高分子量聚对苯二甲酰对苯二胺硫酸溶液热稳定性的研究

高分子量PPTA树脂在浓硫酸中的热稳定性与温度、溶液浓度以及溶解时的搅拌速度有关。随着温度升高,其热稳定性降低;当溶液浓度低于16%(W/W)时,浓度越低其热稳定性越差,当溶液浓度达到16%以上时,浓度对其热稳定性没有明显的影响;溶解时搅拌速度增大,其热稳定性变差;不同分子量的PPTA树脂在硫酸中的热稳定性基本相同。     

PPTA硫酸溶液流变性能及纺丝工艺的研究

采用旋转黏度计测定聚对苯二甲酰对苯二胺(PPTA)溶液的表观黏度,研究了PPTA相对分子质量、溶液浓度以及温度对PPTA溶液流变性能的影响,并对PPTA硫酸溶液进行纺丝,研究纺丝工艺对PPTA纤维性能的影响.结果表明:不同分子量的PPTA硫酸溶液表现出相同的流变行为,PPTA硫酸溶液随着溶液浓度的增大会出现一个临界浓度...     

3,4'-ODA改性PPTA共聚物溶液性质的研究

为了改善聚对苯二甲酰对苯二胺(PPTA)的溶解性能,在PPTA的聚合过程中添加第三单体3,4'-二氨基二苯醚(3.4'-ODA),得到了PPTA的共聚体溶液.主要讨论不同的溶剂体系(NMP或DMAc)中共聚物溶液的凝固性和稳定性,包括凝固剂的种类,溶剂的浓度,CaCl2的含量和温度对溶液的凝固值和临界浓度的影响.实验结果表明:水是非常强的凝固剂;随着凝固液中溶剂浓度的提高,凝固值增大;随着CaCl2含量的增大凝固值逐渐增大;温度影响不是太大,变化趋势比较缓和;共聚物溶液在室温和60℃下都具有非常好的稳定性.     

PPTA低温硫酸溶解工艺研究

针对聚对苯二甲酰对苯二胺(PPTA)在硫酸中的溶解工艺进行实验和研究,系统的对比了PPTA各在固相硫酸中和液相硫酸中的溶解工艺,实验结果表明:固相硫酸溶解PPTA能提高溶解速度、浆液的均匀性和改善浆液的过滤性;同时能防止PPTA溶解时的热降解作用,非常有利于提高纤维的强度。     

PPTA树脂在甲磺酸中的溶解及其溶液性质初探

实验首次用甲磺酸(MSA)对聚对苯二甲酰对苯二胺(PPTA)树脂进行溶解制备PPTA/MSA溶液,并对所形成溶液性质进行研究并制备PPTA浆粕。通过偏光显微镜观察了PPTA树脂在MSA中的溶解规律,用树脂比浓对数粘度随时间的变化研究了树脂在MSA中的稳定性。并通过比表面积(BET)分析、X射线衍射(XRD)分析和热失重分析(TGA)研究了PPTA浆粕的比表面积、结晶度和热性能。结果表明:在低浓度下,PPTA树脂能与MSA混合均匀得到均一稳定的溶液,由所得溶液制备的PPTA浆粕性能优于同条件下用PPTA/硫酸溶液制备的浆粕性能。     

硅烷改性PPTA纤维的表面粘结性能研究

采用未干燥的聚对苯二甲酰对苯二胺(PPTA)纤维,以乙烯基三甲氧基硅烷(VTMS)溶液对其进行表面改性,分析了改性前后PPTA纤维的表面元素、形貌结构以及力学性能的变化,并通过微脱胶法和激光拉曼光谱法研究了PPTA纤维/环氧树脂复合材料的界面剪切强度。结果表明:经VTMS溶液改性后,PPTA纤维表面产生了新的极性官能团,表面粗糙度增加;随着VTMS溶液浓度增大或处理时间增加,PPTA纤维/环氧树脂界面剪切强度逐渐增大,PPTA纤维的力学性能略为降低;较佳改性处理条件为VTMS溶液质量分数6%,处理时间5 min;经VTMS溶液改性处理后,PPTA纤维与树脂间的粘接性能提高,延缓了纤维轴向应力的传递。     

