摘要: 采用热重–差热联用分析(tg-dta)技术和热重红外(tg-ftir)联用系统研究了新型磁性聚苯胺壳聚糖材料在氮气气氛中的热分解过程和非等温热分解机理及动力学。tg-dta分析表明复合材料在190℃~460℃之间发生热分解反应，且分为两个阶段，第一阶段为190℃~380℃，第二阶段为400℃~460℃。运用mkn法、coats-redfern法和唐万军法对复合材料的非等温动力学数据进行分析，得出了热分解反应的机理函数、动力学参数、以及两步分解反应的活化能e和lna。第一步分解的活化能为e = 113.9281 kj∙mol−1，指前因子为lna = 20.705，动力学表达式为lna = 4.95373e 7.43443；第二步分解活化能为e = 184.578 kj∙mol−1，指前因子为lna = 33.95，动力学表达式为lna = 5.09915e 5.61035。
abstract: the thermal decomposition process and non-isothermal decomposition kinetic of magnetic polyaniline chitosan were studied by the differential thermal analysis (dta), thermogravimetric analysis (tg) and tg-ftir. it was demonstrated that the thermal decomposition temperature of magnetic polyaniline chitosan was in the range of 190˚c~460˚c, which was divided into two stages. the first stage was 190˚c~380˚c, and the second stage was 400˚c~460˚c. the mechanism function and kinetic parameters of non-isothermal decomposition of the two steps were discussed, and the e and lna of the process were obtained from the analysis of tg-dta curves by mnk, coats-redfern and tang wanjun methods. the first step activation energy was e = 113.9281 kj∙mol−1, the pre-exponential factor was lna = 20.705, and the kinetic expression was lna = 4.95373e 7.43443. the second step of the activation energy was e = 184.578 kj∙mol−1, the pre-exponential factor was lna = 33.95, and the kinetic expression was lna = 5.09915e 5.61035.
1. 前言
近几年在众多的导电高分子的研究中聚苯胺是人们关注最多的一种，聚苯胺具有比较高的电导率，良好的环境稳定性和电化学性能，原料价格低廉，化学方法制备简单易行等特点，被认为是应用前景广阔的导电高分子。用其制备功能型复合材料已经在吸波材料、防腐、导电、介电复合材料、二次电池等领域得到了广泛应用。
聚苯胺通过质子酸掺杂赋予材料良好的导电性能。尽管聚苯胺分子链中芳环的存在，有助于耐热性的提高，然而，经由质子酸掺杂的导电聚苯胺，由于低分子掺杂剂的存在，其耐热性仍然较差，小分子掺杂剂的不稳定导致了聚苯胺材料在较低的温度下即发生分解 。而且导电高聚物的脱掺杂过程也影响了材料的稳定性，限制了聚苯胺的应用。本研究将聚苯胺、壳聚糖、磁性纳米fe3o4粒子复合，希望利用纳米颗粒的表面效应提高材料耐热性能与稳定性 。通过热重红外(tg-fir)联用技术检测出复合材料在加热过程产生的气体，考察磁性聚苯胺复合材料在程序升温过程中热重–差热联用分析tg-dsc曲线，研究热分解过程，推导出可能的热分解反应的机理模型，得到热分解反应的动力学方程。
2. 实验部分
2.1. 实验试剂
溴化钾、丙酮、乙醇，以上均为分析纯。
聚苯胺、磁性聚苯胺、fe3o4/羧甲基壳聚糖/聚苯胺，以上均为参照相关文献实验室自制。
2.2. 实验仪器
本研究主要用到的设备见。
2.3. 实验方法
2.3.1. 热重–差热联用测试
实验条件：程序控制升温的升温速率15 min−1，平衡温度50℃，平衡时间5 min；实验气氛：氮气(100 ml/min)；温度范围：25℃~800℃。
用氧化铝坩埚作参比，测定(tg-dta)曲线(称样5.0~10.0 mg)。分别对聚苯胺，磁性聚苯胺，fe3o4/羧甲基壳聚糖/聚苯胺进行测试。保存数据留作后期处理。
