CN102173822A - 低氧化硼复合材料 - Google Patents

低氧化硼复合材料 Download PDF

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CN102173822A
CN102173822A CN2011100426513A CN201110042651A CN102173822A CN 102173822 A CN102173822 A CN 102173822A CN 2011100426513 A CN2011100426513 A CN 2011100426513A CN 201110042651 A CN201110042651 A CN 201110042651A CN 102173822 A CN102173822 A CN 102173822A
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boron suboxide
boron
metal
fracture toughness
sintering
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CN102173822B (zh
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G·J·戴维斯
I·希格拉斯
M·赫尔曼
T·沙巴拉拉
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Element Six Production Pty Ltd
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Abstract

一种断裂韧性改善的低氧化硼复合材料，例如由分布在基料相如AlxByOz中的颗粒状或晶粒状的低氧化硼构成。

Description

低氧化硼复合材料
本申请是申请号为200680036958.X、申请日为2006年09月06日、发明名称为“低氧化硼复合材料”的中国专利申请的分案申请。
发明背景
本发明涉及一种低氧化硼复合材料及其制备方法。
金刚石首次实验室合成引发大量工作来设计和研发具有接近乃至改善金刚石性能的组合性能的材料。这些超硬材料最广为人之的是立方体氮化硼(cBN)。同样已知的是富硼化合物提供此类应用的优良备选物。它们产生一大类耐火材料，其具有与其短原子间键长和强烈共价特性有关的独特晶体结构和重要物理及化学性能。结构基于α-菱形硼结构的富硼相包括碳化硼和低氧化硼(名义上为B6O)，其将高硬度与低密度和化学惰性结合，使得它们可用作磨料和其它高磨损应用[1]。
低氧化硼(B6O)结构，空间群R3m，由位于菱形晶胞顶点的八个B12二十面体单元构成。该结构可以看作是B12二十面体的扭曲立方紧密堆积(ccp)。两个O原子位于沿[111]菱形方向的间隙中。
尽管难以合成具有高结晶度的纯材料，但是文献中已经广泛记载低氧化硼(B6O)的合成及其性能的说明。在环境压力或接近环境压力下形成的低氧化硼材料通常是缺氧的(B6Ox，x＜0.9)。它们同样具有低结晶度和非常小的晶粒尺寸。合成B6O期间施加的高压可以显著地增加结晶度、氧化学计量量和产物的晶体尺寸[1]。虽然低氧化硼以标称组成B6O的形式被记载，但是广泛接受的是其为非化学计量的。为简便起见，本说明书中使用标称化学式B6O。
US专利No.3,660,031中公开一种制备低氧化硼的方法。根据该公开内容，低氧化硼通过在1200℃-1500℃用元素硼还原氧化锌形成。据报告其具有化学式B7O，并且还特征在于在100g载荷下其具有38.20GPa的平均硬度值，和2.60g/cm3的密度。并未报告该材料的断裂韧性。
US专利No.3,816,586也公开一种制造低氧化硼的方法。根据该公开内容，低氧化硼通过在适合的温度和压力下热压元素硼和氧化硼的混合物形成。分析时，该低氧化硼产物据称具有给定的80.1wt％的硼和19.9wt％的氧，相当于化学计量的B6O。还报告其具有2.60g/cm3的密度和在100g载荷下30GPa的Knoop硬度(KNH100)。并未报告该材料的断裂韧性。
大量研究已经表明当低氧化硼材料具有极高硬度时，其断裂韧性极低，即该材料是脆性的。根据Itoh等的文献[2]，已经在高温(1400℃-1800℃)和高压(3-6GPa)下制备B6O密实物。这种B6O粉末据报告已经由元素硼和氧化硼加以合成。分析时，该B6O密实物据报告具有31-33GPa的平均硬度和极低断裂韧性。Itoh等[3，4]和Sasai等[5]还分别尝试使用其它硬质材料，例如cBN[3]、碳化硼[4]和金刚石[5]来改善B6O的机械性能，特别是断裂韧性。这些B6O复合材料的硬度是相当大的，但是断裂韧性据报告仍然较低，B6O-金刚石复合材料具有约1MPa.m0.5的断裂韧性，B6O-cBN复合材料具有约1.8MPa.m0.5的断裂韧性，和B6O-B4C复合材料具有约1MPa.m0.5的断裂韧性。
