摘要
电磁波吸收材料在电磁屏蔽、隐身技术等方面具有重要应用。具有吸收强、频带宽、质量轻等优良综合性能的吸波材料的是当前研发的重点。导电高聚物是一种重要的吸波剂,其中聚吡咯(PPy)由于其密度小、合成方便、电导率可控、形貌多样等优点作为吸波剂大有作为。本研究旨在合成不同形貌的聚吡咯,在使用不同掺杂剂和控制不同掺杂程度的条件下所得到PPy的结构和性能,并以PPy为吸波剂制成了吸波复合材料,研究了这些吸波复合材料的吸波性能、探讨了其吸波机理。
采用乳液聚合法制备了球粒状的聚吡咯,并使用十二烷基苯磺酸钠(SDBS)、二(2-乙基己基)琥珀磺酸钠(AOT)、对甲苯磺酸钠(pTSNa)、樟脑磺酸(CSA)对其进行掺杂。研究发现不同的掺杂剂能使聚吡咯的形貌、电导率、热稳定性等发生变化。其中使用SDBS为掺杂剂的聚吡咯其热性能最佳,电导率也达到10’S/cm。随后采用SDBS为掺杂剂制备了不同掺杂程度的聚吡咯,测试结果表明聚吡咯的电导率先随着掺杂率的增加而升高,至SDBS与吡咯单体的摩尔比为0.2(SDBS/Py=0.2)时达到最大值,然后随掺杂剂含量增加电导率下降。
将不同掺杂剂掺杂的球粒状聚吡咯作为吸波剂制备吸波复合材料,对复合材料的电磁参数测量结果表明：介电损耗与掺杂聚吡咯的电导率和掺杂剂阴离子的大小有关,SDBS掺杂的聚吡咯的介电损耗最大。遂以SDBS掺杂聚吡咯为吸波剂,测量不同掺杂程度PPy为吸波剂时复合材料的电磁参数,结果表明介电常数的变化规律与电导率随掺杂率变化相似,即介电常数随掺杂率增加而增大,到SDBS/Py=0.2时达到最大值,然后随掺杂率的增加而下降。通过电磁参数对复合材料吸波性能进行计算得到的结果表明：对于SDBS/Py为0.2的聚吡咯,当其在复合材料中的含量为20wt%时吸波性能最好；亦即在X波段内,厚度为2.3mm的样品其雷达波反射损耗低于-10dB的频率范围为9.5GHz～11.6GHz,最大反射损耗达到-14.8dB。
通过原位聚合法以三氯化铁为氧化剂制备了一系列蒙脱土(MMT)含量不同的蒙脱土/聚吡咯(MMT/PPy)纳米复合材料,并对MMT/PPy纳米复合材料进行了结构性能表征。X射线衍射分析表明：MMT/PPy纳米复合材料中PPy分子链插入到MMT片层间导致MMT层间距离明显扩大,从而形成一种典型的插层型纳米复合材料。通过FTIR分析证实,与纯PPy相比,纳米复合材料中PPy的特征吸收峰发生迁移,据此推断MMT与PPy之间存在相互作用。利用SEM观察了MMT/PPy的形貌,发现它们呈现片层状结构,且用HF酸完全蚀刻掉MMT后,留下的PPy仍呈现片层结构的形貌。PPy与蒙脱土复合后,热稳定性大大提高。MMT/PPy的电导率随PPy含量增加而增大,逾渗值为20wt%；同时发现当PPy含量大于50wt%时,MMT/PPy的电导率高于纯PPy电导率数值。
以SDBS掺杂的MMT/PPy为吸波剂制备了吸波复合材料。利用HP8722ES网络矢量分析仪测定了复合材料的电磁参数,发现不同MMT/PPy含量的复合材料在X波段范围内的介电常数的实部与虚部都随吸波剂含量的增加而增大,而且与球粒状PPy-SDBS为吸波剂的复合材料相比其虚部值更大。由电磁参数对复合材料吸波性能的模拟计算结果表明MMT/PPy吸波剂具有更加优良的吸波性能：当样品厚度为2.8mm,最低反射损耗出现在10.5GHz且峰值为-33dB,低于-10dB的频宽为9～12.4GHz。
以小分子2-蒽-9-基亚甲基-丙二腈(AYM)自组装的纳/微米线为硬膜板,液相条件下制备了PPy与AYM复合物,经溶剂脱除AYM后制得管状聚吡咯。Py与AYM的摩尔比对得到的聚吡咯形貌有影响,当Py与AYM两者之间的比例维持在合理的水平时,可以获得长度达到几十甚至上百微米,直径300nm左右甚至更小的管状聚吡咯。Py含量过低时,产物呈带状和管状混杂的形貌结构；而当单体含量过高时,模板的作用不再明显,产物开始大量团聚,表现出本体聚合时的形貌。
以管状PPy为吸波剂制备石蜡复合材料,测试其电磁参数。发现复合材料的复介电常数的实部和虚部随着管状聚毗咯在复合材料中含量的增加而增大,且其磁导损耗并没有明显的增加,变化也没有规律。通过计算发现复合材料的吸波性能在聚吡咯微管含量20wt%时最好,当样品厚度为2mm时,最小反射损耗为-29.5dB,低于-10dB的带宽为12.4～18GHz。
本论文还重点研究了PPy形貌对复合材料吸波性能的影响。首先,考察了分别在乙醇/水(体积比1:1)和水介质中制备的聚吡咯的吸波性能,前者的粒径为100-200nm,后者为400-800nm。将相同含量的此两种粒径PPy作为吸波剂时,粒径小的PPy为吸波剂的复合材料的介电损耗角正切值大于相同含量下粒径大的PPy为吸波剂的复合材料。因此,发现粒径小的PPy的吸波性能更优,当样品的厚度为3mm,最低反射损耗发生在9.7GHz且峰值为-15.7dB,低于-10dB的反射损耗的频率范围为8.5GHz～11.2GHz。
此外,基于考虑形状的等效电磁参数理论计算了球状、管状、片状PPy的吸收截面和散射截面面积,发现在相同的体积分数下,片状PPy的吸收截面最大,管状次之,而球状PPy吸收截面最小,从理论上阐述了PPy的形貌对吸波性能的影响。从电磁波在不同形貌吸波剂复合材料中传播路径的变化,也可以解释吸波性能的差异。