3,4'-ODA改性PPTA的制备及其性能研究

采用低温溶液缩聚法,在刚性的聚对苯二甲酰对苯二胺(PPTA)聚合体系中引入柔性第三单体3,4'-二氨基二苯醚(3,4'-ODA),得到了比浓对数黏度较高的改性PPTA树脂,讨论了3,4'-ODA含量对改性PPTA的比浓对数黏度、结晶性能、热性能和溶解性能以及改性PPTA薄膜的表面形态和力学性能的影响。结果表明:随着3,4'-ODA含量的增加,PPTA的溶解性变好,能够有效推迟聚合反应相转变的时间,提高相对分子质量;当3,4'-ODA摩尔分数为0~5%时,随着3,4'-ODA含量的继续增加,改性PPTA相对分子质量呈现先增加后下降的趋势,结晶度从54.21%下降为44.73%,但却仍能保持良好的耐热性能,最大分解温度均在590℃左右;引入少量的3,4'-ODA后,改性PPTA溶解性变好且制得的薄膜力学性能良好;当3,4'-ODA摩尔分数为2%时,改性PPTA比浓对数黏度最大为3.57,其薄膜的强度和模量最高,强度为96.30 MPa,模量为2.67 GPa。     

3，4＇-ODA改性PPTA共聚物溶液性质的研究

为了改善聚对苯二甲酰对苯二胺（PPTA）的溶解性能，在PPTA的聚合过程中添加第三单体3,4’-二氨基二苯醚（3．4＇-ODA），得到了PPTA的共聚体溶液。主要讨论不同的溶剂体系（NMP或DMAc）中共聚物溶液的凝固性和稳定性，包括凝固剂的种类，溶剂的浓度，CaCl2的含量和温度对溶液的凝固值和临界浓度的影响。实验结果表明：水是非常强的凝固剂：随着凝固液中溶剂浓度的提高，凝固值增大；随着CaCl2含量的增大凝固值逐渐增大；温度影响不是太大，变化趋势比较缓和；共聚物溶液在室温和60℃下都具有非常好的稳定性。     

微波辐照对铁粉酸溶的影响

文章通过实验研究了微波辐照对铁粉在硫酸溶液中溶解过程的影响。实验结果表明,铁粉经过微波辐照预处理,对于后续的酸溶过程有显著的促进作用;铁粉在微波辐照下在硫酸溶液中的溶解速度随着微波输出功率的增大而增加。     

芳纶1414纺丝过程中聚合体的相对分子质量变化及其控制

芳纶1414是一种高强、高模、耐高温的高性能纤维。聚合体的相对分子质量对纤维的强度有很大的影响。在纺丝过程中,影响聚合体PPTA相对分子质量的因素有很多。在500t/a规模芳纶1414生产线上系统研究了硫酸浓度、溶解温度、溶解方式以及纺程中其它影响PPTA分子质量的因素,并提出合理的控制措施,为1000t/a规模生产线奠定一定的数据基础。     

磷石膏在低浓度硫酸中的溶解及相态变化

湿法磷酸生产过程副产大量磷石膏,因其含有较多杂质而无法直接利用,目前可采用硫酸酸浸处理提高磷石膏品质。为弄清酸浸过程中石膏的溶解性能和结晶形态的变化,本文探讨了在0～80 ℃、0～30%的硫酸浓度条件下,磷石膏在硫酸溶液中的溶解度大小、结晶形貌、物相组成及结晶水含量的变化情况。实验结果表明,磷石膏在硫酸溶液中的溶解度随温度升高而升高,在80 ℃时达最大;随浓度升高呈先升后降的变化,在硫酸浓度为10%时溶解度最大。硫酸浓度小于10%时,磷石膏中二水硫酸钙溶解,但无新相生成,其形貌变化不大;硫酸浓度大于10%时,二水硫酸钙溶解,同时再结晶转化成无水硫酸钙,最终导致磷石膏形貌和相态发生了改变,溶解度随硫酸浓度升高而降低。     

Electro-dissolution of 30Nb–Ti alloys in methanolic sulfuric acid—Optimal conditions for electropolishing

