Films Made by Blending Poly(ε-Caprolactone) with Starch and Flour from Sagu Rhizome Grown at the Venezuelan Amazons

Starch-based composite films have been proposed as food packaging. In this context, the study of non-conventional starch sources (sagu, Canna edulis Kerr) has worldwide special attention, because these materials can impart different properties as carbohydrate polymers. A thorough study of the matrices used (sagu starch and flour) was carried out. In the same way, thermoplastic starch (TPS)/PCL blend and thermoplastic flour (TFS)/PCL blend were obtained by melt mixing followed by compression moulding containing glycerol as plasticizer. In this study, chemical composition of the matrices and their properties were related with the properties of the developed films. Moisture content, water solubility, X-ray diffraction, thermogravimetric analysis and mechanical and microstructural properties were evaluated in the films. Taking into account the results, the sagu flour has great potential as starchy source for food packaging applications. However, concretely the flour had lower compatibility with the PCL compared to the starch/PCL blend.     

New Non-food-Based Composites of Acorn Nutlet and Polycaprolactone: Preparation and Characterization Evaluation

Two dissimilar renewable resource-based thermoplastic acorn nutlet (TPAN) materials were prepared via twin-screw extrusion with the aid of glycerol or monoethanolamine as plasticizers, and then two TPAN/polycaprolactone (PCL) composites with different plasticized systems were prepared. Mechanical test showed that glycerol-based composites had excellent tensile properties, and at a PCL content of 50 wt%, their tensile strength and elongation at break reached 14.4 MPa and 1,361 %, respectively. The micro-morphologic investigation of liquid-nitrogen brittle fracture surface indicated certain interface adhesion between glycerol-based thermoplastic acorn nutlet (GTPAN) and PCL. Dynamic mechanical thermal analysis , differential scanning calorimetry and thermogravimetric analysis demonstrated that the weight ratios of TPAN in composites significantly affected the crystallinity, glass transition temperature (T_g), melting temperature (T_m) and thermal stability of composites. Soil burial degradation analysis displayed that all composites had excellent biodegradability. These results demonstrated that GTPAN/PCL composites had superior mechanical and biodegradable properties, enough to partially replace the conventional thermoplastic plastics.     

Utilization of Sunflower Stalk in Manufacture of Thermoplastic Composite

Dimensional stability and mechanical performance of polypropylene thermoplastic composites filled with sunflower stalk (SS) flour at 30, 40, 50, and 60 wt% contents of the SS flour were investigated. The thickness swelling and water absorption of the specimens increased with increasing SS flour content. The modulus in the flexural and tensile improved with increasing SS flour content while the tensile and flexural strengths of the specimens decreased. The use of maleic anhydride polypropylene (3 wt%) had a positive effect on the dimensional stability and mechanical properties of the polypropylene thermoplastic composites filled with SS flour. The melting temperature of polypropylene decreased with increasing content of the SS flour. The degree of crystallinity of filled polypropylene composites between fibre loading of 0–30 % by weight was higher than that of unfilled polypropylene composites. However, further increment in the filler content decreased the degree of crystallinity. The obtained results showed that SS flour could be potentially suitable raw material in the manufacture of polypropylene composites.     

Injection Molded Wheat Straw and Corn Stem Filled Polypropylene Composites

Environmentally friendly composite materials can be prepared using wood fibers and/or various types of agro-derived fibers as reinforcements. In this study, agro-residues such as wheat straw and corn stem filled polypropylene were prepared and their suitability was investigated as a reinforcing filler in thermoplastics and as an alternative to the wood flour filled plastics. Effect of compounding techniques, compatibilizer and fungal treatment of agro-residues on the mechanical properties of the composites were evaluated. It was found that high shear compounding of wheat straw fibers exhibited similar properties to that produced by the milled wheat straw. This may be due to the extensive fiber breakage occurred during the high shear compounding that results in a similar aspect ratio to that of milled straw. Compatibilizer is needed for improving the strength properties of the agro-residue filled PP composites. Fungal treatment of milled wheat straw did not show much improvement in the strength properties of the composites. Comparison of mechanical properties of the agro-residue filled PP with that of the wood flour and the old newsprint filled PP showed the suitability of the agro-residues as alternative filler for thermoplastics.     