Microwave absorbing materials have shown great potential in the fields of electromagnetic shielding and stealth technology. At the present time, the researching interests have focused on the materials with strong absorbing, wide frequency band and light weight. Conductive polymers were known as one of the important microwave absorbing materials, among which polypyrrole (PPy) has been proved to be a promising absorbing agent due to its low density, easy synthesis, controllable conductivity and multi-morphologies. In this paper, PPy with multi-morphologies were prepared and made into microwave absorbing composites after doped with different dopants and doping degrees. Furthermore, the absorbing properties and mechanisms of those composites were investigated.
First of all, spherulitic PPys were synthesized via emulsion polymerization with the sodium dodecyl benzene sulfonate (SDBS), ferric chloride (FeCl3), bis (2-ethylhexyl) sulfosuccinate sodium salt (AOT), sodium p-toluenesulfonate (p-TSNa), camphor sulfonic acid (CSA) as the dopants, respectively. The testing result showed that the morphologies, the conductivities and the thermostabilities of those variously doped PPys were changed with the different dopant. The thermostabillity of PPy doped with SDBS was the best and its conductivity could reach 101S/cm. The conductivities of SDBS doped PPys with varied doping degrees were measured and it has been found that the conductivity increased with the increasing SDBS concentration, and reached the maximum when the molar ratio of SDBS/Py was 0.2, then the conductivity values reduced with the further SDBS loading.
The microwave absorbing composites were prepared by using the variously doped PPys with absorber. From the electromagnetic parameters measurement testing results, it has been found that the dielectric loss of composite related closely to the conductivity of PPy and the size of dopant anion. Especially, SDBS doped PPy showed the maximum dielectric loss tangent. Therefore, the electromagnetic properties of PPy composites with different SDBS doping degrees were tested and the results indicated that the permittivity showed similar doping degree dependence as the conductivity, i.e., the permittivity increased and then decreased with doping degree, and the maximum appeared when SDBS/Py was 0.2. For the PPy with a SDBS/Py=0.2, when its content was 20wt%, the composite showed an optimum absorbing capacity. Definitely, the peak microwave reflection loss was -14.8dB and the-10dB reflection loss band lay in 9.5-11.6GHz for the sample with a thickness of 2.3mm.