The electro-dissolution behaviour of a (30 at.%) Niobium–Titanium (NbTi) alloy in non-aqueous methanolic sulfuric acid solution using the rotating disc electrode (RDE) was ascertained. The optimal condition for electropolishing and the mechanism were proposed. The influence of the rotation rate, process temperature and sulfuric acid concentration on the dissolution kinetics was investigated. The dissolution rate (limiting current) increases linearly with increase in rotation rate and follows a Levich behaviour confirming a mass transport controlled process. The temperature dependence in terms of Arrhenius plot renders an activation energy value of E_a = 16.1 kJ mol⁻¹ for the process. The dissolution rate shows a strong dependence on the sulfuric acid concentration (1 M, 3 M and 5 M). Higher sulfuric acid concentrations lead to decreased dissolution rates (limiting current). The dissolution process is mass transport controlled in all concentrations of sulfuric acid. From an electrochemical perspective, a 3 M sulfuric acid was chosen as optimum owing to better controllability of the material removal rate. The dissolving ions are the probable rate limiting species, indicating a compact salt-film mechanism. The average root mean square (RMS) roughness value for an electropolished surface was approximately 10 nm, which is significantly lower than a mechanically polished surface.     

高镁磷尾矿中磷和镁在硫酸中的溶解动力学

对高镁磷尾矿中磷和镁在硫酸中的溶解动力学进行了研究,考察了固膜产物的物相形态变化及搅拌强度、反应温度和硫酸质量分数对溶解过程的影响. 结果表明,包含自阻化因素的德罗兹多夫方程能较好地描述P2O5和MgO的溶解过程,且二者溶解的阻缓系数均大于1.6,其表观活化能分别为14.881和11.908 kJ/mol,为固膜内扩散控制.     

Dissolution Kinetics of Nickel(II) and Nickel(III) Oxides in Acid Media

The rate of nickel(II) and nickel(III) oxide dissolution in sulfuric, hydrochloric, and nitric acids was measured as a function of the acid concentration and temperature, and a kinetic model of this process is suggested. The limiting step of the dissolution process is the passage of the complexes forming on the oxide surface into the solution.     

Studies on the semirigid chain polyamide—poly(1,4-phenyleneterephthalamide)

In this article, the polycondensation of terephthaloyl chloride and p-phenylenediamine was systematically studied, including the liquid–crystalline state of the solution and the spinning of poly(1,4-phenyleneterephthalamide) (PPTA). High-molecular-weight PPTA with ε_inh = 5–7 was prepared and the main factors influencing the solution polycondensation of 1,4-phenylenediamine with terephthaloyl chloride were studied in detail. Experimental results showed that the water content of the reaction system, reactant concentration, and volume ratio of mix solvents have a great influence on the inherent viscosity of the poly(1,4-phenyleneterephthalamide) obtained. The highest ε_inh was obtained at 0.3M/liter reactant concentration in a mixed solvent ratio HMPA/DMAC of 4/1 (by volume), at 0.35M/liter reactant concentration in a mixed solvent of HMPA/NMP = 7/3, and at 0.5M/liter of reactant concentration in a mixed solvent of HMPA/THF = 9/1. The water content must be controlled to less than 100 ppm in the polymerization system. In the early stage of the polycondensation process, the ε_inh of the polymer obtained increased rapidly with time. The system gelled within 2 or 3 min, while the monomer conversion reached about 100%. However, the reaction of polycondensation continued after gelation and the ε_inh of the polymer increased appreciably. We have studied the viscosity behavior at 20–155°C for the anisotropic solution of PPTA in 100% sulfuric acid (ε_inh of PPTA 2.5–4.9). Experimental results showed that, at low concentrations the viscosity of isotropic solution increases with the increase of polymer concentration to reach a maxium near the critical polymer concentration, beyond which the solution changes to an anisotropic liquid–crystalline solution. The appropriate spinning region was obtained as shown in the phase diagram determined by viscosity, degree of depolarization anisotropy, and region of thermal depolymerization. Fibers of PPTA with high modulus and high tenacity were obtained by dry-jet wet spinning. The fibers obtained have a tenacity of ～22 g/denier, a modulus of ～600 g/denier, and elongation at break ～3.5%.     

