聚酰胺6/弹性体/无机刚性粒子三元体系的研究
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摘要
针对PA6树脂的增强增韧已经有了很多的研究报道,但对于不同微观形态无机刚性粒子的加入对PA6整体性能的影响并不多见,更多的研究主要集中在处理后的CaCO3粒子与PA6的共混体系。
该论文将相同目数的三种刚性粒子滑石粉,CaCO3,硅灰石分别与POE-g-MAH和PA6共混。无机刚性粒子、POE-g-MAH与PA6经混合、挤出、注射成型等工序制备成标准样品,并按国标进行检测,系统的研究了三种无机刚性粒子的用量、POE-g-MAH的用量对共混体系性能的影响规律,通过SEM、DSC和X射线衍射技术分析了共混物体系的微观结构与宏观力学性能的关系,探讨了三种无机刚性粒子对共混体系的差别化影响。
结果表明,PA6/POE-g-MAH共混体系的缺口冲击强度随着POE-g-MAH含量的增加而升高,当POE-g-MAH含量在10%～15%时,共混物体系出现脆韧转变现象。
针状硅灰石和片状滑石粉的加入明显降低了共混体系的缺口冲击强度,PA6/POE-g-MAH/硅灰石(85/15/2)缺口冲击强度比PA6/POE-g-MAH (85/15)下降了70%；PA6/POE-g-MAH/滑石粉(85/15/2)缺口冲击强度比PA6/POE-g-MAH (85/15)下降了81%。
而CaCO3的加入对共混体系的缺口冲击强度的保持比前两者要好一些,PA6/POE-g-MAH/CaCO3 (85/15/2)的缺口冲击强度比PA6/POE-g-MAH (85/15)的缺口冲击强度下降了57%。
三种无机刚性粒子都没有进行前期处理,其加入都不同程度的降低了共混体系的缺口冲击强度。而由于CaCO3近似球体的微观结构的存在,基体对CaCO3粒子的作用力在两极为拉应力,在赤道附近为压应力,同时由于相互作用力,球型粒子附近的树脂也受到反作用力,多重力的协同作用有助于基体的屈服。由于粒子和界面发生脱离,粒子周围形成空穴,在一定程度上阻止了断裂过程中裂纹的扩展,吸收了大量的能量,从而对共混体系缺口冲击强度的影响比另外两种粒子小。
共混体系冲击断面SEM图片、DSC数据图谱和X-射线衍射图谱都强有力的证明了以上宏观数据的走势和变化。无机刚性粒子的加入不同程度的改变了共混体系的结晶度,改变了基体的晶型,微观的变化决定了基体宏观的力学性能。
Lots of researchs about toughened and strengthened polyamide 6 resin had been reported. But the research about influences on the performance of polyamide 6 by rigid inorganic particles with different morphologies was rare. Many researchs were mainly concentrated on the blends of treated calcium carbonate particals and polyamide 6.
The thesis used wollastonite、CaCO3 and talc as fillers and blended them with POE-g-MAH and polyamide 6. After blended and extruded, the mixture of the rigid inorganic particles, PA6/POE-g-MAH and PA6 was injected and molded to be standard specimens for performance test. Influences of the percentage, components of rigid inorganic particles and POE-g-MAH on the mechanical properties of PA6 composites were systematically studied. Analysised the relationships between the blends' microstructure and macroproperties by the methods of SEM、DSC and X-ray diffraction.
The results showed that the notched impact strength of PA6/POE-g-MAH was enhanced as the quantity of POE-g-MAH raised. The blends of PA6 and POE-g-MAH showed the brittle-ductile transition.
The addition of acicular wollastonite and flaky talc reduced the notched impact strength of blends significantly. The notched impact strength of PA6/POE-g-MAH/wollastonite (85/15/2) is lower than that of PA6/POE-g-MAH (85/15) by 70%; The notched impact strength of PA6/POE-g-MAH/talc (85/15/2) is lower than that of PA6/POE-g-MAH (85/15) by 81%. But the addition of CaCO3 maitained the notched impact strength better than that of wollastonite and talc. The notched impact strength of PA6/POE-g-MAH/CaCO3 (85/15/2) is lower than that of PA6/POE-g-MAH (85/15) by 57%.
These three particals had not been pre-treated, so the bonding strength between the particals and matrix is weak. Thus the addition of particals decreased the notched impact strength of the blends. Due to the microstructure of calcium carbonate which is similar to the sphere. The force of the matrix focused on poles of the calcium carbonate particles was tensile stress while the force near the equator was compressive stress. Because of the detachment of particals and matrix, holes around the particals appeared. Thus it prevented the fracture crack propagation and absorbed a lot of energy, so it had less influence on the notched impact strength of blends than the other two particals.
