Processing and properties of thermoplastic starch and its blends with sodium alginate

Viscosity measurements were carried out on corn starch (CS) and CS–sodium alginate (SA) suspensions at low levels of SA [1 to 10% (w/w)], as a function of temperature. The addition of SA caused the granular CS gelatinization process to occur at a lower onset temperature. CS and CS–SA mixtures were extruded in single‐ and twin‐screw extruders, with 15% glycerol and different water contents. Processing of plasticized CS–SA mixtures required lower temperatures, which is consistent with the viscosity results. Homogeneous and flexible extrudates were obtained by processing in a twin‐screw extruder. Samples in the composition range between 0 and 10% (w/w) SA were examined using tensile tests as a function of water content. Mechanical properties were dependent on the water content and on the SA composition. A significant increase in the Young's modulus value was observed for the blend containing 1% SA. Dynamic mechanical analysis was carried out for CS and CS–SA blends. Two transitions were detected in the temperature range –80 to 150°C. Scanning electron microscopy was used to examine the morphology of the extruded samples. The surfaces of the films were homogeneous, which demonstrated that the CS granules in all samples were characteristically destructured under the conditions used in processing. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 412–420, 2001     

Structure and properties of compression-molded thermoplastic starch materials from normal and high-amylose maize starches

The structural and mechanical properties of compression-molded normal and high-amylose maize starches were studied as a function of processing water content and ageing time. Rubbery thermoplastic starches were produced by compression molding of four maize starches with differences in amylose content and amylopectin structure. Glycerol (30% on the basis of dry starch) and water (between 10 and 35% on the basis of total mass) were used as plasticizers. After processing, the amorphous thermoplastic starch materials crystallized during ageing. The semicrystalline materials contained both E-type and V-type, as well as B-type crystallinity. The properties of the thermoplastic starch materials are dependent on water content during processing, starch source, and ageing time. The normal maize starch materials are highly flexible with elongations between 56 and 104%. The elongations of the high-amylose maize starch materials were between 5–35%. The tensile stress and E-modulus of the normal maize starch materials were in the range of 3.9–6.7 and 27–131 MPa, respectively. The tensile stress and E-modulus of the high-amylose maize starch materials increased from approximately 0.5 to 23 and 5 to 700 MPa, respectively, with increasing water content during processing from 10 to 35%. The differences in mechanical properties of the normal and high-amylose materials were explained by differences in the structure of the amylose and amylopectin structure. It was concluded that both lead to differences in the starch network. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 631–644, 1997     

From microstructure to mechanical properties of compatibilized polylactide/thermoplastic starch blends

Bio‐degradable polymer blends of polylactic acid/thermoplastic starch (PLA/TPS) were prepared via direct melt blending varying order of mixing of ingredients fed into the extruder. The effect of interface interactions between PLA and TPS in the presence of maleic anhydride (MA) compatibilizer on the microstructure and mechanical properties was then investigated. The prepared PLA/TPS blends were characterized by scanning electron microscopy, differential scanning calorimetry (DSC), tensile, and rheological measurements. Morphology of PLA/TPS shows that the introduction of MA into the polymer matrix increases the presence of TPS at the interface region. DSC results revealed the reduction of glass transition temperature of PLA with contributions from both TPS and MA. The crystallization temperature was decreased by the addition of MA leading to reduction of overall crystallization of PLA/TPS blend. The mechanical measurements show that increasing MA content up to 2 wt % enhances the modulus of PLA/TPS more than 45% compared to the corresponding blends free of MA compatibilizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44734.     

