脂肪族聚酰胺由于含有胺基和羰基，易与水分子形成氢键，因此所得到的各种材料在使用时容易吸水，产生增塑效应，导致材料体积膨胀、模量下降，在应力作用下发生明显蠕变等问题。聚己内酰胺和聚己二酸己二胺（尼龙6和尼龙66）是最常用的聚酰胺材料。它们最高能从潮湿空气中吸收质量分数10%的水分，在一般湿度环境下也能吸收质量分数2%到4%的水分，导致各种力学性能变差。尼龙6和尼龙66两种材料在本文讨论范围内区别很小，统称尼龙6/66。本文总结了关于尼龙6/66吸水机理和改善其吸湿性的研究。主要内容如下：
1. 水分对尼龙6/66各性质的影响
尼龙6/66吸水之后，多种性质将发生变化，而且许多性质的改变和吸水量有关系。
1.1. 结晶度和晶体结构
对尼龙6/66的晶体学研究发现，尼龙6/66都是半结晶性材料，成型后都含有晶区和非晶区。在晶区，分子链呈平面锯齿构象，通过酰胺键在链与链之间形成氢键1。在非晶区，分子链构象呈无规状，大多数酰胺键未相互形成氢键，呈“自由”状态，但不排除少数区域形成了局部的氢键。早期尼龙研究中结晶度常通过密度估算2。尼龙6/66的密度比水大。吸水后，这两种材料的密度均反而上升3，结晶度也上升4, 5。经过拉伸取向的尼龙6/66材料常含有部分γ-晶。研究发现，吸水后尼龙材料的γ-晶比例减少，而更稳定的α-晶比例增大6-8。
1.2. 力学性能和分子运动
尼龙吸水之后在力学性能上的变化是明显的。最主要的特点是硬度、模量和拉伸强度下降、屈服点降低、冲击强度增加4, 5, 9-11。
尼龙6/66的分子运动研究方法有核磁共振、动态力学松弛和介电损耗等方法研究尼龙6/66材料的转变发现，其玻璃化转变温度（Tg）对水分比较敏感，吸水之后，Tg大幅下降12-18。例如，尼龙6水含量为0.35%w/w时Tg =94°C，10.33%w/w时Tg=-6°C19；干燥的尼龙66 Tg=78°C，当含水量为11%w/w时Tg=40°C15。同时发现，Tg随吸水量增加而下降的过程具有阶段性。起始下降迅速；当吸水质量分数超过一定值之后，下降缓慢19-21。综合各文献报道，该临界值约在2%~4%。尼龙6/66还在较低温度下表现β和γ转变22，其中β转变只在潮湿的样品中观察到14, 22-24，且其强度随着吸水量的增加而增加16, 17, 25。有的研究还发现，β转变峰强度的增加伴随着γ转变峰的减少，并呈现类似Tg的阶段性26-28。以上现象均表明类似塑化的效果，然而当测试温度进一步降低，超过某临界温度后，水分在尼龙6/66材料中的作用就相反，类似交联硬化12, 29-32。这个临界温度的具体值在不同报道中相差较大，有人提出这与动态力学测试频率、样品的取向程度等条件的不同有关31。
尼龙在长期受到小于屈服点的应力作用后，会发生硬化，这种效果称为“应力老化”（stress aging）33, 34。在吸水后，应力老化的速率加快35, 36。
1.3. 尺寸变化
尼龙6/66吸水后体积将发生膨胀。膨胀时，材料尺寸变化和吸水量变化并不完全同步。尼龙6纤维随着吸水量变化膨胀先快后慢37；而尼龙6薄膜则相反38, 39。经过拉伸取向的样品，膨胀具有各向异性。在拉伸取向的方向上膨胀较明显21, 30, 37。研究发现，尼龙6/66在拉伸作用下，其中的分子间氢键取向沿拉伸的方向靠拢21, 40, 41，因此认为，尼龙6/66吸水膨胀在沿分子间氢键的方向上比较明显。
1.4. 热定型方法
尼龙6/66纤维生产中有湿热定型和干热定型两种方法。研究发现，在结晶度相同的情况下，干热定型样品吸水量比湿热定型的少42。湿热定型的样品染色性能较好9。
2. 尼龙6/66吸水的机理
总结以往研究，目前基本认为水分子只进入尼龙6/66的非晶区域8, 10, 43, 44，吸水后分子链活动性增加，起塑化的作用37, 45-47。这是导致上节提到的晶型转变、Tg下降、出现新的松弛等现象的原因。
