利用角蛋白制备功能材料的研究
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摘要
角蛋白是蛋白质的一种,广泛存在于人和动物的表皮、毛发以及动物的蹄、壳、爪、角等中。角蛋白具有生物可降解性、生物兼容性、无毒、价格低廉等优点,可以用作伤口敷料,起到抵抗细菌活性和加速伤口愈合的作用。因而具有很大的回收利用价值。目前,世界上大量的角蛋白原材料被废弃,如没有纺织价值的羊毛、废弃鸡羽毛和头发等,没能得到广泛有效的利用,造成了资源的严重浪费和环境污染。
为了回收资源和保护环境,文中以羊毛和人发为原料开发了一种质子导电膜材料和新型角蛋白载体缓释尿素肥料,并对其性能进行了考察。并在前人研究还原角蛋白膜的基础上,考察了还原角蛋白膜的性能和氧化条件对膜性能的影响。
首次系统研究了角蛋白质子导电膜,考察了直接氧化法、溶胀后氧化法、还原后氧化法和溶胀后还原氧化法中的氧化条件对电导率的影响。实验结果表明电导率随氧化条件的变化通常呈先升高后降低的趋势,并且四种氧化法中溶胀后还原氧化法的最大电导率值最高,羊毛和头发的最大电导率分别能达到3.19×10~(-3)S·cm~(-1)和8.35×10~(-3)S·cm~(-1)。我们还考察了模压工艺对电导率的影响,结果表明,模压压强、模压温度、粉料质量、粉料尺度等对电导率均有影响。我们还测试了与电导率相关的角蛋白膜的甲醇透过系数,结果表明头发和羊毛质子导电膜的甲醇透过系数均能达到10-6cm2.S-1以下,适当的制备条件可使其低于Nafion膜的甲醇透过系数。我们还考察了膜的力学性能、氢气透过率、含水率和膜密度,结果表明模压条件对以上性能均有影响。
其次为了更清楚的认识还原角蛋白溶液的成膜过程及膜的性能,我们考察了三种氧化条件下的还原角蛋白膜的巯基交联情况。结果表明氧化条件越强烈,膜的交联程度越好,膜的含水率越低,力学性能越强,阻氢性能越好。
我们还首次制备了以角蛋白作为载体的新型尿素缓释肥料,并考察了变性处理后角蛋白粉料对土壤性质的影响及缓释肥料的淋溶速率。结果表明,变性后角蛋白粉料比未经处理的角蛋白原料易于降解。角蛋白在降解过程中可提高土壤内生物活性,使土壤中矿质氮增加、呼吸作用增强,同时还可以调节土壤pH值,提高土壤中的阳离子交换容量。角蛋白载体缓释尿素肥料的淋溶速率可用模压压强、模压温度、角蛋白氧化时间、尿素含量和尿素粒度等条件来调节。角蛋白载体缓释尿素的累积淋出分率可控制在22%-62%之间,接近商品缓释肥Luxecote和SCU的累积淋出分率41.28%和18.01%。
Keratin, a kind of protein, exists widely in human and animal organs including epidermis, hair, wool, feather, hoof and horn. Keratin is a biodegradable, biocompatible, nontoxic and low-cost polymer, which shows potential of wide application. Therefore keratin is a highly useful material and worth being recovered. However at present a majority of keratin are discarded, such as wool unable to be spun, chicken feather and hair which resulting in waste of the natural resource and pollution of the environment.
To recover keratin and protect environment, a proton conducting membrane and a novel slow-release fertilizer from hair and wool is studied in this thesis. The conductivity of the membrane and the release rate of the fertilizer are tested. On the basis of former research, the property of reduced keratin membrane and the effect of oxidation condition on reduced keratin membrane are discussed also.
Firstly the conductivity of keratin proton conducting membrane is studied, the effect of oxidation condition of direct oxidation method, oxidation method after swelled, oxidation method after reduced and oxidation method after swelled and reduced on the conductivity is investigated. The experimental result indicates that the conductivity of the membranes change considerately with the oxidation condition usually. Of the four oxidation methods, the conductivity of the keratin membrane prepared by the oxidation method after swelled and reduced is the highest one. The highest conductivity of wool and hair can reach 3.19×10~(-3)S·cm~(-1)and 8.35×10~(-3)S·cm~(-1) respectively. The effects of moulding conditions on membrane conductivity are also tested. The results show that the moulding pressure, moulding temperature, powder mass, powder scale all have effect on the conductivity. Other properties related with conductivity are also measured. The methanol permeability of keratin membrane can reach under 10-6cm2.S-1 and appropriate preparation condition leads to lower methanol permeability. The mechanical property, H2 permeability, water content and density of the membrane are also determined. All these properties are affected by the moulding condition.
Secondly to clearly understand the membrane forming mechanism and membrane properties, mercapto cross linkages of reduced keratin membrane under three oxidation conditions are studied. The results show that stronger oxidation condition results in denser cross-linked structure, which makes lower water adsorption, higher maximal tensile strength and longer elongation at break, less H2 permeability.
At last a novel slow-release urea fertilizer with keratin carrier is prepared. Effects of keratin powder on soil and leaching ratio of slow-release fertilizer are tested. The denatured keratin powder is more biodegradable than keratin material. Keratin in degradation improves microbe activity, mineral nitrogen and soil respiration. However the pH of soil can be adjusted and the IEC can be improved. The column eluviation experiments show that the release rate could be controlled by moulding pressure, moulding temperature, oxidation time, urea content and urea scale. The cumulative release rate may be controlled between 22%-62% which is very close to that of Luxecote and SCU the two merchandized slow-release fertilizer.