聚乙二醇改性淀粉/聚乳酸薄膜的结构与性质研究

将热塑性淀粉(TPS)与聚乙二醇(PEG)、聚乳酸(PLA)共混后,采用溶剂蒸发法制备出完全生物降解的聚乙二醇改性淀粉/聚乳酸薄膜(SPLA)。研究了SPLA膜的力学性能、耐水性,并对薄膜的结构进行了研究,结果表明聚乳酸可以明显改善淀粉基薄膜的耐水性与力学强度;当w(PLA)≤20%时,共混物各组分间有较好的相容性。SPLA膜的玻璃化转变温度低于淀粉和聚乳酸,XRD显示共混膜中淀粉和聚乳酸的颗粒结晶结构均受到破坏。     

Dynamic mechanical and thermal properties of the composites of thermoplastic starch and lanthanum hydroxide nanoparticles

Nanostructured lanthanum (III)‐oxide (La₂O₃) particles were prepared by a polymer complex solution method and further used for the preparation of lanthanum hydroxide (La(OH)₃) nanoparticles. The La(OH)₃ nanopowder was mixed with glycerol‐plasticized maize starch and the effect of the filler on the thermal, mechanical, and viscoelastic properties of the matrix was investigated. It was expected that this nanofiller, which shows an affinity toward OH groups, would strongly affect the physical properties of thermoplastic starch (TPS). The pure TPS and the TPS‐La(OH)₃ nanocomposite films (with 1, 2, and 3 wt % filler) were conditioned at various relative humidities (RHs) (35, 57, 75, and 99% RH). After conditioning at 99% RH, the pure TPS films exhibited higher affinity toward water than the nanocomposites. Differential scanning calorimetric measurements showed that, due to retrogradation effects, the melting enthalpies of the films increased with increasing RH. Dynamic mechanical analysis revealed that the mechanical properties in the linear range strongly depend on both the humidity conditions and the concentration of the filler. The results also show that La(OH)₃ nanoparticles are good reinforcement for TPS films. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication and properties of thermoplastic starch/montmorillonite composite using dialdehyde starch as a crosslinker

The poor mechanical properties and high water solubility of biodegradable thermoplastic starch (TPS) represent the main disadvantages of TPS in many applications. In this work, TPS film was prepared from a water solution of corn starch modified by 5 wt% dialdehyde starch (DAS) as crosslinking agent and 3 wt% montmorillonite (MMT) as reinforcing additive. Interactions occurring in the TPS films were investigated by Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, XRD, DSC, dynamic mechanical thermal analysis (DMTA) and TGA. The results obtained fom FTIR spectroscopy and DSC suggest the formation of hydrogen bond interactions between the hydroxyl group of starch, DAS, the MMT layers and glycerol. DMTA indicated that the relaxation of films with DAS and MMT appears in a higher and broader temperature range due to the starch backbone stiffness; the extreme increase in the storage modulus confirmed the suggested interactions. The determination of the weight loss of the films in water indicated a significant increase of the water resistance of TPS due to incorporation of DAS and MMT. Changes in mechanical properties of the films containing DAS and clay were determined, showing a substantial increase in tensile strength from 2.7 to 6.7 MPa, while Young's modulus increased by 15 times for TPS modified with 5% DAS and 3% MMT. Therefore, the outcomes of this study confirmed that DAS is a suitable biomacromolecule crosslinker for starch and can significantly enhance TPS and TPS/MMT properties. © 2019 Society of Chemical Industry     

Mechanical properties of thermoplastic elastomeric blends of chitosan and natural rubber latex

Thermoplastic chitosan/natural rubber blends (Cs/NR) were prepared from natural rubber latex and chitosan by solution casting technique. The blends were characterized by mechanical analysis (stress–strain) and the mechanical properties were found to vary with chitosan/natural rubber ratios. Experimental values were compared with different theoretical models. Effect of thermal aging on mechanical properties was also investigated. Dicumyl peroxide was used as the crosslinking agent. The effect of crosslinking on mechanical properties of Cs/NR has also been studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and properties of blends with different thermoplastic polyurethanes and polyolefines