针对Tg及其他性质随吸水量增加而变化的过程呈现分段性的现象，Puffr和Šebenda提出了尼龙6/66分步吸水的机理48，并被大量实验结果支持。该机理认为，水分子进入尼龙6/66无定形区，优先以左图1的形式结合（紧密结合，tightly bound），当水分子继续增多时，出现如左图中的2所示的结合形式（松散结合，loosely bound），更多的水分子将在分子间隙中通过水分子之间的氢键进一步堆积（clustering，如左图中的3所示）。上节提到的尼龙6/66在动态力学松弛20, 23、介电松弛26, 27, 45, 49, 50以及应力老化36等性质随吸水量变化的分段效应，正是P-Š分步吸水机理的体现。在疲劳裂纹生长51和断裂能52等性质上也发现了随吸水量变化的分段效应，可以用P-Š机理来解释。同时，宽线NMR吸收谱47, 53和弛豫时间54也发现尼龙6/66吸收的水分子中只有部分具有可活动性，说明其中含有结合程度不同的两类水分子。正电子湮灭寿命谱研究表明尼龙自由体积随吸水量的增加先下降后上升，也正好与P-Š机理相吻合。
对尼龙吸水的理论描述可用Flory-Huggins方程39, 55, 56或Zimm方程57-59来描述（Zimm方程是Flory-Huggins方程的发展）。将这些理论与实验结果相比较的结果均支持了P-Š两步吸水的机理。另外，通过分子模拟的方法也支持了这一机理60。
3. 解决尼龙6/66吸水问题的方法
由以上的总结可以知道，水对尼龙6/66材料的塑化效果很明显，而且在初始吸水阶段最敏感。仅靠保持干燥环境来保证尼龙6/66材料的性能比较困难。解决尼龙6/66吸水的问题有两类方法，一是通过降低吸水量来减少水分对其性能的影响；二是通过提高尼龙6/66的相关性能期望能抵消吸水的影响。
3.1. 共混和复合
添加酚醛树脂和聚乙烯基苯酚等含酚树酯能减少尼龙6/66的吸水量，提高其Tg，同时对Tm影响较小61-64。研究发现，添加的酚类物质主要存在于尼龙6/66的无定形区域。对于酚类物质的这种效果，研究者是这样解释的：水之所以能破坏尼龙6/66中业已形成的氢键而与羰基或胺基形成新的氢键，就是因为水分子与这羰基或胺基形成氢键的趋势比他们之间要高。酚基与羰基形成氢键的趋势比水分子更高，添加酚类物质之后，酚基占据了尼龙6/66中的羰基和胺基，并因其所含的苯环产生了位阻效应，阻止了水分子的进入65。通过等温吸附实验66、SAXS67和分子模拟68的方法都支持了这种解释。
添加胺基聚醚（Blox）69、磺化聚酯70或含芳聚酰胺71也能减少尼龙6/66的吸水量。尼龙6/66与其他高分子（如PP72, 73、PS74、PC75, 76、ABS77等）共混一般只能减慢吸水速度，并不能降低吸水量。同时如果相容性不好，还会牺牲力学性能78。
无机纳米粒子的效果也不明显79。例如添加粘土只能减慢吸水的速度80，不能减少平衡吸水量81。聚酸胺/层状硅酸盐纳米复合材料除具有所期望的增加和阻燃效果外，也能减慢吸水的速度，但不能减少平衡吸水量。关于聚酰胺/无机纳米复合膜对水蒸汽和氧气的阻隔性增加已有大量报道，这里不再一一引用。
以上的共混和无机纳米复合的方法虽然只能减慢吸水速度而不能降低吸水量，但是并不一定说明这些方法不能改善尼龙6/66因吸水而带来的不良后果。一方面，这些尼龙复合材料吸水后力学性能的下降和尺寸变化不一定像纯尼龙6/66那样明显；另一方面，上文引用的这些共混和无机纳米复合的报道在力学性能上均获得改善，如Tg、模量的提高等等，就算吸水之后力学性能又回落，也能相互抵消。但是目前还没有关于聚酰胺的共混或无机纳米复合材料的力学性能与吸水量（非吸水速率）之间关系的报道。
还有报道通过将尼龙6/66与吸湿性较低、力学强度较高的尼龙11粘合成层状复合材料，由于尼龙11的支架或限制作用，吸水后能保持尺寸和一定的力学强度82。
3.2. 交联
尼龙6/66交联后的力学性能变化是常规的，即Tg上升，刚性和脆性增强83, 84。但是关于交联后的吸水量或水分对材料性能的影响的报道很少，只查到一篇报道称其交联后的尼龙6吸水量有所减少85。
3.3. 表面改性
通过对尼龙6/66材料的表面进行疏水化改性可以减少吸水量。例如，通过表面接枝含氟聚合物86或者在表面形成具有荷叶结构超疏水层87。
4. 总结
1、 尼龙6/66吸水的基本过程是是与水分子接触–氢键结合–塑化。因此，解决尼龙6/66吸水问题可针对与水分子接触（如表面改性）、氢键结合（如添加酚类聚合物）或塑化（如共混和无机纳米复合）三方面来考虑。按照这一思想，应该还能想出比上文更多的方法。
2、 各类改性方法得到的尼龙6/66复合材料的性能与吸水行为关系的研究较少，对实际应用的指导性不足，需要进一步研究。
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