table 1. research equipment
表1. 研究设备
仪器名 |
型号 |
生产厂商 |
傅里叶红外光谱仪 |
nicolet impact380 |
美国热电尼高力公司 |
差式扫描量热仪 |
sdt q6000 |
美国ta公司 |
恒温真空干燥箱 |
dzf-6030 |
上海山连实验设备有限公司 |
2.3.2. 热重–红外联用测试
实验条件设置程序控制升温的升温速率15 min−1，平衡温度50℃，平衡时间20 min；实验气氛：氮气(200 ml/min)；温度范围：25℃~800℃。
3. 实验结果及分析
3.1. 热重–差热联用分析
是干燥的聚苯胺的分解一步完成，在233℃开始分解在592℃分解完成，其失重率约为75%。由知磁性聚苯胺的分解过程也可以认为是一步就完成了，热分解过程主要发生在242℃~406℃，失重率约为81%。与导电聚苯胺相比，磁性聚苯胺热性能()有所提高，400℃以后复合材料基本上不分解，也就是说，纳米fe3o4的加入可以提高导电聚苯胺的耐热性。这可能是由于纳米粒子的强烈吸附作用引起的。由于纳米fe3o4巨大的比表面积，产生高表面能，使其产生强烈的表面吸附效应。另外磁性聚苯胺的失重率高于导电聚苯胺，出现这一反常的现象可能是由于在制取磁性聚苯胺的过程中所含的杂质比较多，且只有少量的铁发生了掺杂。
figure 1. tg-dsc curve of polyaniline
图1. 聚苯胺tg-dsc曲线
figure 2. tg-dsc curve of magnetic polyaniline
图2. 磁性聚苯胺tg-dsc曲线
是复合材料随着温度的升高其剩余质量百分比的变化情况，可以认为干燥的复合材料在180℃开始分解到460℃分解完成，其分解过程可以分为两个阶段，第一阶段为180℃~380℃，第二阶段为400℃~460℃。第一阶段的失重率为32%，第一阶段的失重率为33%，总体的失重率为65%。比较知在聚苯胺中掺杂fe3o4可以提高材料耐热性能与稳定性，同时改善体系的磁性能和降解性能。
figure 3. tg-dsc curve of fe3o4/carboxymethyl chitosan polyaniline
图3. fe3o4/羧甲基壳聚糖/聚苯胺tg-dsc曲线
3.2. 热重红外(tg-ftir)联用分析
由、知fe3o4/羧甲基壳聚糖/聚苯胺的热分解过程分为两个阶段，每个阶段产生了大量的气体，即复合材料发生了分解，与热重曲线相吻合。
figure 4. waterfall figure 1 of fe3o4/carboxymethyl chitosan polyaniline
图4. fe3o4/羧甲基壳聚糖/聚苯胺瀑布图1
figure 5. waterfall figure 2 of fe3o4/carboxymethyl chitosan polyaniline
图5. fe3o4/羧甲基壳聚糖/聚苯胺瀑布图2
3.3. 非等温热分解动力学
由tg和dtg曲线可以得到标题化合物热分解t，α基本数据，将30种固体热分解反应动力学机理函数g(α)分别代入式(3)、式(4)和式(5)，以ln[g(α)t1.1921503] ln[g(α)t1.189466100]和ln[g(α)t2]分别对1/t作图，经过最小二乘法线性回归分析得到不同动力学机理函数的e，lna以及相关系数r的值列于中。比较3种方法所得的结果，找出e和lna值最为接近，且相关系数也较好，符合固体化合物热分解反应动力学参数e = 80~250 kj∙mol−1，lna = 16.191~69.109 s−1范围时的模型。数据结果处理如。
由知聚苯胺最符合条件其非等温动力学方程为(1/3)(1 − α)[−ln(1 − α)]−2/t2 =(ar/βe)e−e/rt，其活化能为e = 122.319 kj∙mol−1，指前因子为lna = 20.806。由知磁性聚苯胺最符合条件其非等温动力学方程为(1/3)(1 − α)[−ln(1 − α)]−2/t2 =(ar/βe)e−e/rt，其活化能为e = 172.8065 kj∙mol−1，指前因子为lna = 34.127。由于e、a受实验条件影响，根据动力学补偿效应表达式：lna =a e b，利用30种机理函数求得的e和lna值，以lna − e用最小二乘法进行线性拟合，聚苯胺，磁性聚苯胺反应的动力学表达式分别为lna = 4.95373e 7.43443、lna = 4.98583e 1.6083。
由、对于第一步，随机成核和随后生长，其非等温动力学方程(1/3(1 − α)[−ln(1 − α)]−3/t2 = (ar/βe)e−e/rt，其活化能为e = 113.9281 kj∙mol−1，指前因子为lna = 20.705。第二步其非等温动力学方程5(1/3)(1 − α)[−ln(1 − α)]−2/t2 = (ar/βe)e−e/rt，其活化能为e = 184.578 kj∙mol−1，指前因子为lna = 33.95。第1、第2步反应的动力学表达式为lna = 4.95373e 7.43443，lna = 5.09915e 5.61035。
