Mechanical and Water Vapor Transmission Properties of Polysaccharide Films

Abstract

The film-forming properties of chitosan, chitosan glutamate, sodium alginate, and hydroxypropyl methylcellulose (HPMC) were investigated. Films were produced by a casting/solvent evaporation method from plasticizer-free and plasticizer-containing aqueous solutions. The water vapor transmission and mechanical properties (puncture strength and % elongation) of the films were investigated as a function of the polymer type and viscosity, plasticizer type (glycerin, propylene glycol, polyethylene glycol, triethyl citrate), plasticizer concentration, and type and concentration of acid used to dissolve chitosan. The effect of storage humidity was also examined. Glycerin and water were good plasticizers for chitosan glutamate. The chitosan film properties were dependent on the type and concentration of acid used to dissolve it, citric acid being a good plasticizer. The mechanical and water vapor transmission properties of alginate and HPMC films were less influenced by the investigated variables.     

Novel low-molecular-weight hypromellose polymeric films for aqueous film coating applications

The concentration of hypromellose (HPMC) is known to significantly impact the viscosity of coating solutions. The purpose of this study was to determine the viscosity of novel low-molecular-weight (LMW) HPMC products as a function of polymer concentration. The mechanical properties and water vapor permeability of free films prepared from these novel LMW HPMC polymers were also determined and the results were compared with films prepared with conventional HPMC. Solutions of LMW and conventional HPMC 2910 and 2906 containing up to 40% polyethylene glycol (PEG) 400 were prepared and the viscosities were measured using a Brookfield viscometer. Solutions were then cast onto glass plates and stored at 30?C and 50% relative humidity until films were formed. A Chatillon digital force gauge attached to a motorized test stand was used to quantify the mechanical properties of the films, whereas water vapor permeabilities were determined according to the ASTM E96 M-05 water method. As expected, the novel LMW polymer solutions exhibited significantly lower viscosities than the conventional comparators at equivalent polymer concentrations. Film strength of the LMW materials was lower than films prepared from the conventional HPMC solutions, although this effect was not as evident for the HPMC 2906 chemistry. Increasing concentrations of the plasticizer resulted in decreased tensile strength and Young?s modulus and increased elongation as well as increased water vapor permeability, irrespective of polymer type. No statistical difference was found between the tensile strength to Young?s modulus ratios of the F chemistry LMW and conventional HPMC polymer films.     

增塑剂对马铃薯淀粉基复合膜物理机械性能的影响

以马铃薯淀粉、普鲁兰多糖、明胶为成膜物质,氯化钙为交联剂,甘油、山梨醇、聚乙二醇为增塑剂,采用流延法制备了马铃薯淀粉基复合膜,研究了3种增塑剂对复合膜物理机械性能的影响。结果表明:复合膜的抗拉强度和弹性模量均随增塑剂含量的增加而显著减小,断裂伸长率随甘油和山梨醇含量的增加而显著增加,聚乙二醇对其影响不显著;复合膜的水蒸气透过率和水溶性均随增塑剂含量的增加而增加;聚乙二醇能够显著降低复合膜的透光率。     

Time-dependent mechanical properties of polymeric coatings used in rupturable pulsatile release dosage forms

The mechanical properties of polymer films used in pharmaceutical coatings of pulsatile drug delivery systems were evaluated in the dry and the wet state by a newly developed puncture test, which allowed the time-dependent measurement of the mechanical properties on the same film specimen. Force, puncture strength, energy at break, modulus, and strain were investigated as a function of water exposure time with respect to the type of polymer and the type and concentration of plasticizer and pore former (hydroxypropyl methylcellulose, HPMC). Eudragit® RS films were very flexible, had a high strain, and broke upon puncture with only small cracks. In contrast, ethylcellulose films were more brittle with a lower strain and showed complete film rupture. Increased amounts of the hydrophilic pore former, HPMC, resulted in a reduced puncture strength and in an increase in water uptake and weight loss of the films. The puncture strength decreased with increasing plasticizer concentration and was lower with the lipophilic dibutyl sebacate than with the hydrophilic triethyl citrate.     

