SrO·6Fe_2O_3磁性丁腈橡胶的摩擦、磨损机理与热氧老化研究
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摘要
丁腈橡胶(NBR)是一种非常重要且用量很大的工业材料,其具有优良的耐油、耐热和耐腐蚀性。丁腈橡胶密封件广泛应用于机械、电子、交通、石油化工、冶金、航空等领域。在高速、高低温、强腐蚀等恶劣工况下,性能不断提高的各种机械电子设备对橡胶密封件的性能要求也日益严格。为了提高密封件的工作能力,除了要考虑密封材料必须的力学性能、弹性和耐油性外,还必须最大限度地提高材料的抗磨、减摩性能,掌握橡胶密封制品的贮存寿命和使用寿命,以及了解密封用橡胶材料的评价指标,从而进行不同密封用橡胶材料之间或同一种密封用橡胶材料不同性能之间的发展程度的比较,最终选择出最适合使用条件的橡胶材料。
本研究课题在总结了前期对填充0%~16%Fe_3O_4的丁腈橡胶的研究,以及调研了国内、外橡胶密封现状和发展的基础上,提出了应用具有尺寸小、比表面积大、表面间形态不同于颗粒内部、表面原子配位不全、表面活性强等特性的纳米磁性粒子对广泛应用的丁腈橡胶进行改性。通过干法混炼制备了纳米SrO·6Fe_2O_3磁性复合丁腈橡胶。
试验表明,当丁腈橡胶填充少量未经分散和表面改性处理的纳米SrO·6Fe_2O_3磁性粒子后,丁腈橡胶的摩擦系数有一定的降低,且在10%时达到最小值。此后加大磁性粒子填充量,试样的摩擦系数值明显大于纯NBR。而且纳米SrO·6Fe_2O_3磁性粒子在丁腈橡胶材料中的质量分数不同,材料的磨损形式也不同。随着填充质量分数的增加,材料的磨损形式由犁削和粘着磨损逐步转变为粘着、疲劳剥落。当填充质量分数超过15%后,由于大量磁性粒子的团聚,使得抗磨减摩效果并不明显。磨损量出现了与摩擦系数同样的变化过程。而填充经过分散和表面改性处理的纳米SrO·6Fe_2O_3磁性粒子后,不论填充量的大小,均使得丁腈橡胶的摩擦系数和磨损量均有了大幅度的降低,且在10%时摩擦系数达到最小值0.2069。这是因为经过分散和表面改性处理的纳米SrO·6Fe_2O_3磁性粒子不仅能稳定地保持单个颗粒存在而不发生团聚,且与丁腈橡胶基体的亲和性增强,从而均匀地分散在丁腈橡胶基体内,而且每个颗粒仍能保持很高的表面能与表面活性,因而其有利于加强丁腈橡胶在摩擦副表面上形成物理吸附膜,该物理吸附膜在摩擦表面具有自修复功能,从而起到了抗磨减摩作用。
本研究课题通过对磁性SrO·6Fe_2O_3丁腈橡胶复合材料进行热氧老化试验研究,利用高分子材料性能变化与老化时间关系式及阿累尼乌斯方程进行了理论推导和数学计算,分别得到了磁性橡胶密封材料在贮存温度下的伸长率保持率与贮存时间、温度的变化规律,以及磁性橡胶密封件在贮存温度下的压缩永久变形与贮存时间、温度的变化规律,建立了其在贮存温度下性能与时间变化的预测方程,预测了该密封材料的贮存以及使用寿命。对以伸长率保持率和压缩永久变形预测贮存和使用寿命结果的进行对比后发现,当纳米SrO·6Fe_2O_3磁性复合丁腈橡胶用于制作动密封件时,具有较低的摩擦系数;用于制作静密封件时,具有较高的寿命。通过讨论可知,橡胶材料的老化对静密封件的使用寿命起到了决定性作用,而橡胶与金属接触面之间的摩擦系数对动密封件的使用寿命起到了决定性作用。
本研究课题基于密封用橡胶材料的使用和评价特点,建立了评价指标体系流程,并明确了评价目的;分析了评价的主要内容为橡胶材料的配方构成、基本性能状况、摩擦磨损情况、老化现象、特殊性能、以及使用经济性等方面;确定了评价指标选取的原则,即科学性、简洁有效性、普遍性、定性指标与定量指标相结合、连续性原则;明确了评价指标体系的功能,即评价功能、监测功能、指导功能、决策功能;建立了评价指标体系。通过实例分析可知此评价指标体系能够对不同密封用橡胶材料之间或同一种密封用橡胶材料不同性能的发展程度的进行比较,从而实现密封用橡胶材料科学、合理发展的评价目的。
本研究课题设计了采用纳米磁性橡胶的轴封组合机构,其不仅具备较低的摩擦因数和磨损率,而且有良好的自修复能力和自密封性能,有效地提高了轴封的密封能力。通过仿真与试验发现,后唇角对油封的稳定性起着重要作用,当系统压力较大时,后唇角宜取较小的值,系统压力较低时,后唇角可以适当取大点。最后简单讨论了纳米SrO·6Fe_2O_3磁性复合丁腈橡胶在密封中的应用以及使用分类情况。
Nitrile-buladiene rubber (NBR), which has excellent characters of oil, heat and corrosion resistance, is a very important kind of industrial materials and has large dosage. NBR seals are widely used in machinery, electronics, transportation, petrochemical, metallurgical, aviation, and so on. With the improving of the properties of mechatronic equipments, the properties of rubber seals are increasingly stringent required under bad conditions of high speed, high-low temperature, deep-etching, and so on. In order to improve the working abilities of seals, the necessary properties of the rubber seals, such as mechanical properties, spring and oil resistance, should be considered, the wear-resistant and antifriction properties of materials must be improved farthest, the storage life and working life of the rubber seals should be mastered, and the evaluating indicators of the rubber materials for sealing should be understood, which could compare the development level of each property in different materials or different properties in same material, so that the most suitable rubber material for working conditions is finally chosen.
