CN114013151B - 一种梯度多层阻尼材料及其制备方法 - Google Patents

一种梯度多层阻尼材料及其制备方法 Download PDF

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CN114013151B
CN114013151B CN202111399419.5A CN202111399419A CN114013151B CN 114013151 B CN114013151 B CN 114013151B CN 202111399419 A CN202111399419 A CN 202111399419A CN 114013151 B CN114013151 B CN 114013151B
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李姜
郭少云
袁念眉
熊光超
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Chengdu Macko Polymer Materials Co ltd
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Abstract

本发明涉及高分子材料技术领域，具体而言，涉及一种梯度多层阻尼材料；包括多层不同玻璃化转变温度的阻尼层和多层不同弹性模量的约束层，多层所述阻尼层与多层所述约束层交替叠放，且按远离被覆基体的方向，多层所述约束层以弹性模量由小到大排列；所述约束层包括多孔聚氨酯层和铝薄片，所述多孔聚氨酯层外包覆有环氧树脂层，所述铝薄片贴覆于所述环氧树脂层的一侧。约束层按弹性模量由小到大排列，弹性模量较小的约束层更靠近基体，阻尼层与约束层剪切损耗由小变大，可将机械振动能量最大程度传递到各个阻尼层中，从而最大程度利用阻尼层的不同温域。同时阻尼层的阻尼温度越高，材料的强度越高，弹性模量较大的约束层与强度更高的阻尼层贴合可以起到更好的束缚作用。

Description

一种梯度多层阻尼材料及其制备方法
技术领域
本发明涉及技术领域，具体而言，涉及一种梯度多层阻尼材料及其制备方法。
背景技术
约束阻尼结构是用于吸收和消耗设备的内能，以降低设备的振动和造噪音。目前应用的级较多为多层约束阻尼材料，通过设置多层的阻尼层，从整体上提高阻尼结构的阻尼性能，扩大阻尼温域。
专利CN112092844A公开了一种轻质宽温域层状约束阻尼降噪型材及制备方法，其在铝型材的表面粘覆IIR/EP层状约束阻尼结构，该层状约束阻尼结构包括多次层的IIR,IIR作为阻尼层，EP作为约束层，多层阻尼层可拓宽阻尼材料的使用温域，以实现阻尼结构轻量化。
但在该方案中，单一成分的约束层对阻尼层的约束力较弱，约束阻尼结构的整体阻尼性较差。
发明内容
本发明的目的在于提供一种梯度多层阻尼材料及其制备方法，其具有多层阻尼层和多层约束层，多层约束层按梯度设置，提高约束层对阻尼层的约束力，并且该约束层具有多孔环氧树脂层，在受力时，约束层也可消耗内能，起到一定的阻尼作用，进而从整体上提高多层阻尼结构的阻尼性能。
本发明的通过以下技术方案实现：
一种梯度多层阻尼材料，包括多层不同玻璃化转变温度的阻尼层和多层不同弹性模量的约束层，多层所述阻尼层与多层所述约束层交替叠放，且按远离被覆基体的方向，多层所述约束层以弹性模量由小到大排列；
所述约束层包括多孔聚氨酯层和铝薄片，所述多孔聚氨酯层外包覆有环氧树脂层，所述铝薄片贴覆于所述环氧树脂层的一侧。
