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Polyacrylonitrile Ternary System Thermodynamic Study of a Water–Dimethylformamide– Polyacrylonitrile Ternary System Lianjiang Tan,1 Ding Pan,1 Ning Pan2 1State Key Laboratory for Chemical Fiber Modification and Polymer Materials, Donghua University, Shanghai 201620, People’s Republic of China 2Biological and Agricultural Engineering Department, University of California, Davis, California 65616 Received 23 October 2007; accepted 6 March 2008 DOI 10.1002/app.28392 Published online 15 September 2008 in Wiley InterScience (www.interscience.wiley.com). ABSTRACT: Experimental cloud-point data were ob- formation. The skin–core structure and fingerlike pores in tained by cloud-point titration. The phase diagram for a polyacrylonitrile fiber may be effectively eliminated if the ternary system of water–dimethylformamide–polyacryloni- composition of the spinning solution is properly chosen, trile was determined by numerical calculation on the basis and consequently, homogeneous polyacrylonitrile fiber of the extended Flory–Huggins theory and was found to with a bicontinuous structure and good mechanical proper- agree well with the cloud-point data. To construct the theo- ties can be obtained through the spinning process. Ó 2008 retical phase diagram, three binary interaction parameters Wiley Periodicals, Inc. J Appl Polym Sci 110: 3439–3447, 2008 were obtained with different methods. The ternary phase diagram was used to investigate the mechanism of fiber Key words: fibers; mixing; phase behavior; thermodynamics INTRODUCTION with the method of cloud-point titration.1–11 At high polymer concentration, however, the interaction Polyacrylonitrile (PAN) is soluble in many polar or- between macromolecules is so strong that the poly- ganic liquids, such as dimethylformamide (DMF), di- mer solution shows signs of crystallization or methyl sulfoxide, and dimethyl acetemide. PAN becomes gel-like.2–5 From our previous studies, we solutions with certain concentrations can be used as learned the ternary phase diagram of a PAN solu- spinning solutions to produce precursor fibers for tion with a concentration over 8% could not be PAN-based carbon fibers, which largely determine the obtained through the cloud-point titration method. quality of PAN carbon fibers. The coagulation mecha- Because the concentration of PAN solution used for nism of PAN fibers during either wet spinning or dry- spinning is usually over 10%, the Flory–Huggins jet wet spinning is very complex because of the coexis- theory for such polymer solutions, also extended by tence of double diffusion and phase separation. During Tompa12 to ternary systems containing nonsolvent, the formation of an as-spun PAN fiber, the concen- solvent, and polymer, is needed to establish the trated polymer solution is transformed into a gel struc- phase diagram, including the binodal curve, spino- ture through a series of steps that involve the mixing dal curve, and critical point. In this study, a ternary and demixing of the components under a variety of system consisting of PAN, DMF, and water (H O), environmental conditions. Thus, it is clearly desirable 2 which is popular in the formation of PAN fibers, to formulate a thermodynamic framework applicable was investigated. Cloud-point titration was per- to the initial stages of fiber formation and using a ter- formed for PAN solutions with low concentrations nary phase diagram is deemed effective in this respect. to obtain the cloud-point curve, and the theoretical When the polymer concentration is low in a ter- ternary phase diagram at a temperature of 258C was nary system, its phase diagram can be constructed numerically calculated. PAN fibers were spun from the PAN solutions with different amount of H2O. Correspondence to: D. Pan ([email protected]). The cross-section morphology and the mechanical Contract grant sponsor: National Basic Research Program properties of the fibers were studied. Some conclu- (973 Program); contract grant number: 2006CB606505. Contract grant sponsor: National Natural Science Founda- sions on thermodynamic problems of fiber formation tion of China; contract grant number: 50333050. were reached after carefully analysis of the results. Contract grant sponsor: Shanghai Fundamental Theory Program; contract grant number: 07DJ14002. EXPERIMENTAL Contract grant sponsor: Specialized Research Fund for the Doctoral Program of Higher Education; contract grant num- Materials ber: 20020255010. PAN copolymers (acrylonitrile/itaconic acid 5 98 : 2) Journal of Applied Polymer Science, Vol. 110, 3439–3447 (2008) were purchased from Shanghai Institute of Synthetic VC 2008 Wiley Periodicals, Inc. Fiber (Shanghai, China) with a weight-average 3440 TAN, PAN, AND PAN molecular weight of 8 3 104 g/mol. DMF (chemi- Fiber formation cally pure) was purchased from Shanghai Chemical Four 20 wt % PAN/DMF spinning solutions contain- Reagent Co., Ltd. (Shanghai, China), and deionized ing different amounts of H O (0, 1, 3, and 5 wt %) H O was used as the nonsolvent. 