CN109952279A - 用于陶瓷制品的釉料 - Google Patents

用于陶瓷制品的釉料 Download PDF

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CN109952279A
CN109952279A CN201780065718.0A CN201780065718A CN109952279A CN 109952279 A CN109952279 A CN 109952279A CN 201780065718 A CN201780065718 A CN 201780065718A CN 109952279 A CN109952279 A CN 109952279A
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glaze
ceramic
doping
boron nitride
feldspar
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M·罗卡南
J·霍夫曼
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Bibesi Austria Holdings Ltd
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Pisce Insulating Materials Austria Co Ltd
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Abstract

釉料由以下原料按重量百分比制备：耐火泥10％‑25％，长石30％‑40％，砂子30％‑40％，硅酸钙8％‑12％，石墨烷(即无序的结晶且氢化的双键碳)5％‑15％或C掺杂的氮化硼(CBN)5％‑15％，作为颜料的各种金属氧化物和水。按陶瓷绝缘体制造过程中的标准上釉操作施加该釉料，并在受控的惰性气体气氛中烧制。

Description

用于陶瓷制品的釉料
本发明涉及用于陶瓷制品的釉料(glaze)。
污染是取决于陶瓷绝缘体的高压变电站的主要问题。导电的空气传播颗粒落在绝缘体表面从而引起闪络(flashover)，这将损坏绝缘体。在最坏的情形中，变电站切断并引起电网停电。可能的损坏很容易就是数百万欧元。
公用事业公司正在进行预防性维护计划以清洁绝缘体，但在污染区域中，必须每6个月或甚至更频繁地进行清洁。绝缘体清洁对公用事业公司来说是沉重的负担。它作为劳动密集型工作是昂贵的，并且出于安全原因，必须关闭电力，这也导致经济损失。
因此，公用事业公司和能源部门对自清洁表面非常感兴趣。经典的解决方案是具有疏水性硅棚的复合绝缘体。增加清洁间隔的另一种方式是RTV涂层(室温硫化)，喷涂在瓷料表面上的液体硅。近年来，研究专注于试图产生莲花效应或使用疏水纳米颗粒的不同涂覆技术。
所有这些技术的弱点都是涂层，其中寿命是主要问题。变电站是重型基础设施，寿命长达几十年。当涂层或硅老化并失去其特性时，在现场条件下通常不可能进行修复，或者在更换老化的绝缘体时更昂贵。
通常，瓷料具有高润湿性，这意味着水滴不会保持为滴状。还存在盐基污染，其可溶于水。这种类型的污染在干燥之后产生，即绝缘体表面上的所谓的“Obenaus干带”(Obenaus Dry Bands)。关于污染闪络的最早科学解释是Obenaus在1930年代提出的理论。干带活动产生的局部电弧与绝缘体的污染部分串联，这表现为串联电阻。各种因素造成局部电弧延伸并桥接足够的绝缘体(约50％)，这将提供必要的推动力从而导致闪络。绝缘体上的污染严重程度的增加是导致闪络的一个因素。
EP 1 124 237 A2公开了一种上釉的陶瓷制品。釉层包含SiO2和Al2O3，并且没有显示出充当疏水或自清洁的特征。
US 5284712描述了一种含水泥的陶瓷制品，其包含40％长石、10％碳酸钙、5％氧化锌、25％滑石、10％硅砂和10％含氧化硅的高岭土的釉层。该釉料不具有风化，但是它未被设计成疏水性或自清洁的。
因此，本发明的一个目的是提供一种容易制造且制造便宜的釉料，从而产生陶瓷体，诸如具有疏水和/或自清洁表面的高电压绝缘体。
本发明的另一个目的是提供一种用于高电压应用(>1000V)中的户外陶瓷绝缘体的带电表面釉料。
为了实现上述目的，根据本发明的一个方面，提供了一种釉料，其包含5％-15％的石墨烷(graphane)或C-掺杂的氮化硼作为主要成分。
在另一个实施方案中，该釉料包含如下作为主要成分：
5％-25％耐火泥，
30％-40％长石，
17％-40％砂子，
8％-23％硅酸盐，
5％-15％的石墨烷或C掺杂的氮化硼。
在另一优选实施方案中，该釉料包含如下作为主要成分：10％-25％的耐火泥，30％-40％的长石，30％-40％的砂子，8％-12％的硅酸钙，5％-15％的石墨烷。可以使用5％-15％的C掺杂氮化硼代替石墨烷。
在本发明的另一实施方案中，该釉料包含：
5-7.5％的耐火泥，
30-38％的长石75K20和55NaK60，
17-22％的石英砂，
5-7.5％的硅灰石，
2.5-4.7％的皂石煅烧的DIN100，
7-10.5％的ZrSiO4，
0.8-3.8％的方解石Carolith，
5-7.5％的耐火黏土(chamotte)，
5-15％石墨烷或C掺杂氮化硼，
而瓷土(China Clay)是一种特殊类型的耐火泥，硅灰石(Wollastoni)是CaSi03，方解石以0-0.2VA研磨等级提供。硅灰石、皂石和ZrSiO4是硅酸盐(此外皂石是层状硅酸盐)。
在本发明的另一个实施方案中，该釉料还包含作为颜料的金属氧化物和水，而金属氧化物是Fe2O3、Cr2O3、MnO、NiO、CoO、ZrO2或TiO2。可以探索其它金属氧化物。
本发明涉及一种具有赋予排斥水和颗粒的特性的带电表面的新型陶瓷釉料及其制备方法和制造方法，本发明属于陶瓷高电压绝缘体改进的技术领域。
新釉料由以下原料按重量百分比制备：耐火泥10％-25％，长石30％-40％，砂子30％-40％，硅酸钙8％-12％，无序的结晶且氢化的双键碳(石墨烷)5-15％或碳-硼-氮化物5％-15％，作为颜料的各种金属氧化物和水。按陶瓷绝缘体制造过程中的标准上釉操作施加该釉料，并在受控的惰性气体气氛中烧制。
具有带电表面的新釉料排斥水和污染颗粒，这在高度污染的条件下赋予改善的性能，因为“Obenaus干带”的产生减少。这将降低使用中闪络的风险和清洁的需要。新釉料本身是自清洁的，这意味着避免了对于各种涂层观察到的剥落或老化的风险。因此，预期寿命等同于陶瓷绝缘体。
该创新是掺杂釉料受体(receipt)使得釉料本身在瓷绝缘体工业的正常单一烧制过程中实现斥水表面。当雨滴在绝缘体表面上滚动并且携带颗粒时，这将在雨中产生自清洁效果。这也将消除涂层的所有与粘附相关的问题以及硅在日光下的老化问题。由于可以使用现有的工业窑炉，因此该创新极具成本效益。
可以使用称为疏水材料的掺杂物质，其支持高达1300℃的烧制过程。具有六方微结构的材料如石墨烷或C掺杂的氮化硼(或碳氮化硼或CBN，显示六方氮化硼的结构，h-BN)都均可用。
石墨烯是无序的结晶且氢化的双键碳。它高度导电，因此不适用于我们的目的，因为它具有非常有序的晶体结构并且存在双键(C＝C键)，所述双键充当自由电子的高速通道。该结构具有Sp2杂化。在石墨烯的氢化时，将产生一种新化合物。这种新化合物也被称为石墨烷或氢化石墨烯，C＝C双键将打开并且杂化将变为Sp3。这种基于石墨烯的化合物是无序的并且是绝缘体，因为其结构中不再存在C＝C双键。底线是氢化石墨烯是绝缘体并且可以用作隔离物。
六方氮化硼(h-BN)，一种类似石墨的层状材料，是一种有前途的电介质。单层h-BN，即所谓的“白色石墨烯”，由于其类似的平面六方结构和润滑特性，是一种具有高导热性和良好抗热冲击性的硬陶瓷材料。与石墨不同的是，它是一种电绝缘体，并且虽然不如可加工陶瓷那样容易机加工，但在这方面优于其它常规陶瓷。在该背景下，优选使用C掺杂的h-BN。
术语“砂子”涉及在该技术领域中使用的常规砂子类型，例如氧化硅砂或石英砂。
这里，釉料是指在物体上形成最终釉面的组合物。在更具体的实施例中，使用以下方法来建立釉料：
它们被研磨并与约40％重量的水混合，颗粒尺寸分布的容差如下：
D90μm：24.0±2.0，
D50μm：5.5±0.5，
D10μm：0.91±0.1，
平均直径μm：9.3±1，
体积密度(升重量)kg/m3：1620±20，
干燥含量％重量：60.5±2.0。
抗沉降剂是羧甲基纤维素(CMC)。在该液体釉料上，将掺杂物质石墨烷或C掺杂的氮化硼添加到乳液中以形成5％-15％的所需量。
这时最终值是：
5-7.5％的耐火泥，
30-38％的长石75K20和55NaK60，
17-22％的石英砂，
5-7.5％的硅灰石，
2.5-4.7％的皂石煅烧的DIN100，
7-10.5％的ZrSiO4，
0.8-3.8％的方解石Carolith，
5-7.5％的耐火黏土，
5-15％的石墨烷或C掺杂的氮化硼。
通过工业喷枪将掺杂的釉料施加在准备好的转动并干燥的瓷体上，作为替代，可以应用浸渍方法。在上釉后，在正常的烧边(firing curb)之后，在氮气氛中直接烧制绝缘体。
本创新具有多种优势。重点是可以使用现有的工业设备，无需修改或仅需微小修改。釉料掺杂适用于瓷器工业中使用的不同类型的釉料。整个过程极具成本效益，并且即使掺杂物质相当昂贵，釉料也只占绝缘体总重量的1％，掺杂物质是釉料的＜10％，这削弱了成本增加。
由于石墨烯颗粒包埋在釉料上，它们将保留在原位并且将不会有剥离效果。老化行为应与正常釉料相同，一年后未观察到变化。