在本发明中，约束层按弹性模量大小，由小到大排列，弹性模量较小的约束层更靠近基体，阻尼层与约束层剪切损耗由小变大，可将机械振动能量最大程度传递到各个阻尼层中，从而最大程度利用阻尼层的不同温域。同时阻尼层的阻尼温度越高，材料的强度越高，弹性模量较大的约束层与强度更高的阻尼层贴合可以起到更好的束缚作用。
在本发明中，约束层中包含有多孔聚氨酯和铝薄片，该约束层中的铝薄片除了可以限制阻尼层的运动外，环氧树脂和聚氨酯还可以提供一定的阻尼作用，使得约束层不仅具有约束阻尼层的作用，还具有一定的阻尼效果。
进一步的，所述环氧树脂层按重量分数计包括以下组分，
环氧树脂70-100份，固化剂10-30份，增强填料5-20份，溶剂5-10份；
其中，所述增强填料为长度在0.1mm-0.5mm内的短切玻璃纤维、短切玄武岩纤维、碳纤维中的一种或多种。
在本发明中，在环氧树脂中加入增强填料，一方面可以通过调节增强填料的比例，来得到不同弹性模量的环氧树脂层，另一方面，加入的短纤维填充在环氧树脂中，提高环氧树脂的强度，并减轻环氧树脂层的重量，进而实现约束层的轻量化。
进一步的，所述环氧树脂层按重量分数计包括以下组分，
环氧树脂70-100份，固化剂10-30份，增强填料5-20份，溶剂5-10份，环糊精30-50份、偶联剂1-5份。
在环氧树脂层中还加入一定量的环糊精，环糊精中存在大量的羟基，羟基与环氧树脂的分子链形成氢键，在受力过程中，氢键不断的断裂重组，消耗内能，使得环氧树脂层也具有一定的阻尼作用，进而提高多层材料的阻尼性。
进一步的，多层所述阻尼层以玻璃化转变温度由低到高排列，且所述铝薄片位于两所述阻尼层之间，所述铝薄片与玻璃化转变温度较低的所述阻尼层粘贴连接。
阻尼层按玻璃化转变温度由低到高排列，约束层按弹性模量由小到大排列，两者相互配合，即小弹性模量配合低玻璃化转变温度，使得阻尼层的阻尼性更大化。即当被覆盖有多层阻尼材料的基体受到振动时，靠近基体一侧最先受力，受力更明显，将玻璃化转变温度低的阻尼层靠近基体，随着力的不断传播，高阻尼温度的阻尼层继续受力变形，产生更多的变形能。结构的阻尼性能主要是由阻尼层的剪切变形引起，阻尼层梯度排列的好处主要是可以使不同的阻尼层在不同的温度下都可以发生剪切变形，从而使阻尼温度扩宽。不同弹性模量的约束层与不同玻璃化转变温度的阻尼层梯度设置，相互配合，可以最大的发挥每层约束层的阻尼贡献。
进一步的，多孔聚氨酯层为聚氨酯硬质泡沫，其厚度为0.1mm-0.5mm，平均孔径为50-100um。
进一步的，所述阻尼层为丁基橡胶或丁基橡胶与氢化双环戊二烯树脂的共混物。
进一步的，相邻所述阻尼层的玻璃化转变温度的差值大于等于5℃。
进一步的，所述约束层的弹性模量为1500MPa-2500MPa，其中相邻两所述约束层的弹性模量差大于等于200MPa。
进一步的，所述阻尼层的厚度为0.2mm-0.5mm，所述约束层的厚度为0.5mm-1.5mm。
本发明的另一目的在于，提供一种梯度多层阻尼材料的制备方法，包括以下步骤
S1将100phr丁基橡胶在双辊开炼机上塑炼10min，加入100phrCaCO3，然后氢化双环戊二烯树脂，得到共混，随后加入硫磺、氧化锌、硬脂酸、促进剂在双辊开炼机上混炼10min，混炼均匀；
S2在平板硫化机上进行模压硫化，硫化条件为165℃×T90，20MPa，其中T90为正硫化时间，由硫化曲线测试获得；随后将硫化后的共混胶置于热压成型机上于130℃、10MPa热压5min，然后在相同压力下冷压至室温成型，制得阻尼层；
S3向环氧树脂中加入各原料，混合均匀，将多孔聚氨酯浸入到环氧树脂中，随后在取出，并将铝薄片负载在多孔聚氨酯的一侧，在室温下固化成型，得到约束层；
S4将步骤S2制备的阻尼层和S3制备的约束层，交错叠放，并将阻尼和约束层相互粘接，得到所述多层阻尼材料。
