Improvement of Physico-mechanical Properties of Chitosan Films by Photocuring with Acrylic Monomers

Natural polymer, chitosan was obtained from dried prawn shell waste through the preparation of chitin and was characterized. Thin film of chitosan was prepared by casting method from its 2% chitosan solution. Mechanical properties like tensile strength (TS), elongation at break (Eb) of chitosan film were studied. Five formulations were developed with 2-ethyl-2-hydroxy methyl-1,3-propandiol trimethacrylate (EHMPTMA), a trifunctional monomer and 2-ethylhexyl acrylate (EHA), a monofunctional monomer in the presence of photoinitiator Darocur-1664 (2%). The film was soaked in those monomer formulations in dissimilar soaking times and irradiated under UV-radiation at different radiation intensities for the improvement of the properties of chitosan film. The cured films were then subjected to various characterization tests like TS, Eb, polymer loading (PL), water absorbency, gel content etc. The formulation, containing 25% EHMPTMA and 73% EHA showed the best performance at 10th UV passes of UV radiation for 4 min soaking time.     

Effect of Urea on the Mechanical Properties of Gelatin Films Photocured with 2-Ethylhexyl Acrylate

Thin films of gelatin were prepared by casting. Then the films were photocured and the mechanical properties were studied. The tensile strength of UV cured gelatin films showed about 10% enhancement than that of raw gelatin films. Minor amount of urea (1–5%) was used as additive in aqueous gelatin solution and films were prepared using same technique. Four formulations were prepared in methanol with 2-ethylhexyl acrylate in the presence of photoinitiator (darocur-1664). The films were soaked in the prepared formulations and then cured under UV radiation at different intensities (5–25 passes). Percentage of urea, monomer concentration, soaking time and radiation intensities were optimized with the extent of polymer loading, TS and elongation at break of the photocured film. The films containing 2% urea, cured with 3% EHA for 3 min at 15th UV pass showed the highest mechanical properties. A significant improvement of TS (31%) occurred when EHA (3%) was incorporated.     

Study on the Thermo-Mechanical and Biodegradable Properties of Shellac Films Grafted with Acrylic Monomers by Gamma Radiation

Shellac (SL) films were prepared by casting and were grafted with various acrylic monomers of different functionalities using gamma radiation. Different formulations of shellac with varying concentrations (3, 5 and 7%) of these acrylic monomers such as 2-hydroxyethyl methacrylate (HEMA), 2-ethylhexyl acrylate (EHA) and 1,4-butanediol diacrylate (BDDA) in methanol were prepared. The pure shellac and other treated films were then irradiated under gamma radiation (Co-60) at different doses (0.5–5 kGy) at a dose rate of 3.5 kGy/h where 1 Gy = 1 J/kg = 100 rads. The mechanical properties like tensile strength (TS) and elongation at break (Eb) of the prepared films were studied. The mechanical properties of the irradiated shellac films demonstrated superior values. Among the formulations, shellac grafted with BDDA (SL-g-BDDA) showed the highest TS and Eb values which were 543 and 168% higher than those of raw shellac films, respectively. The water uptake behavior of raw and treated films was also studied. The raw film showed 11% water uptake but HEMA containing film showed 67%. In the soil burial test, HEMA containing shellac film was rapidly degraded than other raw, EHA and BDDA grafted films. Thermal properties indicated that grafting of acrylic monomers decreased the melting temperature of the pure shellac films.     

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.     