2 2 were prepared with the aforementioned method. Dry-jet wet spinning was used to form the as-spun Determination of the cloud-point curve PAN fibers. The dope was spurted at 708C from a spinneret with a hole (diameter 5 0.8 mm, length–di- The cloud-point curve was determined by the titra- ameter ratio 5 10) and put into the coagulating bath tion method. For this purpose, PAN in DMF solutions with a DMF concentration of 50 wt % at 258C. The air with concentrations of 1, 2, 3, 4, 5, 6, and 7 wt % were gap between the spinneret and the coagulating bath prepared by the mixing of a required amount of was 3 cm. The extrusion velocity was 10.3 m/min, PAN powder and DMF in a round-bottom flask and the linear velocity of the first winding roller was sealed with a rubber septum stopper. The mixture fixed at 20.6 m/min, so the draw ratio was 2. was stirred by an electric paddle stirrer for 2 h at 508C for swelling and for 5 h at 708C for dissolving. During the titration process, the temperature of the Mechanical properties of the as-spun fibers mixture was controlled at 258C with a thermostatic The mechanical properties of the as-spun PAN fibers H2O bath. Deionized H2O was then introduced into the flask through the septum by a microsyringe were measured on an XQ-1 tensile-testing machine while the stirrer was still working for a thorough (custom made by Donghua University, China) under 5 mixing. At the first sight of turbidity, the addition of standard testing conditions (i.e., relative humidity 65 6 2%, temperature 5 27 6 28C) with a crosshead H2O was stopped, and the cloudy solution was agi- tated for 10 min and then left still for another speed of 10 mm/min at gauge length of 20 mm and an applied tension of 0.15 cN. In each case, 10 sam- 10 min. More H2O was added only when the solution became homogeneous again; otherwise, the deter- ples were tested, and the average values of tenacity mined point was considered as the onset of the and Young’s modulus were obtained. cloud point. The composition of the cloud point was then determined by measurement of the amount of Cross-section morphology of the as-spun fibers H2O, DMF, and PAN present in the flask. The cross sections of the as-spun fibers produced from the PAN solutions with different H2O contents Preparation of the PAN solution were made on a Hardy’s thin cross-section sampling A certain amount of PAN copolymer was dispersed device. The micrographs of the cross sections were taken with a JSM-5600LV scanning electron micro- in the mixture of DMF and H2O (the concentration scope (made by Jeol, Tokyo, Japan). of H2O was 2 wt %) in a three-necked bottle. The ex- istence of H2O may accelerate the coagulation of the spinning solution for fiber or film preparation. The resulting slurry was allowed to swell at 50 and 608C RESULTS AND DISCUSSION for 2 h each and was stirred by an electric paddle Cloud-point data stirrer. Subsequently, it was further stirred at 708C for 6 h to produce a viscous solution with 20 wt % Figure 1 shows the cloud-point curve for the H2O– PAN. Then, the solution was deaerated in a vacuum DMF–PAN system, which was the experimental drying oven and kept at 708C. binodal curve denoting the border between the com- positions that were completely stable, metastable, or unstable. Equilibrium swelling PAN films were prepared by a casting method with Determination of the thermodynamic parameters the PAN solution, six strips of 5 3 6mm2 PAN films, each with a weight of about 0.3 g and a thick- To calculate a phase diagram numerically, a set of ness of 50–60 lm. The strips were immersed in an three binary interaction parameter values should be H2O bath at constant temperature of 258C. After 24 h, known. The analysis of the binary systems allowed the strips were removed, passed between tissue us to apply physically realistic values of binary inter- paper, and weighed in a weighting bottle to get their action parameters to the ternary system investigated wet weight [Wwet (g)]. Then, the wet strips were in this study. In the following text, the subscripts 1, dried in a vacuum drying oven at 508C for 12 h so 2, and 3 refer to the nonsolvent, solvent, and poly- that their dry weight [Wdry (g)] was also gained. mer, respectively. Journal of Applied Polymer Science DOI 10.1002/app THERMODYNAMIC STUDY OF AN H2O–DMF–PAN SYSTEM 3441 Figure 2 g / 5 Figure 1 Cloud-point curve for the H O–DMF–PAN Relation between 12 and 2 (temperature 2 8 system. 25 C). H2O–DMF binary system H2O–PAN binary system According to the literature,13–16 the Flory–Huggins To evaluate the interaction parameter of a nonsol- interaction parameters for several solvent–nonsol- vent–polymer (H2O–PAN) binary system (g13), sev- vent binary systems can be expressed by the follow- eral experimental techniques can be used, such as ing equation: equilibrium swelling, adsorption, osmotic pressure, and light scattering.17,18 Among these, the method of b equilibrium swelling is simple and convenient as g12 ¼ a þ (1) 1 À g/2 well as effective.
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