CN102947429A - 用于减小摩擦的包含纳米孔颗粒的润滑油组合物 - Google Patents
用于减小摩擦的包含纳米孔颗粒的润滑油组合物 Download PDFInfo
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Abstract
本发明提供一种用于减小邻接经受润滑的表面的摩擦系数的润滑油组合物。具体地讲,本发明提供能够分散于具有润滑粘度的包含基油的润滑油组合物的纳米孔颗粒。由于本发明的具有纳米大小油溶性孔的纳米孔颗粒减小摩擦系数,并且长期逐渐释放有效成分,包含本发明的纳米孔颗粒的润滑油组合物可作为长期减小摩擦的减摩擦剂,从而显示极佳的润滑作用。
Description
技术领域
本发明涉及包含纳米孔颗粒的润滑油组合物,所述润滑油组合物可减小摩擦,从而提高能量效率或燃料效率。
背景技术
有数种类型润滑剂,例如液体润滑剂、糊润滑剂和包含液体润滑剂的固体润滑剂,其中固体润滑剂已广泛使用。润滑剂可用于机动车发动机、变速箱、轴承、工业齿轮和其它机器,以减小摩擦和磨损,并提高能量效率或燃料效率。
通常,润滑剂组合物包含分散剂、清洗剂、减摩擦剂、抗磨损剂、抗氧化剂和腐蚀抑制剂,但不限于这些剂,也可加入很多其它成分。另外,在大多数润滑过程中,可加入粘度指数改进剂或减摩擦剂作为重要成分。
最近,由于能源变得耗尽并且制定严格的环境法规,日益需要提高燃料效率,并减少废气的排放。为了提高燃料效率,一般向润滑剂加入有机减摩擦剂。然而,通过加入有机减摩擦剂提高燃料效率很受限制。因此,需要研发进一步提高燃料效率的新方法。
提高燃料效率的另一种方法是使用具有较低粘度级别的润滑剂。虽然使用具有较低粘度级别的润滑剂可提高燃料效率,但这样使用可增加摩擦。通过使用抗磨损剂,如ZDTP(O,O-二烷基二硫代磷酸锌),可能部分减小摩擦。然而,ZDTP包含磷酸盐,它可能不利影响用于排放控制的机动车催化剂系统,因此,优选不使用。
发明概述
技术问题
考虑前述情况,迫切需要研发一种通过促进摩擦和磨损减小作用和使用长期稳定的设备提高燃料效率而不负面影响排放控制系统的方法。
问题解决方法
本发明提供一种包含润滑剂和纳米孔颗粒的润滑油组合物。
本发明的有利效果
由于本发明的具有纳米大小油溶性孔的纳米孔颗粒减小摩擦系数,并且长期逐渐释放有效成分,包含本发明的纳米孔颗粒的润滑油组合物可作为长期减小摩擦的减摩擦剂,从而显示极佳的润滑作用。
附图简述
图1为用电子显微镜拍摄的银纳米孔硅颗粒的相片。
发明最佳实施方式
本发明涉及包含润滑剂和纳米孔颗粒的润滑油组合物。
润滑油组合物一般包含分散剂、清洗剂、减摩擦剂、抗磨损剂、抗氧化剂和腐蚀抑制剂,但不限于这些剂,可加入很多其它成分。另外,在大多数润滑过程中,可用粘度指数改进剂或减摩擦剂作为重要成分。本发明提供一种包含能够减小摩擦和减小磨损的高功能纳米孔颗粒的润滑剂。由于具有纳米大小油溶性孔的纳米孔颗粒可减小摩擦系数,并且从长远来看逐渐释放有效成分,包含本发明的纳米孔颗粒的润滑油组合物作为连续减小摩擦的减摩擦剂。
优选本发明涉及一种润滑油组合物,其特征在于纳米孔颗粒选自二氧化硅、二氧化钛、氧化铝、二氧化锡、氧化镁、氧化铈、二氧化锆、粘土、高岭土、二氧化铈、滑石、云母、钼、钨、二硫化钨、石墨、碳纳米管、氮化硅、氮化硼及其混合物。
对要使用的纳米孔颗粒种类没有限制,但优选使用由二氧化硅、二氧化钛、氧化铝或二氧化锡组成的纳米孔颗粒。
另外,本发明涉及一种润滑油组合物,其中纳米孔颗粒具有50nm至5 m的平均粒径,并具有0.01nm至100nm的纳米孔径。.