Effect of Additives on the Improvement of Mechanical and Degradable Properties of Photografted Jute Yarn with Acrylamide

The jute yarn was grafted with acrylamide monomer (AA) under ultraviolet (UV) radiation to modify its mechanical and degradable properties. A number of AA solutions of different concentrations in methanol (MeOH) along with photoinitiator Irgacure 907 [2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanone-1] were prepared. The monomer concentration and irradiation time were optimized. Jute yarn grafted with 30% AA under UV radiation for 60 min showed of the highest polymer loading (PL) value of 22% with a enhanced tensile strength (TS) value of 195% and elongation at break (Eb) value of 256% compared to untreated jute yarn. To further improve the properties of jute yarn, a number of additives (1%) such as urea, polyvinylpyrrolidone, urethane acrylate, and urethane diacrylate were used in the AA (30%) solution. Among all the additives used, urea significantly influenced the PL (27%), TS (230%), and Eb (264%) values of the treated jute yarns. Water uptake and the degradation properties of treated and untreated jute yarn caused by simulated weathering and in soil (25% water) were also studied. The rate of degradation of grafted sample is lower then that of untreated sample. DSC studies showed the thermal stability of the AA plus urea grafted sample.     

Role of Amino Acids on <Emphasis Type="Italic">In Situ</Emphasis> Photografting of Jute Yarn with 3-(Trimethoxysilyl) Propylmethacrylate

To improve the mechanical performance of natural lignocellulosic jute yarn, grafting with [3-(trimethoxysilyl) propylmethacrylate] (TMSPM) monomer has been performed on in situ UV radiation and optimized the monomer concentration (30%) and irradiation time (30 min). Effect of various amino acids (1%) as additives in TMSPM with photografted jute yarn at optimized system has been studied. The polymer loading (PL) and tensile properties like tensile strength (TS) and elongation at break (Eb) of treated samples were enhanced by incorporation of amino acids and the highest properties (TS = 300% and Eb = 386%) achieved by the sample treated with l-Arginine (Arg) with 32.5% PL value. Weak acid like 3% acetic acid and inorganic acid like 1% sulfuric acid were also incorporated in the optimized system of TMSPM grafting and compared their effect on the tensile properties with amino acid treated samples. Water absorption and weathering resistance of treated and untreated samples were also performed and treated sample showed lesser water uptake as well as less weight loss and mechanical properties as compared to untreated samples.     

Influences of Magnesium <Emphasis Type="Italic">tri-</Emphasis>Silicate on the Physical,Mechanical, and Degradable Properties of Ultraviolet (UV) Radiation Cured Plain Board Surface

A series of formulations were prepared with different percentages of oligomer, epoxy diacrylate (EA-1020 ), monomer, 1,6 Hexane diol diacrylate,(HDDA) and different percentages of filler (Magnesium tri-silicate, Mg₂Si₃O₈). Irgacure 369 [2-Benzyl-2-dimethyl-amine-1 (4-morpholinophenyl) butanone-1] was used in the formulations as photoinitiator. Ultraviolet (UV) cured thin polymer films were prepared from these formulating solutions on clean glass plates. Pendulum hardness (PH), gel content and macro scratch hardness (MSH) of the UV cured films were studied. One percent Mg₂Si₃O₈ containing formulation showed the premium properties. The substrates (plain board) were coated by these formulating solutions and cured under the same UV lamp at different intensities of radiation. Various properties of the coated surface such as PH, gloss, adhesion, abrasion and MSH were investigated. The base coat containing 1% Mg₂Si₃O₈ and top coat containing 48% HDDA produced the best performance among all the formulations inspected. The degradable properties in different weathering conditions on PH, gloss, adhesion, abrasion and MSH were measured. The surface cured with the optimized formulation (E) again yielded the minimum loss of the properties.     

