微晶白云母的表面修饰及其与核—壳型ACR共同改性PVC材料的研究
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摘要
PVC是世界五大通用塑料之一,占合成树脂总量的30 %左右,具有不易燃烧、耐腐蚀、绝缘、隔离效果良好等特点,其产量仅次于聚乙烯而居于世界树脂产量的第二位,是应用领域最广的塑料品种之一。随着科学技术的不断进步,其硬制品主要用于管、棒、异型材、建材、室内地板装饰材料、各种板材家具、玩具、运动器材、医用管件、包装涂层等。但其硬制品普遍存在性脆、韧性差、以及耐热性、热稳定性差的缺陷,因此限制了其应用领域。如何有效提高PVC材料的综合性能,拓宽其应用领域,是当今PVC材料研究中急需解决的重要问题之一。
已有研究表明,采用无机刚性粒子可有效提高高分子材料的性能,不但能保持高分子材料自身的一些优异性能,还可以增加高分子材料的韧性,赋予高聚物基复合材料更高的力学性能和电学性能等。但不同类型无机刚性粒子填料对提高高分子性能的程度有一定差异,同时无机刚性粒子在高分子材料基体中容易产生团聚现象,分散性不好。因此,如何选择合适的填料,并选用合适的改性剂和改性工艺对其表面进行修饰,使之在PVC材料基体中均匀分散,在满足制品性能及加工性能要求的同时又提高填充量。
川西地区微晶白云母是一种新型白云母类矿物资源,性能优良,储量丰富,与其他常见的硅酸盐矿物相比,微晶白云母具有高强度、耐热、耐酸碱、绝缘、化学稳定、耐候性、防紫外线、抗老化等优异的性能;与传统的白云母矿物相比,它具有天然粒度细、易磨碎、化学活性高的特性,是一种高品质的无机刚性粒子,在高聚物中具有广阔的应用前景。
论文选用川西地区微晶白云母矿物为填料,硅烷偶联剂KH-550为表面修饰剂,核-壳型ACR树脂为抗冲改性剂,PVC树脂为材料基体,采用熔融共混法制备了微晶白云母/ACR/PVC复合材料。优化了硅烷偶联剂KH-550表面修饰微晶白云母的工艺条件,研究了复合材料的力学性能、热稳定性能、复合加工性能、微观形貌等,探讨了微晶白云母、ACR及其协同改性PVC的机理。论文取得的主要成果如下:
1.采用干法改性技术表面修饰微晶白云母粉体时,搅拌速度、表面修饰时间及表面修饰剂用量等工艺条件对表面修饰效果有明显的影响。在试验研究范围内,当微晶白云母的粒径在1μm~5μm之间,平均粒度为4.825μm时,表面修饰微晶白云母矿物粉体的较佳工艺条件为:搅拌速度25000 r/min、表面修饰时间300 s、硅烷偶联剂KH-550用量1.2 %。
2.微晶白云母是改性PVC材料的高品质无机刚性填料,但直接添加未经表面修饰的微晶白云母,不能有效提高微晶白云母/PVC复合材料的综合性能,这是由于未经表面处理的微晶白云母表面亲水,与PVC的界面相容性很差,处于两相分离状态,随着填料含量的增加,体系中由微晶白云母造成的空洞与缺陷越多,材料能承受的外力越小。
3.在力学性能方面,以硅烷偶联剂KH-550表面修饰后的微晶白云母为填料,能显著提高微晶白云母/PVC复合材料的综合力学性能。随着微晶白云母的添加量的增加,复合材料的拉伸强度和缺口冲击强度均出现先提高后降低的趋势,当微晶白云母的添加量为35～40份时,复合材料的拉伸强度和缺口冲击强度均趋于最高值,分别比纯的PVC提高了24.2 %～26.8 %和28 %～30 %,其杨氏模量、弯曲强度、弯曲模量和硬度随微晶白云母添加量的增加逐渐增大,在试验研究范围内(微晶白云母添加量5～45份),复合材料的杨氏模量、弯曲强度、弯曲模量和硬度最大值分别比纯PVC提高了65.5 %、15.2 %、71.6 %、32.8 %。综合分析认为,当经表面修饰微晶白云母添加量为35～40份时,微晶白云母/PVC复合材料综合力学性能最佳,同时可大幅度降低PVC材料的成本。
4.具有核-壳结构ACR的加入能显著提高微晶白云母/ACR/PVC复合材料的韧性。在试验研究范围内,相同的微晶白云母添加量(35份)下,当ACR的添加量在12份时,微晶白云母/ACR/PVC复合材料的冲击强度达到11.5 KJ/m2,为微晶白云母/PVC复合材料冲击强度的167 %,为纯PVC冲击强度的213 %,但会使复合材料的拉伸强度、杨氏模量等有所降低。综合分析认为,当ACR树脂的添加量在3～9份时,微晶白云母/ACR/PVC复合材料的综合力学性能优良。