Unmodified blends of two thermoplastic polyurethanes (TPU) and six polyolefines were used to study the influence of the component viscosities on the blend morphology and mechanical properties. Blends were produced by melt mixing using a twin screw extruder. Interactions between the blend components could not be detected by DSC, DMA, selective extraction, and SEM micrographs of cryofractures. The variation in tensile strength with blend composition produce a U-shaped curve with the minimum between 40 and 60 wt % of polyolefine. At similar viscosity ratios (η_d/η_m), blends with polyether based TPU (TPU-eth) have a finer morphology than blends with polyester based TPU (TPU-est). This is due to the lower surface free energy of the polyether soft segments compared to the polyester soft segments. Different morphologies also lead to changes in mechanical behavior. Blends with TPU-eth show a lower decrease in tensile strength with blend composition than blends with TPU-est. The viscosity ratio between TPU and polyolefines can be directly correlated to the blend morphology obtained under similar blending conditions. TPU/PE blends show a lower dispersity than TPU/PP blends, due to the higher viscosity ratios of TPU/PE blends. This results in a greater reduction in tensile strength with the disperse phase content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 749–762, 1997     

Preparation and studying properties of polybutene‐1/thermoplastic starch blends

Starch as an inexpensive and renewable source has been used as a filler for environmental friendly plastics for about two decades. In this study, glycerol was used as a plasticizer for starch to enhance the dispersion and the interfacial affinity in thermoplastic starch (TPS)/polybutene‐1(PB‐1) blend. PB‐1 was melt blended with TPS using a single screw extrusion process and molded using injection molding process to investigate the rheological and mechanical properties of these blends. Rheological properties were studied using a capillary rheometer, and the Bagley's correction was performed. Mechanical analysis (stress–strain curves) was performed using Testometric M350‐10 kN. The rheological properties showed that the melt viscosity of the blend is less than that of PB‐1, and the flow activation energy at a constant shear stress of the blend increases with increasing glycerol content in the blend. The mechanical experiments showed that both stress and strain at break of the blends are less than that of PB‐1, whereas the Young's modulus of the most blends is higher than that of PB‐1 which confirms the filling role of TPS in the blend. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of surface photocrosslinking on properties of thermoplastic starch sheets

The surface of glycerol plasticized thermoplastic starch (TPS) sheets was modified by photocrosslinking under ultra violet (UV) irradiation. Sodium benzoate was selected as photosensitizer and induced onto sheet surface layer by soaking the sample sheets in photosensitizer aqueous solution. The effects of concentration of the photosensitizer aqueous solution, soaking time and moisture content in sheets before UV irradiation on the photocrosslinking were investigated. Water contact angle, moisture absorption, and mechanical properties were measured to characterize the influence of the surface photocrosslinking modification on the properties of TPS sheets. The obtained results showed that the surface photocrosslinking treatments markedly reduced the water sensitivity of TPS sheets and enhanced their tensile strength and Young's modulus but decreased the elongation at break. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of biodegradable thermoplastic starch/poly(hydroxy butyrate) blends

The vital differences using three types of thermoplastic starches (TPS), including potato starch, corn starch, and soluble potato starch, with two different gelatinization degrees to blend with poly(hydroxy butyrate) (PHB) are thoroughly discussed in this study. For blends containing a certain amount of PHB, thermal stability remains in a certain degree. In all cases of this study, mechanical properties of TPS blended with PHB confer higher performance than those of pristine TPS. In particular, a significant increase on tensile strength and tear strength is observed for TPS (potato starch) blended with PHB at low gelatinization degree. A suitable degree of gelatinization of starch is critical to achieve optimum performance. The investigation on the morphological observation partly features the supporting evidence of the above findings. The assessment of biodegradability indicates that the values of water absorption and weight loss increase with increasing treatment period and glycerol content, but decrease with increasing amount of PHB content. Among three types of starches investigated, the TPS (soluble starch)/PHB blend gives the highest level of water absorption and weight loss. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2371–2379, 2006     