本发明的一个目的是提供一种生产B6O复合材料的方法，该B6O复合材料与先前报告的B6O复合材料相比，具有相当大的硬度以及更好的断裂韧性。
发明内容
根据本发明的一个方面，提供一种低氧化硼复合材料，其包括分布在基料相中的颗粒状(particulate)或晶粒状(granular)的低氧化硼，所述基料相包括MxByOz，其中
M为金属；
X为4-18；
Y为2-4；
Z为9-33。
该金属优选选自包括铝、锆、钛、镁和镓的组，该金属特别是铝。
该低氧化硼优选构成大于70wt％，特别是约85-约97wt％的复合材料。
该基料相优选构成低于约30wt％，特别是约3-约15wt％的复合材料。
本发明的复合材料优选具有大于约2.5MPa.m0.5的断裂韧性。
根据本发明的另一个方面，一种生产低氧化硼复合材料的方法包括以下步骤：提供低氧化硼颗粒源，优选粉末，优选通过化学气相沉积，用金属或金属化合物涂布低氧化硼颗粒，和在适合生产复合材料的温度和压力下烧结该金属涂布的低氧化硼颗粒。
该金属优选选自包括铝、锆、钛、镁和镓或其化合物的组，该金属特别是铝或其化合物。金属涂布的低氧化硼颗粒的烧结优选使用热压，优选在大于约1600℃，特别是在约1900℃下，以及优选在低于约300MPa，特别是在约50MPa下进行。
在涂布低氧化硼颗粒过程中可以使用活化剂。例如，在铝的情况下，在涂布低氧化硼颗粒的过程中，氯化铵可以用作活化剂。
具体实施方案的说明
本发明的低氧化硼复合材料通过在高温和低压下热压金属涂布的B6O粉末形成。
使用化学气相沉积(CVD)法在适度高温下用金属，在这种情况下，用铝涂布起始B6O粉末。例如，使用具有氧化铝球的turbular混合器将铝(Al)粉与氯化铵(NH4Cl)混合若干小时，通常为1.5小时。氯化铵在涂布过程中用作活化剂。因为大量铝可以在涂布过程中还原B6O，所以将非常小量的铝与氯化铵混合。混合之后，使用氧化铝球将碾磨的B6O粉末与该混合物(Al/NH4Cl)混合若干小时，通常为1.5小时。将新的混合物(B6O/Al/NH4Cl)倒入氧化铝舟皿，并在该混合物之上放置氧化铝细砾。氧化铝细砾起惰性填料的作用并截获炉中释放的一些气体，防止管式炉排气管阻塞。然后将氧化铝舟皿放置在管式炉中，并以低加热速率加热直至约1400℃。
这种CVD法提供以均匀分布形式涂布有Al-B-O化合物的颗粒。虽然为方便起见描述铝，但是应理解也可以通过使用其它金属化合物，例如锆、钛、镁和镓涂布B6O原材料来实施该方法。使用热压在高温(约1900℃)和低压(约50MPa)下烧结所得涂布的B6O粉末。首先，将涂布的粉末倒入氮化硼槽中，然后将其放置在石墨模内。烧结通常在氩气或其它惰性气氛下进行。
然后可以表征所得材料，通常使用X射线衍射、扫描电子显微术、光学显微术和使用阿基米德(Archimedes)原理的密度测量。发现以这种方式形成的低氧化硼复合材料具有优良的机械性能，和大于2.5MPa.m0.5，直至约5MPa.m0.5的断裂韧性。
不希望受理论束缚，据信本发明低氧化硼复合材料的断裂韧性改善是由于烧结过程中在低氧化硼颗粒晶粒间界处的金属的影响。
现已发现纯的烧结B6O的断裂韧性极低。公知的是硼化物基颗粒通常在其上具有薄B2O3涂层。当烧结这种颗粒时，十分薄弱的B2O3相保持在晶粒间界处。晶粒间界处存在这种薄弱相削弱了材料并使裂纹非常容易扩散贯穿该材料。用M-B-O基相涂布该颗粒导致薄弱的B2O3被强得多的MxByOz相置换。结果现在由于晶粒间断裂的裂纹增长困难的多。
这种材料断裂韧性增加的第二个原因据信是在于B6O相和MxByOz相具有不同的热膨胀系数和弹性常数。作为这种性能差异的结果，当材料在烧结之后冷却时，双金属应力在两种不同相之间建立。这种应力可能很高，其的存在可以引起扩散的裂纹偏折，由此使得所述扩散在能量方面代价更大，由此使材料断裂韧性增强。
现在将参考以下非限制性实施例描述本发明。
实施例1
使用具有氧化铝球的行星式球磨机碾磨B6O粉末原料大约4小时。使用氧化铝球，当B6O粉末用铝涂布时，这种氧化铝作为污染物被认为是可接受的。碾磨的B6O粉末中的氧化铝量小于1％，并且因此忽略不计。引入碾磨阶段促进存在于粉末中的附聚物分解。
使用具有氧化铝球的turbular混合器将铝粉(5微米)和氯化铵(NH4Cl)混合1.5小时，形成涂布材料，氯化铵在涂布过程中用作活化剂。因为大量铝可能在涂布过程中还原B6O，所以对于初始实验，仅使用20体积％的Al和80体积％的NH4Cl。
