Thermoplastic cassava starch blend with polyethylene-grafted-maleic anhydride and gelatin core-shell structure compatibilizer.

Thermoplastic starch (TPS) was prepared from cassava starch blended with glycerol (70:30 w/w). Gelatin (Gel) was incorporated into the TPS in water. The TPS/Gel was melt-blended with polyethylene-grafted-maleic anhydride (PEMAH). Maximum tensile strength of the TPS/PEMAH/Gel10 (29.3 MPa) increased significantly compared to the TPS/PEMAH blend (6.3 MPa), while elongation at break was 70%. The morphology of the TPS/PEMAH showed co-continuous morphology, while phase inversion occurred with the addition of Gel. The Gel was dispersed in the TPS matrix and covered the PEMAH. The TPS/PEMAH/Gel was nanoparticles (200 nm) in the TPS matrix. It showed two melting temperatures for PEMAH due to two structures with different crystal sizes. Melt viscosity of the TPS/PEMAH was enhanced with increasing Gel as the reaction induced chain extension. FTIR and rheology measurements confirmed the reaction between -NH groups of Gel and MAH groups of PEMAH. This reaction improved interfacial adhesion, morphology, and the mechanical properties of the blends.

Sericin cocoon bio-compatibilizer for reactive blending of thermoplastic cassava starch.

Cassava starch was blended with glycerol to prepare thermoplastic starch (TPS). Thermoplastic starch was premixed with sericin (TPSS) by solution mixing and then melt-blended with polyethylene grafted maleic anhydride (PEMAH). The effect of sericin on the mechanical properties, morphology, thermal properties, rheology, and reaction mechanism was investigated. The tensile strength and elongation at break of the TPSS10/PEMAH blend were improved to 12.2 MPa and 100.4%, respectively. The TPS/PEMAH morphology presented polyethylene grafted maleic anhydride particles (2 µm) dispersed in the thermoplastic starch matrix, which decreased in size to approximately 200 nm when 5% sericin was used. The melting temperature of polyethylene grafted maleic anhydride (121 °C) decreased to 111 °C because of the small crystal size of the polyethylene grafted maleic anhydride phase. The viscosity of TPS/PEMAH increased with increasing sericin content because of the chain extension. Fourier-transform infrared spectroscopy confirmed the reaction between the amino groups of sericin and the maleic anhydride groups of polyethylene grafted maleic anhydride. This reaction reduced the interfacial tension between thermoplastic starch and polyethylene grafted maleic anhydride, which improved the compatibility, mechanical properties, and morphology of the blend.

Corn starch reactive blending with latex from natural rubber using Na+ ions augmented carboxymethyl cellulose as a crosslinking agent.

A mixture of corn starch and glycerol plasticizer (CSG) was blended with latex natural rubber (LNR) and carboxymethyl cellulose (CMC). The addition of 10 phr of CMC improved the Young's modulus (6.7 MPa), tensile strength (8 MPa), and elongation at break (80%) of the CSG/LNR blend. The morphology of the CSG/LNR/CMC blends showed a uniform distribution of LNR particles (1-3 µm) in the CSG matrix. The addition of CMC enhanced the swelling ability and water droplet contact angle of the blends owing to the swelling properties, interfacial crosslinking, and amphiphilic structure of CMC. Fourier transform infrared spectroscopy confirmed the reaction between the C=C bond of LNR and the carboxyl groups (-COO-) of CMC, in which the Na+ ions in CMC acted as a catalyst. Notably, the mechanical properties of the CSG/LNR/CMC blend were improved owing to the miscibility of CSG/CMC and the CMC/LNR interfacial reaction. The CSG/LNR/CMC biodegradable polymer with high mechanical properties and interfacial tension can be used for packaging, agriculture, and medical applications.

Thermoplastic mung bean starch/natural rubber/sericin blends for improved oil resistance.

Oil resistant thermoplastic elastomers (TPE) were prepared using mung bean thermoplastic starch (MTPS) blending with rubbers and sericin. Sericin was incorporated into MTPS as a compatibilizer. MTPS with sericin (MTPSS) was blended with natural rubber (NR) and epoxidized NR (ENR). Sericin at 5% improved the tensile strength (10 MPa), elastic recovery (52%) and morphology of the MTPSS/ENR blend. The mechanical properties, elastic recovery and morphology of the MTPSS5/NR blend were improved by the addition of ENR. The MTPSS/ENR showed palm (28%) and motor oils (8%) swelling resistance because of the hydrophilicity of MTPS and high polarity of ENR. The MTPSS/ENR/NR showed gasoline swelling resistance (104%) because of the hydrophilicity of MTPS and low polarity of NR. FTIR confirmed a reaction between the -NH groups of sericin and the epoxy groups of ENR. This reaction improved the compatibility, mechanical properties, elastic recovery, morphology and oils swelling resistance of the blends.

Study of crystallization behaviour of electron beam irradiated polypropylene and high-density polyethylene.