5.添加经硅烷偶联剂KH-550表面修饰的微晶白云母,可显著提高PVC材料的热稳定性,随着微晶白云母粉体添加量的增加,微晶白云母/PVC复合材料的玻璃化转变温度和维卡软化温度越高,热稳定性越好。当微晶白云母的添加量为35～40份时,PVC复合材料的玻璃化转变温度和维卡软化温度分别提高了5.1℃～7.9℃和16.4℃～20.2℃。ACR的加入能进一步提高微晶白云母/PVC复合材料的玻璃化转变温度Tg,在相同的微晶白云母添加量(35份)下,ACR添加量在3～9份时, ACR的加入对微晶白云母/PVC复合材料的维卡软化温度影响不大,仍比纯PVC提高了愈14.3℃～17.6℃,改善了复合材料的耐热性,延缓了材料老化。
6.微晶白云母矿物粉体的加入会影响PVC材料的复合加工性能,随着微晶白云母添加量的增多,微晶白云母/PVC复合材料的塑化时间变长,转矩变大,不利于加工。但引入ACR后,复合材料的塑化时间缩短,有利于复合加工。
7.复合材料冲击断面的SEM分析结果表明,以未经表面修饰微晶白云母为填料,其在PVC基体中分布不均,且与PVC基体之间存在明显空隙,界面结合力较弱;以经硅烷偶联剂KH-550表面修饰微晶白云母为填料,其在PVC基体中分布均匀,且颗粒被PVC基体包裹,增强了微晶白云母颗粒与PVC的界面的结合力。随着微晶白云母粒子的增加,PVC材料基体中的微晶白云母粒子之间的距离逐渐靠近,能有效的形成应力传递点,提高了微晶白云母/PVC复合材料的拉伸强度。进一步引入ACR,微晶白云母/ACR/PVC复合材料中出现“微孔”结构,“微孔”尺寸为200 nm,显著提高了复合材料的冲击强度。
8.微晶白云母与ACR协同改性PVC树脂机理研究表明,ACR、微晶白云母与PVC熔融共混后,ACR树脂的壳层PMMA与PVC基体的相容性很好,其分子链互相缠绕;而核层PBA由于是交联结构,不溶不融,不能与PVC分子链相互缠绕,作为弹性体粒子均匀的分散在PVC基体中,在微晶白云母/ACR/PVC复合材料中形成均匀的“微孔”结构,当材料受到冲击时,这种“微孔”结构能吸收大量的冲击能量,因而显著提高该复合材料的韧性。而微晶白云母粒子经硅烷偶联剂KH-550表面修饰后,与PVC基体的相容性很好,也均匀的分散在PVC基体中,且一部分微晶白云母粒子会接触PVC分子链的链段,阻碍PVC分子的链段运动,提高了PVC复合材料的玻璃化转变温度。
Polyvinyl chloride (PVC) is one of the five major general plastics used worldwide, which accounts for about 30% of the total amount of synthetic resin. With its nonflammable and anti-erosive properties as well as good insulation and isolation effects, PVC has the second largest volume of resin production in the world only next to polyethylene, and has been regarded as one of the most widely applied plastic varieties. Along with the advances in science and technology, unplasticized PVC are mainly used in the production of pipes, sticks, building materials, interior flooring materials, furniture boards, toys, sports equipments, medical tube elements, packaging coatings and etc. The application of unplasticized PVC, however, has always been restricted due to its poor properties in terms of fragility, tenacity, heat resistance and thermal stability. Thus, how to improve its comprehensive performance and expand its application is the most urgent task we face right now.
