CN116751060A - 一种高强高韧b4c复合防弹陶瓷材料及制备方法 - Google Patents
一种高强高韧b4c复合防弹陶瓷材料及制备方法 Download PDFInfo
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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Abstract
本申请涉及一种高强高韧B4C复合防弹陶瓷材料及制备方法。包括首先选取B4C、TiC、和SiCw作为原料，以B4C为主相，TiC与B4C经化学反应生成的TiB2与C为第二相，并添加SiCw。然后按照一定体积比例混合粉体，将混合粉体依次经湿法球磨，旋转蒸发仪干燥。最后在放电等离子体烧结炉中对粉体进行烧结，通过调控原料配比以及烧结工艺，制备获得了具有高致密、高强度、高硬度、高韧性等优点的B4C‑TiB2‑SiCw防弹复合材料。采用该方法制备的B4C‑TiB2‑SiCw防弹复合材料各相分布均匀，反应生成的纳米颗粒和层状C具有更好的钉扎与裂纹偏转作用。
Description
技术领域
本申请属于防弹装甲制造技术领域，具体而言，涉及一种高强高韧B4C复合防弹陶瓷材料及制备方法。
背景技术
近年来，陶瓷防弹材料在装甲防护领域占的一席之地，如Al2O3、SiC、B4C等。陶瓷材料较传统金属材料具有低密度、高硬度、高强度、高弹性模量等优异性能，且在生产方面绿色、节能，因此在防弹领域尤为火热。与Al2O3、SiC防弹陶瓷相比，碳化硼陶瓷具有硬度更高、密度更小、抗冲击力更强等优点，因而在高温结构材料、轻质人员和车辆防弹装甲材料等领域应用前景更为广阔。然而B4C共价键含量高导致烧结困难且韧性较差从而限制其广泛应用。
目前有两种方法可以提高 B4C 陶瓷的机械性能，一是优化陶瓷加工和烧结工艺以细化微观结构。另一种是通过第二相增强B4C基体，例如氧化物、碳化物、硼化物、氮化物及其组合。第二相强化可以有效提高B4C基陶瓷的强度，但对断裂韧性的影响有限。TiB2不仅可以增强B4C基陶瓷的导电性，使其满足电火花加工的要求，且纳米级TiB2颗粒还可起到钉扎作用，增加裂纹偏转，提高强韧性。纳米晶须增强陶瓷主要基于晶须桥接、拔出、裂纹偏转和支化等。其中，碳化硅晶须 (SiCw)具有高强度 (20-58 GPa)、高弹性模量(>480 GPa) 和优异的高温抗氧化性，已被广泛用作结构复合材料的增强单元。
专利CN102219519A公开了一种碳化硅防弹陶瓷材料及其制备方法，该制备方法是将碳粉和碳化硅粉按比例加入到混料机中，加适量结合剂混料，筛分后加入到模具中在油压机中成型，经过干燥固化后放入烧结炉，按比例加入金属硅在惰性气氛下进行烧结。该专利的不足：制备周期长、烧结温度高，所制备的碳化硅防弹陶瓷抗弯强度低、断裂韧性低、硬度低。
专利CN104944997A公开了一种轻质量级的氧化铝防弹陶瓷材料的制备方法，其主要含有以下原料：95-99wt.%的α-Al2O3，0.5-1.5wt.%的高岭土，0.5-1.0wt.%的烧滑石，3-8wt.%的BC晶须或 BC 晶粒。采用注凝成型，在1650~1700℃保温3-5 h烧结获得。该专利的不足：陶瓷材料密度高，制备周期长，抗弯强度低，硬度低。
因此，如何提供一种制备方法既使得B4C陶瓷的强度韧性增加，又能使其具有优异导电性以便有更好的电火花加工性能，且能降低烧结温度、缩短制备周期是本领域技术人员亟需解决的问题。
发明内容