The trends and changes of the datas of blends were proved by the method of SEM、DSC and X-ray diffraction. The addition of rigid inorganic particles changed the crystallinity of the blends and the crystal habit. So the microstructure changes determined the macromechanics of the blends.
该论文将相同目数的三种刚性粒子滑石粉,CaCO3,硅灰石分别与POE-g-MAH和PA6共混。无机刚性粒子、POE-g-MAH与PA6经混合、挤出、注射成型等工序制备成标准样品,并按国标进行检测,系统的研究了三种无机刚性粒子的用量、POE-g-MAH的用量对共混体系性能的影响规律,通过SEM、DSC和X射线衍射技术分析了共混物体系的微观结构与宏观力学性能的关系,探讨了三种无机刚性粒子对共混体系的差别化影响。
结果表明,PA6/POE-g-MAH共混体系的缺口冲击强度随着POE-g-MAH含量的增加而升高,当POE-g-MAH含量在10%～15%时,共混物体系出现脆韧转变现象。
针状硅灰石和片状滑石粉的加入明显降低了共混体系的缺口冲击强度,PA6/POE-g-MAH/硅灰石(85/15/2)缺口冲击强度比PA6/POE-g-MAH (85/15)下降了70%；PA6/POE-g-MAH/滑石粉(85/15/2)缺口冲击强度比PA6/POE-g-MAH (85/15)下降了81%。
而CaCO3的加入对共混体系的缺口冲击强度的保持比前两者要好一些,PA6/POE-g-MAH/CaCO3 (85/15/2)的缺口冲击强度比PA6/POE-g-MAH (85/15)的缺口冲击强度下降了57%。
三种无机刚性粒子都没有进行前期处理,其加入都不同程度的降低了共混体系的缺口冲击强度。而由于CaCO3近似球体的微观结构的存在,基体对CaCO3粒子的作用力在两极为拉应力,在赤道附近为压应力,同时由于相互作用力,球型粒子附近的树脂也受到反作用力,多重力的协同作用有助于基体的屈服。由于粒子和界面发生脱离,粒子周围形成空穴,在一定程度上阻止了断裂过程中裂纹的扩展,吸收了大量的能量,从而对共混体系缺口冲击强度的影响比另外两种粒子小。
共混体系冲击断面SEM图片、DSC数据图谱和X-射线衍射图谱都强有力的证明了以上宏观数据的走势和变化。无机刚性粒子的加入不同程度的改变了共混体系的结晶度,改变了基体的晶型,微观的变化决定了基体宏观的力学性能。
Lots of researchs about toughened and strengthened polyamide 6 resin had been reported. But the research about influences on the performance of polyamide 6 by rigid inorganic particles with different morphologies was rare. Many researchs were mainly concentrated on the blends of treated calcium carbonate particals and polyamide 6.
The thesis used wollastonite、CaCO3 and talc as fillers and blended them with POE-g-MAH and polyamide 6. After blended and extruded, the mixture of the rigid inorganic particles, PA6/POE-g-MAH and PA6 was injected and molded to be standard specimens for performance test. Influences of the percentage, components of rigid inorganic particles and POE-g-MAH on the mechanical properties of PA6 composites were systematically studied. Analysised the relationships between the blends' microstructure and macroproperties by the methods of SEM、DSC and X-ray diffraction.
The results showed that the notched impact strength of PA6/POE-g-MAH was enhanced as the quantity of POE-g-MAH raised. The blends of PA6 and POE-g-MAH showed the brittle-ductile transition.
The addition of acicular wollastonite and flaky talc reduced the notched impact strength of blends significantly. The notched impact strength of PA6/POE-g-MAH/wollastonite (85/15/2) is lower than that of PA6/POE-g-MAH (85/15) by 70%; The notched impact strength of PA6/POE-g-MAH/talc (85/15/2) is lower than that of PA6/POE-g-MAH (85/15) by 81%. But the addition of CaCO3 maitained the notched impact strength better than that of wollastonite and talc. The notched impact strength of PA6/POE-g-MAH/CaCO3 (85/15/2) is lower than that of PA6/POE-g-MAH (85/15) by 57%.
These three particals had not been pre-treated, so the bonding strength between the particals and matrix is weak. Thus the addition of particals decreased the notched impact strength of the blends. Due to the microstructure of calcium carbonate which is similar to the sphere. The force of the matrix focused on poles of the calcium carbonate particles was tensile stress while the force near the equator was compressive stress. Because of the detachment of particals and matrix, holes around the particals appeared. Thus it prevented the fracture crack propagation and absorbed a lot of energy, so it had less influence on the notched impact strength of blends than the other two particals.
The trends and changes of the datas of blends were proved by the method of SEM、DSC and X-ray diffraction. The addition of rigid inorganic particles changed the crystallinity of the blends and the crystal habit. So the microstructure changes determined the macromechanics of the blends.
引文
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