Thermoplastic starch/PVAl compounds: Preparation,processing, and properties

As a renewable and native polymeric material, thermoplastic starch is gaining increased acceptance because of resource and environment concerns. This study reports the formulation design of native starch/polyvinyl alcohol (PVAl) compounds; the preparation technology to make them available for thermoplastic processing; and their rheological, mechanical, and degradation properties. Among various plasticizers investigated, a mixture of glycerin and water (50/50 wt %) is found to be the best one for the compounds in terms of rheological behavior, mechanical properties, and environmental stability. The mechanical properties do not increase with the PVAl content to an expected extent, mainly due to the poor interface adhesion between the fibrous PVAl structure and the starch matrix. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2667–2673, 1999     

Effect of metal oxide as antibacterial agent on thermoplastic starch/metal oxide biocomposites properties

ABSTRACT

This research was purposed at studying the effect of the addition of metal oxide (MO) as antibacterial agent on thermoplastic starch (TPS) properties. TPS/MO biocomposites with 0.1 until 2.0 phr of metal oxide were prepared. Antibacterial activity of TPS and TPS/MO biocomposites against bacteria was investigated. The inhibition zone of biocomposite films was dramatically increased along with the increasing of metal oxides contents. The addition of ZnO content resulted in an increase in inhibition zone for E. coli and S. aureus. The incorporation of MO into TPS/MO biocomposites tends to reduce mechanical properties, the mass loss and T50% of TPS/MO biocomposites.     

Formamide as the plasticizer for thermoplastic starch

As a novel plasticizer, formamide was tested in thermoplastic starch (TPS), in which native cornstarch granules were proved to transfer to a continuous phase by scanning electron microscope (SEM) and the hydrogen bond interaction between plasticizer and starch was proved by Fourier transform infrared (FTIR) spectroscopy. Mechanical tests showed that tensile strength and Young's modulus of formamide‐plasticized TPS (FPTPS) were lower than glycerol‐plasticized TPS (GPTPS) and elongation at break and energy break were higher. The effect of formamide and glycerol on the retrogradation of TPS was studied using X‐ray diffractometry. Formamide could effectively restrain the starch retrogradation at three different relative humidity (RH) environments, because it could form the more stable hydrogen bonds with the starch hydroxy group than glycerol. From these results, we found that the elongation at break, energy break, and the retrogradation of TPS were ameliorated by formamide. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1769–1773, 2004     

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     

Morphology and rheological properties of compatibilized low‐density polyethylene/linear low‐density polyethylene/thermoplastic starch blends

Morphology and rheological properties of low‐density polyethylene/linear low‐density polyethylene/thermoplastic starch (LDPE/LLDPE/TPS) blends are experimentally investigated and theoretically analyzed using rheological models. Blending of LDPE/LLDPE (70/30 wt/wt) with 5–20 wt % of TPS and 3 wt % of PE‐grafted maleic anhydride (PE‐g‐MA) as a compatibilizer is performed in a twin‐screw extruder. Scanning electron micrographs show a fairly good dispersion of TPS in PE matrices in the presence of PE‐g‐MA. However, as the TPS content increases, the starch particle size increases. X‐ray diffraction patterns exhibit that with increase in TPS content, the intensity of the crystallization peaks slightly decreases and consequently crystal sizes of the blends decrease. The rheological analyses indicate that TPS can increase the elasticity and viscosity of the blends. With increasing the amount of TPS, starch particles interactions intensify and as a result the blend interface become weaker which are confirmed by relaxation time spectra and the prediction results of emulsion Palierne and Gramespacher‐Meissner models. It is demonstrated that there is a better agreement between experimental rheological data and Coran model than the emulsion models. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44719.     

