研究了不同浓度的甘油对聚乙烯醇-石竹籽胶共混膜性能的影响

لیلا منجذب مرودشتی, مسعود یاورمنش, آرش کوچکی
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In order to increase the workability and flexibility of biodegradable films, various plasticizers, usually poly-ols, have been widely used, glycerol being one of the most preferred and most studied. Plasticizers reduce intermolecular forces, increase the mobility of the biopolymer chains and thereby improve the mechanical properties of the films. Therefore, the aim of the present study were to investigate the effect of different proportions (20e100% w/w) of plasticizer (glycerol) on physicochemical, mechanical, permeability, surface and thermal properties of biodegradable PVA-AHSG blend films. \nPolymer blending is one of the most effective methods to have new material with desired properties. Films formed by blending of polymers usually results in modified physical and mechanical properties compared to films made of individual components. Since synthetic polymers are easily obtained and have low production cost, blending of natural and synthetic polymers improves the cost performance ratio of the resulting films. \nSince Alyssum homolocarpumseed gum (AHSG) is environmentally friendly due to its biodegradability and has good film forming properties, it is considered as a very promising biopolymer. \nSome synthetic polymers from non-renewable sources are also biodegradable, such as polyvinyl alcohol (PVA). PVA is a synthetic, water soluble polymer with excellent film forming, emulsifying, and adhesive properties. It also imparts good tensile strength (TS) and biodegradability and hence has been used in many biomaterial applications. PVA has also been approved for use in packaging meat and poultry products by the USDA (DeMerlis&Schonek, 2003). AHSG contains free hydroxyl and amine groups, and is therefore miscible with PVA due to the formation of hydrogen bonds. \n \nMaterials and methods: The aim of this study was to investigate the possibility of producing a novel biodegradable blend film from PVA-AHSG with glycerol as plasticizer in the different concentrations. Films were prepared by the casting method using PVA and AHSG (60:40 ratio). Glycerol was used ac plasticizer because it is compatible with PVA-AHSG blend improving film flexibility, facilitating its handling and preventing cracks. The PVA–AHSG blend film was prepared with different glycerol concentration (20–70%, w/w).The optical properties such as opacity and color were measured. Water vapor permeability, moisture content, water solubility and density of the films were also investigated. Films were evaluated for mechanical and antitoxin properties. The PVA–AHSG blend films were characterized using DSC, FTIR and scanning electron microscopy. \n \nResults and Discussion: The results of this study showed that blend of PVA and AHSG could be used as a new film-forming material. However, it was not possible to make PVA-AHSG blend films without addition of glycerol as a plasticizer to the formula. Glycerols in 20-70% (w/w) concentration were used to prepare the blend films. At the level of 20% (W/W) of glycerol, PVA-AHSG blend films had the lowest thickness (0.065 mm), moisture sorption (118.76%), water vapor permeability (WVP) values (4.9 g mm m-2 kPa−1 d-1), elongation at break (EB)(2.1%), moisture content (22.5%) and water solubility (16.6%) and the highest values for tensile strength (TS)(64.6 MPa), young modulus (YM) (892 MPa),density (0.109 g cm-3),opacity (0.069 A/mm) and water contact angle (74.52◦). Increasing of glycerol concentration in PVA-AHSG blend films resulted in increase in water vapor permeability and percent of elongation while, decreased tensile strength and surface hydrophobicity. \nIncreasing the glycerol concentration significantly (p < 0.05) diminished