Effect of the Pretreatment with UV and Gamma Radiations on the Modification of Plywood Surface by Photocuring with Epoxy Acrylate

In order to further improve the physical properties of plywood surface that was pretreated with UV and Gamma radiation at different radiation intensities before photocuring. After pretreatment with radiation the plywood surface was coated with different prepared formulations containing epoxyacrylate (EA-1020) as an oligomer, difunctional monomers such as tripropylene glycol diacrylate (TPGDA), 2-hexadioldiacrylate (HDDA), Ethylene Glycol dimethacrylate (EGDMA) and trifunctional monomer trimethyl propen triacrylate (TMPTA) with photoinitiator Darocur 1664. Thin polymer films were prepared on glass plate with these formulated solutions and cured under UV radiation. Pendulum hardness (PH) and gel content of the film were studied for selecting the formulations as top coat and as base coat. The polished plywood surface was coated with selected formulation and cured under UV radiation. Various rheological properties of UV cured plywood surface such as pendulum hardness, scratch hardness, microgloss, adhesion strength, percentage chipped off area and abrasion resistance were studied.     

Improvement of Physico-Mechanical Properties of Photo-Cured Chitosan Films with Ethylene Glycol Dimethacrylate and (2-Hydroxyethyl) Methacrylate

Chitosan, a natural polymer, was prepared by deacetylation of chitin which was obtained from dried prawn shell and was characterized. Thin chitosan film of chitosan was prepared by casting method from 0.2 % chitosan in 2 % acetic acid solution. Five formulations were developed with ethylene glycol dimethacrylate and (2-hydroxyethyl) methacrylate along with photo-initiator, Darocur-1664 (4 %). The chitosan film was soaked in the formulations at different soaking times and irradiated under UV-radiation at different intensities for the improvement of its physical and mechanical properties. The cured chitosan films were then subjected to various mechano-chemical tests like tensile strength, elongation at break, polymer loading, water absorption and gel content. The formulation containing 30 % ethylene glycol dimethacrylate and 66 % (2-hydroxyethyl) methacrylate showed the best performance at the 30th UV pass of UV-radiation for 3 min soaking time.     

Properties of Starch/PVA Blend Films Containing Citric Acid as Additive

Starch/polyvinyl alcohol (PVA) blend films were prepared successfully by using starch, polyvinyl alcohol (PVA), glycerol (GL) sorbitol (SO) and citric acid (CA) for the mixing process. The influence of mixing time, additional materials and drying temperature of films on the properties of the films was investigated. With increase in mixing time, the tensile strength (TS), elongation (%E), degree of swelling (DS) and solubility (S) of the film were equilibrated. The equilibrium for TS, %E, DS and S value was 20.12 MPa, 36.98%, 2.4 and 0.19, respectively. The mixing time of equilibrium was 50 min. TS, %E, DS and S of starch/PVA blend film were examined adding glycerol (GL), sorbitol (SO) and citric acid (CA) as additives. At all measurement results, except for DS, the film adding CA was better than GL or SO because hydrogen bonding at the presence of CA with hydroxyl group and carboxyl group increased the inter/intramolecular interaction between starch, PVA and additives. Citric acid improves the properties of starch/PVA blend film compared to glycerol and sobitol. When the film was dried at low temperature, the properties of the films were clearly improved because the hydrogen bonding was activated at low temperature.     

Preparation and Characterization of Gamma Irradiated Sugar Containing Starch/Poly (Vinyl Alcohol)-Based Blend Films

Blends based on different ratios of starch (35–20%) and plasticizer (sugar; 0–15%) keeping the amount of poly(vinyl alcohol) (PVA) constant, were prepared in the form of thin films by casting solutions. The effects of gamma-irradiation on thermal, mechanical, and morphological properties were investigated. The studies of mechanical properties showed improved tensile strength (TS) (9.61 MPa) and elongation at break (EB) (409%) of the starch-PVA-sugar blend film containing 10% sugar. The mechanical testing of the irradiated film (irradiated at 200 Krad radiation dose) showed higher TS but lower EB than that of the non-radiated film. FTIR spectroscopy studies supported the molecular interactions among starch, PVA, and sugar in the blend films, that was improved by irradiation. Thermal properties of the film were also improved due to irradiation and confirmed by thermo-mechanical analysis (TMA), differential thermo-gravimetric analysis (DTG), differential thermal analysis (DTA), and thermo-gravimetric analysis (TGA). Surface of the films were examined by scanning electron microscope (SEM) image that supported the evidence of crosslinking obtained after gamma irradiation on the film. The water up-take and degradation test in soil of the film were also evaluated. In this study, sugar acted as a good plasticizing agent in starch/PVA blend films, which was significantly improved by gamma radiation and the prepared starch-PVA-sugar blend film could be used as biodegradable packaging materials.     