table 2. decomposition data of polyaniline
表2. 聚苯胺分解数据
函数 编号 |
mkn方程法 |
唐万军法 |
coats-redfe法 |
e/(kj∙mol−1) |
lna |
|r| |
e/(kj∙mol−1) |
lna |
|r| |
e/(kj∙mol−1) |
lna |
|r| |
1 |
60.90642 |
7.364557 |
0.98454 |
61.02708 |
7.409046 |
0.98464 |
60.53753 |
7.170279 |
0.98425 |
2 |
70.52833 |
11.11121 |
0.99255 |
70.64482 |
11.15147 |
0.9926 |
70.16922 |
10.92942 |
0.99242 |
3 |
72.34218 |
10.01951 |
0.99384 |
72.45788 |
10.05904 |
0.99388 |
71.98491 |
9.839852 |
0.99373 |
4 |
76.00752 |
10.85068 |
0.99582 |
76.12163 |
10.8888 |
0.99585 |
75.65398 |
10.67521 |
0.99575 |
5 |
60.90642 |
7.364557 |
0.98454 |
61.02708 |
7.409046 |
0.98464 |
60.53753 |
7.170279 |
0.98425 |
6 |
1.457116 |
−1.13578 |
0.29584 |
1.603569 |
−0.90718 |
0.32212 |
1.027837 |
−1.96602 |
0.21448 |
7 |
46.77988 |
7.692656 |
0.98673 |
46.90667 |
7.744879 |
0.98684 |
46.39665 |
7.475513 |
0.98639 |
8 |
35.61588 |
6.414558 |
0.99647 |
35.74751 |
6.474978 |
0.99651 |
35.2213 |
6.173087 |
0.99634 |
9 |
20.23268 |
3.504514 |
0.99444 |
20.37099 |
3.582909 |
0.99455 |
19.82247 |
3.209322 |
0.99409 |
10 |
12.54108 |
1.869299 |
0.99065 |
12.68272 |
1.964485 |
0.99094 |
12.12306 |
1.523145 |
0.98975 |
11 |
4.849476 |
−0.20073 |
0.96438 |
4.994457 |
−0.06373 |
0.96672 |
4.423643 |
−0.67947 |
0.95616 |
12 |
1.003675 |
−2.24951 |
0.65901 |
1.150325 |
−1.97458 |
0.71138 |
0.573935 |
−3.31891 |
0.43986 |
13 |
20.42629 |
2.195681 |
0.89073 |
20.5801 |
2.277436 |
0.89244 |
19.97061 |
1.890377 |
0.88551 |
14 |
24.70022 |
2.825117 |
0.94432 |
24.85219 |
2.900548 |
0.94516 |
24.24889 |
2.538836 |
0.94177 |
15 |
13.06294 |
0.964709 |
0.70487 |
13.21995 |
1.062451 |
0.70965 |
12.59979 |
0.610775 |
0.69038 |
16 |
8.57081 |
0.666342 |
0.94334 |
8.714177 |
0.776538 |
0.94541 |
8.148758 |
0.273711 |
0.93671 |
17 |
2.202631 |
−1.49611 |
0.70126 |
2.348761 |
−1.50825 |
0.72543 |
1.774109 |
−2.16127 |
0.61582 |
18 |
−0.98146 |
—— |
0.46794 |
−0.83395 |
—— |
0.41225 |
−1.41321 |
—— |
0.60003 |
19 |
45.66161 |
8.78199 |
0.99576 |
45.78889 |
8.834931 |
0.99577 |
45.27724 |
8.56272 |
0.99572 |
20 |
−1.54059 |
—— |
0.41773 |
−1.39284 |
—— |
0.38301 |
−1.97292 |
—— |
0.51027 |
21 |
81.76549 |
14.3472 |
0.99763 |