Fabrication and Characterization of Biodegradable Composite Films Made of Using Poly(caprolactone) Reinforced with Chitosan

Chitosan was dissolved in 2?% aqueous acetic acid solution and the films were prepared by solution casting. Values of tensile strength (TS), tensile modulus (TM), elongation at break (Eb?%) and water vapor permeability (WVP) of the chitosan films were found to be 30?MPa, 450?MPa, 8?% and 4.7?g?mm/m²?day?kPa, respectively. Poly(caprolactone) (PCL) films were prepared from its granules by compression molding and the values of TS, TM, Eb and WVP were 14?MPa, 220?MPa, 70?% and 1.54?g?mm/m²?day?kPa, respectively. PCL was reinforced with chitosan films, and composite films were prepared by compression molding. Amount of chitosan in the composite films varied from 10 to 50?% (w/w). It was found that with the incorporation of chitosan films in PCL, both the values of TS and TM of composite films increased significantly. The highest mechanical properties were found at 50?% (w/w) of chitosan content. The Oxygen transmission rate (OTR) of composite film was found to decrease significantly than PCL films. Thermal properties of the composite were also improved as compared to PCL. The water uptake test of the composite also showed promising results with a good stability of composite films. The interface of the composite was investigated by scanning electron microscopy and showed good interfacial adhesion between PCL and chitosan films.     

Hybrid Composites from Waste Materials

Hybrid composites of thermoplastic biofiber reinforced with waste newspaper fiber (NF) and poplar wood flour (WF) were prepared. The weight ratio of the lignocellulosic materials to polymer was 30:70 (w:w). Polypropylene (PP) and maleic anhydride grafted polypropylene (MAPP) were also used as the polymer matrix and coupling agent, respectively. The mechanical properties, morphology and thermal properties were investigated. The obtained results showed that tensile and flexural modulus of the composites were significantly enhanced with addition of biofibers in both types (fiber and flour), as compared with pure PP. However, the increasing in WF content substantially reduced the tensile, flexural and impact modulus, but improved the thermal stability. This effect is explained by variations in fiber morphological properties and thermal degradation. Increasing fiber aspect ratio improved mechanical properties. The effect of fiber size on impact was minimal compared to the effects of fiber content. Scanning electron microscopy has shown that the composite, with coupling agent, promotes better fiber–matrix interaction. The largest improvement on the thermal stability of hybrid composites was achieved when WF was added more. In all cases, the degradation temperatures shifted to higher values after addition of MAPP. This work clearly showed that biofiber materials in both forms of fiber and flour could be effectively used as reinforcing elements in thermoplastic PP matrix.     

Characterization of Biodegradable Polymer Blends of Acetylated and Hydroxypropylated Sago Starch and Natural Rubber

Development of biodegradable polymers from absolute environmental friendly materials has attracted increasing research interest due to public awareness of waste disposal problems caused by low degradable conventional plastics. In this study, the potential of incorporating natural rubber latex (NRL) into chemically modified sago starch for the making biodegradable polymer blends was assessed. Native sago starch was acetylated and hydroxypropylated before gelatinization in preparing starch thermoplastic using glycerol. They were than casted with NRL into biopolymer films according to the ratios of 100.00/0.00, 99.75/1.25, 98.50/2.50, 95.00/5.00, 90.00/10.00 and 80.00/20.00 wt/wt, via solution spreading technique. Water absorption, thermal, mechanical, morphological and biodegradable properties of the product films were evaluated by differential scanning calorimetry (DSC), universal testing machine (UTM), scanning electron microscopy (SEM) and fourier transform infrared spectroscopy. Results showed that acetylation promoted the incorporating behavior of NRL in sago starch by demonstrating a good adhesion characteristic and giving a uniform, homogenous micro-structured surface under SEM observation. However, the thin biopolymer films did not exhibit any remarkable trend in their DSC thermal profile and UTM mechanical properties. The occurrence of NRL suppressed water adsorption capacity and delayed the biodegradability of the biopolymer films in the natural environment. Despite the depletion in water adsorption capacity, all of the product films degraded 50 % within 12 weeks. This study concluded that biopolymers with desirable properties could be formulated by choosing an appropriate casting ratio of the sago starch to NRL with suitable chemical substitution modes.     

TPS/PCL Composite Reinforced with Treated Sisal Fibers: Property, Biodegradation and Water-Absorption

Sisal fibers bleached with sodium-hydroxide followed by hydrogen peroxide treatment were incorporated in a thermoplastic starch/ε-polycaprolactone (TPS/PCL) blend via extrusion processing. These samples with smooth and homogenous surfaces were examined for their property, biodegradability and water absorption. Scanning electron microscopy revealed that the fibers were well dispersed in the matrix. In addition, it was found that the fibers and matrices interacted strongly. Blends with 20 % (dry weight-basis) fiber content showed some fiber agglomeration. Whereas blends with 10 % fibers showed increased crystallinity and lower water absorption capacity. The CO₂ evolution study showed that the thermoplastic starch samples without any additives had the highest rate and extent of degradation whereas the neat PCL samples had the lowest degradation rate. Addition of fiber to the TPS/PCL blend exhibited the degradation rates and extents that were somewhere in between the pure TPS and neat PCL. This work demonstrates that TPS/PCL composites reinforced with bleached sisal has superior structural characteristics and water resistance and thus, can be used as polymeric engineering composites for different applications.     