本发明至少具有如下优点和有益效果：
在本发明中，该多层阻尼材料包括多层约束层和多层阻尼层，约束层按梯度与阻尼层交替设置，约束层弹性模量由小到大排列，弹性模量较小的约束层更靠近基体，阻尼层与约束层剪切损耗由小变大，可将机械振动能量最大程度传递到各个阻尼层中，从而最大程度利用阻尼层的不同温域。同时阻尼层的阻尼温度越高，材料的强度越高，弹性模量较大的约束层与强度更高的阻尼层贴合可以起到更好的束缚作用。
附图说明
图1为发明的多层阻尼材料的局部剖视示意图；
图标：1-阻尼层，2-约束层，21-多孔聚氨酯层，22-铝薄片，23-环氧树脂层。
具体实施方式
实施例：
阻尼层的制备；将100phrIIR在双辊开炼机上塑炼10min，加入100phrCaCO3，然后加入50,100,150,200phr的HDCPD树脂，制备含有不同HDCPD含量的共混胶，再分别向共患胶中加入硫磺、氧化锌、硬脂酸、促进剂在双辊开炼机上混炼10min，混炼均匀得到不同HDCPD含量的混炼胶，在平板硫化机上进行模压硫化，硫化条件设置为165℃×T90，20MPa，取一定量硫化后的IIR置于热压成型机上于130℃、10MPa热压5min，然后在相同压力下冷压至室温成型，制得不同HDCPD含量的阻尼层片材，依次标号为IIR1,IIR2,IIR3,IIR4；
约束层的制备：选取不同厚度的多孔聚氨酯和铝薄片，向环氧树脂中加入固化剂、短切玻璃纤维、溶剂，随后将多孔聚氨酯浸入到环氧树脂中，取出，并将铝薄片负载在多孔聚氨酯的一侧，在室温下固化成型，得到约束层，分别为E1,E2,E3,E4,其中，按弹性模量大小依次为E1<E2<E3<E4；具体的环氧树脂层的组分配比如表2所示。
多层阻尼材料的制备：以1mm厚的钢板为基材，将阻尼层和约束层交错叠放，利用阻尼层材料的自粘性，将约束层和阻尼层粘接在一起，得到多层结构阻尼材料，并将多层结构阻尼材料粘接在基材上。
表1实施例1-5的多层阻尼材料
表2实施例1-5的环氧树脂层的配方
环氧树脂 固化剂 增强填料 溶剂
E1 100 10 5 10
E2 100 10 10 10
E3 100 10 15 10
E4 100 10 20 10
在表2中，环氧树脂的牌号为E20，固化剂为酚醛胺，增强填料为0.15mm的短切玻璃纤维，溶剂为二缩水甘油酯。在本发明的其他实施例中，还可采用不同长度的短切玄武岩纤维、碳纤维。
对比例1-5：
选取实施例1-5中制备的阻尼层和约束层，按照表2中的层叠方式制备多层约束阻尼材料。其中，对比例1-4均采用与实施例1-4相同的层叠方法，不同之处在对比例1中，多个约束层均E1，未采用梯度排列；在对比例2中，多个约束均为E2；在对比例3中，多个约束层均为E3；在对比例4中，多个约束层按弹性模量由小到大排列，阻尼层按玻璃化转变温度由大到小排列；在对比例5中，阻尼层和约束层的设置方式与实施例5的相同，不同之处在于，在对比例5中，阻尼层厚度不相同。
表3对比例1-5的多层阻尼材料
将负载有上述实施例1-5的阻尼材料的钢材，以及对比例1-5的阻尼材料钢材，通过对悬臂梁进行DMA(动态热机械分析)测试，得到各阻尼结构的复合阻尼因子，其结果如表3所示。
表3实施例1-5和对比例1-5的多层阻尼材料的阻尼因子
实施例1-5所制备的多层阻尼材料中，实施例1、2、5在-30℃-70℃下的阻尼因子在0.14以上，符合船舰阻尼材料的使用标准，即实施例1、2、5的阻尼材料基的有效阻尼温域为-30℃-70℃。