The performance of polymer material can be improved by inorganic rigid particle, because it can not only maintain the polymer material’s excellent performance but also increase its toughness, so the composite material based on polymer will have high mechanical properties and electrical properties. However, different inorganic rigid particles have different impacts on the polymer’s performance, and inorganic rigid particles will lead to the occurrence of agglomeration, so the appropriate filler, modifier and modification process will make the PVC material evenly dispersed in matrix, satisfy the production’s performance and processing performance requirement, and also increase the filling volume.
Micro-crystal muscovite is a new member to the family of micaceous minerals which was discovered in Western Sichuan of China in recent years. Compared with other common silicate minerals (e.g. kaolinite, montmorillonite, illite and bentonite), micro-crystal muscovite is more resistant to heat, acid or alkaline, weather, and ultraviolet with higher intensity and chemostability as well as better insulation and anti-aging effects. In addition, it is also more grindable and chemically active with a smaller grain size when compared with traditional muscovite minerals. This material is a high-quality inorganic rigid particle and it is expected to be widely applied in polymer.
In this paper, micro-crystal muscovite/ACR/PVC composite material was prepared by melt blending, with micro-crystal muscovite as packing material, silane coupling agent KH-550 as surface modifier, core-shell type ACR resin as impact modifier and PVC resin as matrix. This paper also optimized the condition of silane coupling agent KH-550 as surface modifier, the chemical properties of composite material ,the thermal stability, the processing of complex, the microscopic appearance and so on .Furthermore ,this paper also studied the mechanism of combined modification of PVC with micro-crystal muscovite and ACR. Results mainly showed that:
1. The effect of dry surface modification of micro-crystal muscovite is significantly influenced by the stirring speed, dose of surface modifier and duration of surface modification. Within the experimental range, a stirring speed at 25000 r/min, a duration of modification of 300 s, and a dose of silane coupling agent KH-550 at 1.2 % of the weight of micro-crystal muscovite are deemed to be the most appropriate.
2. Surface modification of micro-crystal muscovite using silane coupling agent KH-550 can significantly improve the mechanical properties of the micro-crystal muscovite/PVC composite material. This is because the unmodified micro-crystal muscovite has very poor interfacial compatibility with PVC, which means that adding such micro-crystal muscovite may increase micro-cavities and defects inside the composite material and reduce its physical strength.
3. After surface modification with silane coupling agent KH-550, micro-crystal muscovite can significantly improve the mechanical properties of the micro-crystal muscovite/PVC composite material. The tensile strength and impact strength of the composite material initially increase with the addition of micro-crystal muscovite, and then begin to decrease when the amount of micro-crystal muscovite becomes excessive. The peak values of its tensile strength and impact strength are identified when 35 ~ 40 portions of micro-crystal muscovite have been added, 24.2 %~26.8 % and 28 %~30 % higher than those of normal PVC, respectively. Besides, the Young’s modulus, bending strength, bending modulus and hardness of the micro-crystal muscovite/PVC composite material gradually increase with the addition of micro- crystal muscovite. Within the experimental range, i.e. 5 ~ 45 portions of micro-crystal muscovite, the max of Young’s modulus, bending strength, bending modulus and hardness of the micro-crystal muscovite/PVC composite material are enhanced by 65.5 %, 15.2 %, 71.6 % and 32.8 %, respectively. Based on comprehensive analysis, the most appropriate amount for micro-crystal muscovite addition in the micro-crystal muscovite/PVC composite material is determined to be 35 ~ 40 portions.
4. Adding ACR with core-shell structure can significantly improve the toughness of the micro-crystal/ACR/PVC composite material. In the experiment, with the same addition of the micro-crystal muscovite (35 phr), the micro-crystal/ACR/PVC composite material has a impact strength of 11.5 KJ/m2, which is 167 % of the micro- crystal/ACR/PVC and 213 % of the pure PVC. However, this will make the tensile strength and Young’s modulus decrease. Based on comprehensive analysis, the micro-crystal /ACR/PVC performance will be considered as the best when the ACR is 3 phr~9 phr.
