CN100457250C - 一种合成金刚石用石墨与触媒复合材料的制备方法及设备 - Google Patents

一种合成金刚石用石墨与触媒复合材料的制备方法及设备 Download PDF

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CN100457250C
CN100457250C CNB2006101560716A CN200610156071A CN100457250C CN 100457250 C CN100457250 C CN 100457250C CN B2006101560716 A CNB2006101560716 A CN B2006101560716A CN 200610156071 A CN200610156071 A CN 200610156071A CN 100457250 C CN100457250 C CN 100457250C
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高为鑫
王斌
柯尊斌
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TIANYI SUPERFINE METAL POWDERS CO Ltd JIANGSU
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Abstract

本发明公开了一种合成金刚石用石墨与触媒复合材料的制备方法及设备，首先将清洁的石墨颗粒置于加热室(6)中预加热，加热温度下限应高于镀覆的羰基金属络合物沸点，加热温度上限依所需镀覆的厚度设定；其次将加热的石墨颗粒输送到带有振动或搅拌器(11)的镀覆室(7)内，输入羰基金属络合物蒸汽进行镀覆；最后将镀覆完毕的石墨颗粒输送至冷却钝化室(8)钝化冷却出料，或进入下一轮加热镀覆循环。本发明制备的石墨与触媒复合材料，每个石墨颗粒外表都镀有金属层，用其制作的合成棒内的颗粒之间形成连续性金属接触，在合成时极易形成连续的触媒金属膜，将碳源源不断地传输送给金刚石晶核，促使晶核长成完好的金刚石晶体。

