CN101376276A - 镁基复合材料及其制备方法 - Google Patents

镁基复合材料及其制备方法 Download PDF

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CN101376276A
CN101376276A CNA2007100767583A CN200710076758A CN101376276A CN 101376276 A CN101376276 A CN 101376276A CN A2007100767583 A CNA2007100767583 A CN A2007100767583A CN 200710076758 A CN200710076758 A CN 200710076758A CN 101376276 A CN101376276 A CN 101376276A
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magnesium
composite material
nanoscale
substrate
base composite
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CN101376276B (zh
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陈锦修
陈正士
许光良
王杰
李文珍
姜开利
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Tsinghua University
Hongfujin Precision Industry Shenzhen Co Ltd
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Hongfujin Precision Industry Shenzhen Co Ltd
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Abstract

一种镁基复合材料由镁基金属与分布于该镁基金属中的纳米级增强体组成，所述镁基复合材料为多层结构，该多层结构由至少两层镁基金属层与至少一层镁基复合层交替排布，并且镁基复合层位于镁基金属层之间。一种镁基复合材料的制备方法，包括以下步骤：提供第一镁基板、第二镁基板和多个纳米级增强体；将所述多个纳米级增强体均匀固定于该第一镁基板表面；将第二镁基板覆盖于该纳米级增强体上，以形成一预制体；以及将预制体热压，形成镁基复合材料。采用本发明方法制备的镁基复合材料具有更高的强度和韧性，并且工艺简单、易操作，可广泛地应用于镁基复合材料方面。