81.8771 |
14.38323 |
0.99764 |
81.41779 |
14.17785 |
0.99759 |
22 |
122.3959 |
20.84428 |
0.9929 |
122.4986 |
20.87049 |
0.99293 |
122.0641 |
20.70385 |
0.99284 |
23 |
106.7276 |
15.91779 |
0.87681 |
106.844 |
15.94942 |
0.87717 |
106.3596 |
15.76138 |
0.87576 |
24 |
50.72844 |
10.64175 |
0.87302 |
50.86221 |
10.6932 |
3.35147 |
50.32378 |
10.42688 |
0.87111 |
25 |
33.43444 |
4.503444 |
0.9944 |
33.56702 |
4.565801 |
0.99447 |
33.03764 |
4.256213 |
0.99419 |
26 |
11.10158 |
0.899648 |
0.98141 |
11.24385 |
0.999451 |
0.98202 |
10.6821 |
0.539295 |
0.97948 |
27 |
9.779466 |
0.845569 |
0.96609 |
9.922308 |
0.950356 |
0.96726 |
9.358641 |
0.469806 |
0.96235 |
28 |
25.4388 |
6.623347 |
0.85331 |
25.57485 |
6.694272 |
0.85449 |
25.03388 |
6.350556 |
0.84975 |
29 |
51.66242 |
7.364557 |
0.90203 |
51.79578 |
7.409046 |
0.9025 |
51.2587 |
7.170279 |
0.90062 |
30 |
61.41133 |
11.11121 |
0.88797 |
61.53177 |
11.15147 |
0.88836 |
61.04296 |
10.92942 |
0.88682 |
table 3. decomposition data of magnetic polyaniline
表3. 磁性聚苯胺分解数据
函数 编号 |
mkn方程法 |
唐万军法 |
coats-redfe法 |
e/(kj∙mol−1) |
lna |
|r| |
e/(kj∙mol−1) |
lna |
|r| |
e/(kj∙mol−1) |
lna |
|r| |
1 |
90.64304 |
17.70587 |
0.99445 |
90.73543 |
17.73563 |
0.99446 |
90.34937 |
17.55498 |
0.99441 |
2 |
96.99403 |
18.49565 |
0.99273 |
97.08367 |
18.52351 |
0.99275 |
96.70682 |
18.35036 |
0.99269 |
3 |
99.43935 |
17.55915 |
0.99187 |
99.52793 |
17.5863 |
0.99188 |
99.15462 |
17.41591 |
0.99182 |
4 |
104.3742 |
18.70253 |
0.98986 |
104.4606 |
18.72833 |
0.98988 |
104.0945 |
18.56327 |
0.9898 |
5 |
83.55157 |
13.81526 |
0.99559 |
83.64704 |
13.84731 |
0.9956 |
83.2507 |
13.65761 |
0.99555 |
6 |
120.3962 |
22.3937 |
0.98158 |
120.4757 |
22.41552 |
0.98161 |
120.1327 |
22.26615 |
0.98148 |
7 |
65.624 |
13.06616 |
0.99414 |
65.72725 |
13.10509 |
0.99416 |
65.30492 |
12.88829 |
0.99408 |
8 |
51.33047 |
10.88807 |
0.98409 |
51.43992 |
10.93409 |
0.98416 |
50.99686 |
10.68927 |
0.9839 |
9 |
31.07594 |
6.734113 |
0.98142 |
31.19418 |
6.795101 |
0.98155 |
30.72176 |
−3681.08 |
0.98104 |
10 |
20.94868 |
4.524961 |
0.97789 |
21.07131 |
4.598359 |
0.97812 |
20.58421 |
4.24479 |
0.97721 |
11 |
10.82141 |
2.070523 |
0.96625 |
10.94844 |
