Radiation induced embrittlement of PTFE

The radiochemical degradation of polytetrafluoroethylene (PTFE) samples has been studied in air at dose rate 100 Gy/h for doses up to 5000 Gy, at ambient temperature. The polymer degradation has been monitored by DSC, tensile testing and Essential Work of Fracture (EWF) testing. Some fractured samples have been observed by scanning electron microscopy. The polymer undergoes a fast chain scission, its number average molar mass is divided by about 20 for a dose of 1000 Gy and tends towards a pseudo asymptotic value of ∼20 kg mol⁻¹ (against 6200 kg mol⁻¹ initial value). The modulus and yield characteristics seem to be almost unaffected whereas ultimate properties undergo strong variations. The ultimate elongation ε_R and the EWF plastic work characteristic βw_p first increase and then decrease. The ultimate stress decreases and tends towards a pseudo asymptotic value. The mechanisms of radiation induced ultimate property changes are discussed. The first stage could be due to the destruction of non-extended tie molecules (due to the presence of very long chains) responsible for interfibrillar bridging during fracture. The (more classical) second stage is a progressive embrittlement due to the destruction of the entanglement network. The critical molar mass M′_c for embrittlement is such as M′_c∼50M_e, M_e being the molar mass between entanglements in the melt. This relationship could be a general characteristic of high crystallinity non-polar polymers.     

Preparation conditions and swelling equilibria of dextran hydrogels prepared by some crosslinking agents

Crosslinking reactions of Dextran (Dx) (M_n of 2.0×10⁶ g mol⁻¹) with some selective Cl-, P- and N-containing functional monomers such as epichlorohydrin (ECH), phosphorus oxychloride (POC1₃) and N,N′-methylenebisacrylamide (MBAM) were carried out in the basic aqueous solutions (2.8 N NaOH) at 25-50 °C. The optimum conditions of the effective swelling and crosslinking for the each system studied were found in copper (CuCl₂·2H₂O) solution. The percent swelling, equilibrium swelling, initial rate of swelling, swelling rate of constant, equilibrium water content, and diffusion type and constant values were evaluated for Dx/crosslinker (CL) systems at 1 mg/100 ml copper (CuCl₂·2H₂O) solution. A substantial difference of these parameters observed for the various Dx/CL systems was explained by the effect of nature of crosslinking agents on the mechanism of crosslinking and swelling processes. It was shown that S_eq and M_c values increase depending on the nature of CLs in the following order: ECH>MBAM>POCl₃. General scheme and proposed mechanism of crosslinking reactions in the Dx/CL systems were also described.     

Diffusion of linear macromolecules and spherical particles in semidilute polymer solutions and polymer networks

The dynamics of fluorescently labeled linear macromolecules and spherical particles that are enclosed in semidilute polymer matrixes was studied by fluorescence recovery after photobleaching. The experiments were designed such that the transition from a semidilute solution to a permanent network could be covered. This was achieved by employing a matrix polymer, polyacrylamide, carrying pendant dimethylmaleimide groups. Stepwise irradiation of such samples in the presence of a triplet sensitizer causes successive dimerization of the maleimides leading to progressive crosslinking.Studies were performed with varying concentrations of matrix polymer (20-80 g L⁻¹) as well as different molar masses (200,000-1,300,000 g mol⁻¹) and particle radii (17 and 36 nm) of enclosed labeled probes. Results show notable differences between the behavior of linear and spherical tracers: while the mobility of flexible linear chains remains nearly unaffected by the transition from a semidilute polymer solution into a chemically crosslinked network, spherical tracers get completely immobilized when the degree of crosslinking exceeds a certain threshold.     