如果纳米孔颗粒的粒径小于50nm,则由于类似于粒径的孔径难以制备均匀的多孔颗粒和保持多孔结构。同时,如果粒径超过5 m,具有此大粒径的纳米孔颗粒则作为杂质,而不是作为减摩擦剂,这导致不利影响减摩擦。如果纳米孔颗粒具有0.01nm或更小的纳米孔径,则有油溶性减小的问题。如果它们具有100nm或更大的纳米孔径,则纳米孔颗粒过分溶于油,引起不利的光散射和混浊。
优选本发明涉及一种润滑油组合物,其特征在于包含基于100重量份润滑剂0.01至3.0重量份的纳米孔颗粒。
在纳米孔颗粒的含量低于0.01重量份时,含量太小,以致于不能发挥减摩擦和减磨损作用。当其含量超过3.0重量份时,就有油溶性减小的问题,导致发生混浊或沉淀或对减小摩擦或磨损产生无价值的作用。
更优选本发明涉及一种润滑油组合物,其特征在于润滑剂包含基油、抗氧化剂、金属清洗剂、腐蚀抑制剂、抑泡剂、倾点下降剂、粘度改性剂和分散剂。
以下本发明以包含纳米孔二氧化硅颗粒作为纳米孔颗粒并且详细描述的润滑油组合物为例,但不限于此。
为了制备纳米孔二氧化硅颗粒,用由玻璃或石英与液体溶剂(如乙醇)制成的胶冻类型二氧化硅作为原料。此类型硅胶具有其中固体颗粒互连并且在常温和常压不可破碎的胶体系统。
用于本发明的胶冻类型二氧化硅可通过硅醇盐与水在混合溶剂(如乙醇)中聚合来制备。反应通过水解和水缩合来进行,使醇盐分子连接在一起使硅-氧键形成低聚物。低聚物连接在一起,并形成一个巨分子,这是凝胶的固体部分。在醇盐凝胶中的二氧化硅基质用乙醇填充,具有0.01至100nm宽微囊。凝胶中的这些微囊形成纳米孔,并且使因此得到的醇盐颗粒干燥,以形成纳米孔颗粒。
颗粒可通过冷冻干燥或蒸发来干燥。然而,在冷冻干燥的情况下有多个问题,过程花费数天,并且由于颗粒收缩的出现很难保持细颗粒的孔结构。蒸发过程也导致类似问题,产生令人厌恶的蒸气,并且难以保持均匀孔径。在通过冷冻干燥或蒸发过程保持孔结构的同时干燥的颗粒的产率只为约10%。因此,为了在保持孔径和结构的同时干燥颗粒,优选使用超临界干燥方法。干燥方法利用在高于临界点的温度和压力的任何物质的超临界流体。
这种超临界流体具有气体和液体之间的性质(半气体/半液体相),并且可象气体一样膨胀,但密度和热导率类似于液体。另外,由于具有比液体更低的表面张力,使用超临界流体使得可能在保持凝胶结构的同时使颗粒干燥。即,利用在高于临界点的温度逐渐加热,可使颗粒干燥。此时,从凝胶结构释放的超临界流体可以气相放出,因此干燥的颗粒具有90%或更高的孔体积。
适用于本发明的润滑剂可代表性为具有以下组成的润滑剂,如表1中所列。
表1
成分 | 宽范围(%重量) | 一般范围(%重量) |
基油 | 余量 | 余量 |
抗氧化剂 | 0 ~ 5.0 | 0.01 ~ 3.0 |
金属清洗剂 | 0.1 ~ 15.0 | 0.2 ~ 8.0 |
腐蚀抑制剂 | 0 ~ 5.0 | 0 ~ 2.0 |
抑泡剂 | 0 ~ 5.0 | 0.001 ~ 0.15 |
倾点下降剂 | 0.01 ~ 5.0 | 0.01 ~ 1.5 |
粘度改性剂 | 0.01 ~ 10.0 | 0.25 ~ 7.0 |
分散剂 | 0.5 ~ 5.0 | 1.0 ~ 2.5 |
总计 | 100 | 100 |
以上表1中显示普通润滑剂中使用的添加剂的代表性有效量。表1中所列添加剂的量和类型在本领域熟知,本发明的范围不限于此。另外,以下实施例中所述组合和组合物只用于说明目的,不应解释为限制本发明的范围。
发明实施方式
实施例1~56. 制备包含纳米孔颗粒的润滑油组合物
