CN1890353A - 用于涂覆应用的固体润滑剂附聚物及其生产方法 - Google Patents

用于涂覆应用的固体润滑剂附聚物及其生产方法 Download PDF

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CN1890353A
CN1890353A CNA2004800359930A CN200480035993A CN1890353A CN 1890353 A CN1890353 A CN 1890353A CN A2004800359930 A CNA2004800359930 A CN A2004800359930A CN 200480035993 A CN200480035993 A CN 200480035993A CN 1890353 A CN1890353 A CN 1890353A
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solid lubricant
tackiness agent
fraction
solid
boron nitride
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CN100482775C (zh
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K·哈尔勒
W·瓦豪塞
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Oerlikon Metco Canada Inc
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Sulzer Metco Canada Inc
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Abstract

生产固体润滑剂附聚物的方法，包括将固体润滑剂粉末、无机粘合剂、任选地其他填料和液体混合形成混合物，并且将所述液体除去，以形成干燥的附聚物，随后将其按大小分级，或者研磨并且按大小分级，以生产具有希望的尺寸范围的附聚物。然后对这些附聚物进行处理以将所述粘合剂稳定，借此增强所述粘合剂并且使其在所述液体中不可分散。因为具有未经处理的粘合剂的附聚物可以被重新处理，因此非所要求的尺寸范围的物料可以容易地被循环，借此提高了回收率。

Description

用于涂覆应用的固体润滑剂附聚物及其生产方法
技术领域
本发明涉及用于生产固体润滑剂附聚物的方法，更具体地涉及生产倒角六方形氮化硼附聚物的方法，所述附聚物处于希望的尺寸范围内，并且具有预定的组成和密度。
背景技术
将固体润滑剂，例如六方形氮化硼(hBN)粉末，与形成基质的金属共混或者用形成基质的金属镀覆，并且与其他添加剂共混，而形成热喷涂组合物，该热喷涂组合物被用作可磨蚀的密封材料，用在燃气轮机、涡轮增压器、蒸汽涡轮及其他旋转设备上。这样的应用例如描述于K.Hajmrle等的U.S.5,976,695中。除了其他使用固体润滑剂组合物的热喷涂应用外，还有针对剥蚀的压缩机盘和轮叶的保护，如K.Hajmrle等的U.S.5,601,933中所述。
对于热喷涂及其他应用，与由传统hBN生产技术产生的那些相比较大的粒子是必要的。就其本身而言，hBN的合成产生小于10微米的颗粒，而热喷涂应用要求在20到150微米范围内的粒子。