Degradation of Polycaprolactone Modified with TPS or CaCO3 in Biotic/Abiotic Seawater

This paper is an investigation of the polymer degradation process in two types of seawater (with and without microorganisms) sourced from the Baltic Sea. The chosen polymeric materials were polycaprolactone modified with either thermoplastic starch (PCL/TPS?>?85%) or calcium carbonate (60% PCL/40% CaCO₃) compared directly against unmodified polycaprolactone. All samples were incubated for 28?weeks in seawater with and without microorganisms under laboratory conditions and analysed before and after the degradation process. Weight loss analysis, microscopic observations of polymer surfaces and tensile strength tests were used to determine the progress of polymer degradation. The experimental results obtained indicated, that in each of the experiments, degradation of tested polymeric samples occured. The process was more effective in seawater with microorganisms compared against systems without added microorganisms. The experiment in seawater demonstrated that modification of PCL with calcium carbonate did not encourage the degradation process; and in some circumstances inhibited it.     

Characterization of composites based on expanded polystyrene wastes and wood flour

This paper aims to evaluate the potential for the use of recycled expanded polystyrene and wood flour as materials for the development of wood plastic composites. The effects of wood flour loading and coupling agent addition on the mechanical properties and morphology of wood thermoplastic composites were examined. In addition, a methodology for the thermo-mechanical recycling of expanded polystyrene waste was developed. The results show that the mechanical properties decreased as the wood flour loading increased. On the other hand, the use of poly(styrene-co-maleic anhydride), SMA, as a coupling agent improved the compatibility between the wood flour and polystyrene matrix and the mechanical properties subsequently improved. A morphological study revealed the positive effect of the coupling agent on the interfacial bonding. The density values obtained for the composites were compared with the theoretical values and showed agreement with the rule of mixtures. Based on the findings of this work, it appears that both recycled materials can be used to manufacture composites with high mechanical properties and low density.     

Effects of Incorporating Polycaprolactone and Flax Fiber into Glycerol-Plasticized Pea Starch

This study focused on improving the material properties of pea thermoplastic starch (TPS) with polycaprolactone (PCL) and flax fiber. Accordingly, composites of glycerol-plasticized pea starch, polycaprolactone, and flax fiber were prepared through solid-phase compounding and compression-molding. The specimens were characterized through scanning electron microscopy, tensile test, moisture absorption test, and differential scanning calorimetry. Morphological studies of the tensile fracture surfaces revealed poor TPS-PCL interfacial interaction and limited TPS-flax fiber interfacial bonding. The composites showed significant improvements in tensile strength with reduced moisture absorption capability essentially due to the hydrophobicity of PCL. Individual components of the composites retained their respective thermal properties, an indication of thermodynamic immiscibility.     

Preparation and Biodegradation of Starch/Polycaprolactone Films

Starch granules were modified with trisodium trimetaphosphate (TSTP) and characterized by P³¹-NMR, FTIR and DSC. Seventy-micron films were prepared from modified starch and polycaprolactone blends by solvent casting technique. Three different types of films—PCL (100% polycaprolactone), MOD-ST/PCL (50% modified starch and 50% polycaprolactone blend) and NONMOD-ST/PCL (50% nonmodified starch and 50% polycaprolactone blends)—were prepared, and their thermal, mechanical, and morphologic properties were investigated to show the increased performance of PCL with the addition of starch and also the effect of modification. It was observed that with the addition of starch the Young's modulus of polycaprolactone was increased and became less ductile, whereas tensile strength and elongation at break values decreased. Biodegradation of these films was inspected under different aerobic environments with the presence of Pseudomonas putida, activated sludge, and compost. It was observed that whereas P. putida had almost no effect on degradation during 90 days, with the presence of activated sludge, considerable deformation of films was observed even in the first 7 days of degradation. In a compost environment, degradation was even faster, and all polymer films were broken into pieces within first 7 days of degradation and no film remained after 15 days.     

