CN103732560A - 压铸浆料及由其制成的用于燃气轮机设备的耐火陶瓷 - Google Patents

压铸浆料及由其制成的用于燃气轮机设备的耐火陶瓷 Download PDF

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CN103732560A
CN103732560A CN201280039569.8A CN201280039569A CN103732560A CN 103732560 A CN103732560 A CN 103732560A CN 201280039569 A CN201280039569 A CN 201280039569A CN 103732560 A CN103732560 A CN 103732560A
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die casting
weight
casting slurry
refractory
tackiness agent
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C.阿内基里斯
H.格罗特
F.兰格
N.格拉赫
U.克利佩尔
S.沙福纳
H.斯派克
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Siemens AG
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Siemens AG
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Abstract

本发明涉及一种用于制备用作燃气轮机设备的热气通路中的挡热板的耐火陶瓷的压铸浆料，该压铸浆料包括至少两种具有不同热膨胀系数的材料的微粒混合物以及有机和/或无机的粘合剂和浮选剂，其中所述微粒混合物具有的直径以毫米计的多峰粒径分布为10～20重量%的直径的尺寸范围为1～5mm的粗颗粒、10～20重量%的直径的尺寸范围为0.5～1mm的中等颗粒以及60～80重量%的直径的尺寸范围最高达0.5mm的细颗粒，并且选择颗粒尺寸分布的比例，使得它们相加为100重量%的微粒混合物。

Description

压铸浆料及由其制成的用于燃气轮机设备的耐火陶瓷
技术领域
本发明涉及一种用于制备根据权利要求1的前序部分的用作燃气轮机设备的热气通路中的挡热板的耐火陶瓷的压铸浆料(pressure casting slip)，并且也涉及一种根据权利要求7的前序部分的用作燃气轮机设备的热气通路中的挡热板的耐火陶瓷。
背景技术
燃气轮机设备基本上由压缩机、燃烧器和燃气轮机组成。在已抽入的空气和设置在压缩机增压室的下游燃烧器中的燃烧室中的燃料混合之前，先将其在压缩机中压缩，然后燃烧该混合物。然后，位于燃烧室下游的燃气轮机从所产生的燃烧废气抽出热能并将其转化成机械能。与燃气轮机连接的发电机将该机械能转化成电能来发电。
现如今，燃气轮机设备，跟其它发电设备一样，必须在全部荷载范围内保证最高效率的同时具有非常低的污染物排放。燃烧温度的高低由法定的NOx值来限制。在燃烧器和燃气轮机之间形成热气通路的燃烧室中的温度通常位于约1300～1500摄氏度的数量级。为了能承受这样的高温，必须提供合适的抵抗热气体攻击的燃烧室内衬以便保护围绕热气通路的部件和支撑结构。
该挡热板能够是金属的或陶瓷的。对于燃气轮机设备来说，因为侵蚀性的热气体，优选采用陶瓷材料。相比于金属材料，该耐火陶瓷具有更好的耐高温性和耐腐蚀性，并且也具有较低的导热性。该陶瓷挡热板所基于的材料是高含量α-氧化铝的耐火陶瓷，例如可根据DE102008011820Al所记载的压铸浆料铸造工艺来制备所述耐火陶瓷。
如今，燃气轮机设备必须在非常短的时间内适应普遍的荷载条件。燃气轮机设备的组件和支撑结构(即包括挡热板)上的最高应力出现在快速断开基本荷载的时候。这种情况下，热气体的温度在短时间内能够下降1000开尔文。由此在挡热板中引起的热突变要求该耐火陶瓷具有使高强度和高导热性相结合成为可能的材料性质，并且在高达约1500摄氏度及更高温度下亦然。此外，该耐火陶瓷还必须具有高的抗开裂性。EP1327108A1公开了符合上述性质的耐火陶瓷，出于这个目的，该耐火陶瓷在特别受力的热气体一侧具有不同于相对的较冷的燃烧室壁一侧的平均粒径分布。但是，这样的粒径分布具有以下缺点，在不同的孔径分布的交界处能够诱导额外的内部应力，这能够对挡热板的无源可靠性(passive reliability)产生负面影响。具有经优化的均匀的粒径分布的陶瓷会对整个***的无源可靠性产生正面影响。
发明内容
本发明的目的是提供一种压铸浆料以及由其制成的耐火陶瓷，其具有高的抗热突变性且由此特别适合用作燃气轮机的热气通路中的挡热板。
这一目的是通过具有权利要求1特征的压铸浆料来实现的。
由于该压铸浆料包含具有至少两种不同热膨胀系数的材料的微粒混合物以及有机和/或无机的粘合剂和浮选剂，其中将该混合物的多峰粒径分布的组成为：10～20重量%的直径范围为1～5mm的粗颗粒；10～20重量%的直径范围为0.5～1mm的中等颗粒；以及60～80重量%的直径范围最高达0.5mm的细颗粒，同时必须选择重量分布的比例以便它们相加为100重量%的微粒混合物，从而给出了由所述压铸浆料制造的耐火陶瓷的总孔隙率，该耐火陶瓷特别优选用于燃气轮机设备同时具有特别高的抗热突变性。因而，根据本发明制备的这种耐火陶瓷具有和能够可靠地抵抗在快速断开或也通常在燃气轮机设备的启动和关闭过程出现的快速热循环的材料一致的性能。
中等颗粒组分本身优选包含至少20重量%的具有较小的热膨胀系数的材料。这导致在该压铸浆料的烧制期间在显微结构中出现内部应力，并且这些内部应力导致了由该压铸浆料制成的耐火陶瓷的强度的增加，并且从而导致了挡热板的抗热突变性能的改进。
优选提供黄原胶(xanthan)，特别是浓度最大为压铸浆料的0.05重量%的黄原胶作为粘合剂和浮选剂。黄原胶的使用导致压铸浆料中的多峰粒径分布稳定化。这种稳定性是必要的，特别是对于复杂的挡热板几何结构，以便在由所述压铸浆料制成的整个耐火陶瓷上，获得所需的均一的孔径分布以及由此获得均一的孔隙率。
图1示例性显示了透过根据本发明已经制造的且设计作为用于燃气轮机设备的挡热板陶瓷的耐火陶瓷的示例性断面的扫描电子显微镜图片。在该断面图中，示例性地显示出粗、中和细颗粒的均匀分布，其均匀地贯穿整个耐火陶瓷并且由此在整个陶瓷上造成了约18～20%所需的实质上均一分布的孔隙率。
非常均匀的孔隙率的设置受所使用的粘合剂的影响微不足道。若提供一种硅质粘合剂或多种硅质粘合剂的组合作为粘合剂，就能够获得特别易于调制的压铸浆料。不同于从DE102008011820Al中已知的含粘固剂(cement)的、含磷酸盐的、含氢氧化铝的粘合剂，硅质粘合剂仅在压铸浆料烧结的过程中凝结。为此目的，将由本发明的颗粒混合物组成的可流动的且可泵送的压铸浆料与水性的分散介质和粘合剂体系混合，该颗粒混合物由基于Al2O3、MgO、MgAl2O4、CaO、ZrO2、Cr2O3、CeO2、Y2O3、TiO2、铝矾土、红柱石、白云石、粘土熟料(chamotte)、尖晶石、莫来石的氧化物和/或基于SiC、C的非氧化物和/或包含这些的原材料组成。随后，添加作为硅酸盐粘合剂体系的高岭土或粘土或膨润土或这三种硅酸盐的组合，接着将压铸浆料于超大气压力下引入到以如下方式吸收液体的或可渗透压铸设备的液体的铸模中，由微粒混合物组成的模型是通过透过铸模来除去存在于浆料中的液体在铸模的模塑空间的内部表面上形成的。
任选地，如果提供由两种多糖组成的粘合剂体系作为粘合剂，那么这导致较高的粘度，其通过以加压或减压的方式在铸模中脱水会进一步增加，以便在铸模中的压铸浆料凝固化。这里优选使用由黄原胶和瓜尔豆粉溶液组成的粘合剂体系，或者任选地以作为第一多糖或第二多糖的黄原胶或角豆树种子粉(carob seed flour)或角叉菜胶(carrageenan)或琼脂或西黄芪胶(tragacanth)或梧桐胶(karaya)或***树胶(gum arabic)或塔拉粉(tarakem flour)或魔芋精粉(konjak-mannan)或决明胶(cassia gum)为基础的粘合剂体系。已经出人意料地发现，相比于以相同的量与水混合的单一的多糖，该粘合剂体系的粘度对分散介质/多糖的混合比例表现出更强的依赖性。甚至水/多糖混合物中的水分比例微小的减少就导致该粘合剂粘度的大幅增大。根据本发明，源于通过加压或减压方式在铸模中脱水，该粘合剂体系的使用造成粘度的增加和粘合剂的交联，以便铸模中的模型凝固化。