通过将hBN微粒热压以形成大的附聚物，并且随后将得到的粒子压碎、研磨和分级得到希望的粒度范围，这是本领域中众所周知的。这种方法是昂贵的，因为几个制造步骤具有高成本，特别是高温热压步骤。此外，由于产生必需作为废物丢弃的尺寸过小的物质，并且尺寸过大的粒子必须被进一步压碎和加工，因此产品的成本被进一步提高。尺寸过小的细粒级分实质上降低了工艺的回收率。
由“热压”方法生产的最终产品是相对较软的，这会在进一步的加工中引起问题。例如，当这种材料通过在高压釜中进行湿法冶金金属镀覆而被进一步加工时，粒子碎裂到很高的程度，并且最终产品的粒子尺寸是难以控制的。在这种应用中需要更竖固的粒子。当将两种或多种不同的粉末机械地共混时，较坚固的粒子也是粉末混合物中一个优点。通过热压法制备的软粒子必须更温和地进行处理。
生产大的hBN颗粒的热压工艺的低回收率导致高成本的产品。符合要求的粒子尺寸的级分越窄，则废品率越高，并且产品成本越高。为此，必需作出折衷来使用较宽的粒子尺寸级分，因此需要特殊的工艺或者产品。由于高hBN成本，粒子尺寸的精确控制是不切实际的。这些折衷导致在后续热喷涂中的效率较低，例如沉积效率低，并且hBN在喷涂涂料中的保留较低。
先有技术的hBN颗粒的另一个不利之处是颗粒具有棱角和不规则形状，这在热喷涂期间在粉末进料中可能产生问题。
先有技术的hBN颗粒的另一个不利之处是颗粒的组成和密度不可变。例如，将填料即其他固体颗粒加入hBN组合物受到高温和压力下实施的热压工艺的限制。
因此，本发明的主要目的是提供生产坚固的、倒角的固体润滑剂颗粒的成本有效的方法，所述颗粒处于需求的(并且如果需要的话，狭窄的)尺寸范围内。
本发明的另一个目的是提供生产倒角的附聚物颗粒的方法，例如基于hBN的、基于二硫化钼的或者基于石墨的附聚物，该方法是可靠的和操作简单的，并且基本上不产生废料。
本发明的另一个目的是提供生产倒角的固体润滑剂附聚物的方法，该附聚物具有各种希望的组成，而不需要改变工艺参数，同时容许生产均匀密度的或者多孔的产品颗粒。
本发明的又一个目的是提供生产固体润滑剂附聚物的方法，该固体润滑剂附聚物包含其他的填料和粘合剂，以产生新的复合颗粒组合物。填料可以包括任何固体颗粒，例如微粒聚合物，陶瓷和金属。
发明内容
本发明的这些及其他目的可以通过本发明的方法达到，在本发明方法的宽的方面，其包括将颗粒固体润滑剂、无机粘合剂和液体混合以产生可加工的混合物。还可以将填料加入固体润滑剂-粘合剂-液体混合物中，以降低最终产品的成本或者提高其性能。
上述混合物，其可以具有高或低的粘度，通过将所述液体蒸发而被干燥形成固体附聚物。这些附聚物可以具有对于具体的应用所要求的粒子尺寸，例如当干燥通过喷雾干燥来实施时，或者当附聚物是大的时，所述附聚物可以被粉碎以达到要求的粒子尺寸。在所有情况下，将所述附聚物分级。然后，如果形状不是重要的，可以将尺寸过大的级分重新粉碎，以获得要求的粒子尺寸，或者与所述液体混合并且重新处理。尺寸过小的级分可以与液体混合并且重新处理。
在本发明方法的最优选的实施方案中，颗粒固体润滑剂与粘合剂以大约19∶1到1∶19的固体润滑剂比粘合剂的重量比混合，优选以大约9∶1到4∶6的固体润滑剂比粘合剂的重量比混合，并且更优选以大约8∶2的固体润滑剂比粘合剂的重量比混合，并且与水混合以产生具有大约5到60重量％固体、优选大约20到30重量％固体的浆液。所述浆液可以被喷雾干燥以形成倒角的附聚物。所述粘合剂优选是亲水性的，并且可以选自膨润土、填料土、蒙脱土等等水合的硅酸铝。
虽然喷雾干燥方法是优选的生产所述产品的方式，但是可以使用其他的方法。可以大的量(千cm3或更多)生产重的、粘稠的混合物，然后进行干燥和粉碎。别一种方法是转筒制粒，继之以粉碎和分级。再一种方法是挤出“意大利面条”状的固体润滑剂-填料-粘合剂-液体的物料，然后干燥、粉碎和分级。