Environmental Degradation of Biodegradable Polyesters: 3. Effects of Alkali Treatment on Biodegradation of Poly(ε-Caprolactone) and Poly[(R)-3-Hydroxybutyrate) Films in Controled Soil

The poly(-caprolactone) (PCL) and poly[(R)-3-hydroxybutyrate] (R-PHB) films with a hydrophilic surface were prepared by the alkali treatment of their as-cast films in NaOH solutions of different concentrations. The alkali-treated PCL and R-PHB films, as well as the as-cast PCL and R-PHB films, were biodegraded in soil controlled at 25°C and the effects of alkali treatment or surface hydrophilicities on their biodegradation were investigated by the use of gravimetry, gel permeation chromatography (GPC), scanning electron microscopy (SEM), and polarization optical microscopy. It became evident that the alkali treatment enhanced the hydrophilicities and biodegradabilities of the PCL and R-PHB films in soil. The biodegradabilities of the as-cast aliphatic polyester films in controlled soil decreased in the following order: PCL > R-PHB > PLLA, in agreement with that in controlled static seawater.     

Fiber from DDGS and Corn Grain as Alternative Fillers in Polymer Composites with High Density Polyethylene from Bio-based and Petroleum Sources

The steady increase in production of corn based ethanol fuel has dramatically increased the supply of its major co-product known as distiller’s dried grain with solubles (DDGS). Large amount of DDGS and corn flour are used as an animal feed. The elusieve process can separate DDGS or corn flour into two fractions: DDGS fraction with enhanced protein and oil content or corn flour fraction with high starch content, and hull fiber. This study investigated the feasibility of using fiber from DDGS and corn grain as alternative fillers to wood fiber in high density polyethylene (HDPE) composites made with two different sources of polymers. Two fiber loading rates of 30 and 50% were evaluated for fiber from DDGS, corn, and oak wood (control) to assess changes in various physical and mechanical properties of the composite materials. Two HDPE polymers, a bio-based HDPE made from sugarcane (Braskem), and a petroleum based HDPE (Marlex) were also compared as substrates. The biobased polymer composites with DDGS and corn fibers showed significantly lower water absorption than the Marlex composite samples. The Braskem composite with 30% DDGS fiber loading showed the highest impact resistance (80 J/m) among all the samples. The flexural properties showed no significant difference between the two HDPE composites.     

Physical properties and biodegradability of blends containing poly(ε-caprolactone) and tropical starches

In order to assess feasibility of tropical starches (sago and cassava starches) as biodegradable plastic materials, blending with poly(-caprolactone) (PCL), a biodegradable polymer, was carried out. It was confirmed that the physical properties (tensile strength and elongation) of PCL/sago and PCL/cassava blends were similar to those of PCL/corn blend, suggesting that sago and cassava starches can also be blended with PCL for production of biodegradable plastic. However, the properties of all PCL/starch blends were still low compared with those of polyethylene. Enzymatic degradability evaluation showed that lipase degradation of PCL and-amylase degradation of starch increased as the starch content in the blend increased. Burial test of the blends for 1, 3, and 5 months was carried out and the rate of degradation of the PCL/sago blend was confirmed to be slower than those of PCL/corn and PCL/cassava blends. Observation of the film blends structure by scanning electron microscope revealed that the starch was dispersed in a PCL continuous phase. Furthermore, changes in the film surface before and after enyzme treatments were observed.     

The Effects of Additives on the Biodegradation of Polycaprolactone Composites

Because environmental pollution caused by plastic waste is a major problem investigations concerning biodegradable packaging are important and required. In this study, the biodegradation of PCL composite films with organic (glycerol monooleate and oleic acid) and inorganic additives (organo nano clay) was investigated to understand which additive and the amount of additive was more effective for biodegradation. The relationship between the degree of crystallinity and the effect of additives on the biodegradability of polycaprolactone (PCL) was examined. PCL composite films were prepared using organo nano clay (0.1–0.4–1–3 wt%) and oleic acid (1–3–5 wt%) or GMO (1–3–5 wt%). The 35 films prepared with PCL (P), clay (C), oleic acid (O), or glycerol monooleate (G) are coded as P_C#wt%_O (or G)#wt%. The composite films, P_C0.4_O5 contains 0.4 wt% clay and 5 wt% oleic acid and the P_C3_G1 contains 3 wt% clay and 1 wt% glycerol monooleate. The biodegradation of PCL films in simulated soil was studied for 36 months. The films were periodically removed from the simulated soil and film thicknesses, weight losses, visual changes, crystal structures, and a functional group analyses were performed. PCL composite films are separated into three groups, depending on degradation time, (1) films that degraded before 8 months (fast degradation), (2) films that degraded around 24 months (similar to neat PCL), and (3) films that take longer to degrade (slow degradation). The films in the first group are PCL films with 1 and 3 wt% clay additive and they begin to biodegrade at the 5th month. However, a composite film of PCL with only 0.4 wt% clay and 5 wt% GMO addition has the shortest degradation time and degraded in 5 months. The films in the last group are; P_G3, P_G5, P_C0.1, P_C0.1_O1, and P_C0.1_O5 and they took around 30 months for biodegradation. It was observed that increasing the organo nanoclay additive increases the biodegradability by disrupting the crystal structure and causing a defective crystal formation. The addition of GMO with organo nano clay also accelerates biodegradation. The addition of organo nano clay in an amount as small as 0.1 wt% acts as the nucleating agent, increases the degree of crystallinity of the PCL composites, and slows the biodegradation period by increasing the time.     