Montmorillonite/polypyrrole (MMT/PPy) nanocomposites containing PPy ranged from 10% to 80% were prepared by in-situ polymerization of pyrrole in the presence of MMT in aqueous solution with FeCl3 as oxidant, and the structures and properties of those nanocomposites were characterized. Concretely, the X-ray diffraction result indicated an interlayer spacing enlarging, implying the intercalation of PPy into galleries of MMT. Moreover, the shifting of characteristic absorption peaks of PPy in the FTIR spectra revealed the possible interaction between PPy backbones and MMT layer surface. In the SEM patterns, the novel flaky-like morphology of PPy in MMT/PPy nanocomposites could be observed, which was totally different from those of PPys mentioned above. And the flake-like morphology of PPy was confirmed by removing MMT via HF acid etching. Furthermore, the MMT/PPy nanocomposites displayed improved thermostability. The conductivity of MMT/PPy nanocomposite increased with the increasing PPy content, and the percolation threshold was 20wt%, especially, when the PPy content was 50wt%, the nanocomposite showed an even higher conductivity than the pure PPy.
The microwave absorbing specimens were prepared by using the MMT/PPy-SDBS-50% as the absorber, and their permittivities were measured by means of HP 8722ES network analyser. It has been found that both the real and the imaginary parts of permittivities of the composites increased with the increasing MMT/PPy-SDBS content within the X band, and the imaginary part was even higher compared to that of PPy-SDBS. From the absorbing capacity simulation results, it could be concluded that MMT/PPy-SDBS was a better microwave absorber than PPy-SDBS because its reflection loss was stronger and the frequency bandwidth was wider. As a matter of fact, for the MMT/PPy-SDBS composite with a thickness of 2.8mm, the peak reflection loss could reach-33dB at 10.5GHz, and-1OdB reflection loss band lay in 9-12.4GHz.
The microtubes formed by self-assembling of small molecular AYM were used as the template to synthesis of the PPy/AYM complex, then the microtubes PPy was successfully obtained after removing AYM with CH2Cl2. It has been found the molar ratio of Py monomer over AYM affected the morphology of PPy, and when the molar ratio was well controlled, the PPy microtubes with a length of 101-102μm and the diameter of 300nm or even smaller could be obtained. However, if the Py monomer loading was too low the strip shape PPy would appear except for the tube ones, whereas if Py monomer loading was too high the product would agglomerate and just looked like that from bulk polymerization.
The permittivities and permeabilities of the PPy microtube composites were measured within the frequency range of 2-18GHz. The real and imaginary part of the permittivity increased with the increasing absorber content, however, the permeabilities failed to show obvious increasing and just changed randomly. The simulation indicated the 20wt% content of PPy microtubes in the composite was the optimum condition for the reflection loss of composite. When the thickness of composite was 2mm, the peak reflection loss was -29.5dB at 12.8GHz, and -10dB absorbing band lay in 12.4GHz-18GHz.
In this paper, the influence of the morphologies of PPy on the microwave absorbing has been paid more attention. Firstly, the absorbing abilities of spherulitic PPys obtained respectively in alcohol/water or water medium were investigated, and in fact the former PPy possessed a diameter of 100-200nm while the later was 400-800nm. The results of electromagnetic parameters measurement showed that the dielectric loss tangent of the smaller size particles was higher than that the larger ones, giving a better microwave absorbing ability, definitely, the peak reflection loss values was -15.7dB at 9.7GHz and -10dB reflection loss band lay in 8.5GHz-11.2GHz for the composite sample with a thickness of 3mm. Furthermore, according to the effective electromagnetic parameters theory which considered the absorber morphology effect, the absorption and scatter section area of the spherulitic, tubulous and flake-like PPys were calculated. The results demonstrated the microwave absorption section area for flake-shaped sample were better than the other, which coincided with the experimental results. As the matter of fact, the consideration of transition pathway of microwave in the composites would also be helpful to understand the absorbing ability difference between various types of PPy.
引文
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