叔丁醇/水基料浆冷冻浇注成型制备多孔陶瓷研究
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摘要
本论文针对冷冻浇注成型工艺制备多孔陶瓷开展研究，以叔丁醇/水二元混合溶液作为陶瓷料浆的液相溶剂，通过分析叔丁醇/水二元混合溶液的物化性质，测量计算叔丁醇/水二元混合液及其结晶体与陶瓷间的液-固、固-固界面张力γls、γss，以及二者差值Δγ。得到溶剂-粉体颗粒二元液相系统冷冻凝固初始及结束状态界面行为规律，并通过这一规律分析叔丁醇/水基陶瓷料浆冷冻浇注成型制备多孔陶瓷过程中，不同叔丁醇浓度与孔结构特征的关系，得出该体系料浆冷冻成型过程液相结晶及成孔形貌与界面行为的关联性。在此基础上，选择合适的料浆组分制备具有定向孔结构的SiC多孔陶瓷，及具有纳米孔结构的纳米氧化硅块体隔热材料。
本论文以Young-Good-Girifalco-Fowkes方程理论为基础，采用极性-色散分量方法测量计算出混合溶液及其结晶体与陶瓷间液-固、固-固界面张力，以及二者差值Δγ。结果表明，当TBA浓度为0、30、60、90%时，Δγ为极大值，当TBA浓度为20、50、70、100%时，Δγ为极小值。
采用叔丁醇/水基碳化硅陶瓷料浆冷冻浇注成型制备了具有定向孔结构的多孔陶瓷，孔的形貌呈现狭长片状及柱状两种类型，出现两种类型孔的初始料浆中TBA浓度，分别对应Δγ的极大、极小值，而与液-固表面张力的大小无明显联系。即陶瓷粉体颗粒存在的情况下，此溶剂与颗粒间液-固界面转化为固-固界面的难易程度，影响了结晶体的形貌特征，进而影响了孔结构。Δγ越小，结晶过程越易发生，因此易于形成单位体积内具有较大比表面积的圆型截面柱状孔；反之，Δγ越大，形成新相的难度越大，则更易于形成具有较小比表面积的狭长截面片状孔。
研究中为制备具有均匀微孔结构的氧化硅隔热材料，在非定向分布温度场环境下，选择TBA浓度为15%、20%、40%、70%的混合溶液配制纳米氧化硅粉体料浆冷冻浇注成型。并与纯水及纯叔丁醇基料浆进行比较，结果表明，由于溶液中氢离子存在以及纳米氧化硅粉体水解作用等原因，TBA浓度为40%、70%料浆具有更为细小均匀的微观孔结构，同时为排除液相冷冻凝固过程体积变化因素，选择TBA浓度为40%料浆冷冻成型制备微孔氧化硅块体材料。所制备添加玻璃纤维的样品，经过不同压力干压后，可以得到纳米孔氧化硅块体隔热材料。结果显示，TBA浓度为40%、固含量为13wt%的叔丁醇/水基纳米氧化硅粉体料浆，冷冻浇注成型后，采用15MPa压力压制，可以得到密度0.4g/cm3，平均孔径29.32nm，比表面积265.63m~2/g的纳米孔氧化硅块体隔热材料，经隔热材料加热过程背温测试，结果表明，该材料的热导率优于某种同厚度硅酸铝纸（700oC热导率为0.08W/(m·K)）。
This paper studied on preparation of porous ceramics by freeze-casting formingprocess of TBA/H_2O based ceramics powder suspensions, in which TBA/H_2O mixturewith different TBA concentration acted as cosolvent in slurry. The physical andproperties of TBA/H_2O binary system were studied. The liquid-solid（γls）andsolid-solid（γss）interface tension between the cosolvent and its crystals with ceramicssubstrates (polished SiC and Al_2O_3), as well as their differential value Δγ weremeasured and calculated. Based on the research, the interaction between poresmorphology in oriented porous SiC ceramics and the interface tension wasdemonstrated. Furthermore, nano porous SiO2monolithic insulation was preparedfrom TBA/H_2O based nano SiO2powder slurry by freeze-casting and dry-pressing,subsequently.
In this paper, an optical method based on Young-Good-Girifalco–Fowkesformula was used for measuring γls，γssand Δγ. The results shows that Δγ hasmaximum value with TBA concentration of0,30,60and90%, respectively, and theminimum value with TBA concentration of20,50,70and100%, respectively.
By observation of microstructure of SiC porous ceramics fabricated byfreeze-casting of TBA/H_2O slurries, it was found that laminar and columnar orientedpores were obtained with different TBA concentration, and the two kinds of porescorresponding with the maximum points and the minimum points of Δγ, respectively.The reason for these phenomena was that when liquid-solid interface transfer tosolid-solid interface during freeze process, more energy were need with higher Δγ, solaminar crystals with small specific surface area were preferred to be formed, whileon the contrary, columnar pores with large specific surface area were easily to beformed with lower Δγ.
Based on the former results, a novel method for fabricating nano pores SiO2monolithic insulation was presented by combined freeze-casting with dry-pressingprocess. Nano-sized SiO2powder suspensions with TBA concentration of15,20,40,70%, were selected as the slurries for freeze-casting. The microstructure of these samples showed different regulation with SiC porous ceramics due to the existing ofH+ions and the hydrolyzaion of nano-sized SiO2powders. In this case, slurries withTBA concentration of40and70%were suitable for making porous SiO2monolithwith finer pores. The slurry with TBA=40%, solid loading of13wt%, and with theaddition of2wt%glass fibers was finally chosen for preparation of SiO2porousmonolith by considering the integrative properties of finest pore morphology andsmallest volume changing during freezing process. After pressing of the freeze-castedsamples by pressure of15Mpa, a nano porous SiO2monolithic insulation wasfabricated with density of0.4g/cm3, mean pores of29.32nm, and specific surface areaof265.63m2/g, respectively. The insulation ability evaluated by back side temperaturemeasurment from is higher than Alumina silicates paper (thermal conductivity:0.08W/(m·K)(700oC)) with same thickness.