initial water contact angle of films from 74.52◦ to 37.80◦. It has been shown that the addition of plasticizers diminished the films’ water contact angle, which in turn, decreased hydrophobicity of the films. The higher hydro-philicity of the samples is attributable to the hygro-scopicity (water-binding capacity) of the plasticizer. Plasticizer can diminish interactions between biopolymer molecules and increase solubility due to its hydrophilic nature, giving the polymer molecules higher affinity to attract water. The moisture content increased significantly from 22.5% to 40.9% as the plasticizer content increased (p < 0.05). Because of glycerol acts as a water-holding agent, with the higher number of water molecules in glycerol-plasticized films increasing plasticizing activity.WVP increases as plasticizer content of the film increases due to its hydrophilic nature. WVP can be directly related to the quantity of OH group on the molecule. Also, environmental conditions can significantly affect the WVP. Increasing plasticizer concentration decreased the intermolecular forces between polymer chains and increased free volume and segmental motions, allowing water molecules to diffuse more easily and giving a higher WVP. Mechanical strength of films decreases due to plasticizer addition resulting in decreased tensile strength and increased elongation. The measurement of color values showed that by the increasing of the glycerol concentration in polymers blend matrix, the b and L values increased while a value decreased. Furthermore, the addition of glycerol promoted the interactions among PVA, AHSG and glycerol through hydrogen bonding as reflected on the shifting of main peaks of the glycerol-free film to higher wavenumbers as shown by FTIR spectra. Microscopic views indicated smooth and uniform surface morphology without obvious cracks, breaks, or openings on the surfaces after the incorporation of glycerol as a plasticizer. 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Therefore, the amount of research involving the production and characterization of biodegradable films has increased substantially, mainly due to interest in minimizing the ecological impact caused by the use of synthetic packaging materials. Several biopolymers have been exploited to develop eco-friendly food packaging materials. Usually, films based on biopolymers are highly sensitive to environmental conditions and generally present low mechanical resistance. As a result, several researchers have developed films based on mixtures of biopolymers and synthetic polymers. In order to increase the workability and flexibility of biodegradable films, various plasticizers, usually poly-ols, have been widely used, glycerol being one of the most preferred and most studied. Plasticizers reduce intermolecular forces, increase the mobility of the biopolymer chains and thereby improve the mechanical properties of the films. Therefore, the aim of the present study were to investigate the effect of different proportions (20e100% w/w) of plasticizer (glycerol) on physicochemical, mechanical, permeability, surface and thermal properties of biodegradable PVA-AHSG blend films. \\nPolymer blending is one of the most effective methods to have new material with desired properties. Films formed by blending of polymers usually results in modified physical and mechanical properties compared to films made of individual components. Since synthetic polymers are easily obtained and have low production cost, blending of natural and synthetic polymers improves the cost performance ratio of the resulting films. \\nSince Alyssum homolocarpumseed gum (AHSG) is environmentally friendly due to its biodegradability and has good film forming properties, it is considered as a very promising biopolymer. \\nSome synthetic