Time-Dependent Mechanical Properties of Polymeric Coatings Used in Rupturable Pulsatile Release Dosage Forms

Abstract

The mechanical properties of polymer films used in pharmaceutical coatings of pulsatile drug delivery systems were evaluated in the dry and the wet state by a newly developed puncture test, which allowed the time-dependent measurement of the mechanical properties on the same film specimen. Force, puncture strength, energy at break, modulus, and strain were investigated as a function of water exposure time with respect to the type of polymer and the type and concentration of plasticizer and pore former (hydroxypropyl methylcellulose, HPMC). Eudragit® RS films were very flexible, had a high strain, and broke upon puncture with only small cracks. In contrast, ethylcellulose films were more brittle with a lower strain and showed complete film rupture. Increased amounts of the hydrophilic pore former, HPMC, resulted in a reduced puncture strength and in an increase in water uptake and weight loss of the films. The puncture strength decreased with increasing plasticizer concentration and was lower with the lipophilic dibutyl sebacate than with the hydrophilic triethyl citrate.     

Chitosan tailor‐made films: the effects of additives on barrier and mechanical properties

With the aim of achieving ‘tailor‐made’ chitosan films, the effects of several variables on the properties of chitosan films were studied. These variables were chitosan concentration and molecular weight of thermally depolymerized chitosan, addition of lipids (palmitic acid, beeswax or carnauba wax) and plasticizer (glycerol). The water vapour transmission rate (WVTR) and mechanical properties of these films were measured. The innovative feature of this study is that it provides specific information to support the design of tailor‐made films. These can only be formulated when the effects of the important variables are well understood. It was found that WVTR was reduced by 57% in film made from chitosan that had been thermally treated for 7 h at 100°C (molecular mass 13.7 kDa), while in the emulsion films, the WVTR was increased by incorporation of palmitic acid, beeswax or carnauba wax incorporation. The mechanical properties (tensile strength and elongation at break) were improved when glycerol was used as plasticizer, resulting in more elastic films (increasing the elongation at break by 62%). Copyright © 2008 John Wiley & Sons, Ltd.     

Development of novel guava puree films containing chitosan nanoparticles

One of the overall goals of industries is to use packages that do not cause environmental problems at disposal time, but that have the same properties as the conventional ones. The goal of this study is to synthesize edible films based on hydroxypropyl methylcellulose (HPMC) with guava puree and chitosan (CS) nanoparticles. This was divided into two stages, the first is the synthesis of chitosan nanoparticles and the second is the production of the films. For the nanoparticles, average size and zeta potential measurements were performed. The characterizations of mechanical and thermal properties, solubility and water vapor permeability tests were conducted in the films. It was observed that when the nanoparticles were added to HPMC and guava puree films, they improved their mechanical and thermal properties, as well as decreased the films solubility and permeability. The potential application of the films prepared would be in edible films with flavor and odor to extend the shelf life of products.     

Physical, antibacterial and antioxidant properties of chitosan films incorporated with thyme oil for potential wound healing applications

Chitosan films incorporated with thyme oil for potential applications of wound dressing were successfully prepared by solvent casting method. The water vapor permeability, oxygen transmission rate, and mechanical properties of the films were determined. Surface and cross-section morphologies and the film thicknesses were determined by Scanning Electron Microscopy (SEM). Fourier transform infrared (FT-IR) spectroscopy was conducted to determine functional group interactions between the chitosan and thyme oil. Thermal behaviors of the films were analyzed by Thermal Gravimetry (TGA) and Differential Scanning Calorimetry (DSC). In addition, the antimicrobial and the antioxidant activities of the films were investigated. The antimicrobial test was carried by agar diffusion method and the growth inhibition effects of the films including different amount of thyme oil were tested on the gram negative microorganisms of Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa and a gram positive microorganism of Staphylococcus aureus. The minimum thyme oil concentration in chitosan films showing the antimicrobial activity on all microorganisms used in the study was found as 1.2 % (v/v). In addition, this concentration showed the highest antioxidant activity due to mainly the carvacrol in thyme oil. Water vapor permeability and oxygen transmission rate of the films slightly increased, however, mechanical properties decreased with thyme oil incorporation. The results revealed that the thyme oil has a good potential to be incorporated into chitosan to make antibacterial and permeable films for wound healing applications.     