A rheology theory and method on polydispersity and polymer long-chain branching

Model calculations were performed to investigate the sensitivity of zero-shear melt viscosity (η₀ or Eta0) on the molecular weight (MW) polydispersity of linear polymers. Simulated MW distributions (MWD) were generated with the generalized exponential (GEX) distribution function for various levels of polydispersity M_w/M_n and M_z/M_w. For linear entangled polymeric chains in the melt, the linear viscoelastic properties were predicted by using the double reptation blending rule and the so-called BSW relaxation time spectrum, named after the authors: Baumgaertel, Schausberger and Winter [Baumgaertel M, Schausberger A, Winter HH. Rheol Acta 1990;29:400-8]. Published rheological parameters appropriate for polyethylene were used in the calculations. It was found that Eta0 depended mostly on M_w, but it also significantly depended on the extent of high-MW polydispersity M_z/M_w. A revision to the fundamental MW dependency of Eta0 was proposed to compensate for this polydispersity effect. To offset the polymer polydispersity differences, we propose a new MW average (M_HV or M_x with x = 1.5) to replace M_w in the historical rheological power-law equation of Eta0 ∝ M_w^a, where the literature value of exponent “a” ranges from 3.2 to 3.6. The use of M_HV instead of M_w in the power-law equation made the calculated Eta0 independent of the sample high-MW polydispersity. With the removal of the complication from polydispersity effect, the new Eta0 power law can now provide a more robust base for studying polymer long-chain branching (LCB). A new LCB index is thus proposed based on this new melt-viscosity power law. The values of M_HV in the new power law can be calculated for polymer samples from the conventional gel permeation chromatographic (GPC) slice data.     

Effect of crosslinking on the mobility of PDMS filled with polysilicate nanoparticles: Positron lifetime, rheology and NMR relaxation studies

We study the effect of adding trimethylsilyl-treated polysilicate nanoparticles (Rg ∼ 2.2 nm) to crosslinked poly(dimethylsiloxane) (PDMS) elastomers above the entanglement molecular weight. The results are compared to un-crosslinked PDMS of a similar molecular weight, reported in previous studies and filled with the same polysilicate nanoparticles.Three techniques are used and compared to assess the enhancement or reduction in mobility with addition of filler: positron annihilation lifetime spectroscopy (PALS), rheology and nuclear magnetic resonance (NMR) spin-spin relaxation (T₂) measurements. PALS measurements do not show any clear effect of the filler on the mobility of the chains, as assessed by the size of free volume holes, but reveal a net increase in free volume with temperature increase (from 30 °C to 60 °C). A reduction in the dynamic shear storage modulus (measured at 1 rad s⁻¹) is observed in the filled network relative to the unfilled polymer (from 63 kPa without filler to 44 kPa with 40 w/w% filler), attributed primarily to a partial inhibition of the chemical crosslinking reaction by the particles. The NMR relaxation measurements, instead, show a reinforcement of the polymer network with increasing addition of polysilicate particles, as revealed by the faster T₂ decays at higher filler loadings, caused by increasing polymer bridging and particle flocculation. Similar trends are observed at higher temperatures (up to 80 °C), with a higher overall mobility. The apparent disagreement between rheology and NMR stems from the fact that rheology reflects bulk mobility and is primarily sensitive to chemical crosslinks in the network, while NMR probes segmental dynamics, which are affected by the presence of particles.In un-crosslinked PDMS instead, both rheology and NMR show an initial increase in mobility at low filler content, followed by reinforcement with further particle addition. These results strongly suggest that entanglements and filler-induced packing disruption, rather than free volume, play a major role in polymer dynamics.     

Synthesis, characterization and fluorescence adjustment of well-defined polymethacrylates with pendant π-conjugated benzothiazole via atom transfer radical polymerization (ATRP)

Two compounds containing the benzothiazole moiety, 4-(2-benzothiazole-2-yl-vinyl)-phenyl methacrylate (BVMA) and 2-bromo-2-methyl-propionic acid 4-(2-benzothiazole-2-yl-vinyl)-phenyl ester (BPBVE) were synthesized. Atom transfer radical polymerization (ATRP) of BVMA was conducted at 60 °C using BPBVE and CuBr/2,2′-bipyridine (BPY) as initiator and catalyst, respectively. Chain extension with 4-methacryloxy-hexyloxy-4′-nitrostilbene (MHNS) was conducted using PBVMA as the macroinitiator. The homopolymer PBVMA in DMF solution emitted blue fluorescence, and the copolymer PBVMA-b-PMHNS emitted orange fluorescence at about 610 nm due to the intramolecular energy transfer. ATRP of BVMA was also conducted using 2-bromo-2-methyl-propionic acid 4-nitrostilbene-hexyloxy ester (BPNHE) as an initiator. The obtained polymer was characterized via ¹H NMR and the fluorescence intensity was found to change with increasing number average molecular weight (M_n). The polymer with M_n = 15900 emitted white fluorescence in DMF solution.     