5. Adding micro-crystal muscovite using silane coupling agent KH-550 can also improve the thermal stability of PVC. The glass-transition temperature, Vicat softening temperature and thermal stability increase accordingly with more micro-crystal muscovite added into the micro-crystal/PVC composite material. When the micro-crystal muscovite is 35 phr ~ 40 phr, the PVC composite material’s glass transition temperature increase 5.1℃~7.9℃, and the Vicat softening temperature increase 16.4℃~20.2℃, which significantly improve the thermal stability. Moreover, ACR can further increase the glass-transition temperature of the PVC, with same micro-crystal muscovite addition (35 phr) and ACR addition(3 phr~9 phr), the ACR addition does not significantly affect the Vicat softening temperature with an increase of 14.3℃~17.6℃compared with that of the pure PVC. As a result, micro-crystal muscovite and ACR can modify PVC, improve its thermal stability, slow down its aging and widen its application.
6. Micro-crystal muscovite can affect the composite processing performance of PVC, increase the plant time and torque of the micro-crystal/PVC composite material, which is not conducive to processing. But adding ACR can reduce the plant time and facilitate the processing.
7. By analyzing the composite material’s impact on the fracture sections’SEM, the micro-crystal muscovite without surface modification disperses unevenly and has clear interstices with PVC matrix, so the bending in interface is wake. When the micro-crystal muscovite surface is modified by silane coupling agent KH-550, it will disperse evenly in PVC matrix and enfold by PVC matrix, which will improve the bending. With the addition of micro-crystal muscovite, the distance of micro-crystal muscovite in PVC matrix decreases, which will form the tension delivery point and improve the tensile strength. By adding ACR, the“porous structure”forms in the micro-crystal/ACR/PVC composite material with a size of 200 nm, which will significantly improve the composite material’s impact strength.
8. Adding ACR with core-shell structure can significantly improve the toughness of the micro-crystal/ ACR/PVC composite material. When ACR is melt blended with PVC, the PMMA in the surface has good compatibility with PVC and its molecular chains twine together; while the PBA of core does not melt, so the“porous structure”forms in the micro-crystal/ACR/PVC composite material. These microcellular structure can absorb the power of the impact and greatly increase the toughness of the composite material. The micro-crystal muscovite has good compatibility with PVC matrix when its surface is modified by silane coupling agent KH-550 and is dispersed in PVC matrix. Further more, some of the micro-crystal muscovite particles will contact with PVC molecular chain and obstruct the molecular chain movement, which will increase the glass-transition temperature.
已有研究表明,采用无机刚性粒子可有效提高高分子材料的性能,不但能保持高分子材料自身的一些优异性能,还可以增加高分子材料的韧性,赋予高聚物基复合材料更高的力学性能和电学性能等。但不同类型无机刚性粒子填料对提高高分子性能的程度有一定差异,同时无机刚性粒子在高分子材料基体中容易产生团聚现象,分散性不好。因此,如何选择合适的填料,并选用合适的改性剂和改性工艺对其表面进行修饰,使之在PVC材料基体中均匀分散,在满足制品性能及加工性能要求的同时又提高填充量。