表面活性剂对壳聚糖成膜体系物理特性的影响

目的 为研究不同表面活性剂对壳聚糖成膜体系物理与力学性能的影响,以期制备性能优良的壳聚糖膜。方法 文中配制质量分数为1%的壳聚糖膜液,以壳聚糖质量分数为30%的甘油为增塑剂,分别以质量分数为0.05%的吐温20、40、80,司盘20、40、80为表面活性剂,采用流延法制备可食膜。考察膜液流变性质、表面张力、Zeta电位,成膜力学性能、水分敏感性（水蒸气透过率、溶胀性、溶解性）、透光性,并利用AHP–CRITIC联合评价法对膜性能进行综合评价。结果 在质量分数为1%时,壳聚糖膜液表现为弱胀塑性;表面活性剂的加入能够有效降低膜液表面张力,使其保持稳定状态（Zeta电位>30 mV）;成膜均为淡黄色半透明状,透光范围为45%～77%;对同一系列表面活性剂,随着亲水亲油平衡值（HLB）的增加,成膜力学性能下降,但阻水能力增强,同时,吐温添加组膜的力学性能均优于司盘添加组,而阻水性能则相反。结论 综合评价膜体系性能发现,加入司盘20的壳聚糖膜得分最高,吐温系列最高分为吐温20。研究结果为成膜体系中表面活性剂的选择提供了理论依据。     

Evaluation of the film-forming property of hydrogenated rosin

The film-forming and coating properties of a new biomaterial, hydrogenated rosin (HR), is investigated in the present communication. Films produced by casting method are studied for mechanical, (tensile strength, elongation, and Young's modulus), water vapor transmission, and moisture absorption characteristics. Type of plasticizer and its concentration were observed to play an important role in modifying the film characteristics. Dibutyl sebacate (DBS), a hydrophobic plasticizer, was found to be suitable for development of flexible and smooth films. Film formulations plasticized with DBS were investigated for coating the drug layered nonpareil seeds where plasticization facilitated development of smooth and uniformly coated pellets. The increase in coat buildup, however, did not sustain the drug release significantly. The studies conclude that HR films promise utility as moisture-protective hydrophobic, film-coating materials.     

POSS对壳聚糖膜的阻湿与拉伸性能的影响

目的研究以四甲基铵基笼形聚倍半硅氧烷(Octa TMA POSS)为填料,制备壳聚糖基复合膜,对壳聚糖薄膜的水蒸气阻隔性能和力学性能进行改善。方法采用溶液共混流延法制备复合膜,测定其水蒸气透过系数、表面接触角、溶胀度、溶解度、吸附等温曲线、拉伸性能、成膜液流变性能、微观形貌和X射线衍射等。结果笼形聚倍半硅氧烷的加入可提高复合膜对水分子的阻隔性,尤其是质量分数为3%时,其水蒸气透过系数下降了15.9%。同时,壳聚糖薄膜的力学性能也得到改善,在质量分数低于5%时,壳聚糖薄膜的抗拉强度、弹性模量可同时得到提高。结论四甲基铵基笼形聚倍半硅氧烷的加入可改善壳聚糖薄膜的阻湿性能和力学性能,可大大提升其在食品包装领域的应用潜力。     

The effect of different plasticizer molecular weights and concentrations on mechanical and thermomechanical properties of free films

Plasticizers are usually added to improve the mechanical and conditional (thermomechanical) quality of film coatings. Different molecular weights and concentrations of polyethylene glycol were incorporated as plasticizers in hydroxypropylmethylcellulose (HPMC) films. Thermomechanical and mechanical properties of cast films were tested using tensile and dynamic mechanical thermal analysis (DMTA) testing, respectively.

The results, as expected, showed that addition of plasticizer caused a decrease in both mechanical and thermomechanical properties, but lower grades had more effect than higher molecular weights and concentrations.

The conclusion could be drawn that combining different grades of plasticizers to optimize mechanical and thermomechanical properties is more efficient than using different concentrations of plasticizers.     