Affine deformation of single polymer chain in poly(methyl methacrylate) films under uniaxial extension observed by scanning near-field optical microscopy

The conformation of single poly(methyl methacrylate) chain in the uniaxially stretched film was observed by the combination of the fluorescence labeling technique and scanning near-field optical microscopy (SNOM). The dimension of the individual probe chain (M_w = 1.99 × 10⁶) along the extension axis was evaluated from SNOM image. In the high molecular weight matrix (M_w = 1.89 × 10⁶) the average extension ratio at the single chain level coincided with the macroscopic extension ratio. The distribution of the chain conformation was in good agreement with that of the freely jointed chain followed by affine deformation. On the other hand, the probe chain embedded in the low molecular weight matrix (M_w = 1.76 × 10⁵) showed the smaller extension than that expected from the affine deformation. This suggests that the conformation of the probe chain is affected by the relaxation of the short surrounding chains through disentanglement.     

Cross-linked latex particles grafted with polyisoprene as model rubber-compatible fillers

Model filler particles were obtained by grafting polyisoprene (PIP) chains onto spherical latex particles of polystyrene cross-linked with 12 mol% divinylbenzene. These particles, with a narrow size distribution and a diameter of ca. 400 nm, were synthesized by emulsifier-free starved-feed emulsion polymerization. Acetyl coupling sites were introduced randomly at either low (5 mol%) or high (30 mol%) target substitution levels on the latex particles by Friedel-Crafts acylation with acetyl chloride and AlCl₃ in nitrobenzene. ‘Living’ polyisoprenyllithium chains, generated from isoprene and sec-butyllithium (sec-BuLi), were then coupled with the acetylated particles. The PIP side chains had a high 1,4-polyisoprene microstructure content and a number-average molecular weight (M_n) of either 1.5 × 10³ (1.5 K), 5 × 10³ (5 K), or 3 × 10⁴ (30 K). The PIP content of the grafted particles was determined from the yield of isolated particles and by ¹H NMR spectroscopy analysis. The grafted latex particles were blended in solution with linear polyisoprene (M_n = 3.95 × 10⁵, 395 K). The influence of the filler-matrix interactions on the rheological behavior of the blends was determined by dynamic mechanical analysis for the different filler blends. Increases in complex viscosity and storage modulus, and decreased damping factors were observed in all cases relatively to the pure matrix polymer. The enhancements, decreasing in the order 30 mol% > 5 mol% acetylation, and with the grafted PIP chain length as 30 K > 5 K ≈ 1.5 K, are deemed to reflect the extent of interactions between the filler particles and the polymer matrix.     

A convenient route to high molecular weight highly isotactic polystyrene using Ziegler-Natta catalysts and ultrasound

Ziegler-Natta (TiCl₄/AlEt₃) catalysts and ultrasound were used to prepare highly isotactic polystyrene (ca. 99%) with a molecular weight of 4.7×10⁶ mol g⁻¹ and low molecular weight distribution (M_w/M_n=1.6) via a convenient method. Ultrasound was most effective if applied only during an initial stage in the polymerisation, most likely permitting dispersion of catalyst particles which were subsequently coated and separated by growing polymer chains. Yields could be improved by varying the amount of catalyst and reaction time.     

Molecular weight and temperature dependence of self-diffusion coefficients in polyethylene and polystyrene melts investigated using a modified n.m.r. field-gradient technique

Self-difusion in polyethylene and polystyrene melts has been investigated using a modified n.m.r. field-gradient technique. In both polymer examples, self-diffusion coefficients were found to be proportional to M^?2.0±0.1_w above and below the critical molecular weight M_c. The observation of undeuterated chains in deuterated matrices of varying chain length indicates only relatively weak matrix effects. The influence of internal field gradients, which have previously been reported for polyethylene melts, is demonstrated and discussed. Certain peculiarities have been observed in the temperature dependences of the diffusion coefficients.     

Termination rate coefficients for acrylamide in the aqueous phase at low conversion