川西地区微晶白云母是一种新型白云母类矿物资源,性能优良,储量丰富,与其他常见的硅酸盐矿物相比,微晶白云母具有高强度、耐热、耐酸碱、绝缘、化学稳定、耐候性、防紫外线、抗老化等优异的性能;与传统的白云母矿物相比,它具有天然粒度细、易磨碎、化学活性高的特性,是一种高品质的无机刚性粒子,在高聚物中具有广阔的应用前景。
论文选用川西地区微晶白云母矿物为填料,硅烷偶联剂KH-550为表面修饰剂,核-壳型ACR树脂为抗冲改性剂,PVC树脂为材料基体,采用熔融共混法制备了微晶白云母/ACR/PVC复合材料。优化了硅烷偶联剂KH-550表面修饰微晶白云母的工艺条件,研究了复合材料的力学性能、热稳定性能、复合加工性能、微观形貌等,探讨了微晶白云母、ACR及其协同改性PVC的机理。论文取得的主要成果如下:
1.采用干法改性技术表面修饰微晶白云母粉体时,搅拌速度、表面修饰时间及表面修饰剂用量等工艺条件对表面修饰效果有明显的影响。在试验研究范围内,当微晶白云母的粒径在1μm~5μm之间,平均粒度为4.825μm时,表面修饰微晶白云母矿物粉体的较佳工艺条件为:搅拌速度25000 r/min、表面修饰时间300 s、硅烷偶联剂KH-550用量1.2 %。
2.微晶白云母是改性PVC材料的高品质无机刚性填料,但直接添加未经表面修饰的微晶白云母,不能有效提高微晶白云母/PVC复合材料的综合性能,这是由于未经表面处理的微晶白云母表面亲水,与PVC的界面相容性很差,处于两相分离状态,随着填料含量的增加,体系中由微晶白云母造成的空洞与缺陷越多,材料能承受的外力越小。
3.在力学性能方面,以硅烷偶联剂KH-550表面修饰后的微晶白云母为填料,能显著提高微晶白云母/PVC复合材料的综合力学性能。随着微晶白云母的添加量的增加,复合材料的拉伸强度和缺口冲击强度均出现先提高后降低的趋势,当微晶白云母的添加量为35～40份时,复合材料的拉伸强度和缺口冲击强度均趋于最高值,分别比纯的PVC提高了24.2 %～26.8 %和28 %～30 %,其杨氏模量、弯曲强度、弯曲模量和硬度随微晶白云母添加量的增加逐渐增大,在试验研究范围内(微晶白云母添加量5～45份),复合材料的杨氏模量、弯曲强度、弯曲模量和硬度最大值分别比纯PVC提高了65.5 %、15.2 %、71.6 %、32.8 %。综合分析认为,当经表面修饰微晶白云母添加量为35～40份时,微晶白云母/PVC复合材料综合力学性能最佳,同时可大幅度降低PVC材料的成本。
4.具有核-壳结构ACR的加入能显著提高微晶白云母/ACR/PVC复合材料的韧性。在试验研究范围内,相同的微晶白云母添加量(35份)下,当ACR的添加量在12份时,微晶白云母/ACR/PVC复合材料的冲击强度达到11.5 KJ/m2,为微晶白云母/PVC复合材料冲击强度的167 %,为纯PVC冲击强度的213 %,但会使复合材料的拉伸强度、杨氏模量等有所降低。综合分析认为,当ACR树脂的添加量在3～9份时,微晶白云母/ACR/PVC复合材料的综合力学性能优良。
5.添加经硅烷偶联剂KH-550表面修饰的微晶白云母,可显著提高PVC材料的热稳定性,随着微晶白云母粉体添加量的增加,微晶白云母/PVC复合材料的玻璃化转变温度和维卡软化温度越高,热稳定性越好。当微晶白云母的添加量为35～40份时,PVC复合材料的玻璃化转变温度和维卡软化温度分别提高了5.1℃～7.9℃和16.4℃～20.2℃。ACR的加入能进一步提高微晶白云母/PVC复合材料的玻璃化转变温度Tg,在相同的微晶白云母添加量(35份)下,ACR添加量在3～9份时, ACR的加入对微晶白云母/PVC复合材料的维卡软化温度影响不大,仍比纯PVC提高了愈14.3℃～17.6℃,改善了复合材料的耐热性,延缓了材料老化。
6.微晶白云母矿物粉体的加入会影响PVC材料的复合加工性能,随着微晶白云母添加量的增多,微晶白云母/PVC复合材料的塑化时间变长,转矩变大,不利于加工。但引入ACR后,复合材料的塑化时间缩短,有利于复合加工。
7.复合材料冲击断面的SEM分析结果表明,以未经表面修饰微晶白云母为填料,其在PVC基体中分布不均,且与PVC基体之间存在明显空隙,界面结合力较弱;以经硅烷偶联剂KH-550表面修饰微晶白云母为填料,其在PVC基体中分布均匀,且颗粒被PVC基体包裹,增强了微晶白云母颗粒与PVC的界面的结合力。随着微晶白云母粒子的增加,PVC材料基体中的微晶白云母粒子之间的距离逐渐靠近,能有效的形成应力传递点,提高了微晶白云母/PVC复合材料的拉伸强度。进一步引入ACR,微晶白云母/ACR/PVC复合材料中出现“微孔”结构,“微孔”尺寸为200 nm,显著提高了复合材料的冲击强度。
8.微晶白云母与ACR协同改性PVC树脂机理研究表明,ACR、微晶白云母与PVC熔融共混后,ACR树脂的壳层PMMA与PVC基体的相容性很好,其分子链互相缠绕;而核层PBA由于是交联结构,不溶不融,不能与PVC分子链相互缠绕,作为弹性体粒子均匀的分散在PVC基体中,在微晶白云母/ACR/PVC复合材料中形成均匀的“微孔”结构,当材料受到冲击时,这种“微孔”结构能吸收大量的冲击能量,因而显著提高该复合材料的韧性。而微晶白云母粒子经硅烷偶联剂KH-550表面修饰后,与PVC基体的相容性很好,也均匀的分散在PVC基体中,且一部分微晶白云母粒子会接触PVC分子链的链段,阻碍PVC分子的链段运动,提高了PVC复合材料的玻璃化转变温度。
Polyvinyl chloride (PVC) is one of the five major general plastics used worldwide, which accounts for about 30% of the total amount of synthetic resin. With its nonflammable and anti-erosive properties as well as good insulation and isolation effects, PVC has the second largest volume of resin production in the world only next to polyethylene, and has been regarded as one of the most widely applied plastic varieties. Along with the advances in science and technology, unplasticized PVC are mainly used in the production of pipes, sticks, building materials, interior flooring materials, furniture boards, toys, sports equipments, medical tube elements, packaging coatings and etc. The application of unplasticized PVC, however, has always been restricted due to its poor properties in terms of fragility, tenacity, heat resistance and thermal stability. Thus, how to improve its comprehensive performance and expand its application is the most urgent task we face right now.