The influence of electron-beam irradiation on polypropylene (PP) and high-density polyethylene (HDPE) was investigated with a focus on crystallization. A high-temperature (200°C) creep test revealed that the HDPE gradually increased cross-linking density in the range 30-120 kGy, while the PP underwent a chain scission which was quantitatively evaluated by gel permeation chromatography. The mechanical properties were measured in the range -150 to 200°C by a dynamic mechanical analysis. A small presence of C=C and C=O bonds was found in the irradiated PP by a Fourier transform infrared spectroscopy. Crystallization kinetics measured by differential scanning calorimetry and hot-stage optical microscopy results were influenced tremendously by irradiation for HDPE and to a lesser extent for PP. Irradiation caused a decrease in both the number of nucleation centres and the growth rate of individual spherulites. Crystallization was analysed in detail with the help of Hoffman-Lauritzen, Avrami and Arrhenius equations. Interestingly an increasing ß-crystal formation with an increasing irradiation level was discovered for PP by X-ray diffraction. A generation of defects in the crystalline structure owing to irradiation was discussed.

Effect of sodium benzoate and chlorhexidine gluconate on a bio-thermoplastic elastomer made from thermoplastic starch-chitosan blended with epoxidized natural rubber.

Thermoplastic elastomer (TPE) was developed by blending thermoplastic starch (TPS) with rubber. Thermoplastic starch-chitosan (TPSC) was prepared by the solution mixing of cassava starch, chitosan (CTS) and glycerol in acidified water (lactic acid 1 wt%) at 80 °C follow by melt mixing at 130 °C. Sodium benzoate (BEN) and chlorhexidine gluconate (Cl) were added during the solution mixing as additives for antimicrobial properties. TPSC was melt-mixed with epoxidized natural rubber (ENR) (70/30 wt/wt). The tensile strength and elongation at break of the TPSC/ENR increased with the additive content. Elastic recovery was improved by the addition of Cl. A new peak in the FTIR data confirmed the reaction between the reactive functional groups of the CTS and the additives with the epoxy groups of ENR. These reactions and miscibility of the TPSC/ENR/additives blends improved the mechanical properties, elasticity, morphology, and antimicrobial properties of the blends.

Microsphere Adhesion on Rubber Films Accompanied by Sphere Sedimentation.

Understanding the adhesion process between a rigid material (filler) and a viscoelastic material is important for designing an enhanced industrial material. However, the adhesion process is not simple because the properties of the adhesive, adherend, and interface are intricately influenced by this process. Here we investigate the adhesion of microspheres onto rubber films to clarify the dominant factor in the adhesion process. A rubber meniscus first forms on the sphere surface, followed by sedimentation of the sphere into the rubber film. This sedimentation is even observed when the surface free energy of the sphere is lower than that of the rubber film, which indicates that the driving force of meniscus formation obeys Young's equation on a tangential line of the sphere. The dominant factor of the sedimentation behavior is investigated by using atomic force microscopy force-sample deformation curve measurements and creep tests on the rubber films. These experimental results demonstrate that the adhesion process is strongly dominated by the viscoelastic property of the bulk rubber as opposed to the sphere and interface properties.

PET/Graphene Compatibilization for Different Aspect Ratio Graphenes via Trimellitic Anhydride Functionalization.

Two trimellitic anhydride-functionalized, thermally reduced graphenes with different aspect ratios, A f, and the same C/O ratio (8:1) were prepared and melt-mixed into poly(ethylene terephthalate) (PET), and the mechanical properties of the resulting nanocomposites were studied with a focus on plastic deformation behavior. A slight increase in the G' of the melt was observed for the surface-modified low-A f graphene composites (A f = 20) below the percolation threshold, whereas a significant enhancement in G' was observed for higher-A f graphene composites (A f = 80) at all graphene loadings, both below and above the percolation concentration. Furthermore, the use of modified low-A f graphene caused an improvement both in Young's modulus and elongation at break of the resulting PET nanocomposites because of enhancement of interfacial adhesion between filler and matrix which resulted in the formation of a coupled network via covalent bonding and the suppression both of strain-induced orientation and strain-induced crystallization. By contrast, the use of modified higher-A f surface graphene in nanocomposites caused a drastic improvement in Young's modulus but lower elongation-at-break than with the unmodified counterpart; the former effect is due to the formation of denser coupled networks and stronger interfacial adhesion as a result of graphene surface modification and the latter is due to the added geometrical restriction in unentangling chains from the PET matrix in the presence of higher-A f graphene. The preceding observations demonstrate the potential impacts of tuning both surface chemistry and aspect ratio of graphene in the fabrication of PET/graphene composites.

Higher-Order Structure in Amorphous Poly(ethylene terephthalate)/Graphene Nanocomposites and Its Correlation with Bulk Mechanical Properties.