Claims (6)

1.用于陶瓷制品的釉料，其包含如下作为主要成分：5％-15％的石墨烷或C-掺杂的氮化硼。
2.根据权利要求1所述的用于陶瓷制品的釉料，其包含如下作为主要成分：
5％-25％的耐火泥，
30％-40％的长石，
17％-40％的砂子，
8％-23％的硅酸盐，
5％-15％的石墨烷或C掺杂的氮化硼。
3.根据权利要求1或2所述的用于陶瓷制品的釉料，其包含如下作为主要成分：
10％-25％的耐火泥，
30％-40％的长石，
30％-40％的砂子，
8％-12％的硅酸钙，
5％-15％的石墨烷或C掺杂的氮化硼。
4.根据权利要求1或2所述的用于陶瓷制品的釉料，其包含如下作为主要成分：
5-7.5％的耐火泥，
30-38％的长石75K20和55NaK60，
17-22％的石英砂，
5-7.5％的钙硅石，
2.5-4.7％的皂石煅烧的DIN100，
7-10.5％的ZrSiO4，
0.8-3.8％的方解石Carolith，
5-7.5％的耐火黏土，
5-15％的石墨烷或C掺杂的氮化硼。
5.根据权利要求1至4任一项所述的釉料，其中所述釉料还包含：
作为颜料的金属氧化物和水。
6.陶瓷制品，优选高电压隔离器本体，其包含由根据权利要求1至5之一的釉料组合物制成的表面釉料。
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