二氧化硅粒子对热塑性木薯淀粉稳定性能的影响

通过添加二氧化硅(SiO2)到木薯淀粉(TPS)中,采用熔融共混法制备热塑性TPS/SiO2复合材料,研究复合材料的吸水性、生物降解性和熔融行为。结果表明,随着SiO2添加量的增加,TPS吸水率呈下降趋势,且添加经过硅烷偶联剂(KH550)表面处理后的纳米SiO2比未处理的吸水率低。随着生物降解时间的增加,TPS/SiO2复合材料的生物降解率提高;随着SiO2用量的增加,TPS的生物降解率呈下降变化,且SiO2表面处理后能明显提高TPS的生物降解性。随着SiO2用量的增加,TPS的熔融峰增加,且添加SiO2表面处理后的TPS熔融峰比未经表面处理的SiO2高。     

Thermoreversible crosslinked thermoplastic starch

A novel furan‐modified thermoreversible crosslinked thermoplastic starch was synthesized. The crosslinking mechanism was based on a thermoreversible furan/maleimide adduct formed by the Diels ? Alder reaction. Thermoplastic starch (TPS) was first modified by forming a urethane linkage between the product of the reaction of furfuryl alcohol with 4,4‐methylene diphenyldiisocyanate and a starch hydroxyl group. Crosslinking was then achieved by the addition of 1,1′‐(methylene‐di‐4,1‐phenylene) bismaleimide to the furan‐grafted starch in solution (dimethylsulfoxide) and in the molten state during conventional extrusion. The materials were characterized by Fourier transform infrared and ¹H NMR spectroscopy. The thermoreversible reaction was assessed by viscosity measurement and ¹H NMR, for the system in dimethylsulfoxide, and by solubility tests, hot‐pressing experiments and dynamic mechanical analysis measurements for the extruded product. The crosslinked product showed a higher storage modulus and water resistance than its non‐crosslinked counterpart, opening novel opportunities to widen the range of TPS applications. © 2015 Society of Chemical Industry     

PBTA/TPS共混物的结构、性能和断裂行为

将热塑性淀粉(TPS)与聚(对苯二甲酸丁二醇酯-己二酸丁二醇酯)(PBAT)挤出共混并注塑成型,制备了可完全生物降解的TPS/PBAT复合材料制品。采用扫描电子显微镜研究了注塑复合材料的层次结构与微观形态,测试了不同组分复合材料的性能和应力应变行为。结果表明：TPS在PBAT中呈皮芯结构分布,随含量增加逐渐由芯层向皮层分布。当含量为45%时,芯层到皮层形成均匀的以纤维为主的分散相形态,提高了复合材料的力学性能。加入TPS后会改变复合材料的形变行为,由类似半结晶聚合物的应力应变行为转变为屈服-冷拉行为。     

Rheological,mechanical, thermal,and morphological properties of blends poly(butylene adipate-co-terephthalate), thermoplastic starch,and cellulose nanoparticles

The objective of the present study was the preparation and characterization of poly(butylene adipate-co-terephthalate) (PBAT) and thermoplastic starch (TPS) blends reinforced with cellulose nanoparticles (CNCs) by extrusion. The work was conducted in four steps. Initially, the CNCs were prepared from eucalyptus cellulose pulp by acid hydrolysis. The second step was the preparation of the nanocomposite (TPS-CNC), composed of cassava starch, CNC, glycerol, and citric and stearic acids, by double screw extrusion. The third step was the preparation of PBAT/TPS-CNC blends in twin-screw extruders. In the fourth step, the films were produced by flat extrusion. Blends exhibited similar rheological behavior, increasing the CNC concentration in blends increased the viscosity as a function of the shear rate, and altered the behavior of the shear storage (G′) and shear loss (G″) curves as a function of the oscillation frequency (ω). The presence of CNC in blend provided improvements significant in mechanical properties, with 120% increase in Young's modulus, and 46% increase in maximum tensile. Thermal behavior (thermogravimetric analysis and differential scanning calorimetry) was altered with the incorporation of the CNC, showing a single melt peak (T_m) and a slight increase in T_g, indicating good dispersion between the phases of the blends, corroborating with the fracture surface microscopy of films.