Biodegradability of Chemically Modified Starch (RS4)/PVA Blend Films: Part 2

Biodegradable films were successfully prepared by using cornstarch (CS), chemically modified starch (RS4), polyvinyl alcohol (PVA), glycerol (GL), and citric acid (CA). The physical properties and biodegradability of the films using CS, RS4, and additives were investigated. The results of the investigation revealed that the RS4-added film was better than the CS-added film in tensile strength (TS), elongation at break (%E), swelling behavior (SB) and solubility (S). Especially, the RS4/PVA blend film with CA as an additive showed physical properties superior to other films. Furthermore, when the film was dried at low temperature, the properties of the films clearly improved because the hydrogen bonding was activated at low temperature. The biodegradation of films was carried out using the enzymatic, microbiological and soil burial test. The enzyme used in this study was amyloglucosidase (AMG), α-amylase (α-AM) and β-amylase (β-AM). At the enzymatic degradation test, the GL-added films had an approximately 60% degradation, while the CA-added films were degraded about 25%. The low degradation value on CA-added film is attributed to low pH of film added CA that deactivated the enzymatic reaction. The microbiological degradation teat was performed by using Bacillus subtilis and Aspergillus niger.     

The Effect of Nanoclays on the Properties of PLLA-modified Polymers Part 1: Mechanical and Thermal Properties

Organically modified montmorillonite clays were incorporated at a 5% loading level into film grade of poly-L-lactic acid (PLLA) using a variety of masterbatches based on either semi-crystalline or amorphous poly-(lactic acid), as well as biodegradable aromatic aliphatic polyester. The PLLA masterbatches and compounded formulations were prepared using a twin screw compounding extruder, while the films were prepared using a single screw cast film extruder. The thermal and mechanical properties of the films were examined in order to determine the effect of the clay and different carriers on the polymer–clay interactions. In the optimal case, when a PLLA-based masterbatch was used, the tensile modulus increased by 30%, elongation increased by 40%, and the cold crystallization temperature decreased by 15 °C, compared to neat PLLA. The properties improvement of PLLA films containing nano clays demonstrated the possibility to extend the range of biodegradable film applications, especially in the field of packaging.     

Mechanical,Barrier and Antioxidant Properties of Chitosan Films Incorporating Cinnamaldehyde

Chitosan films (CF) [1 and 2% w/v] alone and with cinnamaldehyde (CNE) [0.25, 0.5 and 1% v/v] were prepared using an emulsion method, and the obtained films were characterized in terms of water vapor permeability (WVP), water solubility and optical, mechanical and antioxidant properties. The incorporation of CNE at 1% (v/v) significantly decreased the water solubility of the film by approximately 4% for the 1 and 2% CF films, whereas the WVP increased (2.5–3.5 times). The incorporation of CNE (0.25 and 0.5%) into 2% CF significantly increased the tensile strength (TS) (62 and 34%, respectively) and the percent elongation (%E) values, 26, 30 and 52% for CF that contained 0.25, 0.5 and 1% CNE, respectively. The largest value of the elasticity modulus (EM) was observed for 2% CF with 0.25% CNE. All films exhibited a yellow appearance (b*), but the CNE content had a marked impact on the coloration of the films. The CNE recoveries of the CF films (1 and 2%) with 1% of CNE were high (43 and 67%). The antioxidant activities indicated that the incorporation of 1% CNE into CF films (1 and 2%) increased the antioxidant activity. The protective effects of the films with and without CNE on erythrocytes were very strong (36–72% hemolysis inhibition). These results suggest there are potential applications for CF-CNE films as active packaging for the preservation of food products.     