2.16686 |
0.96692 |
10.44665 |
1.720797 |
0.96414 |
12 |
5.757781 |
0.566198 |
0.94007 |
5.887 |
0.688888 |
0.94229 |
5.377879 |
0.133929 |
0.93277 |
13 |
45.64898 |
8.822685 |
0.98994 |
45.7609 |
8.872134 |
0.98999 |
45.30961 |
8.613735 |
0.98981 |
14 |
47.47054 |
8.859022 |
0.98825 |
47.58167 |
8.907322 |
0.9883 |
47.13302 |
8.653469 |
0.9881 |
15 |
40.60496 |
8.281725 |
0.9934 |
40.71906 |
8.334637 |
0.99344 |
40.26046 |
8.062525 |
0.9933 |
16 |
15.58592 |
3.057296 |
0.9898 |
15.71088 |
3.140543 |
0.98994 |
15.21601 |
2.747433 |
0.98936 |
17 |
7.246245 |
0.904171 |
0.98097 |
7.374818 |
1.016567 |
0.98157 |
6.867854 |
0.504577 |
0.97905 |
18 |
3.076405 |
−0.60898 |
0.94785 |
3.206787 |
−0.45219 |
0.95156 |
2.693779 |
−1.15501 |
0.93413 |
19 |
64.63792 |
14.04951 |
0.96651 |
64.7416 |
14.08887 |
0.96663 |
64.31784 |
13.87036 |
0.96618 |
20 |
2.583367 |
−0.27129 |
0.35096 |
2.713963 |
−0.10282 |
0.36631 |
2.20024 |
−0.85874 |
0.30432 |
21 |
112.094 |
22.68231 |
0.98617 |
112.1771 |
22.70612 |
0.98619 |
111.8222 |
22.54892 |
0.98609 |
22 |
172.8576 |
34.15594 |
0.98676 |
172.9144 |
34.16776 |
0.98677 |
172.6475 |
34.05776 |
0.98671 |
23 |
233.6212 |
45.50803 |
0.98703 |
233.6516 |
45.51158 |
0.98705 |
233.4728 |
45.43407 |
0.987 |
24 |
80.3039 |
18.40241 |
0.94554 |
80.40078 |
18.43559 |
0.94569 |
79.99973 |
18.24147 |
0.9451 |
25 |
48.4083 |
8.798078 |
0.98731 |
48.51901 |
8.845805 |
0.98736 |
48.07172 |
8.59422 |
0.98715 |
26 |
19.01871 |
3.457396 |
0.98325 |
19.14218 |
3.533945 |
0.98344 |
18.65228 |
3.167724 |
0.98268 |
27 |
17.23269 |
3.315032 |
0.98729 |
17.35693 |
3.394866 |
0.98744 |
16.86444 |
3.015473 |
0.98681 |
28 |
38.63281 |
10.23045 |
0.80477 |
38.74777 |
10.28484 |
0.80569 |
38.28631 |
10.00685 |
0.80204 |
29 |
62.66577 |
16.01556 |
0.82518 |
62.77031 |
16.0558 |
0.82571 |
62.34368 |
15.83379 |
0.82363 |
30 |
62.66577 |
16.01556 |
0.82518 |
62.77031 |
16.0558 |
0.82571 |
62.34368 |
15.83379 |
0.82363 |
table 4. phase 1 decomposition data of fe3o4/carboxymethyl chitosan polyaniline
表4. 磁性聚苯胺壳聚糖第一阶段分解数据
函数 编号 |
mkn方程法 |
唐万军法 |
coats-redfe法 |
e/(kj∙mol−1) |
lna |
|r| |
e/(kj∙mol−1) |
lna |
|r| |
e/(kj∙mol−1) |
lna |
|r| |
1 |
47.88089 |