The performance of polymer material can be improved by inorganic rigid particle, because it can not only maintain the polymer material’s excellent performance but also increase its toughness, so the composite material based on polymer will have high mechanical properties and electrical properties. However, different inorganic rigid particles have different impacts on the polymer’s performance, and inorganic rigid particles will lead to the occurrence of agglomeration, so the appropriate filler, modifier and modification process will make the PVC material evenly dispersed in matrix, satisfy the production’s performance and processing performance requirement, and also increase the filling volume.
Micro-crystal muscovite is a new member to the family of micaceous minerals which was discovered in Western Sichuan of China in recent years. Compared with other common silicate minerals (e.g. kaolinite, montmorillonite, illite and bentonite), micro-crystal muscovite is more resistant to heat, acid or alkaline, weather, and ultraviolet with higher intensity and chemostability as well as better insulation and anti-aging effects. In addition, it is also more grindable and chemically active with a smaller grain size when compared with traditional muscovite minerals. This material is a high-quality inorganic rigid particle and it is expected to be widely applied in polymer.
In this paper, micro-crystal muscovite/ACR/PVC composite material was prepared by melt blending, with micro-crystal muscovite as packing material, silane coupling agent KH-550 as surface modifier, core-shell type ACR resin as impact modifier and PVC resin as matrix. This paper also optimized the condition of silane coupling agent KH-550 as surface modifier, the chemical properties of composite material ,the thermal stability, the processing of complex, the microscopic appearance and so on .Furthermore ,this paper also studied the mechanism of combined modification of PVC with micro-crystal muscovite and ACR. Results mainly showed that:
1. The effect of dry surface modification of micro-crystal muscovite is significantly influenced by the stirring speed, dose of surface modifier and duration of surface modification. Within the experimental range, a stirring speed at 25000 r/min, a duration of modification of 300 s, and a dose of silane coupling agent KH-550 at 1.2 % of the weight of micro-crystal muscovite are deemed to be the most appropriate.
2. Surface modification of micro-crystal muscovite using silane coupling agent KH-550 can significantly improve the mechanical properties of the micro-crystal muscovite/PVC composite material. This is because the unmodified micro-crystal muscovite has very poor interfacial compatibility with PVC, which means that adding such micro-crystal muscovite may increase micro-cavities and defects inside the composite material and reduce its physical strength.