polymers from non-renewable sources are also biodegradable, such as polyvinyl alcohol (PVA). PVA is a synthetic, water soluble polymer with excellent film forming, emulsifying, and adhesive properties. It also imparts good tensile strength (TS) and biodegradability and hence has been used in many biomaterial applications. PVA has also been approved for use in packaging meat and poultry products by the USDA (DeMerlis&Schonek, 2003). AHSG contains free hydroxyl and amine groups, and is therefore miscible with PVA due to the formation of hydrogen bonds. \\n \\nMaterials and methods: The aim of this study was to investigate the possibility of producing a novel biodegradable blend film from PVA-AHSG with glycerol as plasticizer in the different concentrations. Films were prepared by the casting method using PVA and AHSG (60:40 ratio). Glycerol was used ac plasticizer because it is compatible with PVA-AHSG blend improving film flexibility, facilitating its handling and preventing cracks. The PVA–AHSG blend film was prepared with different glycerol concentration (20–70%, w/w).The optical properties such as opacity and color were measured. Water vapor permeability, moisture content, water solubility and density of the films were also investigated. Films were evaluated for mechanical and antitoxin properties. The PVA–AHSG blend films were characterized using DSC, FTIR and scanning electron microscopy. \\n \\nResults and Discussion: The results of this study showed that blend of PVA and AHSG could be used as a new film-forming material. However, it was not possible to make PVA-AHSG blend films without addition of glycerol as a plasticizer to the formula. Glycerols in 20-70% (w/w) concentration were used to prepare the blend films. At the level of 20% (W/W) of glycerol, PVA-AHSG blend films had the lowest thickness (0.065 mm), moisture sorption (118.76%), water vapor permeability (WVP) values (4.9 g mm m-2 kPa−1 d-1), elongation at break (EB)(2.1%), moisture content (22.5%) and water solubility (16.6%) and the highest values for tensile strength (TS)(64.6 MPa), young modulus (YM) (892 MPa),density (0.109 g cm-3),opacity (0.069 A/mm) and water contact angle (74.52◦). Increasing of glycerol concentration in PVA-AHSG blend films resulted in increase in water vapor permeability and percent of elongation while, decreased tensile strength and surface hydrophobicity. \\nIncreasing the glycerol concentration significantly (p < 0.05) diminished initial water contact angle of films from 74.52◦ to 37.80◦. It has been shown that the addition of plasticizers diminished the films’ water contact angle, which in turn, decreased hydrophobicity of the films. 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引用次数: 8

摘要

简介:包装是食品工业的一个重要因素,主要是石油衍生聚合物。因此,涉及可生物降解薄膜的生产和表征的研究数量大幅增加,主要是因为人们对最大限度地减少使用合成包装材料造成的生态影响感兴趣。一些生物聚合物已被用于开发环保食品包装材料。通常,基于生物聚合物的膜对环境条件高度敏感,并且通常表现出低的机械阻力。因此,一些研究人员开发了基于生物聚合物和合成聚合物混合物的薄膜。为了提高可生物降解膜的可加工性和柔韧性,各种增塑剂,通常是聚乙烯醇,已经被广泛使用,甘油是最优选和研究最多的增塑剂之一。增塑剂减少了分子间作用力,增加了生物聚合物链的迁移率,从而提高了薄膜的机械性能。因此,本研究的目的是研究不同比例(20e100%w/w)的增塑剂(甘油)对可生物降解的PVA-AHSG共混膜的物理化学、力学、渗透性、表面和热性能的影响。聚合物共混是获得具有所需性能的新材料的最有效方法之一。与由单个组分制成的膜相比,通过聚合物共混形成的膜通常会导致物理和机械性能的改变。由于合成聚合物易于获得且生产成本低,天然聚合物和合成聚合物的共混提高了所得膜的性价比。由于Alyssum homocarpumseed gum(AHSG)具有良好的生物降解性和成膜性能,因此被认为是一种非常有前途的生物聚合物。一些来自不可再生资源的合成聚合物也是可生物降解的,例如聚乙烯醇(PVA)。PVA是一种合成的水溶性聚合物,具有优异的成膜、乳化和粘合性能。它还具有良好的拉伸强度(TS)和生物降解性,因此已被用于许多生物材料应用中。PVA也已被美国农业部批准用于肉类和家禽产品的包装(DeMerlis&Schonek,2003)。AHSG含有游离的羟基和胺基,因此由于氢键的形成而与PVA混溶。材料和方法:本研究的目的是研究以不同浓度的甘油为增塑剂,由PVA-AHSG制备新型可生物降解共混膜的可能性。使用PVA和AHSG(60:40比例)通过流延法制备薄膜。甘油之所以被用作增塑剂,是因为它与PVA-AHSG共混物相容,提高了薄膜的柔韧性,有助于处理和防止裂纹。制备了不同甘油浓度(20–70%,w/w)的PVA–AHSG共混膜。测量了其不透明度和颜色等光学性能。研究了薄膜的透水性、含水量、水溶性和密度。对薄膜的机械性能和抗毒素性能进行了评估。用DSC、FTIR和扫描电子显微镜对PVA–AHSG共混膜进行了表征。结果与讨论:本研究结果表明,PVA和AHSG的共混物可以作为一种新型的成膜材料。然而,在不向配方中添加甘油作为增塑剂的情况下,不可能制备PVA-AHSG共混膜。