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纳米金刚石应用
纳米金刚石应用

纳米金刚石

 

金刚石为碳的同素异形体,也就是我们常说的钻石,它是一种由纯碳组成的矿物,属原子晶体,金刚石是自然界中最坚硬的物质。纳米金刚石就是粒径在1nm~100nm范围内的金刚石,是碳纳米家族中的一个新的重要的成员。纳米金刚石具有硬度大、光学透明性、热传导性、电绝缘性、耐高压和抗风化等物理学特性,这些独特的性质使得它在涂料、润滑油、聚合物添加剂、电子器件、传感器和电化学领域得到了广泛的应用。

自从苏联和美国同时于1988年用爆轰法制备出金刚石后,纳米金刚石的制备工艺和应用得到了迅速发展。以俄罗斯为首,日本、美国等都已建立了爆轰法制备纳米金刚石的产业,制备工艺日益成熟,规模达到年产吨级。同时,各国对纳米金刚石在材料增强、润滑剂、超硬耐磨复合涂层、雷达吸收剂材料等方面的应用开发也表现出极大兴趣。目前,俄罗斯“阿尔泰”科研生产联合体、白俄罗斯“辛塔”科研生产联合体、乌克兰“阿立特”公司,以及“阿尔泰”在美国办的“超分散技术公司”都建有年产20t的生产线。我国于20世纪90年代初开始进行爆轰法合成纳米金刚石的研究,主要研究单位有中科院兰州化学物理研究所、北京理工大学、第二炮兵工程学院、中国工程物理研究所西南物理研究所、西北核技术研究所等。

  1. 纳米金刚石的制备方法

目前,人工合成金刚石的方法主要有三种,前两种为静压法和沉积法。第三种方法是动压法,是利用瞬时产生的高压高温条件来生成金刚石,动压法根据合成金刚石的原料不同,可以分为以下三类:第一类是冲击波法,利用高速飞片撞击石墨靶板,使石墨在撞击的过程中生成微米级金刚石,国内最早开始这一方面研究是中科院物理研究所。第二类是爆炸法或是称作爆轰波法,就是将石墨与高能炸药混合,在炸药爆轰的过程中压缩石墨使其变为金刚石。最后一类是爆轰产物法,也就是利用负氧平衡炸药爆轰来得到晶粒度在纳米量级的纳米金刚石。

爆轰法与前面两种动压法的最大区别在于前两种方法需要提供碳源制备的金刚石粒度大部分在微米级或者更大。而最后一种方法是不需要提供额外碳源的,炸药本身既提供高压高温条件还提供碳源。爆轰法制备纳米金刚石的基本原理如下负氧平衡炸药在保护介质环境中爆炸,爆炸过程中多余的碳原子经过聚集、晶化等一系列物理化学过程形成纳米尺度的碳颗粒集团,其中包括金刚石相、石墨相和无定形碳。经过选择性的氧化化学处理去除非金刚石相碳后得到纳米尺度的纳米金刚石粉末,也叫纳米金刚石灰粉。

  1. 纳米金刚石灰粉的成分

纳米金刚石粉中的C元素含量和金刚石相含量是两个不同的概念,需要澄清。从目前所有制备的纳米金刚石粉的测试结果来看,纳米金刚石中主要元素为C,其质量分数含量w(C)由于制备方法的不同有所变化,但大部分都在85%~90%之间。其它较多的元素杂质如氢w(H)≤1%,氮w(N)≤6%,氧w(O)≤10%,还含有其它的杂质,如铝Al、硅Si、钙Ca、铁Fe等,其含量在10-4到10-6量级(表1) 。从表1的测试结果可以看出,在制备纳米金刚石时,由于使用不同材质的爆炸容器,对纳米金刚石中的金属杂质含量有绝对的影响。

表1 纳米金刚石中其他杂质元素的含量,w(10-6

样品

1

2

3

4

5

容器材质

复合板

复合板

16MnR

16MnR

16MnR

钙(Ca)含量

<1

19

237

214

227

铬(Cr)含量

<1

2

33

37

10

铜(Cu)含量

<1

3

27

2

19

铁(Fe)含量

310

367

1682

393

1735

钾(K)含量

8

11

318

169

159

镁(Mg)含量

4

5

353

116

229

锰(Mn)含量

<1

<1

161

38

95

钠(Na)含量

23

22

6125

289

1239

硅(Si)含量

129

79

5479

5323

4723

锌(Zn)含量

<1

3

37

4

21

钴(Co)含量

 