本论文以Young-Good-Girifalco-Fowkes方程理论为基础，采用极性-色散分量方法测量计算出混合溶液及其结晶体与陶瓷间液-固、固-固界面张力，以及二者差值Δγ。结果表明，当TBA浓度为0、30、60、90%时，Δγ为极大值，当TBA浓度为20、50、70、100%时，Δγ为极小值。
采用叔丁醇/水基碳化硅陶瓷料浆冷冻浇注成型制备了具有定向孔结构的多孔陶瓷，孔的形貌呈现狭长片状及柱状两种类型，出现两种类型孔的初始料浆中TBA浓度，分别对应Δγ的极大、极小值，而与液-固表面张力的大小无明显联系。即陶瓷粉体颗粒存在的情况下，此溶剂与颗粒间液-固界面转化为固-固界面的难易程度，影响了结晶体的形貌特征，进而影响了孔结构。Δγ越小，结晶过程越易发生，因此易于形成单位体积内具有较大比表面积的圆型截面柱状孔；反之，Δγ越大，形成新相的难度越大，则更易于形成具有较小比表面积的狭长截面片状孔。
研究中为制备具有均匀微孔结构的氧化硅隔热材料，在非定向分布温度场环境下，选择TBA浓度为15%、20%、40%、70%的混合溶液配制纳米氧化硅粉体料浆冷冻浇注成型。并与纯水及纯叔丁醇基料浆进行比较，结果表明，由于溶液中氢离子存在以及纳米氧化硅粉体水解作用等原因，TBA浓度为40%、70%料浆具有更为细小均匀的微观孔结构，同时为排除液相冷冻凝固过程体积变化因素，选择TBA浓度为40%料浆冷冻成型制备微孔氧化硅块体材料。所制备添加玻璃纤维的样品，经过不同压力干压后，可以得到纳米孔氧化硅块体隔热材料。结果显示，TBA浓度为40%、固含量为13wt%的叔丁醇/水基纳米氧化硅粉体料浆，冷冻浇注成型后，采用15MPa压力压制，可以得到密度0.4g/cm3，平均孔径29.32nm，比表面积265.63m~2/g的纳米孔氧化硅块体隔热材料，经隔热材料加热过程背温测试，结果表明，该材料的热导率优于某种同厚度硅酸铝纸（700oC热导率为0.08W/(m·K)）。
This paper studied on preparation of porous ceramics by freeze-casting formingprocess of TBA/H_2O based ceramics powder suspensions, in which TBA/H_2O mixturewith different TBA concentration acted as cosolvent in slurry. The physical andproperties of TBA/H_2O binary system were studied. The liquid-solid（γls）andsolid-solid（γss）interface tension between the cosolvent and its crystals with ceramicssubstrates (polished SiC and Al_2O_3), as well as their differential value Δγ weremeasured and calculated. Based on the research, the interaction between poresmorphology in oriented porous SiC ceramics and the interface tension wasdemonstrated. Furthermore, nano porous SiO2monolithic insulation was preparedfrom TBA/H_2O based nano SiO2powder slurry by freeze-casting and dry-pressing,subsequently.
In this paper, an optical method based on Young-Good-Girifalco–Fowkesformula was used for measuring γls，γssand Δγ. The results shows that Δγ hasmaximum value with TBA concentration of0,30,60and90%, respectively, and theminimum value with TBA concentration of20,50,70and100%, respectively.
By observation of microstructure of SiC porous ceramics fabricated byfreeze-casting of TBA/H_2O slurries, it was found that laminar and columnar orientedpores were obtained with different TBA concentration, and the two kinds of porescorresponding with the maximum points and the minimum points of Δγ, respectively.The reason for these phenomena was that when liquid-solid interface transfer tosolid-solid interface during freeze process, more energy were need with higher Δγ, solaminar crystals with small specific surface area were preferred to be formed, whileon the contrary, columnar pores with large specific surface area were easily to beformed with lower Δγ.
Based on the former results, a novel method for fabricating nano pores SiO2monolithic insulation was presented by combined freeze-casting with dry-pressingprocess. Nano-sized SiO2powder suspensions with TBA concentration of15,20,40,70%, were selected as the slurries for freeze-casting. The microstructure of these samples showed different regulation with SiC porous ceramics due to the existing ofH+ions and the hydrolyzaion of nano-sized SiO2powders. In this case, slurries withTBA concentration of40and70%were suitable for making porous SiO2monolithwith finer pores. The slurry with TBA=40%, solid loading of13wt%, and with theaddition of2wt%glass fibers was finally chosen for preparation of SiO2porousmonolith by considering the integrative properties of finest pore morphology andsmallest volume changing during freezing process. After pressing of the freeze-castedsamples by pressure of15Mpa, a nano porous SiO2monolithic insulation wasfabricated with density of0.4g/cm3, mean pores of29.32nm, and specific surface areaof265.63m2/g, respectively. The insulation ability evaluated by back side temperaturemeasurment from is higher than Alumina silicates paper (thermal conductivity:0.08W/(m·K)(700oC)) with same thickness.
引文
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