粘合剂可以是固体、液体例如硅酸钠或者液体浆液，或者其任何混合物。
填料可以是一种或多种颗粒固体材料，其可以降低产品成本或者改善产品性能，例如颗粒聚合物，陶瓷或者金属，或者其混合物。填料可以以占所述固体最高40体积％的量加入。
固体润滑剂至少是以下物质之一：六方形氮化硼、石墨、氟化钙、氟化镁、氟化钡、二硫化钨和二硫化钼粉末，优选六方形氮化硼或者二硫化钼粉末。
本发明的一个主要优点是，通过选择本发明的粘合剂，所述方法达到了几乎100％的回收率，即使当要求所述产品具有极其窄的特定颗粒尺寸时也是如此。这有两种实质性优点：固体润滑剂例如hBN的成本是很高的，因此回收率的任何提高都能显著地降低最终产品的成本。虽然例如喷雾干燥是低成本方法，但是其对生产成本的影响比hBN的成本低得多。第二种优点在于可以生产窄的粒子尺寸级分的事实，所述窄的粒子尺寸级分根据热喷涂工艺要求的得到完全地控制。结果是远远更高的和更可控制的沉积效率，并且因此导致较低的施涂涂层的成本。
用于本发明方法的粘合剂优选是无机的。有机粘合剂不能经受其中火焰温度一直高于2000℃的热喷涂方法温度。当有机粘合剂被燃烧时，附聚的颗粒崩解，并且热喷涂方法变得无法控制。无机粘合剂在高温下是很稳定的，并且因此更适合于热喷涂应用。最适当的无机粘合剂是在高于湿混合物的干燥温度的温度下被稳定的那些。本发明中考虑的干燥混合物的低温方法不使粘合剂稳定，并且超出可使用范围的所述颗粒可以容易地通过将粘合剂和固体润滑剂以及任何填料重新分散在液体中而被重新处理。只是在正确的粒子尺寸级分被生产以后，所述粘合剂才被稳定而变成非可分散的，并且可以用于热喷涂。在这里，稳定的是指粘合剂不能重新分散到液体中。
附图说明
现在将参考附图描述本发明的方法，其中：
图1是举例说明本发明方法优选的实施方案的流程图；和
图2是用于本发明方法中的喷雾干燥系统实施方式的示意图。
优选实施方案的描述
参考图1，其中举例说明了本发明方法优选的实施方案，其中将固体润滑剂颗粒例如hBN颗粒，其可以是具有小于-325目(45微米)的尺寸的粉碎的hBN或者细hBN颗粒，与由膨润土粉末代表的粘合剂共混，其中hBN比粘合剂的重量比为大约1∶19到19∶1、优选大约9∶1到大约4∶6，并且更优选大约8∶2，并且在水中在混合容器10中浆液化，以提供在水中含有大约5到60重量％固体、优选大约20到30重量％固体的浆液，然后输送到耐火材料槽11。
其中均匀地悬浮着固体的水-固体浆液在其中通有加热的干燥空气的喷雾室12中可以被雾化成微滴。水从微滴中被蒸发，并且从所述室中连续地收集固体产品。粘合剂将细的hBN颗粒粘结在一起而形成附聚物。
图2中详细地描述了一种典型的喷雾干燥室，其包括具有锥形底部16的圆筒形容器14，液体-固体浆液在顶部进口18进料到其中，来自鼓风机20和热交换器21的加热的干燥空气在侧面进口22在切线方向进入，干燥空气在下部的切线出口24排放，并且干燥的产品级分25在底部顶点出口26排放。排放的干燥空气通过用于收集细粉级分30的旋风分离器28。该细粉级分被加入循环物流36。
在图1中，产品25被进料到第一道筛网32，以除去尺寸过大的物料34，其被加入循环物流36。来自筛网32的尺寸过小的物料38被进料到第二道筛网40，用于除去作为第一产品级分42的尺寸过大的物料，并且尺寸过小的物料44被进料到第三道筛网46，用于除去第二产品级分48。来自筛网46的尺寸过小的颗粒50被加入循环物流36。循环物流36以有利于连续运转和完全回收的比例被加入混合槽10。产品级分42和48被输送到烘箱52，并且被加热到至少850℃，以将粘合剂稳定，这样使颗粒变得难熔和坚固，并且不溶于水，所述稳定的粘合剂具有不溶解的陶瓷的特征。