Effect of Poly(dioxolane) as Compatibilizer in Poly(ɛ-caprolactone)/Tapioca Starch Blends

The influence of poly(dioxolane) (PDXL), a poly(ethylene oxide-alt-methylene oxide), as compatibilizer on poly(ɛ-caprolactone) (PCL)/tapioca starch (TS) blends was studied. In order to facilitate blending; PCL, PDXL and TS must be blended together directly; so that PDXL is partially adhered at the TS surface as shown by scanning electron microscopy. The molecular weight effect of PDXL on the PCL/TS blends showed that mechanical properties of PCL/TS/PDXL blends from low molecular weight (M _n=10,000) and high molecular weight (M _n=200,000) PDXL were rather dependent on TS content. The enzymatic degradability of PCL/TS/PDXL blends using α-amylase increased as the TS content increased but was independent on the dispersion of tapioca starch in the PCL matrix.     

Effects of Waste Paper Sludge on the Physico-Mechanical Properties of High Density Polyethylene/Wood Flour Composites

The objective of this work was to determine some physical and mechanical properties of the high density polyethylene (HDPE) composites reinforced with various mixtures of the paper sludge and the wood flour, and to evaluate the coupling agent performance. The waste sludge materials originating from two different sources including paper making waste water treatment sludge (PS) and ink-eliminated sludge (IES) were characterized in terms of physico-chemical properties. In the experiment, four levels of paper sludge (20, 30, 40 and 60 wt%), three levels of wood flour (20, 40 and 60 wt%), and two levels of coupling agent (MAPE) content (2 and 3 wt%) were used. The flexural properties of the composites were positively affected by the addition of the sludge. Especially, tensile modulus improved with the increase of paper sludge content. With the addition of MAPE, flexural properties improved considerably compared with control specimens (without any coupling agent). The results showed that the water absorption (WA) and thickness swelling (TS) values of the samples decreased considerably with increasing sludge content in the composite, while they increased with increasing wood flour content. It is to be noted that with incorporation of MAPE in the composite formulation, the compatibility between the wood flour and HDPE was enhanced through esterification, which reduced the WA and TS and improved the mechanical properties. Composites made with IES exhibited superior physico-mechanical properties compared with the PS filled composites. Overall results suggest that the waste paper sludge materials were capable of serving as feasible reinforcing fillers for thermoplastic polymer composites.     

Action of soil microorganisms on PCL and PHBV blend and films

Poly(hydroxybutyrate-co-valerate) (PHBV) and poly(ε-caprolactone) (PCL) PCL/PHBV (4:1) blend films were prepared by melt-pressing. The biodegradation of the films in response to burial in soil for 30 days was investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG). The PHBV film was the most susceptible to microbial attack, since it was rapidly biodegraded via surface erosion in 15 days and completely degraded in 30 days. The PCL film also degraded but more slowly than PHBV. The degradation of the PCL/PHBV blend occurred in the PHBV phase, inducing changes in the PCL phases (interphase) and resulting in an increase of its crystalline fraction.     

Thermoplastic Blends from Albumin and Zein: Plastic Formation and Mechanical Properties Including Modeling

The use of proteins in blending with traditional polymers in the formation of thermoplastics can produce plastics with properties that are superior to traditional petroleum-based plastics. We investigated the physical and thermal properties of albumin and zein thermoplastic blends plasticized with glycerol and mixed with varying amounts of low-density polyethylene (LDPE). Several mechanical models were utilized to determine how tensile properties will be altered when varying amounts of protein/LDPE were added into the thermoplastic blend. When analyzed for thermal properties, we found that as the amount of LDPE in the thermoplastic blend increased, the resulting plastic possessed thermal properties that were more similar to pure LDPE plastics. In terms of mechanical properties, comparison between the experimental data and model predictions points to a synergistic effect between albumin and LDPE that leads to higher modulus, while a potential lack of compatibility between zein and LDPE leads to a plastic with lower modulus. Based on our results, the use of albumin and zein proteins when blended with LDPE in the production of thermoplastics has potential use in the areas of medical and food packaging applications.