8.720122 |
0.86034 |
48.07479 |
8.729796 |
0.86094 |
47.78596 |
8.487987 |
0.85856 |
2 |
49.35888 |
8.449814 |
0.86613 |
49.55876 |
8.458555 |
0.8667 |
49.27208 |
8.220183 |
0.86446 |
3 |
49.87528 |
7.092861 |
0.86811 |
50.07725 |
7.101286 |
0.86867 |
49.79133 |
6.864086 |
0.86647 |
4 |
50.90889 |
7.387026 |
0.87193 |
51.11505 |
7.394827 |
0.87246 |
50.83063 |
7.159935 |
0.87036 |
5 |
45.60385 |
5.85916 |
0.85176 |
45.78853 |
5.870304 |
0.85242 |
45.49638 |
5.622998 |
0.8498 |
6 |
54.0847 |
8.287273 |
0.88276 |
54.30372 |
8.293237 |
0.88323 |
54.02392 |
8.065132 |
0.88138 |
7 |
33.72845 |
6.197135 |
0.84489 |
33.86503 |
6.217439 |
0.84581 |
33.55559 |
5.935579 |
0.84216 |
8 |
21.87471 |
4.210167 |
0.83346 |
21.96329 |
4.243621 |
0.83495 |
21.63659 |
3.910341 |
0.82901 |
9 |
11.67351 |
1.95916 |
0.76672 |
11.72078 |
2.011696 |
0.77013 |
11.37922 |
1.597665 |
0.75637 |
10 |
6.572908 |
0.592814 |
0.66356 |
6.599525 |
0.662794 |
0.67059 |
6.250542 |
0.163504 |
0.642 |
11 |
1.472309 |
−1.62619 |
0.28001 |
1.478271 |
−1.51077 |
0.30141 |
1.12186 |
−2.38921 |
0.21529 |
12 |
−1.07799 |
—— |
0.26852 |
−1.08236 |
—— |
0.24027 |
−1.44248 |
—— |
0.34676 |
13 |
20.70458 |
3.154752 |
0.82048 |
20.78843 |
3.189877 |
0.82214 |
20.46002 |
2.849868 |
0.81554 |
14 |
21.09 |
2.868994 |
0.8249 |
21.17541 |
2.903568 |
0.8265 |
20.84756 |
2.565813 |
0.82013 |
15 |
19.576 |
3.495004 |
0.80666 |
19.65528 |
3.53183 |
0.80849 |
19.32523 |
3.184907 |
0.80117 |
16 |
5.423557 |
0.108789 |
0.5947 |
5.445519 |
0.184606 |
0.60348 |
5.094863 |
−0.34716 |
0.56784 |
17 |
0.706075 |
−2.51011 |
0.13994 |
0.708934 |
−2.37238 |
0.16365 |
0.351407 |
−3.75416 |
0.0696 |
18 |
−1.65267 |
—— |
0.3963 |
−1.65936 |
—— |
0.37161 |
−2.02032 |
—— |
0.4634 |
19 |
24.33972 |
4.96288 |
0.85697 |
24.43828 |
4.993102 |
0.85817 |
24.11517 |
4.672737 |
0.85338 |
20 |
−6.34703 |
—— |
0.99704 |
−6.37273 |
—— |
0.99699 |
−6.74053 |
—— |
0.9972 |
21 |
52.4783 |
10.02985 |
0.87744 |
52.69081 |
10.03674 |
0.87794 |
52.40868 |
9.805258 |
0.87597 |
22 |
83.08189 |
15.46507 |
0.88864 |
83.41834 |
15.458 |
0.88893 |
83.18077 |
15.27742 |
0.88778 |
23 |
113.6855 |
20.76539 |
0.89373 |
114.1459 |
20.7488 |
0.89394 |
113.9529 |