基于上述技术问题，本申请旨在提供一种高强高韧B4C复合防弹陶瓷材料及其制备方法。其中，采用纳米TiB2颗粒和纳米层状C、SiCw增强增韧B4C防弹复合陶瓷，该复合材料导电性能好。利用先进的SPS烧结技术能有效缩短烧结时间，便于后续电加工，并且产物物相纯度高，组元分布均匀，在确保B4C陶瓷低密度与高硬度的同时，提高B4C复合材料的抗弯强度与断裂韧性。
有鉴于此，本申请提出了一种高强高韧B4C复合防弹陶瓷材料及制备方法，包含以下体积分数的原料：52-67vol.%的B4C，0-15vol.%的SiCw，20vol.%的TiB2和13vol.%的C。
根据本申请的第二方面内容，提出了制备上述实施例中B4C复合防弹陶瓷材料的方法，包括以下步骤：
（1）将B4C粉、TiC粉和SiCw粉体混合，球磨后得到悬浊液；其中B4C粉和TiC粉的摩尔比为1:2，SiCw与B4C粉的含量为0-15vol.%和52-67vol.%；
（2）将悬浊液40-55℃，干燥0.5-1h后研磨，得到待烧粉体；
（3）将所述待烧粉体置于石墨模具内，进行放电等离子体烧结。烧结条件：真空，1700-2000 ℃，30-80 MPa，，保温1-20min；
（4）随炉冷却，将陶瓷样品与模具取出分离即可。
本申请涉及反应方程式 B4C+ 2TiC =2TiB2+3C。
优选的步骤（3）中放电等离子体烧结温度1900 ℃，保温时间10min。
根据本申请的一个实施例，B4C粉纯度99.9%，平均粒径0.5 μm；TiC粉纯度99.5%，平均粒径2.0μm；SiCw粉纯度99.9%，粒径d＞100 nm，晶须的长度L为10-20 μm。
优选的B4C粒度选用0.5 μm级，B4C含量50.5%、TiB2含量20%、SiCw含量10%、C含量13%。
根据本申请的一个实施例，步骤（1）中球磨过程为：步骤（1）中球磨过程为：将混合粉料放进聚四氟乙烯罐中，加入无水乙醇，用氧化锆球球磨，随后超声分散成悬浊液；球料质量比为1：1。
根据本申请的一个实施例，球磨转速300r/min，时间4-12h，超声分散时间0.5-2h。
优选的步骤（1）中球磨混料时间为6 h，球磨机转速为300 r/min。
本申请球磨结束后将浆料与ZrO2球磨球分离，随后采用旋转蒸发仪对浆料进行干燥，干燥后研磨备用。
根据本申请的一个实施例，步骤（3）中放电等离子体烧结工艺参数如下：烧结气氛为真空；升温速率：室温-1000 ℃为100 ℃/min；1000 ℃-1500 ℃，为80 ℃/min；1500 ℃-2000 ℃为50 ℃/min。
通过以上技术方案，本申请提出了一种包含TiB2与SiCw的B4C防弹片，具有如下技术效果：
（1）本申请通过反应放电等离子体烧结所获得的B4C防弹陶瓷相对密度达到100%，所制备的B4C基防弹复合材料具有密度低、硬度高、强度高、韧性强的特点。采用纳米SiC晶须和纳米TiB2颗粒为主要增韧相，尺寸极小的层状纳米C分布于晶界处形成弱界面，可使得裂纹沿界面偏转或晶粒拔出。TiB2与C由B4C和TiC反应生成。高强度的SiC晶须与B4C基体有良好的润湿性，反应生成TiB2与C晶粒更加细小，分布更加均匀，与B4C晶界结合更加紧密，能够有效提升B4C韧性。本申请制备的B4C-TiB2-SiCw复合陶瓷，体积密度2.8-2.9g/cm3,弯曲强度500-700 MPa，维氏硬度30-35GPa，断裂韧性4.3-6.0 MPa·m1/2。
（2）本申请提供的防弹片为利用纳米SiC晶须与纳米TiB2颗粒协同增韧B4C防弹陶瓷的制备方法，重复性好，步骤简单，易于实现。
附图说明
图1是本申请实施例2与其同配比不同温度下所制备的B4C-TiB2-SiCw复合材料XRD；