The kinetics of acrylamide (AAm) free radical polymerization at low conversion of monomer to polymer in the aqueous phase was investigated at 50 °C using γ-radiolysis relaxation, which is sensitive to radical-loss processes. The values of the termination rate coefficients for AAm ranged from 8×10⁶ to 3×10⁷ M⁻¹ s⁻¹ as the weight fraction of polymer ranged from 0.002 to 0.0035, which is significantly lower than the low-conversion values for monomers such as styrene (2×10⁸ M⁻¹ s⁻¹) and methyl methacrylate (4×10⁷ M⁻¹ s⁻¹) in organic media. These can be quantitatively explained by applying a chain-length-dependent model of free-radical polymerization kinetics [Russell GT, Gilbert RG, Napper DH. Macromolecules 1992;25:2459. [19]] in which termination kinetics are expressed in terms of a diffusion-controlled encounter of radicals which ultimately yields an expression for the chain-length-averaged termination rate coefficient, 〈k_t〉. The lower 〈k_t〉 for AAm arises due to a combination of the high k_p value, promoting rapid formation of slower terminating long chains, and the slow diffusion of short propagating chains, relative to other common monomers. The chain transfer to monomer constant for AAm in water at 50 °C, C_M, was estimated using the chain-length-distribution method with correction for band-broadening [Castro JV, van Berkel KY, Russell GT, Gilbert RG. Aust J Chem 2005;58:178. [21]] and found to be 1.2×10⁻⁴ (±10%). The diffusion characteristics for AAm were adapted from those obtained for a similar aqueous system (hydroxyethyl methacrylate) together with a 0.5 exponent for the power law dependence on penetrant degree of polymerization at zero weight fraction polymer. This provides an adequate fit to the 〈k_t〉 data. This is the first application of the chain-length-dependent model to describe experimental termination rate coefficients for an aqueous system at low conversion to polymer. The result that the experimental termination rate coefficients can be reproduced with an a priori model with physically reasonable parameters supports the physical assumptions underlying that model.     

Synthesis of star polymer by means of the living polymerization of [(o-trifluoromethyl)phenyl]acetylene using a MoOCl4-based catalyst and the linking method

A star polymer was synthesized by addition of 1,4-diethynyl-2,5-dimethylbenzene as linking agent (30 °C, 24 h) after living polymerization of [(o-trifluoromethyl)phenyl]acetylene (o-CF₃PA) with MoOCl₄-n-Bu₄Sn-EtOH catalyst (in anisole, 30 °C, 20 min; [Mo]=10 mM, [P^∗]/[Mo]=40%, [o-CF₃PA]₀=200 mM). The M_n values of the living and star polymers were 8.1×10³ and 5.3×10⁴, respectively, according to gel permeation chromatography, while these values determined by multi-angle laser light scattering (MALLS) were 7.8×10³ and 2.5×10⁵. The M_w/M_n and arm number of the star polymer were 1.04 and 29, respectively, according to MALLS. The molecular weight and arm number of star polymer increased with increasing linking agent concentration and polymerization temperature.     

Swelling behavior of amphiphilic gels based on hydrophobically modified dimethylaminoethyl methacrylate

The amphiphilic gels based on hydrophobically modified dimethylaminoethyl methacrylate with different 1-bromoalkanes (1-C_nH_2n+1Br, n = 2, 4, 6, 8, 12) were synthesized by radiation-induced polymerization and crosslinking. The length of alkyl side chains had significant influence on the swelling behavior of the resulting gels. The swelling degree of the gels decreased with the increase of side chain length, and the gel hardly swelled when n = 12. The effect of temperature and ionic strength on the swelling behavior of the resulting gels revealed that (1) the gels with longer side chains (n ≥ 8) had upper critical solution temperature, while other gels were not thermo-sensitive. (2) Antipolyelectrolyte effect was observed when immersing the gels (n ≥ 8) in NaCl solutions in certain concentration range. The dramatic difference in swelling behavior was attributed to the different gel structures. The gels with short side chains (n ≤ 6) had cellular structure of normal polyelectrolyte gels. The gels (n ≥ 8) had an aggregation gel structure caused by the hydrophobic interaction among alkyl groups and the formation of ion-cluster between tetra-alkyl ammonium cation and Br⁻, which had been analyzed with the aid of SEM, Br⁻-selective electrode and fluorescence molecular probe.     

Lyotropic liquid crystal formation of polystyrene polymacromonomers in dichloromethane

Liquid crystallinity of dichloromethane (DCM) solutions of five samples of polymacromonomer F65 consisting of 65 styrene residues in each side chain was studied by birefringence observation and phase separation experiments at different temperatures in a molecular weight range from 9.4 × 10⁵ to 4.1 × 10⁶. Dilute-solution characterization was also made by light scattering and viscometry in DCM at 20 °C. The polymer concentration c_I on the phase boundary between the isotropic and biphasic regions was lower than the previously determined c_I for a polymacromonomer with a shorter side-chain length of 33 styrene residues at the same molecular weight, reflecting the higher chain stiffness and larger diameter of the F65 polymer. The molecular weight dependence of c_I for the two polymacromonomers (at 20 °C) was explained almost quantitatively by the scaled-particle theory for worm-like cylinders with the model parameters (the Kuhn length, the linear mass density, and the chain diameter) describing gyration radius and intrinsic viscosity data in DCM but without chain-end effect. It was concluded that this theory is capable of predicting the phase boundary concentration of brush-like polymers with essentially the same degree of accuracy as that known for linear, stiff chains.     