用表2中所示的润滑剂组合A或B制备润滑剂。通过使硅醇盐转化成凝胶类型,并用超临界流体(如,二氧化碳)干燥,制备纳米孔颗粒。下一步,以基于100重量份润滑剂的表3的量加入如此制备的纳米孔颗粒,从而制备实施例1至56的润滑油组合物。
纳米孔二氧化硅如下代表性制备。首先使50ml TEOS(原硅酸四乙酯)与40ml乙醇混合,随后依次加入35ml乙醇、70ml水、0.275ml 30%氨溶液和0.2ml 0.5M氟化铵。在此,氨和氟化铵作为催化剂。将所得溶液在和缓搅拌下完全混合,以诱导胶凝,从而形成醇盐凝胶。胶凝进行2小时。在胶凝完成后,将醇盐凝胶放入压热器。将二氧化碳(CO2)注入压热器,并调节压热器的温度和压力到高于CO2的临界点(31℃和72.4atm)。从压热器缓慢释放醇盐凝胶12小时。通过此方法,在保持纳米孔结构的同时干燥释放的颗粒,从而得到二氧化硅气凝胶(孔径:20nm,直径:400nm)。
根据上述方法,得到用醇钛和醇超临界流体制备的纳米孔二氧化钛颗粒(孔径:30nm,直径500nm);通过生成醇铝,使其转化成凝胶类型,并用二氧化碳超临界流体干燥制备的纳米孔氧化铝颗粒(孔径:25nm,直径:100nm);和通过生成醇锡,使其转化成凝胶类型,并用醇超临界流体干燥制备的纳米孔二氧化锡颗粒(孔径:40nm,直径:180nm)。根据表3的组合物比率,将如此得到的纳米孔颗粒加入到润滑剂,从而制备润滑油组合物。
表2
表3
比较性实施例1~37. 制备具有类似于实施例的物理性质的包含纳米孔颗粒的润滑油组合物
用表2中所示的润滑剂组合A或B制备润滑剂。通过使硅醇盐转化成凝胶类型,并用超临界流体(如,二氧化碳)干燥,制备纳米孔颗粒。下一步,以基于100重量份润滑剂的表4的量加入如此制备的纳米孔颗粒,从而制备比较性实施例1至37的润滑油组合物。
纳米孔二氧化硅如下代表性制备。首先使50ml TEOS(原硅酸四乙酯)与40ml乙醇混合,随后依次加入35ml乙醇、70ml水、0.275ml 30%氨溶液和0.2ml 0.5M氟化铵。在此,氨和氟化铵作为催化剂。将所得溶液在和缓搅拌下完全混合,以诱导胶凝,从而形成醇盐凝胶。胶凝进行2小时。在胶凝完成后,将醇盐凝胶放入压热器。将二氧化碳(CO2)注入压热器,并调节压热器的温度和压力到高于CO2的临界点(31℃和72.4atm)。从压热器缓慢释放醇盐凝胶12小时。通过此方法,在保持纳米孔结构的同时干燥释放的颗粒,从而得到二氧化硅气凝胶(孔径:20nm,直径:400nm)。
根据上述方法,得到用醇钛和醇超临界流体制备的纳米孔二氧化钛颗粒(孔径:30nm,直径500nm);通过生成醇铝,使其转化成凝胶类型,并用二氧化碳超临界流体干燥制备的纳米孔氧化铝颗粒(孔径:25nm,直径:100nm);和通过生成醇锡,使其转化成凝胶类型,并用醇超临界流体干燥制备的纳米孔二氧化锡颗粒(孔径:40nm,直径:180nm)。根据表4的组合物比率,将如此得到的纳米孔颗粒加入到润滑剂,从而制备润滑油组合物。
表4
比较性实施例38~100. 制备具有不同于实施例的物理性质的包含纳米孔颗粒的润滑油组合物
用表2中所示的润滑剂组合A或B制备润滑剂。通过使硅醇盐转化成凝胶类型,并用超临界流体(如,二氧化碳)干燥,制备纳米孔颗粒。下一步,以基于100重量份润滑剂的表5的量加入如此制备的纳米孔颗粒,从而制备比较性实施例38至100的润滑油组合物。