图2是实施例2中制备的B4C-TiB2-SiCw烧结体断口和裂纹偏转SEM。
图3是对比例1中制备的B4C-TiB2-SiCw烧结体表面SEM。
具体实施方式
为了能够更清楚地理解本申请的上述目的、特征和优点，下面结合附图和具体实施方式对本申请进行进一步的详细描述。需要说明的是，在不冲突的情况下，本申请的实施例及实施例中的特征可以相互组合。
在下面的描述中阐述了很多具体细节以便于充分理解本申请，但是，本申请还可以采用其他不同于在此描述的其他方式来实施，因此，本申请的保护范围并不受下面公开的具体实施例的限制。
本申请实施例所用的B4C粉购于郑州嵩山硼业科技有限公司，其平均粒径0.5 μm，纯度99.9%。所用的TiC粉购于阿法埃莎(中国)化学有限公司，平均粒径2 μm，纯度99.5%。所用的SiCw粉购于北京德科岛金有限公司，平均粒径为d＞100 nm，晶须的长度L=10~20 μm，纯度99.9%。
实施例1
B4C-TiB2-SiCw防弹陶瓷材料由如下物相组成：62vol.% B4C、20vol.%TiB2、5vol.%SiCw、13vol.%C。
B4C-TiB2-SiCw防弹陶瓷材料的制备方法如下：
1）原料混合粉体配制：选择B4C粉、TiC粉和SiCw粉为原料，将B4C粉和TiC粉按摩尔比为1:2称量配料、再按配比为5vol.%的SiCw与62vol.%的B4C粉混合。
2）球磨：将混合粉体置于聚四氟乙烯罐，并添加等质量的ZrO2球磨球，无水乙醇作为球磨介质，采用行星球磨机进行球磨，球磨时间6 h，转速300 r/min，超声分散2h。
3）干燥：将分散后的混合浆料与ZrO2球磨球分离，紧接着采用旋转蒸发仪对浆料进行干燥，干燥后的混合粉体经研磨后备用。
4）烧结：称取上述干燥混合粉体，置于石墨模具，随后经放电等离子体烧结，烧结温度1900oC，压强60 MPa，保温保压时间10 min。烧结完成后随炉冷却，取出模具后将烧结体与模具分离，即得到B4C-TiB2-SiCw防弹陶瓷材料。
本实施例所制得的B4C-TiB2-SiCw防弹陶瓷材料的维氏硬度为26.61GPa、抗弯强度为652.3 MPa、断裂韧性为4.36 MPa·m1/2。
实施例2
B4C-TiB2-SiCw防弹陶瓷材料由如下物相组成：57vol.% B4C、20vol.%TiB2、10vol.%SiCw、13vol.%C。
B4C-TiB2-SiCw防弹陶瓷材料的制备方法如下：
1）原料混合粉体配制：选择B4C粉、TiC粉和SiCw粉为原料，将B4C粉和TiC粉按摩尔比为1:2称量配料、再按配比为10vol.%的SiCw与57vol.%的B4C粉混合。
2）球磨：将混合粉体置于聚四氟乙烯罐，并添加等质量的ZrO2球磨球，无水乙醇作为球磨介质，采用行星球磨机进行球磨，球磨时间6 h，转速300 r/min，超声分散2h。
3）干燥：将分散后的混合浆料与ZrO2球磨球分离，紧接着采用旋转蒸发仪对浆料进行干燥，干燥后的混合粉体经研磨后备用。
4）烧结：称取上述干燥混合粉体，置于石墨模具，随后经放电等离子体烧结，烧结温度1900oC，压强60 MPa，保温保压时间10 min。烧结完成后随炉冷却，取出模具后将烧结体与模具分离，即得到B4C-TiB2-SiCw防弹陶瓷材料。
本实施例所制得的B4C-TiB2-SiCw防弹陶瓷材料的维氏硬度为30.35GPa、弯曲强度为639.4 MPa、断裂韧性为5.52 MPa·m1/2。
将实施例2中制备的B4C-TiB2-SiCw防弹陶瓷材料进行XRD测试（如图1），结果表明，该方法所制备的复合材料均为纯相，组元分别为B4C、TiB2、SiCw、C，反应物无残留。