3. After surface modification with silane coupling agent KH-550, micro-crystal muscovite can significantly improve the mechanical properties of the micro-crystal muscovite/PVC composite material. The tensile strength and impact strength of the composite material initially increase with the addition of micro-crystal muscovite, and then begin to decrease when the amount of micro-crystal muscovite becomes excessive. The peak values of its tensile strength and impact strength are identified when 35 ~ 40 portions of micro-crystal muscovite have been added, 24.2 %~26.8 % and 28 %~30 % higher than those of normal PVC, respectively. Besides, the Young’s modulus, bending strength, bending modulus and hardness of the micro-crystal muscovite/PVC composite material gradually increase with the addition of micro- crystal muscovite. Within the experimental range, i.e. 5 ~ 45 portions of micro-crystal muscovite, the max of Young’s modulus, bending strength, bending modulus and hardness of the micro-crystal muscovite/PVC composite material are enhanced by 65.5 %, 15.2 %, 71.6 % and 32.8 %, respectively. Based on comprehensive analysis, the most appropriate amount for micro-crystal muscovite addition in the micro-crystal muscovite/PVC composite material is determined to be 35 ~ 40 portions.
4. Adding ACR with core-shell structure can significantly improve the toughness of the micro-crystal/ACR/PVC composite material. In the experiment, with the same addition of the micro-crystal muscovite (35 phr), the micro-crystal/ACR/PVC composite material has a impact strength of 11.5 KJ/m2, which is 167 % of the micro- crystal/ACR/PVC and 213 % of the pure PVC. However, this will make the tensile strength and Young’s modulus decrease. Based on comprehensive analysis, the micro-crystal /ACR/PVC performance will be considered as the best when the ACR is 3 phr~9 phr.
5. Adding micro-crystal muscovite using silane coupling agent KH-550 can also improve the thermal stability of PVC. The glass-transition temperature, Vicat softening temperature and thermal stability increase accordingly with more micro-crystal muscovite added into the micro-crystal/PVC composite material. When the micro-crystal muscovite is 35 phr ~ 40 phr, the PVC composite material’s glass transition temperature increase 5.1℃~7.9℃, and the Vicat softening temperature increase 16.4℃~20.2℃, which significantly improve the thermal stability. Moreover, ACR can further increase the glass-transition temperature of the PVC, with same micro-crystal muscovite addition (35 phr) and ACR addition(3 phr~9 phr), the ACR addition does not significantly affect the Vicat softening temperature with an increase of 14.3℃~17.6℃compared with that of the pure PVC. As a result, micro-crystal muscovite and ACR can modify PVC, improve its thermal stability, slow down its aging and widen its application.
6. Micro-crystal muscovite can affect the composite processing performance of PVC, increase the plant time and torque of the micro-crystal/PVC composite material, which is not conducive to processing. But adding ACR can reduce the plant time and facilitate the processing.
7. By analyzing the composite material’s impact on the fracture sections’SEM, the micro-crystal muscovite without surface modification disperses unevenly and has clear interstices with PVC matrix, so the bending in interface is wake. When the micro-crystal muscovite surface is modified by silane coupling agent KH-550, it will disperse evenly in PVC matrix and enfold by PVC matrix, which will improve the bending. With the addition of micro-crystal muscovite, the distance of micro-crystal muscovite in PVC matrix decreases, which will form the tension delivery point and improve the tensile strength. By adding ACR, the“porous structure”forms in the micro-crystal/ACR/PVC composite material with a size of 200 nm, which will significantly improve the composite material’s impact strength.
8. Adding ACR with core-shell structure can significantly improve the toughness of the micro-crystal/ ACR/PVC composite material. When ACR is melt blended with PVC, the PMMA in the surface has good compatibility with PVC and its molecular chains twine together; while the PBA of core does not melt, so the“porous structure”forms in the micro-crystal/ACR/PVC composite material. These microcellular structure can absorb the power of the impact and greatly increase the toughness of the composite material. The micro-crystal muscovite has good compatibility with PVC matrix when its surface is modified by silane coupling agent KH-550 and is dispersed in PVC matrix. Further more, some of the micro-crystal muscovite particles will contact with PVC molecular chain and obstruct the molecular chain movement, which will increase the glass-transition temperature.
引文
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