为了回收资源和保护环境,文中以羊毛和人发为原料开发了一种质子导电膜材料和新型角蛋白载体缓释尿素肥料,并对其性能进行了考察。并在前人研究还原角蛋白膜的基础上,考察了还原角蛋白膜的性能和氧化条件对膜性能的影响。
首次系统研究了角蛋白质子导电膜,考察了直接氧化法、溶胀后氧化法、还原后氧化法和溶胀后还原氧化法中的氧化条件对电导率的影响。实验结果表明电导率随氧化条件的变化通常呈先升高后降低的趋势,并且四种氧化法中溶胀后还原氧化法的最大电导率值最高,羊毛和头发的最大电导率分别能达到3.19×10~(-3)S·cm~(-1)和8.35×10~(-3)S·cm~(-1)。我们还考察了模压工艺对电导率的影响,结果表明,模压压强、模压温度、粉料质量、粉料尺度等对电导率均有影响。我们还测试了与电导率相关的角蛋白膜的甲醇透过系数,结果表明头发和羊毛质子导电膜的甲醇透过系数均能达到10-6cm2.S-1以下,适当的制备条件可使其低于Nafion膜的甲醇透过系数。我们还考察了膜的力学性能、氢气透过率、含水率和膜密度,结果表明模压条件对以上性能均有影响。
其次为了更清楚的认识还原角蛋白溶液的成膜过程及膜的性能,我们考察了三种氧化条件下的还原角蛋白膜的巯基交联情况。结果表明氧化条件越强烈,膜的交联程度越好,膜的含水率越低,力学性能越强,阻氢性能越好。
我们还首次制备了以角蛋白作为载体的新型尿素缓释肥料,并考察了变性处理后角蛋白粉料对土壤性质的影响及缓释肥料的淋溶速率。结果表明,变性后角蛋白粉料比未经处理的角蛋白原料易于降解。角蛋白在降解过程中可提高土壤内生物活性,使土壤中矿质氮增加、呼吸作用增强,同时还可以调节土壤pH值,提高土壤中的阳离子交换容量。角蛋白载体缓释尿素肥料的淋溶速率可用模压压强、模压温度、角蛋白氧化时间、尿素含量和尿素粒度等条件来调节。角蛋白载体缓释尿素的累积淋出分率可控制在22%-62%之间,接近商品缓释肥Luxecote和SCU的累积淋出分率41.28%和18.01%。
Keratin, a kind of protein, exists widely in human and animal organs including epidermis, hair, wool, feather, hoof and horn. Keratin is a biodegradable, biocompatible, nontoxic and low-cost polymer, which shows potential of wide application. Therefore keratin is a highly useful material and worth being recovered. However at present a majority of keratin are discarded, such as wool unable to be spun, chicken feather and hair which resulting in waste of the natural resource and pollution of the environment.
To recover keratin and protect environment, a proton conducting membrane and a novel slow-release fertilizer from hair and wool is studied in this thesis. The conductivity of the membrane and the release rate of the fertilizer are tested. On the basis of former research, the property of reduced keratin membrane and the effect of oxidation condition on reduced keratin membrane are discussed also.
Firstly the conductivity of keratin proton conducting membrane is studied, the effect of oxidation condition of direct oxidation method, oxidation method after swelled, oxidation method after reduced and oxidation method after swelled and reduced on the conductivity is investigated. The experimental result indicates that the conductivity of the membranes change considerately with the oxidation condition usually. Of the four oxidation methods, the conductivity of the keratin membrane prepared by the oxidation method after swelled and reduced is the highest one. The highest conductivity of wool and hair can reach 3.19×10~(-3)S·cm~(-1)and 8.35×10~(-3)S·cm~(-1) respectively. The effects of moulding conditions on membrane conductivity are also tested. The results show that the moulding pressure, moulding temperature, powder mass, powder scale all have effect on the conductivity. Other properties related with conductivity are also measured. The methanol permeability of keratin membrane can reach under 10-6cm2.S-1 and appropriate preparation condition leads to lower methanol permeability. The mechanical property, H2 permeability, water content and density of the membrane are also determined. All these properties are affected by the moulding condition.
Secondly to clearly understand the membrane forming mechanism and membrane properties, mercapto cross linkages of reduced keratin membrane under three oxidation conditions are studied. The results show that stronger oxidation condition results in denser cross-linked structure, which makes lower water adsorption, higher maximal tensile strength and longer elongation at break, less H2 permeability.
At last a novel slow-release urea fertilizer with keratin carrier is prepared. Effects of keratin powder on soil and leaching ratio of slow-release fertilizer are tested. The denatured keratin powder is more biodegradable than keratin material. Keratin in degradation improves microbe activity, mineral nitrogen and soil respiration. However the pH of soil can be adjusted and the IEC can be improved. The column eluviation experiments show that the release rate could be controlled by moulding pressure, moulding temperature, oxidation time, urea content and urea scale. The cumulative release rate may be controlled between 22%-62% which is very close to that of Luxecote and SCU the two merchandized slow-release fertilizer.
引文
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