将本实施例制备的B4C-TiB2-SiCw防弹陶瓷材料断口进行SEM扫描（如图2）。结果表明，在陶瓷断裂时，纳米TiB2颗粒具有一定拔出和钉扎作用，SiC晶须在基体中有拔出与桥接。反应生成的层状纳米C在基体中分散均匀，对界面的弱化使得裂纹偏转，且产生较多拔出效果。而SiCw在高温下有所降解，或生长为颗粒，断裂时SiC晶粒内产生部分阶梯位错，以上微观结构能够有效提升B4C韧性。
实施例3
B4C-TiB2-SiCw防弹陶瓷材料由如下物相组成：67vol.% B4C、20vol.%TiB2、0vol.%SiCw、13vol.%C。
B4C-TiB2-SiCw防弹陶瓷材料的制备方法如下：
1）原料混合粉体配制：选择B4C粉和TiC粉为原料，将B4C粉和TiC粉按摩尔比为1:2称量配料。
2）球磨：将混合粉体置于聚四氟乙烯罐，并添加等质量的ZrO2球磨球，无水乙醇作为球磨介质，采用行星球磨机进行球磨，球磨时间6 h，转速300 r/min，超声分散2h。
3）干燥：将分散后的混合浆料与ZrO2球磨球分离，紧接着采用旋转蒸发仪对浆料进行干燥，干燥后的混合粉体经研磨后备用。
4）烧结：称取上述干燥混合粉体，置于石墨模具，随后经放电等离子体烧结，烧结温度1900oC，压强60 MPa，保温保压时间10 min。烧结完成后随炉冷却，取出模具后将烧结体与模具分离，即得到B4C-TiB2-SiCw防弹陶瓷材料。
本实施例所制得的B4C-TiB2-SiCw防弹陶瓷材料的维氏硬度为34GPa、抗弯强度为915.4 MPa、断裂韧性为5.18 MPa·m1/2。
对比例1
B4C-TiB2-SiCw防弹陶瓷材料由如下物相组成：47vol.% B4C、20vol.%TiB2、20vol.%SiCw、13vol.%C。
B4C-TiB2-SiCw防弹陶瓷材料的制备方法如下：
1）原料混合粉体配制：选择B4C粉、TiC粉和SiCw粉为原料，将B4C粉和TiC粉按摩尔比为1:2称量配料、再按配比为20vol.%的SiCw与47vol.%的B4C粉混合。
2）球磨：将混合粉体置于聚四氟乙烯罐，并添加等质量的ZrO2球磨球，无水乙醇作为球磨介质，采用行星球磨机进行球磨，球磨时间6 h，转速300 r/min，超声分散2 h。
3）干燥：将分散后的混合浆料与ZrO2球磨球分离，紧接着采用旋转蒸发仪对浆料进行干燥，干燥后的混合粉体经研磨后备用。
4）烧结：称取上述干燥混合粉体，置于石墨模具，随后经放电等离子体烧结，烧结温度1900oC，压强60 MPa，保温保压时间10 min。烧结完成后随炉冷却，取出模具后将烧结体与模具分离，即得到B4C-TiB2-SiCw防弹陶瓷材料。
本对比例所制得的B4C-TiB2-SiCw防弹陶瓷材料的维氏硬度为29GPa、弯曲强度为608.3 MPa、断裂韧性为4.81 MPa·m1/2；在本对比例中将SiCw含量增加至20%，其得到的防弹陶瓷材料烧结体表面SEM如图3所示，过量的SiCw会使得晶须团聚，生长为更大的SiC颗粒，这将导致B4C-TiB2-SiCw防弹陶瓷材料硬度和韧性降低。其中与实施例2对比可知，适量的SiCw能够提升材料力学性能，过量的SiCw由于团聚加重，导致性能下降。
对比例2
B4C-TiB2-SiCw防弹陶瓷材料由如下物相组成：80vol.% B4C、0vol.%TiB2、20vol.%SiCw、0vol.%C。
B4C-TiB2-SiCw防弹陶瓷材料的制备方法如下：
1）原料混合粉体配制：选择B4C粉和SiCw粉为原料，再按配比为20vol.%的SiCw与80vol.%的B4C粉混合。