Based on the summary of early study on Fe_3O_4 magnetic nitrile-buladiene rubber of which the mass percent of Fe_3O_4 particles is controlled at 0%~16%, and the investigation of the actual and new progress about oversea and domestic rubber seals, in this research topics, application of nanometer technique in nitrile-buladiene rubber was put forward, because the nano-particles possess some unique advantages, such as small size, big specific surface area, different shape between the surface and the inside particle, defective coordination of surface atoms, strong surface active. Then nano-SrO·6Fe_2O_3 magnetic nitrile-buladiene rubber (nano-SrO·6Fe_2O_3 MNBR) was prepared through dry process.
The test results show that the friction coefficient of the NBR added a few unmodified nano-SrO·6Fe_2O_3 particles would have certain reduction, and reached the minimum at 10%. After that, the friction coefficient of the samples would be evidently lager than the NBR by increasing the mass percent of nano-SrO·6Fe_2O_3 particles. And because the mass percent of nano-SrO·6Fe_2O_3 was different, the wearied forms of the rubber materials were different. The wear forms of materials were changed from the ploughing and adhesive wear to the adhesive and fatigue flake. When the mass percent of nano-SrO·6Fe_2O_3 exceeded 15%, the wear-resistant and antifriction effect was unconspicuous because a large number of magnetic particles was in the reunion. The abrasion loss had the same variation. However, the friction coefficient and abrasion loss of the NBR added modified nano-SrO·6Fe_2O_3 particles would be reduced by a large margin, and the friction coefficient reached the minimum 0.2069 at 10%. Why did this phenomena appear? First, the modified nano-SrO·6Fe_2O_3 particles not only existed in individual steadily, but also had a strong affinity with NBR, which uniformly scattered themselves on the NBR; secondly, each particle could still remain strong surface energy and surface active; thirdly, such magnetic particles was propitious to strengthen NBR, and then the compounded rubber could form a physisorption film on the surface of rubbing pair that had self-repairing capability, which played a role in wear-resistant and antifriction effect.