20.60242 |
0.89313 |
24 |
26.96994 |
6.446111 |
0.87737 |
27.07916 |
6.473216 |
0.87834 |
26.75988 |
6.165119 |
0.87448 |
25 |
21.28444 |
2.641563 |
0.82708 |
21.37064 |
2.675848 |
0.82865 |
21.04308 |
2.339227 |
0.82239 |
26 |
6.180556 |
−0.1178 |
0.64176 |
6.205584 |
−0.04596 |
0.64934 |
5.85603 |
−0.55537 |
0.61851 |
27 |
5.797446 |
0.067497 |
0.61881 |
5.820923 |
0.141289 |
0.62697 |
5.47081 |
−0.37892 |
0.59379 |
28 |
0.798541 |
−1.32938 |
0.57467 |
0.801775 |
−1.19539 |
0.62994 |
0.444383 |
−2.45253 |
0.36029 |
29 |
5.560091 |
1.731638 |
0.96609 |
5.582607 |
1.80642 |
0.96751 |
5.236091 |
1.280851 |
0.96137 |
30 |
10.32597 |
3.571166 |
0.97933 |
10.36779 |
3.627417 |
0.97983 |
10.02427 |
3.196355 |
0.97778 |
table 5. phase 2 decomposition data of fe3o4/carboxymethyl chitosan polyaniline
表5. 磁性聚苯胺壳聚糖第二阶段分解
函数 编号 |
mkn方程法 |
唐万军法 |
coats-redfe法 |
e/(kj∙mol−1) |
lna |
|r| |
e/(kj∙mol−1) |
lna |
|r| |
e/(kj∙mol−1) |
lna |
|r| |
1 |
71.43082 |
12.97894 |
0.92694 |
71.72008 |
12.98292 |
0.92723 |
71.36564 |
12.75893 |
0.92608 |
2 |
84.7467 |
14.99816 |
0.93522 |
85.08989 |
14.99695 |
0.93544 |
84.75483 |
14.79198 |
0.93457 |
3 |
90.2315 |
14.59386 |
0.93811 |
90.59689 |
14.59075 |
0.93831 |
90.26983 |
14.39271 |
0.93752 |
4 |
101.3484 |
16.81126 |
0.94286 |
101.7588 |
16.80463 |
0.94302 |
101.4479 |
16.61938 |
0.94237 |
5 |
60.63102 |
8.444572 |
0.92078 |
60.87655 |
8.453547 |
0.92115 |
60.50638 |
8.211144 |
0.91969 |
6 |
138.5958 |
24.13743 |
0.95277 |
139.157 |
24.12128 |
0.95287 |
138.9004 |
23.97022 |
0.95247 |
7 |
50.78285 |
9.376433 |
0.91947 |
50.9885 |
9.39078 |
0.91991 |
50.60399 |
9.128236 |
0.91814 |
8 |
53.94052 |
10.67305 |
0.93787 |
54.15896 |
10.68558 |
0.9382 |
53.77905 |
10.42992 |
0.93687 |
9 |
32.24 |
6.496445 |
0.92399 |
32.37056 |
6.5246 |
0.92466 |
31.95905 |
6.208971 |
0.922 |
10 |
21.38974 |
4.266648 |
0.9053 |
21.47636 |
4.307263 |
0.90651 |
21.04905 |
3.941111 |
0.90165 |
11 |
10.53948 |
1.761667 |
0.84286 |
10.58216 |
1.823777 |
0.84647 |
10.13905 |
1.36039 |
0.83161 |
12 |
5.114349 |
0.167668 |
0.70979 |
5.13506 |
0.251738 |
0.72039 |
4.684047 |
−0.33697 |
0.67583 |
13 |
41.0168 |
7.277298 |
0.92348 |
41.1829 |
7.298141 |