使用浓度为20-70%(w/w)的甘油来制备共混膜。在甘油含量为20%(W/W)的情况下,PVA-AHSG共混膜的厚度(0.065 mm)、吸湿性(118.76%)、水蒸气渗透性(WVP)值(4.9 g mm m-2 kPa−1 d-1)、断裂伸长率(EB)(2.1%)、含水量(22.5%)和水溶性(16.6%)最低,拉伸强度(TS)(64.6 MPa)、杨氏模量(YM)(892 MPa)、密度(0.109 g cm-3)最高,不透明度(0.069 A/mm)和水接触角(74.52◦). PVA-AHSG共混膜中甘油浓度的增加导致水蒸气渗透性和伸长率的增加,而拉伸强度和表面疏水性的降低。甘油浓度的增加显著降低了膜的初始水接触角(p<0.05),从74.52◦ 至37.80◦. 研究表明,增塑剂的加入降低了薄膜的水接触角,进而降低了薄膜疏水性。样品的较高亲水性归因于增塑剂的吸湿性(水结合能力)。增塑剂可以减少生物聚合物分子之间的相互作用,并由于其亲水性而增加溶解度,使聚合物分子具有更高的亲和力来吸引水。随着增塑剂含量的增加,水分含量从22.5%显著增加到40.9%(p<0。 05)。由于甘油具有保水剂的作用,随着甘油增塑膜中水分子数的增加,增塑活性增强。WVP由于其亲水性而随着膜中增塑剂含量的增加而增加。WVP可以与分子上OH基团的数量直接相关。此外,环境条件会显著影响WVP。增塑剂浓度的增加降低了聚合物链之间的分子间力,增加了自由体积和节段运动,使水分子更容易扩散,并产生更高的WVP。薄膜的机械强度由于增塑剂的加入而降低,导致拉伸强度降低和伸长率增加。颜色值的测量表明,随着聚合物共混基质中甘油浓度的增加,b和L值增加,而a值降低。此外,甘油的加入通过氢键促进了PVA、AHSG和甘油之间的相互作用,这反映在无甘油膜的主峰向更高波数的移动上,如FTIR光谱所示。显微镜观察表明,加入甘油作为增塑剂后,表面光滑均匀,没有明显的裂纹、断裂或开口。扫描电子显微镜研究表明,PVA-AHSG共混膜的微观结构对其物理力学性能有着至关重要的影响,这在食品包装应用中具有重要意义。
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THE EFFECT OF DIFFERENT CONCENTRATIONS OF GLYCEROL ON PROPERTIES OF BLEND FILMS BASED ON POLYVINYL ALCOHOL-ALLYSUMHOMOLOCARPUM SEED GUM
Introduction:Packaging is an important factor in food industry and is dominated by petroleum-derived polymers. Therefore, the amount of research involving the production and characterization of biodegradable films has increased substantially, mainly due to interest in minimizing the ecological impact caused by the use of synthetic packaging materials. Several biopolymers have been exploited to develop eco-friendly food packaging materials. Usually, films based on biopolymers are highly sensitive to environmental conditions and generally present low mechanical resistance. As a result, several researchers have developed films based on mixtures of biopolymers and synthetic polymers. In order to increase the workability and flexibility of biodegradable films, various plasticizers, usually poly-ols, have been widely used, glycerol being one of the most preferred and most studied. Plasticizers reduce intermolecular forces, increase the mobility of the biopolymer chains and thereby improve the mechanical properties of the films. Therefore, the aim of the present study were to investigate the effect of different proportions (20e100% w/w) of plasticizer (glycerol) on physicochemical, mechanical, permeability, surface and thermal properties of biodegradable PVA-AHSG blend films. Polymer blending is one of the most effective methods to have new material with desired properties. Films formed by blending of polymers usually results in modified physical and mechanical properties compared to films made of individual components. Since synthetic polymers are easily obtained and have low production cost, blending of natural and synthetic polymers improves the cost performance ratio of the resulting films. Since Alyssum homolocarpumseed gum (AHSG) is environmentally friendly due to its biodegradability and has good film forming properties, it is considered as a very promising biopolymer. Some synthetic polymers from non-renewable sources are also biodegradable, such as polyvinyl alcohol (PVA). PVA is a synthetic, water soluble polymer with excellent film forming, emulsifying, and adhesive properties. It also imparts good tensile strength (TS) and biodegradability and hence has been used in many biomaterial applications. PVA has also been approved for use in packaging meat and poultry products by the USDA (DeMerlis&Schonek, 2003). AHSG contains free hydroxyl and amine groups, and is therefore miscible with PVA due to the formation of hydrogen bonds. Materials and methods: The aim of this study was to investigate the possibility of producing a novel biodegradable blend film from PVA-AHSG with glycerol as plasticizer in the different concentrations. Films were prepared by the casting method using PVA and AHSG (60:40 ratio). Glycerol