Effects of molecular weight on poly(ω-pentadecalactone) mechanical and thermal properties

A series of poly(ω-pentadecalactone) (PPDL) samples, synthesized by lipase catalysis, were prepared by systematic variation of reaction time and water content. These samples possessed weight-average molecular weights (M_w), determined by multi-angle laser light scattering (MALLS), from 2.5 × 10⁴ to 48.1 × 10⁴. Cold-drawing tensile tests at room temperature of PPDL samples with M_w between 4.5 × 10⁴ and 8.1 × 10⁴ showed a brittle-to-ductile transition. For PPDL with M_w of 8.1 × 10⁴, inter-fibrillar slippage dominates during deformation until fracture. Increasing M_w above 18.9 × 10⁴ resulted in enhanced entanglement network strength and strain-hardening. The high M_w samples also exhibited tough properties with elongation at break about 650% and tensile strength about 60.8 MPa, comparable to linear high density polyethylene (HDPE). Relationships among molecular weight, Young's modulus, stress, strain at yield, melting and crystallization enthalpy (by differential scanning calorimetry, DSC) and crystallinity (from wide-angle X-ray diffraction, WAXD) were correlated for PPDL samples. Similarities and differences of linear HDPE and PPDL molecular weight dependence on their mechanical and thermal properties were also compared.     

RAFT polymerization and self-assembly of thermoresponsive poly(N-decylacrylamide-b-N,N-diethylacrylamide) block copolymers bearing a phenanthrene fluorescent α-end group

Phenanthrene α-end-labeled poly(N-decylacrylamide-b-N,N-diethylacrylamide) (PDcA_n-b-PDEA_m) block copolymers consisting in a highly hydrophobic block (n = 11) and a thermoresponsive block with variable length (79 ≤ m ≤ 468) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. A new phenanthrene-labeled chain transfer agent (CTA) was synthesized and used to control the RAFT polymerization of a hydrophobic acrylamide derivative, N-decylacrylamide (DcA). This first block was further used as macroCTA to polymerize N,N-diethylacrylamide (DEA) in order to prepare diblock copolymers with the same hydrophobic block of PDcA (number average molecular weight: M_n = 2720 g mol⁻¹, polydispersity index: M_w/M_n = 1.13) and various PDEA blocks of several lengths (M_n = 10,000-60,000 g mol⁻¹) with a very high blocking efficiency. The resulting copolymers self-assemble in water forming thermoresponsive micelles. The critical micelle concentration (CMC) was determined using Förster resonance energy transfer (FRET) between phenanthrene linked at the end of the PDcA block and anthracene added to the solution at a low concentration (10⁻⁵ M), based on the fact that energy transfer only occurs when phenanthrene and anthracene are located in the core of the micelle. The CMC (∼2 μM) was obtained at the polymer concentration where the anthracene fluorescence intensity starts to increase. The size of the polymer micelles decreases with temperature increase around the lower critical solution temperature of PDEA in water (LCST ∼ 32 °C) owing to the thermoresponsiveness of the PDEA shell.     

Molecular characteristics of poly(1-trimethylsilyl-1-propyne) in dilute solutions

Samples and fractions of a membrane-forming polymer, poly(1-trimethylsilyl-1-propyne) (PTMSP), were studied by methods of molecular hydrodynamics (velocity sedimentation, translational isothermal diffusion and viscometry) in cyclohexane in the molecular mass range 60<M×10⁻³ g mol⁻¹<430. The following molecular-mass dependencies of the hydrodynamic characteristics (intrinsic viscosity [η] (cm³ g⁻¹), sedimentation coefficient s₀(s) and translational diffusion coefficient D₀ (cm² s⁻¹)) were established: [η]=0.198 M^0.50±0.06; s₀=8.66×10⁻¹⁶M^0.50±0.04; D₀=9.30×10⁻⁵M^{−0.50±0.04}. On the basis of the hydrodynamics data the equilibrium rigidity and hydrodynamic diameter of PTMSP chains were evaluated. The equilibrium properties of the different disubstituted polyacetylenes molecules are compared on the base of the normalised scaling plots.     