This research topics did accelerated thermal-oxygen aging test for nano-SrO·6Fe_2O_3 MNBR. Through theoretical derivation and mathematical computation of the Arrhenius equation and the relational expression between performance changes and aging time of polymer materials, two kinds of evolution were obtained. One was the relational expression among the three factors which are elongation retention, period of storage and storage temperature in the storage temperature for magnetic rubber sealing materials; the other was the relational expression among the three factors which are compression set, period of storage and storage temperature in the storage temperature for magnetic rubber seals. Then the predictive equation between performance and time in the storage temperature was established, and the storage life and working life of the sealing materials was forecasted. Compare these two forecast results of life, it can be found that dynamic seals of nano-SrO·6Fe_2O_3 MNBR had lower friction coefficient, and static seals of nano-SrO·6Fe_2O_3 MNBR had longer life. From discussion, it can be known that the aging of rubber materials played a pivotal role in the working life of static seals, and the friction coefficient between rubber materials and metal surfaces played a pivotal role in the working life of dynamic seals.
In this research topics, according to the characteristics of use and evaluation of rubber materials for sealing, the construction flow of evaluation index system was established, the purposes of evaluation were defined, and the contents of evaluation, such as constitution, basic performance status, friction and wear, aging, special features, and use economy, was analysed. Based on the principles of scientific, simple and effective, universal, qualitative and quantitative, and continuity, and considering the functions of evaluation, monitoring, guidance, and decision-making, the evaluation index system was established. Through the case study, it can be known that the evaluation index system could compare the development level of each property in different materials or different properties in same material, so that the purpose of evaluation making rubber materials for sealing achieve scientific and reasonable development could be realized.
A kind of shaft seal composite structure adopting nano-SrO·6Fe_2O_3 MNBR was designed in this research topics. This structure had not only lower friction coefficient and abrasion loss, but also better self-repairing and self-sealing capability, which enhanced the sealing capability effectively. The simulation and experimental results showed that the posterior lib angle played an important role for the stability of oil seal. The value of the posterior lib angle should be smaller as the pressure of system was higher. The value of the posterior lib angle should be larger as the pressure of system was lower. At last, the applications and classified information of nano-SrO·6Fe_2O_3 MNBR in sealing structure was simply discussed.
本研究课题在总结了前期对填充0%~16%Fe_3O_4的丁腈橡胶的研究,以及调研了国内、外橡胶密封现状和发展的基础上,提出了应用具有尺寸小、比表面积大、表面间形态不同于颗粒内部、表面原子配位不全、表面活性强等特性的纳米磁性粒子对广泛应用的丁腈橡胶进行改性。通过干法混炼制备了纳米SrO·6Fe_2O_3磁性复合丁腈橡胶。