Effects of Plasticizers on Water Permeation and Mechanical Properties of Cellulose Acetate: Antiplasticization in Slightly Plasticized Polymer Film

The effects of plasticizers, triacetin and three different molecular weights of polyethylene glycol, on the water permeation and mechanical properties of cellulose acetate were investigated. At 37°C, the water permeability of cellulose acetate was found to decrease with increasing plasticizer to a minimum and then to increase with higher concentrations of plasticizer. Low plasticizer concentrations caused a decrease in water permeability by antiplasticization. Antiplasticization arose from an interaction between the polymer and the plasticizer molecules and decreases the molecular mobility of the polymer. This effect was confirmed by mechanical measurements of polymer free films at the same experimental temperature. However, when the temperature was raised above the glass transition temperature, T_g, of the polymer films, the polymer films contain enough energy to overcome the interaction between the polymer and plasticizer molecules, and the antiplasticization effect disappeared.     

Effects of Plasticizers on Water Permeation and Mechanical Properties of Cellulose Acetate: Antiplasticization in Slightly Plasticized Polymer Film

Abstract

The effects of plasticizers, triacetin and three different molecular weights of polyethylene glycol, on the water permeation and mechanical properties of cellulose acetate were investigated. At 37°C, the water permeability of cellulose acetate was found to decrease with increasing plasticizer to a minimum and then to increase with higher concentrations of plasticizer. Low plasticizer concentrations caused a decrease in water permeability by antiplasticization. Antiplasticization arose from an interaction between the polymer and the plasticizer molecules and decreases the molecular mobility of the polymer. This effect was confirmed by mechanical measurements of polymer free films at the same experimental temperature. However, when the temperature was raised above the glass transition temperature, T_g, of the polymer films, the polymer films contain enough energy to overcome the interaction between the polymer and plasticizer molecules, and the antiplasticization effect disappeared.     

Effects of glycerol and sorbitol on optical,mechanical, and gas barrier properties of potato peel‐based films

Potato peel is a by‐product of potato‐based food production and seen as a zero‐ or negative‐value waste of which millions of tons are produced every year. Previous studies showed that potato peel is a potential material for film development when plasticized with 10% to 50% glycerol (w/w potato peel). To further investigate potato peel as a film‐forming material, potato peel‐based films containing the plasticizer sorbitol were prepared and investigated on their physicochemical properties in addition to films containing glycerol. Due to sufficient producibility and handling of casted films in preliminary trials, potato peel‐based films containing 50%, 60%, or 70% glycerol (w/w potato peel) and films containing 90%, 100%, or 110% sorbitol (w/w potato peel) were prepared in this study. Generally, with increasing plasticizer concentration, water vapor and oxygen permeability of the films increased. Films containing glycerol showed higher water vapor and oxygen permeabilities than films containing sorbitol. Young's modulus, tensile strength, and elongation at break decreased with increasing sorbitol concentration, whereas no significant effect of plasticizer content on elongation at break was shown in films containing glycerol. Due to crystallization of films containing sorbitol as a plasticizer, potato peel‐based films containing 50% glycerol (w/w) were identified as the most promising films, characterized by a water vapor transmission rate of 268 g 100 μm m^?2 d^?1 and an oxygen permeability of 4 cm³ 100 μm m^?2 d^?1 bar^?1. Therefore, potato peel‐based cast films in this study showed comparable tensile properties with those of potato starch‐based films, comparable water vapor barrier with those of whey protein‐based films, and comparable oxygen barrier with those of polyamide films.     

甘油含量对NMMO工艺天然纯纤维素膜性能的影响

以棉纤维素为原料,以NMMO(N-甲基吗啉-N-氧化物)为溶剂,以甘油为增塑剂制取天然纯纤维素包装膜,研究了不同甘油含量对纤维素膜性能的影响。结果表明,随着甘油含量的增加,纤维素膜的断裂伸长率随之增加,拉伸强度随之降低,二者变化幅度都很大;当甘油含量从2%增加到5%,纤维素膜的透油系数增加了13.4%,氧气透过率增加了3.0%,透湿系数增加了16.7%,透光率增加了22.4%,横向热收缩率增加了58.8%,纵向热收缩率增加了54.7%。可见,甘油含量对膜的透氧性影响较为微弱,但对力学性能、透油性、透湿性、透明度、热收缩率影响均较为显著。     

Evaluation of hydroxypropyl methylcellulose phthalate 50 as film forming polymer from aqueous dispersion systems