在实施例1-5中，其采用的阻尼层、阻尼层梯度排列顺序、约束层厚度均与对比例1-5的相同，但在实施例1-5中，其各约束层的弹性模量与对比例1-5的不同，实施例1-5对约束层进行梯度设置。具体的，实施例1中约束层梯度设计后的阻尼因子明显优于对比例1中未进行约束层梯度设计的阻尼因子。同理，实施例2中约束层梯度设计后的阻尼因子明显优于对比例1中未进行约束层梯度设计的阻尼因子。通过将约束层设置为不同弹性模量，并按照一定的梯度排列，可明显得提高多层阻尼材料的阻尼性能。
实施例1其采用的阻尼层、阻尼层梯度排列顺序、约束层弹性模量均与实施例2、3相同，实施例1中采用的约束层厚度与实施例2、3不同。具体的，实施例1中约束层厚度为0.5mm的阻尼因子明显优于对比例2约束层厚度为1mm的阻尼因子。实施例2中约束层厚度为1mm的阻尼因子明显优于对实施例3中约束层厚度1.5mm的阻尼因子。通过约束层厚度将在0.5mm-1.5mm的范围内，将约束层厚度越小，多层阻尼材料的阻尼性能提高的越多，在本发明中，将约束层的厚度设在0.5-1.5mm内，其得到的多层阻尼材料可满足舰船的需要。。
实施例1其采用的阻尼层、约束层厚度、约束层弹性模量均与实施例4相同，实施例1中采用的阻尼层梯度排列顺序与实施例4不同。具体的，实施例1中阻尼层梯度排列顺序为IIR1、IIR2、IIR3、IIR4按照玻璃化转变温度由低到高排列，实施例4中阻尼层梯度排列顺序为IIR4、IIR3、IIR2、IIR1按照玻璃化转变温度由高到低排列；在-30℃-40℃之间，实施例1的阻尼因子略高于实施例4的阻尼因子，而在50-70℃之间时，实施例4的阻尼因子高于实施例1的阻尼因子，说明将阻尼层梯度排列顺序按照玻璃化转变温度由低到高排列，可明显得提高多层阻尼材料的阻尼性能。
实施例1其采用的阻尼层、阻尼层梯度排列顺序、约束层厚度均与实施例5相同，实施例1中采用的约束层梯度排列顺序与实施例5不同。具体的，实施例1中约束层梯度排列顺序为E1、E2、E3、E4按照弹性模量由低到高排列，实施例5约束层梯度排列顺序为E4、E3、E2、E1按照弹性模量由高到低排列，其实施例1的阻尼因子均高于实施例5的阻尼因子，说明约束层梯度排列顺序按照弹性模量由低到高排列，可明显得提高多层阻尼材料的阻尼性能，但相对于对比例中的约束层未按梯度排列的，实施例1和实施例5的阻尼因子较对比例的高，说明通过梯度设置约束层，可提高多层阻尼材料的阻尼性能。
实施例6-10
与实施例1-5不同之处在于，实施例6-10的约束层的原料配方不相同，具体的，实施例6-10的环氧树脂层的配方如表5所示；
表5实施例6-10的环氧树脂层配方
环氧树脂 固化剂 增强填料 溶剂 环糊精 偶联剂
E1 100 30 5 10 50 5
E2 70 15 10 10 30 4
E3 80 20 15 5 35 3
E4 90 25 20 5 45 1
以表5的配比制备环氧树脂层，其中实施例6多层阻尼材料的阻尼层、约束层的厚度和排列方式与实施例1的相同，实施例7的与实施例2相同，实施例8与实施例3相同，实施例9与实施例4相同，实施例10与实施例5相同。
将实施例6-10制备的阻尼材料，采用相同的测试手段，测试实施例6-10的多层阻尼材料在不同温度下的阻尼因子，其结构如表6所示。
表6实施例6-10的多层阻尼材料的阻尼因子
温度/℃ -30 -20 -10 0 10 20 30 40 50 60 70
实施例6 0.299 0.292 0.295 0.171 0.163 0.171 0.176 0.251 0.194 0.156 0.189
实施例7 0.263 0.255 0.287 0.163 0.158 0.169 0.170 0.222 0.178 0.165 0.203