Effect of Pretreatment with UV Radiation on Physical and Mechanical Properties of Photocured Jute Yarn with 1,6-Hexanediol Diacrylate (HDDA)

Jute yarns were grafted with a single impregnating monomer 1,6-hexanediol diacrylate (HDDA) in order to improve the physicomechanical properties. Jute yarns soaked for different soaking times (3, 5, 10, and 30 minutes) in HDDA+MeOH solutions at different proportions (1–10% HDDA in MeOH [v/v] along with photoinitiator Darocur-1664 [3%]) were cured under UV lamp at different UV radiation intensities (two, four, six, and eight passes). Concentration of monomer, soaking time, and intensity of UV radiation were optimized with extent of mechanical properties such as tensile strength, elongation at break, and modulus. Enhanced tensile strength (67%), modulus (108%), and polymer loading (11%) were achieved with 5% HDDA concentration, 5-minute soaking time, fourth pass of UV radiation. To further improve the mechanical properties, the jute yarns were pretreated with UV radiation (5, 10, 15, 30, and 50 passes) and treated with optimized monomer concentration (5%). UV-pretreated samples showed the enhanced properties. The tensile strength and modulus increase up to 84% and 132%, respectively, than that of virgin jute yarn. An experiment involving water absorption capacity shows that water uptake by treated samples was much lower than that of the untreated samples. During the weathering test, treated yarns exhibited less loss of mechanical properties than untreated yarns.     

Formulation of a Photosensitized Polyethylene Film; Its Structure and Property Variation Under the Weathering Conditions of Tehran

To develop an environmentally degradable polymer material, a masterbatch pro-oxidant system was blended into low-density polyethylene. The polymer film samples were prepared by compression molding. The prepared films were placed under the natural environment of Tehran for weathering studies and accelerated conditions were also performed for UV aging in UV chamber. At different time intervals, the changes in chemical structure of photosensitized polyethylene samples were studied by FTIR and compared to that of the control polyethylene films. Also the mechanical properties of photosensitized polyethylene films were determined in comparison with the control films by measuring the tensile strength and elongation at break after exposure to the natural environment and UV radiation. Results showed that the overall rate of degradation process is clearly dependent on the polyethylene composition, test conditions (natural or accelerated), season of the year, and the duration of the weathering of the samples.     

Effects of Electron-Beam Irradiation and Ultraviolet Light (365 nm) on Polylactic Acid Plastic Films

Strips of Ca-I [polylactic acid (PLA) monolayer plastic films from Cargill Dow Polymers LLC, Minnetonka, MN] cut in the machine and nonmachine directions were irradiated with an electron beam using a CIRCLE III Linear Accelerator (MeV Industries S.A., Jouy-en-Josas, Cedex, France). The effects of 33-kGy irradiation on the physical properties of the Ca-I strips were studied. In addition, the effects of ultraviolet (UV) light (365-nm) illumination on the degradation of three PLA plastic films, Ch-I (PLA monolayer plastic films from Chronopol, Golden, CO), GII (PLA trilayer plastic films from Cargill Dow Polymers LLC), MN), and Ca-I (PLA monolayer plastic films from Cargill Dow Polymers LLC) were analyzed by a modified ASTM D5208-91 method. Results showed that irradiation had decreased the weight-average molecular weight (M _w), stress at break, percentage of elongation, and strain energy of Ca-I by 35.5, 26.7, 32.3, and 44.8%, respectively (P < 0.01). The shelf life of the irradiated Ca-I strips at 5°C and <20 ± 5% RH was about 6 months. The degradation rate of Ch-I, GII, and Ca-I with no UV light treatment at 55°C and 10% RH was 2512, 5618, and 3785 M _w/week, respectively. Under the UV light illumination (365 nm), the degradation rate of Ch-I, GII, and Ca-I, was 2982, 8722, and 7467 M _w/week, respectively. Hence, the degradation rate of GII and Ca-I was increased 55 and 97% by UV light (P < 0.008), respectively. This trend was not observed in Ch-I because its starting M _w (78,000 g/mol) was close to the tensile strength lost range (50,000 to 75,000 g/mol) of PLA films. To our knowledge, this is the first study to demonstrate that UV light does further enhance the degradation of PLA films.     