纳米孔二氧化硅如下代表性制备。首先使50ml TEOS(原硅酸四乙酯)与40ml乙醇混合,随后依次加入35ml乙醇、70ml水、0.275ml 30%氨溶液和0.2ml 0.5M氟化铵。在此,氨和氟化铵作为催化剂。将所得溶液在和缓搅拌下完全混合,以诱导胶凝,从而形成醇盐凝胶。胶凝进行1小时。在胶凝完成后,将醇盐凝胶放入压热器。将二氧化碳(CO2)注入压热器,并调节压热器的温度和压力到高于CO2的临界点(31℃和72.4atm)。从压热器缓慢释放醇盐凝胶6小时。通过此方法,在保持纳米孔结构的同时干燥释放的颗粒,从而得到二氧化硅气凝胶(孔径:400nm,直径:600nm)。
根据上述方法,得到用醇钛和醇超临界流体制备的纳米孔二氧化钛颗粒(孔径:200nm,直径800nm);通过生成醇铝,使其转化成凝胶类型,并用二氧化碳超临界流体干燥制备的纳米孔氧化铝颗粒(孔径:250nm,直径:650nm);和通过生成醇锡,使其转化成凝胶类型,并用醇超临界流体干燥制备的纳米孔二氧化锡颗粒(孔径:300nm,直径:700nm)。根据表5的组合物比率,将如此得到的纳米孔颗粒加入到润滑剂,从而制备润滑油组合物。
表5
比较性实施例101~158. 制备具有不同于实施例的物理性质的包含纳米孔颗粒的润滑油组合物
用表2中所示的润滑剂组合A或B制备润滑剂。通过使硅醇盐转化成凝胶类型,并用超临界流体(如,二氧化碳)干燥,制备纳米孔颗粒。下一步,以基于100重量份润滑剂的表6的量加入如此制备的纳米孔颗粒,从而制备比较性实施例101至158的润滑油组合物。
纳米孔二氧化硅如下代表性制备。首先使50ml TEOS(原硅酸四乙酯)与40ml乙醇混合,随后依次加入35ml乙醇、70ml水、0.275ml 30%氨溶液和0.2ml 0.5M氟化铵。在此,氨和氟化铵作为催化剂。将所得溶液在和缓搅拌下完全混合,以诱导胶凝,从而形成醇盐凝胶。胶凝进行1小时。在胶凝完成后,将醇盐凝胶放入压热器。将二氧化碳(CO2)注入压热器,并调节压热器的温度和压力到高于CO2的临界点(31℃和72.4atm)。从压热器缓慢释放醇盐凝胶6天。通过此方法,在保持纳米孔结构的同时干燥释放的颗粒,从而得到二氧化硅气凝胶(孔径:20nm,直径:6 m)。
根据上述方法,得到用醇钛和醇超临界流体制备的纳米孔二氧化钛颗粒(孔径:30nm,直径8 m);通过生成醇铝,使其转化成凝胶类型,并用二氧化碳超临界流体干燥制备的纳米孔氧化铝颗粒(孔径:25nm,直径:8.5 m);和通过生成醇锡,使其转化成凝胶类型,并用醇超临界流体干燥制备的纳米孔二氧化锡颗粒(孔径:40nm,直径:10 m)。根据表6的组合物比率,将如此得到的纳米孔颗粒加入到润滑剂,从而制备润滑油组合物。
表6
试验实施例1. 测量摩擦系数、牵引系数、磨损度、运动粘度和粘度指数
使用Mini Traction Machine牵引机(MTM,PCS-仪器),使在实施例1至56和比较性实施例1至158制备的润滑油组合物经过摩擦系数、牵引系数和磨损度测量。此时,利用50N,SRR 50%施加负荷,同时使温度从40℃改变到120℃,进行摩擦系数、牵引系数和磨损度的测量。因此测量的摩擦系数、牵引系数和磨损度的平均值显示于表7和8。
另外,测量运动粘度作为润滑剂的重要物理性质之一,并测量代表根据温度的粘度改变的粘度指数。粘度用粘度计(Cannon)在40℃测量,粘度指数基于40℃和100℃的粘度。
表7
表8
通过将实施例和比较性实施例中所述量的不同种类纳米孔颗粒加入到表7和8中所示的组合制备润滑剂,然后测量减摩擦和减磨损作用。结果显示于表7和表8中。
具体地讲,在加入过量纳米孔颗粒而不是比较性实施例1至37中所述适量的情况下,有过量增加无机物质含量的问题,由此在长期使用时减小减摩擦和减磨损作用。