Description

一种合成金刚石用石墨与触媒复合材料的制备方法及设备
技术领域
本发明涉及复合材料的制备方法及设备，具体涉及一种利用四羰基镍、五羰基铁、十羰基二锰、八羰基二钴等羰基金属络合物在石墨颗粒表面分解形成镍、铁、锰、钴等触媒元素单层或复合镀层的方法及设备，尤其是一种利用加热的石墨颗粒所带的热量使羰基镍、铁、锰、钴蒸汽在石墨表面分解形成镍、铁、锰、钴镀覆层的方法及设备，石墨与镍、铁、锰、钴触媒的复合材料用于压制合成棒合成金刚石。
背景技术
静高压合成金刚石必须借助过渡金属或合金的催化作用，以实现高温高压下石墨向金刚石的转化。传统的合成工艺是将片状Ni70Mn25Co5合金触媒与石墨交替组装在合成腔内合成，金刚石沿触媒片与石墨片相邻的边生长。近年兴起的粉末触媒工艺，促进了金刚石合成转化率的提高。唐敬友等在《片状与粉末触媒对石墨转化成金刚石的催化效率研究》中认为，采用粉末触媒工艺，石墨粉与触媒粉充分混合，相互之间具有较大的接触面积，石墨转化为金刚石不需长程扩散，石墨变成金刚石的转化率会大大增加。在合成条件相同的情况下，粉末状触媒的单产和转化体积分数甚至为片状触媒的5倍。方啸虎在《中国超硬材料新技术与发展》中阐述，“金属粉与石墨粉均应取粒径200目以细的为好，并按合适的工艺进行搅拌”，“金属与石墨粉尽量采用较低比例合适”，“粉末触媒合成过程中，必须要有一层金属膜，凡是没有或金属膜不完整的，其金刚石必定生长不好。金属膜的作用是传递输送碳源给金刚石晶核，促其长大，在整个过程中，何时出现不良状况，何时就停止，或晶体发育得不完全。粉末触媒的特点是比较容易形成金属膜，而且金属膜与金刚石核是一种单体，孤立、呈小球状、全方位的一个小球，它的存在至关重要，一旦形成并保持到金刚石整个生长阶段终止，这颗金刚石就是相当完好的单晶”。
上述粉末触媒工艺都是以金属粉与石墨粉混合为基础的，由于金属粉末与石墨的密度相差很大，易在混合中产生偏析，加之金属粉在石墨粉中的分布是非连续的，就整个合成腔或单个石墨粉粒外表而言，其环境都难以形成连续的金属膜，影响了金刚石晶体的生长。
发明内容
本发明的目的是提供一种合成金刚石用石墨与触媒复合材料的制备方法及所用的设备，利用羰基金属络合物在石墨颗粒上热分解形成金属镀覆层制备出石墨与金属触媒复合材料，以代替目前通用的金属粉与石墨粉混合物用于合成金刚石，用石墨与金属触媒复合材料制作的合成棒内的金属形成连续性接触，在合成金刚石时，无论是整个合成腔还是单个石墨颗粒的外表都极易形成连续的金属膜，源源不断地将碳输送给金刚石晶核，使其长大成完好的金刚石晶体。
本发明的目的通过以下技术方案来达到：根据合成不同规格的金刚石的需要，对不同粒径或不同粒径分布的石墨进行预加热，利用加热的石墨所带热量，使镍、铁、钴、锰的羰基金属络合物在石墨表面分解，使石墨表面均匀地镀上铁、镍、钴、锰等触媒元素的单层或它的复合层金属镀覆层。
所述方法包括以下步骤：
a.将清洁无污染的高纯石墨颗粒置于加热室中，在真空或氮气、氩气等保护气氛下对石墨颗粒进行预加热。
b.将加热的石墨颗粒输送到带有振动或搅拌器的镀覆室内，打开作为镀覆物的羰基金属络合物蒸汽进汽开关，向镀覆室输入羰基金属络合物蒸汽，开动振动或搅拌器，利用加热的石墨所带热量，使羰基金属络合物在石墨表面分解，使石墨表面均匀地镀上触媒金属层；
c.将镀覆完毕的石墨颗粒输送至冷却钝化室钝化冷却出料，或进入下一轮加热镀覆循环，直至达到所需的镀覆厚度，最终冷却钝化出料、纯化、包装。
所述对石墨进行预加热，加热温度下限应高于用于镀覆的羰基金属络合物的沸点，温度上限依所需镀覆的厚度设定，需要的镀覆层厚，温度就设定高，需要的镀覆层薄，温度就设定较低，具体根据所分解单位摩尔体积的羰基金属络合物所需热量经计算确定。
本发明中对石墨进行预加热，加热温度选择在作为镀覆物的羰基金属络合物的沸点温度tf以上，至tf+800℃范围，优选在tf+50℃至tf+600℃温度范围。
所述作为镀覆物的羰基金属络合物选自Fe(CO)5、Co2(CO)8、Ni(CO)4、Mn2(CO)10中的至少一种。
所述触媒金属镀覆层含有选自Fe、Co、Ni、Mn中的至少一种材料。
所述下一轮加热镀覆循环，可以镀覆上一轮相同的羰基金属络合物，以增加该种元素的镀覆厚度；也可以变换羰基金属络合物的品种，镀覆其它元素，每种元素的镀覆可以交替或混合进行。
一种上述的制备方法所用的设备，其特征是：由一个或多个加热室，一个或多个镀覆室，一个或多个羰基金属络合物汽化室及一个冷却钝化室组成；加热室安装连接内带振动或搅拌器的镀覆室，镀覆室安装连接汽化室和冷却钝化室，各室上都设保护气进出气口和相互连通的开关；所述多个加热室、镀覆室、汽化室可串联亦可并联组装，实现封闭、连续的单层或多层、单元素或多元素镀覆。
本发明所述制备方法制备的石墨与触媒复合材料，每个石墨颗粒外表都镀有触媒金属层，用其制作的合成棒内的金属形成连续性接触，在合成时，无论是整个合成腔还是单个石墨颗粒的外表都极易形成连续的金属膜，将碳源源不断地输送给金刚石晶核，促使其长大成完好的金刚石晶体；本发明所述方法是一种区别于以往颗粒表面镀覆金属镀层方法的新方法，工艺简单，而且克服了传统的金属有机物化学气相沉积方法镀覆时镀覆物蒸汽与被镀覆物表面吸附作用差，镀覆层不均匀的缺点。
附图说明
图1为本发明的工艺流程结构示意图。
图中：1.石墨进料斗，2.开关(0～n)，3.保护气进气口(1～n)，4.羰基金属络合物蒸汽入口(1～n)，5.成品出料口，6.加热室(1-n)，7.镀覆室(1-n)，8.冷却钝化室，9.保护气出气口或抽真空口(1～n)，10.汽化室(1～n)，11.振动或搅拌器(1～n)。
具体实施方式
本发明所述方法具体包括下列步骤：
a.将清洁无污染的高纯石墨颗粒置于加热室6中，为使石墨颗粒在加热过程中不被氧化和污染，须使加热室在真空或氮气、氩气等保护气氛下对石墨颗粒进行加热，温度下限应高于用于镀覆的羰基金属络合物沸点，温度上限视所需镀覆的厚度设定，需要的镀覆层厚温度就设定高，需要的镀覆层薄温度就设定较低，具体要根据所分解单位摩尔体积的羰基金属络合物所需热量经计算确定；
b.将加热至所需温度的石墨颗粒输送到带有振动或搅拌装置11的镀覆室7内，打开羰基金属络合物蒸汽入口4，向镀覆室7输入羰基金属络合物蒸汽，同时开动振动或搅拌装置11进行镀覆；
c.将镀覆完毕的石墨颗粒输送至冷却钝化室8钝化冷却出料，或进入下一轮加热镀覆循环，直至达到所需的镀覆厚度，最终冷却钝化出料、纯化、包装。
本发明中对石墨进行预加热，加热温度选择在作为镀覆物的羰基金属络合物的沸点温度tf以上，至tf+800℃范围，优选在tf+50℃至tf+600℃温度范围。
所述作为镀覆物的羰基金属络合物选自Fe(CO)5、Co2(CO)8、Ni(CO)4、Mn2(CO)10中的至少一种。
所述触媒金属镀覆层含有选自Fe、Co、Ni、Mn中的至少一种材料。
所述下一轮加热镀覆循环，可以镀覆上一轮相同的羰基金属络合物，以增加该种元素的镀覆厚度；也可以变换羰基金属络合物的品种，镀覆其它元素，每种元素的镀覆可以交替或混合进行。
本发明的制备方法所用的设备包括一个或多个加热室6，一个或多个镀覆室7，一个或多个羰基金属络合物汽化室10及一个冷却钝化室8；加热室6安装连接内带振动或搅拌装置11的镀覆室7，汽化室10安装连接镀覆室7，镀覆室7安装连接冷却钝化室8，各部件上都设保护气进出气口3、9和相互连通的开关2；所述多个加热室6、镀覆室7、汽化室10可串联亦可并联组装，实现封闭、连续的单层或多层、单元素或多元素镀覆。
以石墨镀铁为例结合图1说明如下：
1.将石墨颗粒通过石墨进料斗1加入加热室6-1，关闭开关2-0；
2.将整个系统抽真空或用N2、Ar2置换；
3.接通加热室6-1的热源对石墨加热至800℃；
4.接通汽化室10-1的热源对汽化室预热至104℃以上；
5.步骤3、4达到预定温度时，打开加热室6-1与镀覆室7-1之间的开关2-1，将加热室6-1的热石墨送至镀覆室7-1，关闭加热室6-1与镀覆室7-1之间的开关2-1，向汽化室10-1投入Fe(CO)5，打开汽化室10-1与镀覆室7-1之间的开关2-2，向镀覆室7-1输送Fe(CO)5蒸汽，开动振动或搅拌装置11-1实施镀覆；
6.关闭汽化室10-1与镀覆层7-1之间的开关2-2，打开镀覆室7-1与冷却钝化室8之间的开关2-10，将镀覆完毕的石墨输送至冷却钝化室8，冷却钝化出料，此步操作限一次镀覆或多次镀的最后一次镀覆后；
7.或打开开关2-5，将镀覆过的石墨输送至加热室6-2再加热，进入下轮镀覆，如此循环，直至达到预期镀覆厚度再送入冷却钝化室8钝化；
8.将镀覆完毕并冷却钝化的石墨与触媒复合材料从材料出料口5放出，纯化包装。