Description

镁基复合材料及其制备方法
技术领域
本发明涉及一种复合材料及其制备方法，尤其涉及一种镁基复合材料及其制备方法。
背景技术
镁合金是现代结构金属材料中最轻的一种，纯镁的密度约为1.74克每立方厘米，为铝密度的2/3，钢密度的1/4。镁合金的优点是密度小，比强度、比钢度高，减震性好，同时还具有优良的铸造性能、切削加工性能、导热性能和电磁屏蔽性能，被广泛应用于汽车制造业、航空、航天、光学仪器制造和国防等领域。
根据成形工艺及合金元素的不同，镁合金材料主要分为铸造镁合金和变形镁合金两大类。变形镁合金通过在合金中加入有利于提高其形变特性的元素，挤压、轧制、锻造的方法固态成形，通过变形生产尺寸多样的板、棒、管、型材及锻件产品。由于变形加工消除了铸造组织缺陷及细化了晶粒，故与铸造镁合金相比，变形镁合金具有更高的强度、更好的延展性和更好的力学性能，同时生产成本更低。
但是，现有技术中制备的镁合金的韧性及强度均不能达到工业上的要求。为了解决这一问题，一般采用向镁合金中加入纳米级增强体的方式提高材料的强度和韧性(Goh C.S.，Wei J.，Lee L.C.，Gupta M.，Nanotechnology，vol17，p7(2006))。然而，现有技术中制备镁基复合材料一般采用铸造方法，如粉末冶金、熔体渗透、搅拌铸造，等。以上述这些方法形成的镁基复合材料一般为铸锭形式，并且纳米级增强体在其中均匀分布。在后续加工中需要通过挤压、轧制、锻造等方法制成所需型材。并且，在镁合金熔融状态中分散纳米级增强体容易引起纳米级增强体的团聚，造成分散不均匀；使用粉末冶金方法虽然可以使这一问题相对改善，但是粉末冶金法在生产过程中存在金属粉末燃烧、爆炸等危险。另外，这些方法制备工艺均相对复杂、设备成本高、不易大规模工业化生产。
有鉴于此，提供一种纳米级增强体在镁基金属中均匀分布的镁基复合材料及一种简单易行、适合工业化生产的镁基复合材料的制备方法实为必要。
发明内容
以下将以实施例说明一种纳米级增强体在镁基中均匀分布的镁基复合材料及一种工序简单、适合工业化生产的镁基复合材料的制备方法。
一种镁基复合材料由镁基金属与分布于该镁基金属中的纳米级增强体组成，所述镁基复合材料为多层结构，该多层结构由至少两层镁基金属层与至少一层镁基复合层交替排布，并且镁基复合层位于镁基金属层之间。一种镁基复合材料的制备方法，包括以下步骤:提供第一镁基板、第二镁基板和多个纳米级增强体；将所述多个纳米级增强体均匀固定于该第一镁基板表面；将第二镁基板覆盖于该纳米级增强体上，以形成一预制体；以及将预制体热压，形成镁基复合材料。
与现有技术相比较，所述的镁基复合材料采用将纳米级增强体直接均匀固定于镁基体的表面，通过热压的方式将纳米级增强体与镁基体形成镁基复合层并设置于镁基金属层之间，其中纳米级增强体在镁基中呈均匀的层状分布，进而提高该复合材料的强度和韧性；而且，利用多层镁基板与均匀分散有纳米级增强体的镁基复合层进行层叠，可以生产出不同厚度，包含多层镁基复合层的板带材，镁基复合层层数越多，在镁基复合材料中增强增韧的效果越明显；另外，此过程工艺简单、易操作、可以实现生产过程连续化和批量生产，适合工业化生产的要求。
附图说明
图1是本技术方案镁基复合材料的制备方法的流程示意图。
图2是本技术方案第一实施例镁基复合材料预制体示意图。
图3是本技术方案第一实施例对镁基复合材料预制体进行热压过程的示意图。
图4是本技术方案第一实施例所制备的镁基复合材料示意图。
图5是本技术方案第二实施例所制备的镁基复合材料示意图。
具体实施方式
下面将结合附图及具体实施例，对本技术方案提供的一种镁基复合材料及其制备方法作进一步的详细说明。
镁基复合材料的制备方法如图1所示，其第一实施例具体包括以下步骤:
(一)提供第一镁基板、第二镁基板和多个纳米级增强体。
如图2所示，本实施方式所提供之第一镁基板和第二镁基板可以是纯镁板或镁合金板。当所提供之镁基板为镁合金板时，该镁合金板的组成元素除镁外，还含有锌、锰、铝、锆、钍、锂、银、钙等合金元素的一种或多种，其中镁元素占镁合金板总质量百分比80％以上，其它元素占镁合金板总质量百分比20％以下。并且，该第一镁基板与第二镁基板可以具有相同的元素组成，也可以具有不同的元素组成。镁基板厚度为0.1毫米(mm)至1mm，优选为0.3mm。将第一镁基板和第二镁基板在金属板材裁剪机上裁剪出一相同的尺寸。
该纳米级增强体可以是碳纳米管(CNTs)、碳化硅(SiC)纳米颗粒、氧化铝(Al2O3)纳米颗粒及碳化钛(TiC)纳米颗粒等以及它们的混合体。本实施例中采用化学气相沉积法制备的碳纳米管粉末作为纳米级增强体。纳米级增强体直径在1纳米(nm)至100nm之间，优选为10nm至50nm。纳米级增强体质量为镁基复合材料总质量的0.5％至2％，优选为1％。
(二)将多个纳米级增强体均匀固定于第一镁基板表面。
请参阅图2，将纳米级增强体130均匀固定于第一镁基板110表面。固定纳米级增强体130的方法可以采用在第一镁基板110表面涂覆粘结剂层120的方式，将纳米级增强体130铺设在附有粘结剂层120的第一镁基板110上。如果采用碳纳米管作为纳米级增强体130，也可以将碳纳米管直接生长于第一镁基板110表面。本实施例中采用将第一镁基板110一表面均匀涂覆粘结剂层120的方式，将纳米级增强体130均匀铺设于附有粘结剂层120的镁基板110表面。铺设方式为将纳米级增强体130均匀的洒在粘结剂层120上。该粘结剂层120的材料具有在低温下具有粘性，在高温下易挥发的性质，本实施例中粘结剂层120材料优选为亚敏胶。
(三)将第二镁基板覆盖于上述纳米级增强体上，以形成一预制体。