试验表明,当丁腈橡胶填充少量未经分散和表面改性处理的纳米SrO·6Fe_2O_3磁性粒子后,丁腈橡胶的摩擦系数有一定的降低,且在10%时达到最小值。此后加大磁性粒子填充量,试样的摩擦系数值明显大于纯NBR。而且纳米SrO·6Fe_2O_3磁性粒子在丁腈橡胶材料中的质量分数不同,材料的磨损形式也不同。随着填充质量分数的增加,材料的磨损形式由犁削和粘着磨损逐步转变为粘着、疲劳剥落。当填充质量分数超过15%后,由于大量磁性粒子的团聚,使得抗磨减摩效果并不明显。磨损量出现了与摩擦系数同样的变化过程。而填充经过分散和表面改性处理的纳米SrO·6Fe_2O_3磁性粒子后,不论填充量的大小,均使得丁腈橡胶的摩擦系数和磨损量均有了大幅度的降低,且在10%时摩擦系数达到最小值0.2069。这是因为经过分散和表面改性处理的纳米SrO·6Fe_2O_3磁性粒子不仅能稳定地保持单个颗粒存在而不发生团聚,且与丁腈橡胶基体的亲和性增强,从而均匀地分散在丁腈橡胶基体内,而且每个颗粒仍能保持很高的表面能与表面活性,因而其有利于加强丁腈橡胶在摩擦副表面上形成物理吸附膜,该物理吸附膜在摩擦表面具有自修复功能,从而起到了抗磨减摩作用。
本研究课题通过对磁性SrO·6Fe_2O_3丁腈橡胶复合材料进行热氧老化试验研究,利用高分子材料性能变化与老化时间关系式及阿累尼乌斯方程进行了理论推导和数学计算,分别得到了磁性橡胶密封材料在贮存温度下的伸长率保持率与贮存时间、温度的变化规律,以及磁性橡胶密封件在贮存温度下的压缩永久变形与贮存时间、温度的变化规律,建立了其在贮存温度下性能与时间变化的预测方程,预测了该密封材料的贮存以及使用寿命。对以伸长率保持率和压缩永久变形预测贮存和使用寿命结果的进行对比后发现,当纳米SrO·6Fe_2O_3磁性复合丁腈橡胶用于制作动密封件时,具有较低的摩擦系数;用于制作静密封件时,具有较高的寿命。通过讨论可知,橡胶材料的老化对静密封件的使用寿命起到了决定性作用,而橡胶与金属接触面之间的摩擦系数对动密封件的使用寿命起到了决定性作用。
本研究课题基于密封用橡胶材料的使用和评价特点,建立了评价指标体系流程,并明确了评价目的;分析了评价的主要内容为橡胶材料的配方构成、基本性能状况、摩擦磨损情况、老化现象、特殊性能、以及使用经济性等方面;确定了评价指标选取的原则,即科学性、简洁有效性、普遍性、定性指标与定量指标相结合、连续性原则;明确了评价指标体系的功能,即评价功能、监测功能、指导功能、决策功能;建立了评价指标体系。通过实例分析可知此评价指标体系能够对不同密封用橡胶材料之间或同一种密封用橡胶材料不同性能的发展程度的进行比较,从而实现密封用橡胶材料科学、合理发展的评价目的。
本研究课题设计了采用纳米磁性橡胶的轴封组合机构,其不仅具备较低的摩擦因数和磨损率,而且有良好的自修复能力和自密封性能,有效地提高了轴封的密封能力。通过仿真与试验发现,后唇角对油封的稳定性起着重要作用,当系统压力较大时,后唇角宜取较小的值,系统压力较低时,后唇角可以适当取大点。最后简单讨论了纳米SrO·6Fe_2O_3磁性复合丁腈橡胶在密封中的应用以及使用分类情况。
Nitrile-buladiene rubber (NBR), which has excellent characters of oil, heat and corrosion resistance, is a very important kind of industrial materials and has large dosage. NBR seals are widely used in machinery, electronics, transportation, petrochemical, metallurgical, aviation, and so on. With the improving of the properties of mechatronic equipments, the properties of rubber seals are increasingly stringent required under bad conditions of high speed, high-low temperature, deep-etching, and so on. In order to improve the working abilities of seals, the necessary properties of the rubber seals, such as mechanical properties, spring and oil resistance, should be considered, the wear-resistant and antifriction properties of materials must be improved farthest, the storage life and working life of the rubber seals should be mastered, and the evaluating indicators of the rubber materials for sealing should be understood, which could compare the development level of each property in different materials or different properties in same material, so that the most suitable rubber material for working conditions is finally chosen.
Based on the summary of early study on Fe_3O_4 magnetic nitrile-buladiene rubber of which the mass percent of Fe_3O_4 particles is controlled at 0%~16%, and the investigation of the actual and new progress about oversea and domestic rubber seals, in this research topics, application of nanometer technique in nitrile-buladiene rubber was put forward, because the nano-particles possess some unique advantages, such as small size, big specific surface area, different shape between the surface and the inside particle, defective coordination of surface atoms, strong surface active. Then nano-SrO·6Fe_2O_3 magnetic nitrile-buladiene rubber (nano-SrO·6Fe_2O_3 MNBR) was prepared through dry process.