Claims (8)

1.一种用于制备用作燃气轮机设备的热气通路中的挡热板的耐火陶瓷的压铸浆料，包含至少两种具有不同热膨胀系数的材料的微粒混合物，以及有机和/或无机的粘合剂和浮选剂，其中所述微粒混合物具有多峰的粒径分布，其特征在于，所述多峰粒径分布的组成为：
-10～20重量%的直径范围为1～5mm的粗颗粒，
-10～20重量%的直径范围为0.5～1mm的中等颗粒，以及
-60～80重量%的直径范围最高达0.5mm的细颗粒，并且
-选择重量分布的比例，使得它们相加为100重量%的微粒混合物。
2.权利要求1所述的压铸浆料，其特征在于，所述中等颗粒部分本身包含至少20重量%的具有较小的热膨胀系数的材料。
3.权利要求1或2所述的压铸浆料，其特征在于，提供黄原胶，特别是浓度最大为压铸浆料的0.05重量%的黄原胶作为所述粘合剂和浮选剂。
4.权利要求1或2所述的压铸浆料，其特征在于，提供由两种多糖组成的粘合剂体系作为粘合剂。
5.权利要求4所述的压铸浆料，其特征在于，所述粘合剂体系由黄原胶和瓜尔豆粉溶液组成。
6.权利要求1或2所述的压铸浆料，其特征在于，提供一种硅质粘合剂或多种硅质粘合剂的组合作为所述粘合剂。
7.一种由权利要求1～6中任一项所述的压铸浆料通过干燥和煅烧而制成的用作燃气轮机设备的热气通路中的挡热板的耐火陶瓷，其特征在于，所述耐火陶瓷整体具有18～20%的孔隙率。
8.权利要求7所述的耐火陶瓷，其特征在于，干燥和煅烧前分配所述压铸浆料中的颗粒尺寸，从而形成具有实质上均一孔径分布的耐火陶瓷。
CN201280039569.8A 2011-08-16 2012-08-01 压铸浆料及由其制成的用于燃气轮机设备的耐火陶瓷 Pending CN103732560A (zh)

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