实施例8 0.252 0.244 0.262 0.159 0.149 0.150 0.162 0.169 0.177 0.172 0.179
实施例9 0.292 0.271 0.263 0.162 0.144 0.152 0.164 0.212 0.199 0.183 0.211
实施例10 0.293 0.265 0.266 0.198 0.175 0.171 0.198 0.214 0.195 0.191 0.199
从表6中可以得出，通过在环氧树脂层中加入了环糊精和偶联剂，由该环氧树脂制备的约束层，具有一定的阻尼作用，将该约束层用户制备多层阻尼材料，其在各温度下的阻尼值均有所提高(与实施例1-5相比)。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (7)

1.一种梯度多层阻尼材料，其特征在于：包括多层不同玻璃化转变温度的阻尼层和多层不同弹性模量的约束层，多层所述阻尼层与多层所述约束层交替叠放，且按远离被覆基体的方向，多层所述约束层以弹性模量由小到大排列；
所述约束层包括多孔聚氨酯层和铝薄片，所述多孔聚氨酯层外包覆有环氧树脂层，所述铝薄片贴覆于所述环氧树脂层的一侧；
所述梯度多层阻尼材料的制备方法包括以下步骤：
S1将100phr丁基橡胶在双辊开炼机上塑炼10min，加入100phrCaCO3，然后氢化双环戊二烯树脂，得到共混，随后加入硫磺、氧化锌、硬脂酸、促进剂在双辊开炼机上混炼10min，混炼均匀；
S2在平板硫化机上进行模压硫化，硫化条件为165℃×T90，20MPa，其中T90为正硫化时间，由硫化曲线测试获得；随后将硫化后的共混胶置于热压成型机上于130℃、10MPa热压5min，然后在相同压力下冷压至室温成型，制得阻尼层；
S3向环氧树脂中加入各原料，混合均匀，将多孔聚氨酯层浸入到环氧树脂中，随后在取出，并将铝薄片负载在多孔聚氨酯的一侧，在室温下固化成型，得到约束层；
S4将步骤S2制备的阻尼层和S3制备的约束层，交错叠放，并将阻尼和约束层相互粘接，得到所述多层阻尼材料；
所述环氧树脂层按重量分数计包括以下组分，
环氧树脂70-100份，固化剂10-30份，增强填料5-20份，溶剂5-10份；
其中，所述增强填料为长度在0.1mm-0.5mm内的短切玻璃纤维、短切玄武岩纤维、碳纤维中的一种或多种；
所述多孔聚氨酯层为聚氨酯硬质泡沫，其厚度为0.1mm-0.5mm，平均孔径为50-100um。
2.根据权利要求1所述的梯度多层阻尼材料，其特征在于：所述环氧树脂层按重量分数计包括以下组分，
环氧树脂70-100份，固化剂10-30份，增强填料5-20份，溶剂5-10份，环糊精30-50份、偶联剂1-5份。
3.根据权利要求1所述的梯度多层阻尼材料，其特征在于：多层所述阻尼层以玻璃化转变温度由低到高排列，且所述铝薄片位于两所述阻尼层之间，所述铝薄片与玻璃化转变温度较低的所述阻尼层粘贴连接。
4.根据权利要求1所述的梯度多层阻尼材料，其特征在于：所述阻尼层为丁基橡胶或丁基橡胶与氢化双环戊二烯树脂的共混物。
5.根据权利要求1所述的梯度多层阻尼材料，其特征在于：相邻所述阻尼层的玻璃化转变温度的差值大于等于5℃。
6.根据权利要求1所述的梯度多层阻尼材料，其特征在于：所述约束层的弹性模量为1500MPa-2500MPa，其中相邻两所述约束层的弹性模量差大于等于200MPa。
7.根据权利要求1所述的梯度多层阻尼材料，其特征在于：所述阻尼层的厚度为0.2mm-0.5mm，所述约束层的厚度为0.5mm-1.5mm。
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