<1

 

<1

<1

镍(Ni)含量

 

2

 

15

4

铝(Al)含量

44

45

82

600

240

 

 

3纳米金刚石的应用

3.1超精密抛光

抛光是金刚石应用的传统领域。即使在今天,抛光(包括超精磨)仍是仪表和机械制造工艺过程中的一个最重要环节。可是目前常用的磨料尺寸均大于0. 1μm(100nm),纳米金刚石不仅硬度高,而且颗粒尺寸比最好的磨料要小于一个量级,且碳表面极易受化学改变性的影响,能和任何极性介质兼容,这种特点使纳米金刚石颗粒有可能在载体中均匀分布,因此,纳米金刚石颗粒被视为超精抛光的新一代理想磨料,表1中列出了不同硬度和弹性材料的抛光结果。

表1 纳米金刚石抛光不同材质的结果

材质

Rmax,nm

材质

Rmax,nm

硬质合金

1~5

熔融氧化硅

0.5~1.0

5~6

0.5~1.5

蓝宝石

5~6

NaCl晶体

2~3

石英

0.5~1.5

KBr晶体

2~3

 

 

值得指出的是,含有纳米金刚石的抛光系统具有以下优越性:
(1) 超细尺寸的纳米金刚石能确保表面粗糙度的最小值和抛光系统胶体的稳定性;
(2) 纳米金刚石的化学稳定性,在化学上可以用于抛光系统的活性添加剂和抛光系统的还原;
(3) 降低抛光表面材料的分量, 减少材料的损耗;
(4) 由于纳米金刚石的离子交换和吸附活性,可以减小其表面的离子和分子产物的活动性;
(5) 纳米金刚石团聚体的团聚结构有利于悬浮的抛光系统中聚结的调节作用,且无毒;
(6) 含纳米金刚石的抛光系统,可以提高抛光产品的质量和竞争的能力,以确保难加工材料抛光的加工性。

3.2润滑

高效合理的润滑技术是保证和改进机械设备节能、高效、长期正常运转的基本措施,是机械运输的命脉。目前全世界机械能源有效利用平均只有30 %左右,据德国洛格甫尔教授测算全世界生产能源的1/3到1/2 损失在摩擦磨损上,而英国焦斯特教授指出世界消耗能源的30 %~40 %消耗在摩擦损耗上。从设备的润滑观点来讲,干摩擦是有害的,主要表现在能量的损失和机件的磨损上。

金刚石由于有极高的硬度,对摩擦面上的尖凸能进行自由磨削,迅速去除摩擦副表面凹凸不平的微峰,属于极其精密的研磨抛光过程,是普通机械加工无法做到的。这种作用使摩擦副之间的接触面积迅速增大,加速了磨合过程,提高了磨合精度。而纳米金刚石的球形和准球形颗粒镶嵌于摩擦副之间的接触微凹之中,有优异的承载力,摩擦表面形成滚珠轴承效应,表现出良好的润滑性,将滑动摩擦变成了滚动摩擦,摩擦阻力变小,避免了干磨现象的发生。如Daniel Kamman和Vitaly Komarov的研究表明,使用core 和shell 金刚石符合传统的润滑液,可降低磨损、摩擦系数和摩擦温度,以及提高设备部件的载荷和使用寿命。

表2 工业用润滑剂的性能(用core和shell Ultradiamond改性)

试验条件

改进性能

与不加纳米金刚石的比较

0.1%纳米金刚石加入ISO-220油

摩擦系数

降低0.50~0.052

0.05%加入SN-150发动机油

摩擦系数

降级50%

承载压力

从1000N/mm2增加到1200 N/mm2

0.1%加入润滑油

摩擦系数

降低0.60~0.16

承载极限

增加50%~60%

油温

降低50℃

磨损速率

减少50%~90%

0.25%加入传动油HyKonol k80W-90

磨损速率

降低70%~80%

0.1%加入工业油

时间4~6月

承载寿命

增加6~12个月

维修周期

减少60%

主轴过热

减少或消除

摩擦表面的划痕

减少或消除

油的泄漏

减少后消除

油的适用

减少50%~67%

 

