to the composite decreased the water absorption kinetics without affecting significantly the thermal and mechanical properties of the material.     

Preparation and characterization of melt-extruded thermoplastic starch/clay nanocomposites

A series of gelatinized starch–clay nanocomposites which exhibit intercalated and exfoliated structures have been developed. Various nanoclay dispersions were prepared (either by standard mixing or through the use of ultrasonics) prior to their combination with a high amylose content starch using high-speed mixing and extrusion technology. Intercalated and exfoliated type structures were observed in the sheet extruded nanocomposites using X-ray diffraction and transmission electron microscopy (TEM). Due to the hydrophilic nature of the gelatinized starch nanocomposite a novel preparatory technique was developed to produce nano scale sections for TEM. A range of plasticiser levels were used in conjunction with different unmodified nanoclays (sodium montmorillonite (Na-MMT) and fluorohectorite (Na-FHT)) having different cationic exchange capacities. It was shown that an optimum level of both plasticiser and nanoclay existed to produce a gelatinized starch film with the highest levels of exfoliation, resulting in superior properties. The use of ultrasonics was only advantageous in terms of clay dispersions at medium clay concentrations in the Na-MMT nanocomposites and higher clay concentrations in the Na-FHT, most probably due to the difference in cationic exchange capacity; however when the level of clay, water and starch was optimised an exfoliated structure was produced via standard mixing which exhibited comparable improvements in mechanical properties to ultrasonically treated samples.     

热塑性乙酰化淀粉/聚乳酸的性能及形态

采用熔融共混的方法制备了热塑性乙酰化淀粉(TPAS)/聚乳酸(PLA)复合材料, 研究了TPAS/PLA复合材料力学性能、 热性能和形态结构。TPAS以乙酰化改性淀粉为基体, 甘油为增塑剂。实验结果表明: 随着TPAS含量的增加, TPAS/PLA复合材料韧性明显提高, 当TPAS加入量为40%(质量分数)时, 断裂伸长率提高4倍多, 同时TPAS的加入对复合材料的热稳定性影响不大。DSC、 DMTA和SEM分析结果表明, PLA与TPAS是不相容的。     

Morphological and thermomechanical characterization of thermoplastic starch/montmorillonite nanocomposites

A combination of starch and clay for the preparation of nanocomposite materials is proposed. In this work, starch was plasticized by pequi (Caryocar brasiliense) oil, and thermoplastic starch (TPS)/montmorillonite (MMT) nanocomposites were analyzed by X-ray diffraction (XRD), thermogravimetry (TG), thermomechanical analyses (TMA) and scanning electron microscopy (SEM). Exfoliated and intercalated nanocomposites were found to be dependent on MMT content. Exfoliation is the predominant mechanism of clay dispersion for low filler loading. Increase of the clay loading (>5 wt.%) causes intercalation. The introduction of low content (?5 wt.%) of MMT improves the thermal stability and the stiffness of the materials. There is a limit content of clay that can be added to improve the thermal and thermomechanical properties of the composites. Beyond that value the composite presents properties below the original polymer.     

The influence of starch swelling on the material properties of cooked potatoes

Cooked potatoes have a wide range of food applications, but the mechanism by which softening occurs on heating is not clearly understood. Heating potato parenchyma tissue results in two independent, concurrent events; weakening of the binding between cells and swelling of intra-cellular starch. Potato plants containing starches with a range of high amylose contents and reduced swelling properties were available. This provided the opportunity to separate cooking effects of inter-cellular pectin from swelling of intra-cellular starch. Their individual contribution to the separation of cells and the softening of cooked potato tissue was established by studying the influence of heat on the material properties of a range of starch-modified potatoes. For all potato lines studied, the strength of the heated tissue decreased markedly following 30 minutes at 80°C or 5 minutes at 100°C. Microscopy of the line in which there was minimal starch swelling, indicated that the cells of the cooked tissue principally contained fluid, in contrast to the controls in which the cells were filled with swollen starch on cooking. Since all the lines followed the same trend with regard to the thermal weakening of the tissue, we conclude that weakening of potato tissue on cooking is primarily controlled by thermal degradation of the middle lamella.     

High molecular weight plasticizers in thermoplastic starch/polyethylene blends

In this study thermoplastic starch (TPS) was prepared with four different molecular weight polyol plasticizers: glycerol, sorbitol, diglycerol and polyglycerol. Diglycerol-TPS (DTPS) and polyglycerol-TPS (PTPS) show significantly lower moisture uptake and a higher temperature stability when compared to conventional glycerol-TPS (GTPS). TPS formulations were blended with HDPE at a concentration of 20 TPS/80 HDPE wt% and a range of interfacial modifier contents via a one-step extrusion process. The emulsification curves of the blends, which track the volume and number average diameter of the dispersed TPS domains with per cent interfacial modifier, show significantly different profiles and a non-correspondence between the d _n and d _v values at the critical concentration for interfacial saturation. The addition of small amounts of interfacial modifier to the blends prepared with diglycerol and polyglycerol results in TPS dispersed phases of wide polydispersity with droplets in the order of 200–300 nm coexisting with droplets of 5–7 µm. This wide polydispersity of TPS phase size can give insight into the mechanism of droplet formation in these systems with interfacial modifier and is indicative of an erosion-type mechanism, where small portions of the TPS droplet break off at the outer part of the droplet. Blends prepared with GTPS and sorbitol-TPS do not display this behaviour and show a more classic correspondence of d _n and d _v at the critical concentration. Dynamic mechanical analysis shows miscible behaviour for DTPS and PTPS and partially miscible behaviour for GTPS. This phenomenon was attributed to the presence of ether bonds in the chemical structure of diglycerol and polyglycerol. The increased chain flexibility and lower cohesive energy forces of diglycerol and polyglycerol lead to a more homogeneous TPS phase and consequently an erosion-type compatibilization at the interface. The mechanical properties of blends prepared with polyglycerol and diglycerol show a similar overall behaviour to glycerol.     

Enzymatic degradation of starch thermoplastic blends using samples of different thickness

The material studied was a thermoplastic blend of corn starch with a poly(ethylene-vinyl alcohol) copolymer, SEVA-C. The influence of both the material's exposed surface and enzyme concentration on degradation kinetics was studied. As alpha-amylase is present in the blood plasma, experiments were performed, varying the material thickness and the alpha-amylase between 50 and 100 units/l, at 37 degrees C, lasting up to 90 days. Four different batches using SEVA-C and starch samples of different thickness were performed. The positive correlation between degradation rate and the exposed material surface was confirmed, since thin films with larger exposed surfaces were degraded faster than thick square plates having the same total mass. The degradation extent depends on the total amount of amorphous starch present in the formulation rather than on the amount of enzyme used and the minimum thickness to ensure maximum degradation was estimated to be close to 0.25 mm.