Graphene of two different aspect ratios, A f, was melt mixed with poly(ethylene terephthalate) (PET) to form amorphous PET/graphene composites with less than 5% crystallinity. The higher-order structure and mechanical properties of poly(ethylene terephthalate) (PET) in these composites were investigated using techniques such as differential scanning calorimetry and dynamic mechanical analysis, whereas transmission electron microscopy, melt rheology, and electrical conductivity were used to study the graphene dispersion. A decrease in heat capacity changes, ΔC p, of PET in nanocomposites at the glass transition temperature, T g, without T g change suggests that a rigid amorphous fraction (RAF) of PET was formed at the PET/graphene interface. The stiffening effect of graphene below 1 wt % loading is quite small in the glassy state region and independent of the A f of graphene. Above 2 wt %, graphene forms a mechanical percolation network with the RAF of PET and the PET chains are geometrically restricted by the incorporation of graphene with a high A f, resulting in an unexpectedly higher modulus of nanocomposites both below and above T g.

Structural Changes in Poly(trimethylene adipate) and Poly(trimethylene succinate) During Melt Crystallization Studied Using In Situ Infrared Spectroscopy.

This paper investigates the structural changes occurring in poly(trimethylene adipate) (PTAd) and poly(trimethylene succinate) (PTSu) during melt crystallization using differential scanning calorimetry (DSC) and in situ Fourier transform infrared (FT-IR) spectroscopy. Cooling thermograms revealed that PTAd had a faster crystallization rate than PTSu. Infrared (IR) bands of the two polyesters were assigned by correlating with the IR bands of polymers containing the trimethylene and the diacid segments. The bands at 1478, 1459, 1393, and 1364 cm-1 in PTAd and 1475, 1459, 1393, and 1361 cm-1 in PTSu were designated to the CH2 of the trimethylene segment. Changes in the IR band absorbance intensities of the CH2 and the C-O-C groups were monitored with time during melt crystallization. Structural changes of the trimethylene and diacid segments of PTAd occurred synchronously, while in PTSu the two segments changed sequentially. Normalized band intensities showed a time lag between the trimethylene and succinic acid segments. The acid segment showed a faster change compared to the trimethylene segment. Fourier transform infrared spectroscopy is shown to be a useful technique to study conformational changes during crystallization in polymers.

Reactive blending of thermoplastic starch and polyethylene-graft-maleic anhydride with chitosan as compatibilizer.

Cassava starch was melt-blended with glycerol (70/30wt%/wt%) at 140°C to prepare thermoplastic starch (TPS). Chitosan (CTS) was premixed with starch and glycerol, in acidified water (lactic acid 2wt%), at 1, 5 and 10wt%/wt%. TPS/CTS was then melt-blended (160°C) with polyethylene-graft-maleic anhydride (PE-MAH). Phase determination and scanning electron microscopy indicated TPS/PE-MAH/CTS had a co-continuous morphology and CTS-induced phase inversion to give dispersed PE-MAH particles in a TPS matrix. Tensile strength at break and elongation, melt viscosity, fracture toughness and water contact angle of TPS/PE-MAH were improved by CTS incorporation. TPS/PE-MAH/CTS blends decreased the melting temperature of TPS and PE-MAH compared to the neat polymers. FTIR confirmed a reaction had occurred between amino groups (NH2) of CTS and the MAH groups of PE-MAH. This reaction and the enhanced miscibility between TPS and CTS improved the mechanical properties of the TPS/PE-MAH/CTS blend, particularly at 5wt%/wt% CTS.

AFM probing of polymer/nanofiller interfacial adhesion and its correlation with bulk mechanical properties in a poly(ethylene terephthalate) nanocomposite.

The interfacial adhesion between polymer and nanofiller plays an important role in affecting the properties of nanocomposites. The detailed relationship between interfacial adhesion and bulk properties, however, is unclear. In this work, we developed an atomic force microscopy (AFM)-based abrasive scanning methodology, as applied to model laminate systems, to probe the strength of interfacial adhesion relevant to poly(ethylene terephthalate) (PET)/graphene or clay nanocomposites. Graphite and mica substrates covered with ∼2 nm thick PET films were abrasively sheared by an AFM tip as a model measurement of interfacial strength between matrix PET and dispersed graphene and clay, respectively. During several abrasive raster-scan cycles, PET was shear-displaced from the scanned region. At temperatures below the PET glass transition, PET on graphite exhibited abrupt delamination (i.e., full adhesive failure), whereas PET on mica did not; rather, it exhibited a degree of cohesive failure within the shear-displaced layer. Moreover, 100-fold higher force scanning procedures were required to abrade through an ultimate "precursor" layer of PET only ∼0.2-0.5 nm thick, which must be largely disentangled from the matrix polymer. Thus, the adhesive interface of relevance to the strength of clay-filler nanocomposites is between matrix polymer and strongly bound polymer. At 90 °C, above the bulk PET glass transition temperature, the PET film exhibited cohesive failure on both graphite and mica. Our results suggest that there is little difference in the strength of the relevant interfacial adhesion in the two nanocomposites within the rubbery dynamic regime. Further, the bulk mechanical properties of melt mixed PET/graphene and PET/clay nanocomposites were evaluated by dynamic mechanical analysis. The glassy dynamic storage modulus of the PET/clay nanocomposite was higher than that of PET/graphene, correlating with the differences in interfacial adhesion probed by AFM.