如图2所示，将通过粘结剂层120固定于第一镁基板110表面的纳米级增强体130上覆盖一第二镁基板140，以形成一预制体100。该预制体100由第一镁基板110与第二镁基板140及纳米级增强体130组成，并且该纳米级增强体130通过第一镁基板110表面上的粘结剂层120固定于第一镁基板110与第二镁基板140之间。
(四)对预制体进行热压。
本实施例为在一热压机200中对预制体100进行热压。如图3所示，热压机200包括一上压板210，一下压板220，一模腔230。此模腔230可以抽成真空或通入惰性气体。将预制体100装入热压机200的模腔230内，置于上压板210与下压板220之间，使镁基板110与上压板210贴合，镁基板140与下压板220贴合。将热压机200的模腔230内抽成真空或通入惰性气体。在高温下，热压机200上下压板对预制体100施加一压力，以进行热压。保持该温度及压力一段时间后，将压力降至常压。将经过热压后的产物放置于空气中冷却至室温。具体热压条件为:温度范围300℃至400℃，压强范围50至100MPa，保温保压时间5至15小时。通过此热压过程，镁基金属渗入纳米级增强体间隙中，与纳米级增强体复合，形成一复合层，通过此镁基复合层将该复合层两侧的镁合金板结合为一个整体。
(五)对热压后的产物进行退火处理，得到镁基复合材料。
该退火处理是在高真空加热炉中进行的。退火温度为180℃至320℃，退火时间为2至3小时。将热压后的产物在高真空加热炉中进行退后处理后，即得到镁基复合材料300。通过将热压后的产物进行退货处理，可以清除热压时在镁基板内产生的内应力。
本实施例所得到的镁基复合材料300如图4所示。镁基体渗入纳米级增强体130间隙中，与纳米级增强体130复合，形成一镁基复合层330，在镁基复合材料300中通过该镁基复合层330将第一镁基板110与第二镁基板120结合为一整体。可以发现，此镁基复合材料300包含三层结构，第一镁基金属层310、第二镁基金属层320、镁基复合层330。镁基复合层330位于第一镁基金属层310与第二镁基金属层320之间。第一镁基金属310与第二镁基金属层320厚度为0.2至0.4mm，镁基复合层330厚度为1nm至100nm。
可以理解，纳米级增强体130是通过均匀铺洒于粘结剂层120上，或通过直接生长于第一镁基板110表面的方式铺设，并在该纳米级增强体130上覆盖第二镁基板140后直接热压，此种方法比在熔融态镁基金属中加入碳纳米管更易于使碳纳米管在基体中分布均匀。另外，将纳米级增强体130分布于镁基复合层330中比将纳米级增强体130分布于整个镁基复合材料中更易于实施。
如图5所示，本技术方案第二实施例提供了一种具有五层结构的镁基复合材料400，其包含第一镁基金属层410、第二镁基金属层420、第三镁基金属层430，及第一镁基复合层440、第二镁基复合层450，镁基金属层与镁基复合层交替排列，每一镁基复合层位于两镁基金属层之间，并且，纳米级增强体在镁基复合层中均匀分布。镁基金属层厚度为0.2至0.4mm，镁基复合层厚度为1nm至100nm。
此镁基复合材料制备方法与第一实施例基本相同。与第一实施例不同的是，所述预制体的形成过程进一步包括以下步骤:提供第一镁基板、第二镁基板、第三镁基板和多个纳米级增强体；将所述多个纳米级增强体均匀固定于该第一镁基板表面；将第二镁基板覆盖于该纳米级增强体上；在所述第二镁基板远离第一镁基板的表面均匀涂敷一粘结剂层，在所述粘结剂层上均匀铺设多个纳米级增强体；以及在所述纳米级增强体上覆盖第三镁基板形成一预制体。将通过上述步骤得到的预制体进行热压及热处理，得到一镁基复合材料400。
此镁基复合材料制备方法也可以为:在第一实施所述之镁基复合材料300一表面均匀涂敷一粘结剂层，在所述粘结剂层上均匀铺设大量纳米级增强体，在所述纳米级增强体上覆盖第三镁基板。将通过上述步骤得到的预制体进行热压及热处理，得到一镁基复合材料400。
可以理解，上述镁基复合材料的制备方法可以推广到多层镁基板与多层纳米级增强体层形成的预制体。将此预制体热压后所得到的纳米级增强体复合材料中包含多层镁基复合层及多层镁基金属层交替排布，并且，每层镁基复合层均位于两镁基金属层之间。
所述实施方式不局限于采用碳纳米管(CNTs)、碳化硅(SiC)纳米颗粒、氧化铝(Al2O3)纳米颗粒及碳化钛(TiC)纳米颗粒等以及它们的混合体作为镁基复合材料增强体，任何其它增强相，如纤维材料，只要能够起到与上述碳纳米管(CNTs)、碳化硅(SiC)纳米颗粒、氧化铝(Al2O3)纳米颗粒及碳化钛(TiC)纳米颗粒等以及它们的混合体相同的增强增韧效果，均在本发明限定范围内。本实施方式不局限于采用在镁基板表面涂覆粘结剂的方式使纳米级增强体固定于镁基板表面，任何其他方式，如直接在镁基板表面生长碳纳米管，或直接将纳米级增强体散布于镁基板表面，只要能起到上述将纳米级增强体置于镁基板表面之效果，均在本发明限定范围内。
所述的镁基复合材料的制备方法通过在热压前通过形成预制体的方式，使碳纳米管在镁基板表面均匀分布，从而保证热压后的纳米级增强体在镁基复合材料中分布均匀，并呈层状排列，大大提高镁基复合材料的强度和韧性。并且，利用多层镁基板与纳米级增强体进行层叠，可以生产出不同厚度，包含多层镁基复合层的板带材，镁基复合层的层数越多，在镁基复合材料中增强增韧的效果越明显。另外，利用固态热压的方法直接将镁基板与纳米级增强体复合，工艺简单、易操作、适合工业化生产的应用。此种复合材料将形变镁合金强度高、延展性及力学性能好的特点与纳米级增强体的增强增韧作用相结合，得到具有较好综合机械性能的镁基复合材料。
可以理解，对于本领域的普通技术人员来说，可以根据本技术方案和技术构思做出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。