Claims (9)

1.一种合成金刚石用石墨与触媒复合材料的制备方法，其特征在于该方法包括以下步骤：
a.将清洁无污染的高纯石墨颗粒置于加热室中，在真空或氮气、氩气保护气氛下对石墨颗粒进行预加热；
b.将加热的石墨颗粒输送到带有振动或搅拌器的镀覆室内，打开作为镀覆物的羰基金属络合物蒸汽进汽开关，向镀覆室输入羰基金属络合物蒸汽，开动振动或搅拌器，利用加热的石墨所带热量，使羰基金属络合物在石墨表面分解，使石墨表面均匀地镀上触媒金属层；
c.将镀覆完毕的石墨颗粒输送至冷却钝化室钝化冷却出料，或进入下一轮加热镀覆循环，直至达到所需的镀覆厚度，最终冷却钝化出料、纯化、包装。
2.根据权利要求1所述合成金刚石用石墨与触媒复合材料的制备方法，其特征在于：利用经加热的石墨颗粒所带热量分解Fe、Co、Ni、Mn的羰基金属络合物。
3.根据权利要求1所述合成金刚石用石墨与触媒复合材料的制备方法，其特征在于：所述对石墨颗粒进行预加热，加热温度选择在作为镀覆物的羰基金属络合物沸点温度tf以上，至tf+800℃范围。
4.根据权利要求3所述合成金刚石用石墨与触媒复合材料的制备方法，其特征在于：所述对石墨颗粒进行预加热，加热温度选择在tf+50℃至tf+600℃温度范围。
5.根据权利要求1所述合成金刚石用石墨与触媒复合材料的制备方法，其特征在于：所述作为镀覆物的羰基金属络合物为Fe(CO)5、Co2(CO)8、Ni(CO)4、Mn2(CO)10中的至少一种。
6.根据权利要求1所述合成金刚石用石墨与触媒复合材料的制备方法，其特征在于：所述触媒金属镀覆层含有选自Fe、Co、Ni、Mn中的至少一种材料。
7.根据权利要求1所述合成金刚石用石墨与触媒复合材料的制备方法，其特征在于：所述步骤c中的下一轮加热镀覆循环，可以镀覆上一轮相同的羰基金属络合物，也可以变换羰基金属络合物的品种，镀覆其它元素，几种元素的镀覆可以交替或混合进行。
8.根据权利要求1所述合成金刚石用石墨与触媒复合材料的制备方法的设备，其特征在于：由一个或多个加热室(6)，一个或多个镀覆室(7)，一个或多个羰基金属络合物汽化室(10)及一个冷却钝化室(8)组成；加热室(6)安装连接带振动或搅拌器(11)的镀覆室(7)，汽化室(10)安装连接镀覆室(7)，镀覆室(7)安装连接冷却钝化室(8)，各室都设保护气的进出口(3、9)和相互连通的开关(2)。
9.根据权利要求8所述合成金刚石用石墨与触媒复合材料的制备方法的设备，其特征在于：其特征在于：加热室(6)、镀覆室(7)、汽化室(10)可多个串联亦可多个并联组装，实现封闭、连续的单层或多层、单元素或多元素镀覆。
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