以上结果证明,润滑剂的摩擦和磨损减小作用随加入的纳米孔颗粒的直径、孔径和量显著改变。在纳米孔颗粒的孔结构在某些高温或高压力条件下变得破碎时,类似于新油的结构囊内的不完全酸化润滑剂可能引起初始性能水平的部分恢复,并且在某些情况下显示冷却作用。另外,由于它们的囊具有开放结构,润滑剂可在开始的时候混合。然而,由于毛细管力,润滑剂可能相对较小受温度或压力升高影响,这引起相对低水平的氧化。因此,通过用于在相互摩擦的界面作为隔离物的颗粒之间提供新油,可期望得到例如提供新油的作用,并且更积极地防止磨损。
与依靠化学反应机制的现有技术减小摩擦系统比较,对机械摩擦和磨损减小的这些作用很可靠,并且可甚至在极端可变条件下以相对较高可靠性保持极佳的摩擦减小作用。
如表7和8所示,如果纳米孔材料的量基于100重量份润滑剂低于0.01重量份,则量太小以致不能显示所需的作用,同时,如果量超过3重量份,则产生大量灰,或者增大摩擦而不是减小,因为有过量无机物质。因此,重要的是保持适量的纳米孔材料。另外,当孔径太大时,孔结构之间的囊体积和表面积显著减小,导致所需的作用减小。图1为用电子显微镜拍摄的代表性纳米孔二氧化硅(孔径:20nm,直径400nm)的放大相片,显示纳米孔颗粒具有约20nm的孔径。
如在上述实施例和比较性实施例中看到,虽然润滑剂的基本性质(例如,粘度和粘度指数)可根据纳米孔颗粒的量和直径改变,但它们的影响不太大。另外,由于加入的纳米孔颗粒的量可认为是适度的,因此,它们不直接影响润滑剂的粘度和粘度指数。因此,已发现,由于加入纳米孔颗粒对润滑剂的基本性质(例如,粘度和粘度指数)的影响不显著。
现已详细参考示例性实施方案描述了本发明。然而,本领域的技术人员应了解,可在不脱离本发明的范围和精神下在那些实施方案中作出改变,其范围在附加权利要求和及其等价中限定。
Claims (6)
1. 一种润滑油组合物,所述润滑油组合物包含:
100重量份润滑剂;和
0.01至3.0重量份纳米孔颗粒。
2. 权利要求1的润滑油组合物,其中纳米孔颗粒选自二氧化硅、二氧化钛、氧化铝、二氧化锡、氧化镁、氧化铈、二氧化锆、粘土、高岭土、二氧化铈、滑石、云母、钼、钨、二硫化钨、石墨、碳纳米管、氮化硅、氮化硼及其混合物。
3. 权利要求1或2的润滑油组合物,其中纳米孔颗粒具有50nm至5 m的平均粒径。
4. 权利要求1或2的润滑油组合物,其中纳米孔颗粒具有0.01nm至100nm的孔径。
5. 权利要求1的润滑油组合物,其中润滑剂进一步包含基油、抗氧化剂、金属清洗剂、腐蚀抑制剂、抑泡剂、倾点下降剂、粘度改性剂和分散剂。
6. 权利要求3的润滑油组合物,其中纳米孔颗粒具有90%或更高的孔体积。
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Also Published As
Publication number | Publication date |
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WO2011118935A2 (en) | 2011-09-29 |
KR20110108081A (ko) | 2011-10-05 |
US20130005619A1 (en) | 2013-01-03 |
RU2512379C1 (ru) | 2014-04-10 |
CN102947429B (zh) | 2016-04-27 |
WO2011118935A3 (en) | 2012-01-26 |
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