第一次混合之后，使用氧化铝球将碾磨的B6O粉末和该混合物(Al/NH4Cl)混合1.5小时，质量比为4∶0.3(B6O∶Al/NH4Cl)。将混合物(B6O/Al/NH4Cl)倒入氧化铝舟皿中，并将氧化铝细砾放置在混合物顶部起惰性填料的作用并截获窑炉中释放的一些气体，防止管式炉排气管阻塞。然后将氧化铝舟皿放置在管式炉中，并以10℃/分钟的速率加热直至约1400℃。随着在大约350℃形成AlCl3和释放气体，在该温度存在1小时的驻留点。该时段期间进行以下反应：
Al(s)+3NH4Cl(s)→AlCl3(s)+3NH3+3/2H2(g)
在1400℃保持第二个6小时的驻留时间，以便使涂布工艺完全，然后以10℃/分钟的速率进行冷却。涂布的B6O粉末含有氧化铝和一些痕量的硼化铝(AlB12)。然后将其放置在氮化硼槽(石墨模内)并使用氩气气氛下、1900℃和50MPa的热压烧结约20分钟。
测定以这种方式形成的低氧化硼复合材料在5kg载荷下具有29GPa的硬度，与现有技术相比毫不逊色。但是，最重要地，测定本发明的复合材料具有约3MPa.m0.5的断裂韧度值，据信其大于低氧化硼复合材料的任何先前报告的值。
实施例2
重复实施例1的条件，除了这次增加Al/NH4Cl混合物的质量。混合粉末的质量比为4∶0.5(B6O∶Al/NH4Cl)。在制备该试样中使用实施例1中使用的涂布和热压条件。抛光所得试样然后用Vickers压头测试硬度和断裂韧性，并且测定具有约25-28GPa的硬度(5kg载荷)和约3.5MPa.m0.5的断裂韧性。
实施例3
重复实施例1的条件，除了再次增加Al/NH4Cl混合物的质量。混合粉末的质量比为4∶0.75(B6O∶Al/NH4Cl)。在制备该试样中使用实施例1中使用的涂布和热压条件。抛光所得试样然后用Vickers压头测试硬度和断裂韧性，并且测定具有约24-27GPa的硬度(5kg载荷)和3.5MPa.m0.5的断裂韧性。
实施例4
重复实施例1的条件，并且再次增加Al/NH4Cl混合物的质量。混合粉末的质量比为4∶1(B6O∶Al/NH4Cl)。在制备该试样中使用实施例1中使用的涂布和热压条件。抛光所得试样然后用Vickers压头测试硬度和断裂韧性，并且测定具有约24.5GPa的硬度(5kg载荷)和约4.75MPa.m0.5的断裂韧性。
为了确定以上实施例中所得结果的可再现性，使用与实施例1中相同的(涂布和热压)条件涂布一批新的合成的B6O。以下表1列出所有结果，包括重复的试样。一些热压B6O复合材料(具有相同的Al含量)的性能存在微小的差别，但是归因于密度的差异，其同样在一定程度上与表面孔隙度或分解有关。
作为由在烧结之后形成硼酸铝所产生的增强结果，与表1中对比例的热压“纯”B6O材料相比，本发明的热压B6O复合材料具有更高的断裂韧性值。
表1
Figure BDA0000047420400000061
＊痕量Al4B2O9
参考文献
1.H.Hubert，L.Garvie，B.Devouard，P.Buseck，W.Petuskey，P.McMillan，Chemistry of materials，10，1530-1537页，1998年。
2.H.Itoh，I.Maekawa和H.Iwahara，Journal of Material ScienceSociety，Japan，47，No.10，1000-1005页，1998。
3.H.Itoh，R.Yamamoto和H.Iwahara，Journal of AmericanCeramic Society，83，501-506页，2000。
4.H.Itoh，I.Maekawa和H.Iwahara，Journal of MaterialScience，35，693-698页，2000。
5.R.Sasai，H.Fukatsu，T.Kojima和H.Itoh，Journal of MaterialScience，36，5339-5343页，2001。

Claims (7)

1.一种生产低氧化硼复合材料的方法，包括以下步骤：提供低氧化硼颗粒源，用金属或金属化合物涂布低氧化硼颗粒，和在适合生产复合材料的温度和压力下烧结该金属涂布的低氧化硼颗粒。
2.根据权利要求1的方法，其中低氧化硼颗粒以粉末形式提供。
3.根据权利要求1的方法，其中低氧化硼颗粒通过化学气相沉积涂布。
4.根据权利要求1的方法，其中金属选自包括铝、锆、钛、镁和镓，或其化合物的组。
5.根据权利要求1的方法，其中金属为铝，或其化合物。
6.根据权利要求1的方法，其中使用在大于约1600℃的温度和低于约300MPa的压力下的热压，进行该金属涂布的低氧化硼颗粒的烧结。
7.根据权利要求6的方法，其中在约1900℃的温度和约50MPa的压力下进行烧结。
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