3.3纳米金刚石的复合镀

材料的复合化是材料发展的必然趋势,随着现代工业的发展,机械零件需要在复杂、荷刻的条件和环境下工作,对材料表面性能提出了越来越高的要求。作为一种行之有效的表面改性措施,表面涂覆技术应运而生并获得广泛应用。

然而对于某些主要因接触疲劳或高温磨损而失效缸体、活塞环、模具、曲轴、轴承等,单一涂层已很难满足要求。

可是复合电镀膜中的固体颗粒(金刚石、碳化硅等) 均为毫米和微米级,而镀液中的固体颗粒越细,复合镀层中微粒的分散性越好,镀层的强化效果越明显。因此,纳米金刚石则具有显著的优势。因为它不但具有金刚石的超硬、高抗磨、耐热防腐性能,而且颗粒表面有丰富的羟基、羧基、羰基等官能团,与镀覆表面有极强的结合力,用量小,性能提高显著,十分适合于复合镀,不仅可用于金属表面,也可用于橡胶、塑料、玻璃等表面的涂敷。

纳米金刚石金属复合镀具有以下一些通性;高的耐磨性和显微硬度;高的抗蚀性和小的孔隙度;非常低的摩擦系数;很高的内聚力和附着力;电解液具有高的扩散能力,因此,引起工程技术专家的极大兴趣和关注。纳米金刚石金属复合镀的应用中将导致电化学和化学镀技术的革新。

3.4纳米金刚石用于磁性录音系统

首先,纳米金刚石在磁带和磁盘的铁磁镀膜中,应用作为减磨的添加剂和物理的变性剂;其次,将其添加剂电化学的复合膜中可改善磁性录音的稳定性 。

(1) 纳米金刚石添加剂到铁磁层中明显地减小磁畴(铁磁体的颗粒) ,即录音密度明显地增大。纳米金刚石引入磁头洁净的专用膜中,其耐磨性明显地增大。含有纳米金刚石的软磁信息载体具有以下的优越性:磁载体层的磨损下降,能确保磁头和读数的最佳工作条件,磁载体摩擦减小及其运转稳定性的提高。

(2) 与纯CoP膜比较,CoP纳米金刚石软磁的非晶质膜显示显微硬度增大30 %;耐磨性提高3. 5 倍,摩擦系数减小28. 6 %,磁头铁芯的使用寿命增加1 倍。与纯电化学或化学镀CoP镀层比较,CoP纳米金刚石的硬磁多晶体的显微硬度提高20 %,腐蚀电流减小37. 5 % ,磁性录音载体的使用寿命增大。添加纳米金刚石时,无论是软磁的非晶质的,还是硬磁镀层的磁性特性都没有变化。当层厚1. 10-6m时,纳米金刚石的单位消耗为1m2约1克拉。

3.5纳米金刚石用于医疗

纳米金刚石异常高的吸附能力,大的比表面积,表面上的大量自由电子数(数目多的原子供体),纳米尺寸,晶体表面上大量的含氧官能团,颗粒的化学惰性,表面的亲水特性,对其可能用于治疗的药剂是重要的。

纳米金刚石可应用肿瘤学,肠胃学、心脏学、血管疾病的诊治等,它们没有致癌的或诱变的性质,没有细胞毒性。

纳米金刚石对致病的病毒,微生物和细菌来说显示非常高的活性,由于高的吸附能力和其它的独特性,它们将被强烈地吸收,它们是超活性的吸附剂。在生物学上降低活性物质的迁移率,是急剧强化药用试剂作用的手段,纳米金刚石的应用诱致血压的正常化。此外,当肠胃系统患病,纳米金刚石是有效的,是防止烧伤、不同皮肤病、内脏中毒后效的最好手段。

纳米金刚石应用于水性的和油性的悬浮液,有利于对肿瘤药用试剂的强化,以及减少和消除痛苦的作用,肠道蠕动的正常化,改善血液指标,提高生命和免疫系统的活性,病毒从机体内排出等。

纳米金刚石的应用与化学的和射线疗法结合起来显示出很好的前景。恶性赘瘤治疗时用于防止有疗效的药剂的诱变性,而且纳米金刚石不会降低其疗效,以及可以预防正常细胞和在防止癌药作用下继发性肿瘤的诱导作用突变的发生。

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