Block copolymer dynamic mechanical

This chapter deals almost exclusively with neat, or pure, diblock copolymer melts. Polymer blends are discussed in Chapter 9, micellar solutions in Chapter 12, and stabilized suspensions in Chapter 6. In the following, Section 13.2 briefly reviews the thermodynamics of block copolymers, and Section 13.3 describes the rheological properties and flow alignment of lamellae, cylinders, and sphere-forming mesophases of block copolymers. More thorough reviews of the thermodynamics and dynamics of block copolymers in the liquid state have been written by Bates and Fredrickson (1990 Fredrickson and Bates 1996). The processing of block copolymers and mechanical properties of the solid-state structures formed by them are covered in Folkes (1985). Biological applications are discussed in Alexandridis (1996). 

Multiblock polyethylene-polydimethylsiloxane copolymers were obtained by the reaction of silane terminated PDMS and hydroxyl terminated polyethylene oligomers in the presence of stannous octoate as the catalyst 254). The reactions were conducted in refluxing xylene for 24 hours. PDMS block size was kept constant at 3,200 g/mole, whereas polyethylene segment molecular weights were varied between 1,200 and 6,500 g/mole. Thermal analysis and dynamic mechanical studies of the copolymers showed the formation of two-phase structures with crystalline polyethylene segments. 

Short fiber reinforcement of TPEs has recently opened up a new era in the field of polymer technology. Vajrasthira et al. [22] studied the fiber-matrix interactions in short aramid fiber-reinforced thermoplastic polyurethane (TPU) composites. Campbell and Goettler [23] reported the reinforcement of TPE matrix by Santoweb fibers, whereas Akhtar et al. [24] reported the reinforcement of a TPE matrix by short silk fiber. The reinforcement of thermoplastic co-polyester and TPU by short aramid fiber was reported by Watson and Prances [25]. Roy and coworkers [26-28] studied the rheological, hysteresis, mechanical, and dynamic mechanical behavior of short carbon fiber-filled styrene-isoprene-styrene (SIS) block copolymers and TPEs derived from NR and high-density polyethylene (HOPE) blends. 

The dynamic mechanical behavior of the block copolymers of HB and HI are typified by the results obtained for the HIBI series which are given in Figure 15A and B which display spectra for different composition ratios. The transition behavior of the HBIB series is so similar that it will not be repeated here. The samples used for this study were compression molded and they all had been stored at room temperature between one to two months before use. The experiments were run at 110 Hz. The behavior of HB, represented by HIBI 100, is similar to that given in Figure 14B. 

The dynamic mechanical behavior indicates that the glass transition of the rubbery block is basically independent of the butadiene content. Moreover, the melting temperature of the semicrystalline HB block does not show any dependence on composition or architecture of the block copolymer. The above findings combined with the observation of the linear additivity of density and heat of fusion of the block copolymers as a function of composition support the fact that there is a good phase separation of the HI and HB amorphous phases in the solid state of these block copolymers. Future investigations will focus attention on characterizing the melt state of these systems to note if homogeneity exists above Tm. 

Recently, Kroeze et al. prepared polymeric iniferter 34 including poly(BD) segments in the main chain [152]. They successfully synthesized poly(BD)-block-poly(SAN), which was characterized by gel permeation chromatography, elemental analysis, thermogravimetric analysis, NMR, dynamic mechanical thermal analysis, and transmission electron microscopy. By varying the polymerization time and iniferter concentration, the composition and the sequence length were controlled. The analysis confirmed the chain microphase separation in the multiblock copolymers. 

Fig. 2a, b. Dynamic mechanical spectra of imide-aryl ether phenylquinoxaline block copolymers, copolymer 3a (---) and copolymer 3b (---)... 

Fig. 5. Dynamic mechanical spectrum of imide-perfluoroalkyl ether block copolymer 4a.

The mechanical properties at low strain rates, dynamic mechanical properties, creep-recovery behaviour, thermal expansion and thermal conductivity of foams manufactured from blends of LDPE with an EVA and with an isoprene-styrene block copolymer were studied as a function of the LDPE content in the blends. The experimental results demonstrated important aspects related to the modification of the foam properties by blending. 16 refs. 

The characterization of block or graft copolymers is generally much more difficult than that of random copolymers (see Sect. 23.2.7). Especieilly, DSC measurements are useful for the characterization of the different segments (determination of Tg). Also dynamic-mechanical measurements are used to distinguish statistical copolymers from those with block or graft structure. 

Cohen, R.E., Tschoegl,N.W, Dynamic mechanical properties of block copolymer blends—a study of the effects of terminal chains in elastomeric materials. I. Torsion pendulum measurements. Intern. J, Polymeric Mater. 2, 49-69 (1972) II. Forced oscillation measurements. Ibid 2, 205-223 (1973) III. A mechanical model for entanglement slippage. Ibid (in press). 

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