was used ac plasticizer because it is compatible with PVA-AHSG blend improving film flexibility, facilitating its handling and preventing cracks. The PVA–AHSG blend film was prepared with different glycerol concentration (20–70%, w/w).The optical properties such as opacity and color were measured. Water vapor permeability, moisture content, water solubility and density of the films were also investigated. Films were evaluated for mechanical and antitoxin properties. The PVA–AHSG blend films were characterized using DSC, FTIR and scanning electron microscopy. Results and Discussion: The results of this study showed that blend of PVA and AHSG could be used as a new film-forming material. However, it was not possible to make PVA-AHSG blend films without addition of glycerol as a plasticizer to the formula. Glycerols in 20-70% (w/w) concentration were used to prepare the blend films. At the level of 20% (W/W) of glycerol, PVA-AHSG blend films had the lowest thickness (0.065 mm), moisture sorption (118.76%), water vapor permeability (WVP) values (4.9 g mm m-2 kPa−1 d-1), elongation at break (EB)(2.1%), moisture content (22.5%) and water solubility (16.6%) and the highest values for tensile strength (TS)(64.6 MPa), young modulus (YM) (892 MPa),density (0.109 g cm-3),opacity (0.069 A/mm) and water contact angle (74.52◦). Increasing of glycerol concentration in PVA-AHSG blend films resulted in increase in water vapor permeability and percent of elongation while, decreased tensile strength and surface hydrophobicity. Increasing the glycerol concentration significantly (p < 0.05) diminished initial water contact angle of films from 74.52◦ to 37.80◦. It has been shown that the addition of plasticizers diminished the films’ water contact angle, which in turn, decreased hydrophobicity of the films. The higher hydro-philicity of the samples is attributable to the hygro-scopicity (water-binding capacity) of the plasticizer. Plasticizer can diminish interactions between biopolymer molecules and increase solubility due to its hydrophilic nature, giving the polymer molecules higher affinity to attract water. The moisture content increased significantly from 22.5% to 40.9% as the plasticizer content increased (p < 0.05). Because of glycerol acts as a water-holding agent, with the higher number of water molecules in glycerol-plasticized films increasing plasticizing activity.WVP increases as plasticizer content of the film increases due to its hydrophilic nature. WVP can be directly related to the quantity of OH group on the molecule. Also, environmental conditions can significantly affect the WVP. Increasing plasticizer concentration decreased the intermolecular forces between polymer chains and increased free volume and segmental motions, allowing water molecules to diffuse more easily and giving a higher WVP. Mechanical strength of films decreases due to plasticizer addition resulting in decreased tensile strength and increased elongation. The measurement of color values showed that by the increasing of the glycerol concentration in polymers blend matrix, the b and L values increased while a value decreased. Furthermore, the addition of glycerol promoted the interactions among PVA, AHSG and glycerol through hydrogen bonding as reflected on the shifting of main peaks of the glycerol-free film to higher wavenumbers as shown by FTIR spectra. Microscopic views indicated smooth and uniform surface morphology without obvious cracks, breaks, or openings on the surfaces after the incorporation of glycerol as a plasticizer. Scanning electron microscopy showed that the microstructure of PVA-AHSG blend films have a critical effect on their physical and mechanical properties that is important in food packaging applications.
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