Dimensions and viscosity behavior of polyelectrolyte brushes in aqueous sodium chloride. A polymacromonomer consisting of sodium poly(styrene sulfonate)

Nine samples of a polymacromonomer consisting of sodium poly(styrene sulfonate) and having a side-chain polymerization degree of 15 are investigated by light scattering, small-angle X-ray scattering, and viscometry with 0.05 M aqueous NaCl at 25 °C as the solvent. The (total) weight-average molecular weight M_w ranges from 2.2 × 10⁴ to 7.1 × 10⁶. The radii of gyration, scattering functions, and intrinsic viscosities determined as functions of M_w are analyzed in terms of the cylindrical wormlike chain model. The estimated Kuhn segment length of about 120 nm is much larger than that (16 nm) for the polystyrene polymacromonomer with the equivalent side-chain length in toluene, a good solvent, while the chain thickness (5.5 nm) is comparable to or only slightly larger than that (5 nm) of the nonionic polymer. It is thus concluded that the electrostatic repulsion between side chains significantly stiffens the main chain of the polyelectrolyte brush.     

Adhesion and friction behaviours of polydimethylsiloxane - A fresh perspective on JKR measurements

The self-adhesion of a variety of polydimethylsiloxanes (PDMS) has been investigated using a newly developed JKR apparatus that can also determine the associated friction behaviour of the same sample. The results have been interpreted using the complete JKR model by incorporating the indentation data also in the analysis. By varying the molecular mass M_c of PDMS from 6 to 28 kg/mol the elastic modulus E decreases from 1.16 to 0.71 MPa while the work of adhesion remains about constant. In contrast measurements of the friction of the same systems indicate an increase of the friction force. Introduction of dangling chains leads to a strong decrease of E from 1.16 to 0.56 MPa for low M_c and from 0.71 to 0.09 MPa for high M_c and again only to minor changes in W. The latter results can be understood from an inward distribution of the dangling ends.     

Electrospinning of linear homopolymers of poly(methyl methacrylate): exploring relationships between fiber formation, viscosity, molecular weight and concentration in a good solvent

A series of seven linear homopolymers of poly(methylmethacrylate) ranging from 12,470 to 365,700 g/mol M_w, were utilized to further explore scaling relationships between viscosity and concentration in a good solvent at 25 °C and to investigate the impact of these relationships on fiber formation during electrospinning. For each of the polymers investigated, chain dimensions (hydrodynamic radius and radius of gyration) were measured by dynamic light scattering to determine the critical chain overlap concentration, c^*. The experimentally determined c^*, was found to be in good agreement with the theoretically determined value that was calculated by the criteria c^*∼1/[η], where the intrinsic viscosity was estimated from the Mark-Houwink parameters, K and a (at 25 °C in dimethyl formamide) obtained from the literature. The plot of the zero shear viscosity vs. c/c^* distinctly separated into different solution regimes, viz. dilute (c/c^*<1), semidilute unentangled (1<c/c^*<3) and semidilute entangled (c/c^*>3). The crossover between semidilute unentangled and semidilute entangled regimes in the present investigation occurred at c/c^*∼3, which, therefore, marked the onset of the critical chain entanglement concentration, c_e, according to the procedure utilized by Colby and co-workers [Colby RH, Rubinstein M, Daoud M. J de Phys II 1994;4(8):1299-310. [52]]. Electrospinning of all solutions was carried out at identical conditions to ascertain the effects of solution concentration, molecular weight, molecular weight distribution and viscosity on fiber formation and morphological features of the electrospun material. Only polymer droplets were observed to form from electrospinning of solutions in the dilute concentration regime due to insufficient chain overlap. As the concentration was increased, droplets and beaded fibers were observed in the semidilute unentangled regime; and beaded as well as uniform fibers were observed in the semidilute entangled regime. Uniform fiber formation was observed at c/c^*∼6 for all the narrow MWD polymers (M_w of 12,470-205,800 g/mol) but for the relatively broad MWD polymers (M_w of 34,070 and 95,800 g/mol), uniform fibers were not formed until higher concentrations, c/c^*∼10, were utilized. Dependence of fiber diameter on concentration and viscosity was also determined, viz. fiber dia∼(c/c^*)^3.1 and respectively. These scaling relationships were in general agreement with that observed by Mckee et al. [McKee MG, Wilkes GL, Colby RH, Long TE. Macromolecules 2004;37(5):1760-67. [33]].