CN103796951A - 石墨制品 - Google Patents

石墨制品 Download PDF

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CN103796951A
CN103796951A CN201280037768.5A CN201280037768A CN103796951A CN 103796951 A CN103796951 A CN 103796951A CN 201280037768 A CN201280037768 A CN 201280037768A CN 103796951 A CN103796951 A CN 103796951A
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特蕾西·阿伯斯
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Graftech International Holdings Inc
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Abstract

辐照石墨在辐照加工之后的一种用途是将其再循环到新的石墨人工制品中。这类人工制品的例子包括用于放射性核素的电极、用于铀加工的石墨或碳制品、用于HTGR(特别是GENIVHTGR)的减速剂、用于核设施、炭过滤器、碳化硅应用的其它类型的石墨产品等。这类石墨人工制品可以由最多20pph的炭黑形成，所述炭黑是由玻璃化辐照石墨形成的。任选地所述石墨人工制品可以由最多75pph的沥青形成。

Description

石墨制品
发明背景
本发明公开了一种石墨制品，其是由炭黑形式的玻璃化辐照石墨形成的。
随着核能变为更普遍的能源，高温气体反应器(HTGR)的使用也将增多。这将增加每年生产的辐照石墨的量。有关处置或再循环辐照石墨的方案将进入最前沿。
发明概述
一种方案是在加工成新的石墨人工制品之后再循环辐照石墨。这类人工制品的例子包括用于放射性核素的电极、用于铀加工的石墨或碳制品、用于HTGR(特别是GEN IV HTGR)的减速剂、用于核设施、炭过滤器、碳化硅应用的其它类型的石墨产品等。
这类石墨人工制品可以由最多20pph的炭黑形成，所述炭黑是由玻璃化辐照石墨形成的。任选地所述石墨人工制品可以由最多75pph的沥青形成。在本文上下，“pph”是百分之一的缩写，基于100份的焦炭填料。
附图说明
图1是可以怎样再循环辐照石墨的原理图。
图2是根据实施例制备的石墨的显微图象。
图3-6是根据实施例制备的石墨样品的测量结果的图表。
详细说明
如图1所示，10指的是用于再循环辐照石墨的方法的一个实施方案的概述。12显示的是辐照的整体石墨的样品。所述石墨被玻璃化和转化成炭黑14。炭黑14可被用来形成新的石墨人工制品16。石墨人工制品16的一种用途是应用在核电站、特别是具有HTGR、更特别是GEN IV HTGR的电站中。
石墨人工制品16至少由炭黑14、沥青和石油焦炭形成。通常，人工制品16的配料设计基于100份焦炭。如果需要，可以使用用于人工制品16的其它前体。这种备用的前体可以包括碳纤维、交联剂、加工助剂等。根据期望的最终应用，可以使用各种类型的碳纤维。选择的纤维可被用来提高人工制品16的绝缘性能、强度性能、传导性能或其组合。
在一个实施方案中，人工制品16可以由最多20pph的炭黑14形成。在一个具体实施方案中，可使用最多约10pph的炭黑14来形成人工制品16。在另一实施方案中，可使用最多约5pph的炭黑14来形成人工制品16。在进一步的具体实施方案中，人工制品16可由最多约75pph的沥青、优选约60pph的沥青、更优选最多约50pph的沥青形成。
人工制品16不局限于由任何特定的成型技术来形成。人工制品16可以为挤压的、模制的或等压模制(isomolded)的石墨。通常用于前述类型的石墨的加工技术可用于形成人工制品16。在使用更高负载量的炭黑14或(在某些情形下)碳纤维的情况下，使用强有力的(aggressive)混合技术来提高前体混合物的均质性可能是有利的。
制造人工制品16的示例性步骤包括，将前体研磨至要求的尺寸，混合所述前体，和形成所述人工制品。通常随后将所形成的人工制品加热至600-1400℃的温度来使人工制品16碳化。然后可对所述碳化的人工制品进行人工制品16要求的次数的浸渍和碳化步骤，以达到要求的密度。然后将该适当地致密化的人工制品石墨化成人工制品16。
实施例
制造了含有0-10%炭黑(%炭黑基于配料设计的干分数)的七(7)种不同石墨材料的两个样品，以评价随着所述石墨内的炭黑分数的增大所发生的性能变化。
在制造之后，表征材料的热膨胀系数、声波模数(sonic modulus)、比电阻、密度和抗弯强度。另外，还使用光学显微术来评价所形成的人工制品的结构。
使用石油焦炭、粘结剂(煤焦油)沥青与不同分数的炭黑添加剂构成的混合物制造了小型的石墨电极。 这些成分是在室温下使用固态沥青混合在一起的。 预制的混合物在炭黑含量方面按照以下表1所示来变化：
Figure 448712DEST_PATH_IMAGE001
各个混合物中的沥青量已经针对制造条件和变化的炭黑分数加以优化。例如，用更高量的炭黑制备的人工制品使用了额外分数的粘结剂沥青。
混合物"G"不能进行加工，因为在最终的人工制品的选定区域产生了大的炭黑团聚体且其变得非常脆。
为本研究所制造的最终石墨人工制品的代表性区域的光学显微图象如图2所示。在所述人工制品中均匀结构是很明显的，除了炭黑团聚体以外(其可能随着增大负载量的不可石墨化颗粒而出现)。假定了增长的混合时间会有助于克服炭黑聚集体的形成并进而提高最终材料的整体加工性能、均匀性和品质。
对所述石墨人工制品进行的其它分析包括密度、抗弯强度(图3)、热膨胀系数(图4)、热导率(图5)、杨氏模量和比电阻(图6)。所有的图都显示了针对每个炭黑填充量值所测试的两个样品。
尽管测量到了石墨人工制品的性能的一些变动，但没有观察到超出可接受的性能范围之外的显著偏差。
炭黑可在新的石墨人工制品中用作填充材料。这些材料可以使用各种加工技术来制造。
在下面完成的工作已经证明炭黑负载量很容易达到材料的干分数的最多5pph。
在此给出的石墨的最终性能在对核废料的玻璃化来说"可接受的"石墨材料的范围内。也可以做进一步的研究工作来显著强化这些材料和进一步增强所述石墨的其它基本性能。