Zinc deposition and dissolution in sulfuric acid onto a graphite–resin composite electrode as the negative electrode reactions in acidic zinc-based redox flow batteries

Electrodeposition and dissolution of zinc in sulfuric acid were studied as the negative electrode reactions in acidic zinc-based redox flow batteries. The zinc deposition and dissolution is a quasi-reversible reaction with a zinc ion diffusion coefficient of 4.6 × 10^?6 cm² s^?1 obtained. The increase of acid concentration facilitates an improvement in the kinetics of zinc electrodeposition–dissolution process. But too high acid concentration would result in a significant decrease in charge efficiency. The performance of the zinc electrode in a three-electrode system with magnetic stirring was also studied as a function of Zn(II) ion concentration, sulfuric acid concentration, current density, and the addition of additives in 1 M H₂SO₄ medium. The optimum electrolyte composition is suggested at high zinc(II) concentration (1.25 M) and moderate sulfuric acid concentration (1.0–1.5 M) at a current density range of 20–30 mA cm^?2. Whether in acid-free solution or in sulfuric acid solution with or without additives, no dendrite formation is observed after zinc electrodeposition for 1 h at 20 mA cm^?2. The energy efficiency is improved from 77 % in the absence of additives in 1 M H₂SO₄ medium to over 80 % upon the addition of indium oxide or SLS–Sb(III) combined additive as hydrogen suppressants.     

Phase behavior and mechanical properties of poly-p-phenylene terephthalamide/amorphous nylon molecular composites

Poly(p-phenylene terephthalamide) (PPTA)/amorphous nylon (AN) molecular composites were prepared from sulfuric acid solution by rapidly coagulating in distilled water. The regenerated films appear homogeneous and transparent. However, the rod-like and flexible macromolecules are probably entrapped in a single phase during rapid coagulation, thus thermodynamically unstable and undergoing phase segregation upon thermal treatment. The miscibility between PPTA/AN was identified by a dielectric relaxation method. Phase behavior and kinetics of phase separation in PPTA/AN mixtures were thoroughly investigated by time-resolved light scattering as well as optical microscope. A pseudo phase diagram reminiscent of a lower critical solution temperature (LCST) was established by a cloud point measurement. Several temperature-jump experiments were undertaken from ambient to a two-phase temperature region. The low PPTA content molecular composites were prepared by coagulating in a non-solvent, then by compression molding below the phase separation temperatures. The 30 wt% PPTA molecular composite exhibits over three-fold increase in tensile modulus relative to that of the neat AN, however, there is little or no improvement in the tensile strength. On the other hand, by a slight addition of AN into PPTA, the tensile and compressive failures of spun fibers may be improved.     

Dynamic rheological properties and microstructures of liquid-crystalline poly(<Emphasis Type="Italic">p</Emphasis>-phenyleneterephthalamide) solutions in the presence of single-walled carbon nanotubes

The rheological properties and microstructures of both poly(p-phenylene terephthalamide)/sulfuric acid(PPTA/H₂SO₄) and poly(p-phenylene terephthalamide)/ single-walled carbon nanotubes/sulfuric acid (PPTA/SWNT/H₂SO₄) dopes were investigated with flat plate rotational rheometer, polarized optical microscope and differential scan calorimeter. The results showed that, the two types of dopes presented typical shear thinning behaviour even at low frequencies, at various temperatures as well as at all polymer concentrations, and that the relationships between complex viscosity and freqency and between zero shear viscosity and weight average molecular weight implied the tight PPTA chain contacts, somewhat the feature of flexible polymer entanglements. The protonation due to concentrated sulfuric acid allowed SWNT to be well dispersed in PPTA/SWNT/H₂SO₄ dopes. At the concentrations of SWNT, approximately over 0.2 wt%, a novel type of single phase nematic liquid crystal was formed. The dopes can be used to fabricate high performance fibers by dry-jet wet spinning process.     

鹤峰磷矿在硫、磷混酸中的溶解动力学

对鹤峰磷矿在硫、磷混酸中的溶解动力学进行了研究,考查了硫酸质量分散及反应温度对酸解过程的影响;选用考虑了自阻化因素的德罗兹多夫方程In100/(100-Kp)-βKKp%=kt描述酸解过程的动力学.研究结果表明:鹤峰磷矿在硫、磷混酸中的反应速率常数随温度升高而增加,随硫酸质量分效的增加而减小.该反应属于扩散控制,平均反应活化能约为32.7kJ/mol.