2）球磨：将混合粉体置于聚四氟乙烯罐，并添加等质量的ZrO2球磨球，无水乙醇作为球磨介质，采用行星球磨机进行球磨，球磨时间6 h，转速300 r/min，超声分散2h。
3）干燥：将分散后的混合浆料与ZrO2球磨球分离，紧接着采用旋转蒸发仪对浆料进行干燥，干燥后的混合粉体经研磨后备用。
4）烧结：称取上述干燥混合粉体，置于石墨模具，随后经放电等离子体烧结，烧结温度1900oC，压强60 MPa，保温保压时间10 min。烧结完成后随炉冷却，取出模具后将烧结体与模具分离，即得到B4C-SiCw防弹陶瓷材料。
本对比例所制得的B4C-SiCw防弹陶瓷材料的维氏硬度为20 GPa、弯曲强度为498.3MPa、断裂韧性为5.09 MPa·m1/2。
在本对比例中仅有20vol.%的SiCw，TiB2和C含量为0vol.%，钉扎和拔出增强增韧效果差，导致对比例样品的强度和硬度急剧下降。结果表明，过量SiCw造成的团聚，TiB2和C的缺少是材料力学性能明显降低的主要原因，与实施例2相比，TiB2和层状C 由于钉扎作用能有效提升材料的力学性能，TiB2和层状C的缺少则会大大降低材料各项性能。
以上仅为本申请的优选实施例而已，并不用于限制本申请。应当理解的是，对于本领域的技术人员来说，无需创造性劳动就可以根据本申请的构思作出诸多修改和变化，根据本申请构思加以改进和变换，所作的任何修改、等同替换、改进等，所有的这些改进和变换都应属于本申请所附权利的要求的保护范围。因此，凡依本申请的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在由权利要求书所确定的保护范围内。
Claims (7)
1.一种高强高韧B4C复合防弹陶瓷材料，其特征在于，包含以下体积分数的原料：52-67%的B4C，0-15%的SiCw，20%的TiB2和13%的C。
2.一种高强高韧B4C复合防弹陶瓷材料的制备方法，其特征在于，用于制备权利要求1中所述的防弹陶瓷材料，包括以下步骤：
（1）将B4C粉、TiC粉和SiCw粉体混合，球磨后得到悬浊液；其中B4C粉和TiC粉的摩尔比为1:2，SiCw与B4C粉的体积分数为0-15%和52-67%；
（2）将所述悬浊液40-55℃，旋蒸干燥0.5-1h后研磨，得到待烧粉体；
（3）将所述待烧粉体置于石墨模具内，进行放电等离子体烧结。
3.烧结条件：真空，1700-2000 ℃，30-80 MPa，，保温1-20 min；
（4）随炉冷却，将陶瓷样品与模具取出分离即可。
4.根据权利要求2所述的方法，其特征在于，所述B4C粉纯度99.9%，粒径为d50= 0.5 μm；所述TiC粉纯度99.5%，粒径为d50= 2.0 μm；所述SiCw纯度99.9%，粒径为d＞100 nm，晶须的长度L为10-20 μm。
5.根据权利要求2所述的方法，其特征在于，步骤（1）中所述球磨过程为：将混合粉料放进聚四氟乙烯罐中，加入无水乙醇，用氧化锆球球磨混合成悬浊液；球料质量比为1：1。
6.根据权利要求2所述的方法，其特征在于，所述球磨转速为300r/min，时间为4-12h，超声分散0.5-2h。
7.根据权利要求2所述的方法，其特征在于，步骤（3）中放电等离子体烧结工艺参数如下：所述烧结气氛为真空；升温速率：室温-1000 ℃为100 ℃/min；1000 -1500 ℃，为80℃/min；1500 -2000 ℃为50 ℃/min。
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