0.92401 |
40.78417 |
7.01094 |
0.92191 |
14 |
45.09367 |
7.733974 |
0.92898 |
45.27628 |
7.751929 |
0.92943 |
44.88349 |
7.475725 |
0.92765 |
15 |
−11.7003 |
—— |
0.99997 |
−11.7477 |
—— |
0.99997 |
−12.2367 |
—— |
0.99997 |
16 |
9.486923 |
1.250741 |
0.79182 |
9.525341 |
1.316037 |
0.79666 |
9.080696 |
0.836536 |
0.77675 |
17 |
2.604268 |
−1.04074 |
0.46797 |
2.614814 |
−0.93618 |
0.48955 |
2.160147 |
−1.69508 |
0.39996 |
18 |
−0.83706 |
—— |
0.21962 |
−0.84045 |
—— |
0.18027 |
−1.30013 |
—— |
0.32806 |
19 |
86.006 |
17.13182 |
0.95363 |
86.35428 |
17.13018 |
−0.95379 |
86.02106 |
16.92683 |
0.95315 |
20 |
16.77451 |
3.768519 |
0.92208 |
16.84244 |
3.816505 |
0.92338 |
16.40841 |
3.418739 |
0.91812 |
21 |
119.0421 |
22.50686 |
0.9484 |
119.5242 |
22.49535 |
0.94853 |
119.239 |
22.32772 |
0.94802 |
22 |
184.1437 |
34.01195 |
0.95134 |
184.8893 |
33.98718 |
0.95142 |
184.699 |
33.86687 |
0.95111 |
23 |
249.2452 |
45.39353 |
0.95273 |
250.2545 |
45.35958 |
0.95279 |
250.159 |
45.2718 |
0.95256 |
24 |
125.6509 |
25.58108 |
0.9609 |
126.1597 |
25.56793 |
0.961 |
125.8842 |
25.4062 |
0.96062 |
25 |
47.21839 |
7.891773 |
0.93145 |
47.4096 |
7.90834 |
0.93186 |
47.0199 |
7.637446 |
0.93021 |
26 |
16.96631 |
2.665646 |
0.88251 |
17.03502 |
2.713297 |
0.88432 |
16.60127 |
2.317044 |
0.87699 |
27 |
13.00324 |
2.012318 |
0.84768 |
13.05589 |
2.068049 |
−10.7599 |
12.61637 |
1.635321 |
0.83884 |
28 |
100.5812 |
21.25775 |
0.96363 |
100.9885 |
21.25136 |
0.96374 |
100.6765 |
21.06528 |
0.96331 |
29 |
156.4523 |
32.22137 |
0.96612 |
157.0858 |
32.20155 |
0.96618 |
156.8552 |
32.06363 |
0.96592 |
30 |
212.3234 |
42.8954 |
0.96727 |
213.1832 |
43.02969 |
0.96732 |
213.0339 |
42.9247 |
0.96713 |
4. 结论
本研究采用热重–差热联用分析(tg-dta)技术测试了新型fe3o4/羧甲基壳聚糖/聚苯胺材料的热分解过程，其tg-dsc曲线表明复合物的分解分为两个阶段，掺杂后的聚苯胺的热性能有所提高：第一阶段为180℃~380℃，第二阶段为400℃~460℃；第一阶段的失重率为32%，第二阶段的失重率为33%，总体的失重率为65%。利用热重红外(tg-ftir)联用技术得到复合物的热分解瀑布图，根据非等温动力学的相关知识算出了其第一步分解的非等温动力学方程为(1/3(1 − α)[−ln(1 − α)]−3/t2 = (ar/βe)e−e/rt (活化能e = 113.9281 kj∙mol−1、指前因子为lna = 20.705)，动力学表达式为lna= 4.95373e 7.43443；第二步非等温动力学方程为(1/3)(1 − α)[−ln(1 − α)]−2/t2 = (ar/βe)e−e/rt (活化能为e = 184.578 kj∙mol−1、指前因子为lna = 33.95)，动力学表达式为lna = 5.09915e 5.61035。