Claims (15)

1.一种镁基复合材料，包括镁基金属与分布于该镁基金属中的纳米级增强体，其特征在于，所述镁基复合材料为多层结构，该多层结构包括至少两层镁基金属层与至少一层镁基复合层交替排布，该镁基复合层位于镁基金属层之间。
2.如权利要求1所述的镁基复合材料，其特征在于，所述纳米级增强体在镁基复合层中均匀分布。
3.如权利要求1所述的镁基复合材料，其特征在于，所述纳米级增强体为碳纳米管(CNTs)、碳化硅(SiC)纳米颗粒、氧化铝(Al2O3)纳米颗粒及碳化钛(TiC)纳米颗粒等以及它们的混合体。
4.如权利要求3所述的镁基复合材料，其特征在于，所述纳米级增强体直径为1至100纳米，所述纳米级增强体质量为镁基复合材料总质量的0.5％至2％。
5.如权利要求1所述的镁基复合材料，其特征在于，所述镁基金属为纯镁或镁合金。
6.如权利要求5所述的镁基复合材料，其特征在于，所述镁合金的组成元素除镁外，还含有锌、锰、铝、锆、钍、锂、银、钙等合金元素的一种或多种。
7.如权利要求6所述的镁基复合材料，其特征在于，所述镁合金中镁元素占金属总质量百分比80％以上，其他元素占金属总质量百分比20％以下。
8.一种镁基复合材料的制备方法，其包括以下步骤:
提供第一镁基板、第二镁基板和多个纳米级增强体；
将所述多个纳米级增强体均匀固定于该第一镁基板表面；
将第二镁基板覆盖于该纳米级增强体上，形成一预制体；以及
将预制体热压，形成镁基复合材料。
9.如权利要求8所述的镁基复合材料的制备方法，其特征在于，所述的镁基板在形成预制体之前进一步包括一裁剪过程。
10.如权利要求8所述的镁基复合材料的制备方法，其特征在于，所述纳米级增强体均匀固定于镁基板上为在镁基板表面涂覆粘结剂，并将纳米级增强体通过粘结剂层固定。
11.如权利要求10所述的镁基复合材料的制备方法，其特征在于，所述的粘结剂为亚敏胶。
12.如权利要求8所述的镁基复合材料的制备方法，其特征在于，所述的热压过程为在惰性气体保护或真空条件下在热压机中进行，其包括如下步骤:
将预制体置于热压机中；
对预制体上下表面施加一压力，同时升高热压机内温度；
保持该温度和压力一段时间；以及
去除压力，并于室温中冷却。
13.如权利要求12所述的镁基复合材料的制备方法，其特征在于，所述的温度在300℃至400℃范围内，所述的压强在50至100兆帕范围内，所述热压时间为5至15小时范围内。
14.如权利要求8所述的镁基复合材料的制备方法，其特征在于，进一步包括一对镁基复合材料的退火处理过程。
15.如权利要求8所述的镁基复合材料的制备方法，其特征在于，所述预制体的形成进一步包括以下步骤:
提供第一镁基板、第二镁基板、第三镁基板和多个纳米级增强体；
将所述多个纳米级增强体均匀固定于该第一镁基板表面；
将第二镁基板覆盖于该纳米级增强体上；
在所述第二镁基板远离第一镁基板的表面均匀固定多个纳米级增强体；以及
在所述纳米级增强体上覆盖第三镁基板形成一预制体。
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