Claims (7)

1.一种石墨人工制品，其是由1-19pph的炭黑形成的，所述炭黑是由玻璃化辐照石墨形成的。
2.权利要求1的石墨人工制品，其具有最多10pph的炭黑。
3.权利要求2的石墨人工制品，其具有最多5pph的炭黑。
4.权利要求1的石墨人工制品，其中所述石墨包括挤压的石墨。
5.权利要求1的石墨人工制品，其中所述石墨包括模制的石墨。
6.权利要求1的石墨人工制品，其是由最多75pph的沥青形成的。
7.权利要求6的石墨人工制品，其是由最多50pph的沥青形成的。
CN201280037768.5A 2011-07-28 2012-07-27 石墨制品 Pending CN103796951A (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3092437A (en) * 1958-12-18 1963-06-04 Union Carbide Corp Process for making carbon articles
JPS6259508A (ja) * 1985-09-06 1987-03-16 Tokai Carbon Co Ltd 炭素質薄板の製造方法
CN1732538A (zh) * 2002-12-26 2006-02-08 昭和电工株式会社 用于形成导电材料的碳质材料及其应用

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Publication number Priority date Publication date Assignee Title
US7658902B2 (en) 2006-09-12 2010-02-09 Graftech International Holdings Inc. Low CTE highly isotropic graphite

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3092437A (en) * 1958-12-18 1963-06-04 Union Carbide Corp Process for making carbon articles
JPS6259508A (ja) * 1985-09-06 1987-03-16 Tokai Carbon Co Ltd 炭素質薄板の製造方法
CN1732538A (zh) * 2002-12-26 2006-02-08 昭和电工株式会社 用于形成导电材料的碳质材料及其应用

Non-Patent Citations (3)

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M. I. OJOVAN ET AL.: "Self sustaining vitrification for immobilisation of radioactive and toxic waste", 《GLASS TECHNOLOGY》 *
PETER J. PAPPANO ET AL.: "Preliminary data on processing and characterization of recycled irradiated graphite", 《CARBON》 *
徐世江等: "《核工程中的炭核石墨材料》", 31 December 2010 *

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Application publication date: 20140514