Modification of Thermo-Mechanical Properties of Recycled PET by Vinyl Acetate (VAc) Monomer Grafting Using Gamma Irradiation

Vinyl acetate (VAc) monomer of different percentage was grafted onto the recycled polyethylene terephthalate (r-PET) films using gamma irradiation. The properties of these modified films were characterized by Fourier transform infrared spectroscopy (FTIR), mechanical properties testing (Tensile strength, Elongation at break), dynamic mechanical analysis (DMA) and thermo-gravimetric analysis (TGA). The Tensile Strength (TS) of the modified PET film increased by 132.25?% to the highest value of 50.12 MPa at 15% VAc monomer concentration at 3 kGy gamma dose, while the elongation at break (EB) decreased by 31.83?%. FTIR was used to investigate the molecular interaction of the modified films. TGA revealed that curve of the modified PET film shifted toward higher temperature region by 95?°C, which is very close to that of PET film made from virgin flakes. The results indicate that modified PET films of better mechanical and thermal properties were successfully prepared using VAc monomer grafting by gamma irradiation technique.     

Mechanical Properties with the Functional Group of Additives for Starch/PVA Blend Film

This paper deals with the mechanical properties and degree of swelling (DS) of starch/PVA blend film with the functional groups i.e., hydroxyl and carboxyl group, of additives. Starch/PVA blend films were prepared by using the mixing process. Glycerol (GL) with 3 hydroxyl group, sorbitol (SO) with 6 hydroxyl group, succinic acid (SA) with 2 carboxyl group, malic acid (MA) with 1 hydroxyl and 2 carboxyl group, tartaric acid (TA) with 2 hydroxyl and 2 carboxyl group and citric acid (CA) with 1 hydroxyl and 3 carboxyl group were used as additives. The results of measured tensile strength (TS) and elongation (%E) verified that both hydroxyl and carboxyl group as a functional groups increased the flexibility and strength of the film. Values of DS for GL-added and SA-added films were low. However, DS values of the films added MA, TA or CA with both hydroxyl and carboxyl group were comparatively high. When the film was dried at low temperature, the properties of the films were evidently improved. The reason is probably because the hydrogen bonding was activated at low temperature.     

Extruded Cornstarch-Glycerol-Polyvinyl Alcohol Blends: Mechanical Properties, Morphology, and Biodegradability

Elongation properties of extruded cornstarch were improved by blending with glycerol. Further blending of starch-glycerol with polyvinyl alcohol (PVOH) resulted in significant improvements in both tensile strength (TS) and elongation at break. Samples of starch-glycerol without PVOH equilibrated at 50% relative humidity had a TS of 1.8 MPa and elongation of 113%, whereas those containing PVOH had a TS and elongation of 4 MPa and 150%, respectively. Dynamic mechanical analysis (DMA) of starch-glycerol-PVOH blends showed that decreases in glass transition temperatures (T _g values) were proportional to glycerol content. Scanning electron microscopy (SEM) of fractured surfaces revealed numerous cracks in starch-glycerol (80:20) samples. Cracks were absent in starch-glycerol (70:30) samples. In both blends, many starch granules were exposed at the surface. No exposed starch granules were visible in blends with added PVOH. Starch-glycerol samples incubated in compost lost up to 70% of their dry weight within 22 days. Addition of PVOH lowered both the rate and extent of biodegradation.