如果附聚物产品在热喷涂应用中的使用不要求立即的稳定化，则未稳定的产品可以被热喷涂到表面上，并且热喷涂的热量使粘合剂稳定，或者粘合剂可以通过在所述涂层在升高的温度下使用期间的热量被稳定。
在典型的操作中，喷雾干燥的产品将被顺序地输送到100目(149微米开口)筛网32、200目(74微米开口)筛网40和325目(45微米开口)筛网46，其中将100目以上的尺寸过大的级分和325目以下的尺寸过小的级分转移到循环物流36。-100+200目级分和-200+325目级分作为分开的产品级分收集并且在烘箱52中被加热。
材料的生产费用由原材料成本和产品的制造成本控制。两种成本都很低，这使得该方法从成本角度讲是很有吸引力的。例如，细粉hBN的成本比粗粒hBN的成本低许多倍。此外，细粉hBN粒子可以从许多廉价的来源获得，相比之下粗粒hBN粒子只能从很少的生产商获得。另一个主要优点是，与“热压-粉碎-筛选”方法的高成本相比，生产喷雾干燥的粒子具有很低的成本，而且材料回收率高，通常高于95％，并且在很多情况下接近于100％。
虽然所述描述参考了膨润土作为粘合剂和hBN作为要借助于所述粘合剂附聚的固体润滑剂粒子的使用，应当理解，优选的粘合剂是亲水性的，并且由膨润土、漂白土和蒙脱土代表，其是水合的硅酸铝。虽然应当理解不受假设的推理的束缚，相信可以可逆地脱水的水合硅酸铝的粘合剂允许固体润滑剂粒子在尺寸过小和尺寸过大的附聚物向着混合器10中的水循环时在水中分散。
可以单独使用或者与hBN混合使用不同于hBN的固体润滑剂和粘合剂，以降低成本或者为产品提供其他性能。其他的固体润滑剂是以下的至少一种：石墨、氟化钙、氟化镁、氟化钡、二硫化钨和二硫化钼粒子。
在某些热喷涂应用中，产品中的高孔隙度是所希望的。这可以通过在组合物中加入短效的材料例如可消耗的聚合物来达到，以提供具有提高的孔隙度的附聚物产品。颗粒聚合物粉末，例如尺寸小于325目的聚酯，可以在容器10(图1)中以占具有所述固体润滑剂和粘合剂粉末的组合物的大约1到大约40％体积的量共混，优选以大约10到25％的量共混。所述短效的聚合物随后被蒸发或者燃烧，以产生多孔的、低密度的开孔产品。
所述方法还提供了允许加入其他填料材料的灵活性，以降低成本或者改善产品性能。例如，可以将颗粒金属和陶瓷例如氧化铝或者石英加入所述混合物。
稳定化的产品适合于湿法冶金加工，例如金属合金镀覆，或者可以将所述产品与用于热喷涂的金属合金例如CoCrAlYSi合金共混，以生产可磨蚀的密封材料或者抗剥蚀涂层。
应当理解，对于本领域的技术人员而言，本发明的其他实施方式和实例将是显而易见的，本发明的范围在所附权利要求中限定。

Claims (26)

1.一种生产固体润滑剂附聚物的方法，所述方法包括以大约19∶1到大约1∶19的重量比将颗粒固体润滑剂和无机粘合剂混合，并且将液体加入，以生产具有大约5到60重量％固体的混合物，将该混合物干燥以生产干燥的附聚物，并且将所述干燥的附聚物按大小分级或者研磨和按大小分级，以获得具有希望的粒子尺寸的级分。
2.权利要求1的方法，其中通过分级产生附聚物的尺寸过小的粒子级分和尺寸过大的粒子级分，然后通过将所述附聚物在最初的液体中再分散来对所述尺寸过小的附聚物级分进行重新处理，并且通过在最初的液体中进行再分散或者通过粉碎和回收处于所希望的粒子尺寸级分中的粒子来重新处理所述尺寸过大的附聚物粒子。