The test results show that the friction coefficient of the NBR added a few unmodified nano-SrO·6Fe_2O_3 particles would have certain reduction, and reached the minimum at 10%. After that, the friction coefficient of the samples would be evidently lager than the NBR by increasing the mass percent of nano-SrO·6Fe_2O_3 particles. And because the mass percent of nano-SrO·6Fe_2O_3 was different, the wearied forms of the rubber materials were different. The wear forms of materials were changed from the ploughing and adhesive wear to the adhesive and fatigue flake. When the mass percent of nano-SrO·6Fe_2O_3 exceeded 15%, the wear-resistant and antifriction effect was unconspicuous because a large number of magnetic particles was in the reunion. The abrasion loss had the same variation. However, the friction coefficient and abrasion loss of the NBR added modified nano-SrO·6Fe_2O_3 particles would be reduced by a large margin, and the friction coefficient reached the minimum 0.2069 at 10%. Why did this phenomena appear? First, the modified nano-SrO·6Fe_2O_3 particles not only existed in individual steadily, but also had a strong affinity with NBR, which uniformly scattered themselves on the NBR; secondly, each particle could still remain strong surface energy and surface active; thirdly, such magnetic particles was propitious to strengthen NBR, and then the compounded rubber could form a physisorption film on the surface of rubbing pair that had self-repairing capability, which played a role in wear-resistant and antifriction effect.
This research topics did accelerated thermal-oxygen aging test for nano-SrO·6Fe_2O_3 MNBR. Through theoretical derivation and mathematical computation of the Arrhenius equation and the relational expression between performance changes and aging time of polymer materials, two kinds of evolution were obtained. One was the relational expression among the three factors which are elongation retention, period of storage and storage temperature in the storage temperature for magnetic rubber sealing materials; the other was the relational expression among the three factors which are compression set, period of storage and storage temperature in the storage temperature for magnetic rubber seals. Then the predictive equation between performance and time in the storage temperature was established, and the storage life and working life of the sealing materials was forecasted. Compare these two forecast results of life, it can be found that dynamic seals of nano-SrO·6Fe_2O_3 MNBR had lower friction coefficient, and static seals of nano-SrO·6Fe_2O_3 MNBR had longer life. From discussion, it can be known that the aging of rubber materials played a pivotal role in the working life of static seals, and the friction coefficient between rubber materials and metal surfaces played a pivotal role in the working life of dynamic seals.
In this research topics, according to the characteristics of use and evaluation of rubber materials for sealing, the construction flow of evaluation index system was established, the purposes of evaluation were defined, and the contents of evaluation, such as constitution, basic performance status, friction and wear, aging, special features, and use economy, was analysed. Based on the principles of scientific, simple and effective, universal, qualitative and quantitative, and continuity, and considering the functions of evaluation, monitoring, guidance, and decision-making, the evaluation index system was established. Through the case study, it can be known that the evaluation index system could compare the development level of each property in different materials or different properties in same material, so that the purpose of evaluation making rubber materials for sealing achieve scientific and reasonable development could be realized.
A kind of shaft seal composite structure adopting nano-SrO·6Fe_2O_3 MNBR was designed in this research topics. This structure had not only lower friction coefficient and abrasion loss, but also better self-repairing and self-sealing capability, which enhanced the sealing capability effectively. The simulation and experimental results showed that the posterior lib angle played an important role for the stability of oil seal. The value of the posterior lib angle should be smaller as the pressure of system was higher. The value of the posterior lib angle should be larger as the pressure of system was lower. At last, the applications and classified information of nano-SrO·6Fe_2O_3 MNBR in sealing structure was simply discussed.
引文
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