Hydroxypropyl methylcelluose phthalate 50 (HPMCP 50) was evaluated as a film forming polymer from aqueous dispersion systems. The influence of plasticizer type and level on the elasticity of HPMCP 50 free films prepared by the casting method was studied by measuring Young's modulus using an Instron Material Testing System. The release of a water soluble drug in various dissolution media from pellets coated with HPMCP 50 with 30% plasticizer containing various levels of hydroxypropyl cellulose (HPC) or hydroxypropyl methylcellulose (HPMC) was also studied. The influence of coating level on drug release from pellets was also investigated. Results showed that HPMCP 50 alone without a plasticizer does not form a film. However, when a plasticizer was added HPMCP 50 did form a film. Also, as the concentration of the plasticizer triethyl citrate was increased the elasticity of HPMCP 50 films was increased. Similar results were obtained with the plasticizer diethyl phthalate. For pellets a high coating level was required to achieve adequate protection in 0.06 N HCl. Drug release from coated pellets was found to be dependent upon the type and the level of the water soluble polymer incorporated with HPMCP 50. Drug release was increased as the percentage of HPC was increased. Higher release rates were obtained with HPMC compared to HPC. Coating level significantly influenced drug release in 0.06 N HCl; however, less of an effect was observed at pH 5.5.     

Fast release of liquid antisolvent precipitated fenofibrate at high drug loading from biocompatible thin films

Motivated by recent papers on nano and micro-particle slurry casting of poorly water-soluble drugs forming biocompatible films with enhanced properties, this work explores incorporation of liquid antisolvent (LAS) precipitated suspensions of fenofibrate, a model poorly soluble drug using both semi-synthetic (HPMC E15 LV) and natural (sodium alginate, SA) polymer as film formers. Centrifugation and subsequent resuspension were employed to minimize residual solvent and increase drug loading (～20%) in the LAS suspensions and in the film. Film’s critical quality attributes (CQAs), including drug distribution and uniformity, mechanical properties, and dissolution were assessed. Crystalline nature of FNB was largely preserved in the film without any polymorphic changes confirmed by XRD, DSC, and Raman. The NIR chemical imaging, corroborated by SEM imaging and drug content relative standard deviation (RSD) indicates that the drug is uniformly distributed without any observable large agglomerates. The films with SA showed lower mechanical strength as compared to HPMC due to SA’s low molecular weight. All films exhibited immediate drug release as has been the case using FNB nano particles in previous papers. Interestingly, although addition of plasticizer improved film dissolution, HPMC-based films had a faster dissolution compared to SA-based films in spite of higher mechanical strength of the former.     

茶多酚对壳聚糖/聚乙烯醇复合膜性能的影响

目的以茶多酚为改性剂对壳聚糖/聚乙烯醇复合膜进行共混改性,制备一种综合性能良好的绿色包装材料。方法采用溶液共混法制备不同茶多酚质量分数的壳聚糖/聚乙烯醇复合膜,并对其进行红外光谱分析,以及力学性能、水溶性、气体阻隔性、抗氧化性能的测试。结果茶多酚与壳聚糖/聚乙烯醇基质间发生了分子间相互作用,当茶多酚的质量分数为2%时复合膜的综合性能最好,拉伸强度提高了4.99%,且可保持较高的断裂伸长率,水溶性、水蒸气透过率和氧气透过率分别降低了82.43%,51.40%和72.77%,抗氧化能力增强了58.54%。结论添加适量的茶多酚能够提高壳聚糖/聚乙烯醇复合膜的力学性能和耐水性,并改善其气体阻隔性和抗氧化性能。     

有机酸溶剂体系中壳聚糖膜性能的研究进展

目的 有机酸溶剂体系对壳聚糖的成膜性能至关重要,探讨其潜在的分子机制,可为壳聚糖膜的相关研究提供理论参考。方法 综述壳聚糖的化学组成和成膜机制,以及壳聚糖在不同有机酸溶剂体系中成膜的力学性能、溶胀性、氧气透过率、水蒸气透过率等特性。结果 有机酸溶剂体系可为壳聚糖的溶解提供更多的质子,从而促进壳聚糖分子在水中的溶解。此外,有机酸分子结构中羧酸和羟基数量、碳链长度不同,其与壳聚糖分子间形成的氢键和离子作用力不同,进而可在很大程度上影响壳聚糖的成膜性能。结论 有机酸溶剂体系对壳聚糖膜的性能具有较为显著的影响,这有助于提高其作为可食用膜在改善食品品质和保鲜方面的适用性。