3.权利要求2的方法，其中在通过分级获得了希望的粒子尺寸的级分之后，使在所希望的粒子尺寸的级分中的粘合剂在所述最初的液体中不可分散。
4.权利要求3的方法，其中固体润滑剂是至少一种选自以下的润滑剂：六方形氮化硼、石墨、氟化钙、氟化镁、氟化钡、二硫化钨和二硫化钼粒子。
5.权利要求4的方法，以占所述固体最高40体积％的量向所述固体润滑剂和粘合剂中加入填料。
6.权利要求4的方法，其中所述固体润滑剂是六方形氮化硼，并且以大约9∶1到4∶6的六方形氮化硼比粘合剂的重量比与粘合剂混合。
7.权利要求6的方法，其中所述液体是水，并且所述粘合剂是水合硅酸铝，该水合硅酸铝在所希望的粒子尺寸级分中在高于850℃的温度下被稳定化。
8.权利要求7的方法，其中所述粘合剂是以下物质的至少一种：膨润土、漂白土或者蒙脱土。
9.一种生产倒角的、固体润滑剂附聚物的方法，其包括在混合机中在水中以大约19∶1到大约1∶19的固体润滑剂比粘合剂的重量比将颗粒固体润滑剂和无机粘合剂混合，以生产具有大约5到60重量％固体的浆液，并且将该浆液的微滴干燥以形成干燥的、倒角的固体润滑剂附聚物。
10.权利要求9的方法，其包括将所述固体球状附聚物分级，以产生尺寸过大的级分、尺寸过小的级分和产品级分，将尺寸过大和尺寸过小的级分成浆并且循环到混合机，并且使产品级分在最初的液体中变得不可分散。
11.权利要求10的方法，其中固体润滑剂是至少一种选自以下的润滑剂：六方形氮化硼、石墨、氟化钙、氟化镁、氟化钡、二硫化钨和二硫化钼粒子。
12.权利要求11的方法，其中固体润滑剂以大约9∶1到4∶6的固体润滑剂与粘合剂的重量比与粘合剂混合。
13.权利要求12的方法，其中所述粘合剂是水合硅酸铝，其在高于850℃的温度下在所希望的粒子尺寸级分中被稳定化。
14.权利要求9的方法，其中所述固体润滑剂是六方形氮化硼，并且以大约9∶1到4∶6的六方形氮化硼比粘合剂粉末的重量比与粘合剂混合。
15.权利要求11的方法，其中所述粘合剂是以下物质的至少一种：膨润土、漂白土、蒙脱土或者其混合物。
16.权利要求9的方法，其中所述固体润滑剂是六方形氮化硼，并且以大约9∶1到4∶6的六方形氮化硼与粘合剂粉末的重量比与粘合剂粉末混合，并且用水浆液化，以生产包含大约20到30重量％固体的浆液。
17.权利要求10的方法，其中所述固体润滑剂是六方形氮化硼，并且以大约9∶1到4∶6的六方形氮化硼与粘合剂粉末的重量比与粘合剂混合，并且用水浆液化，以生产包含5到60重量％固体的浆液，并且其中所述粘合剂粉末选自膨润土、漂白土、蒙脱土和其混合物。
18.权利要求10的方法，其中所述固体润滑剂是六方形氮化硼，其以大约8∶2的六方形氮化硼与粘合剂粉末的重量比与粘合剂混合，并且用水浆液化，以生产包含大约20到30重量％固体的浆液，并且其中所述粘合剂是水合硅酸铝。
19.权利要求18的方法，其中所述水合硅酸铝是以下物质的至少一种：膨润土、漂白土或者蒙脱土。
20.权利要求2的方法，其中所述粘合剂是硅酸钠。
21.权利要求17的方法，还包括以占所述固体最高40体积％的量向所述固体润滑剂和粘合剂中加入填料。
22.通过权利要求8的方法生产的固体润滑剂附聚物。
23.通过权利要求9的方法生产的倒角的固体润滑剂附聚物。
24.通过权利要求17的方法生产的倒角的固体润滑剂附聚物。
25.通过权利要求5的方法生产的固体润滑剂附聚物。
26.通过权利要求21的方法生产的倒角的固体润滑剂附聚物。
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