Synthesis and copolymerization of new phosphorus‐containing acrylates

Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003     

The Mixed Spin-1/2 and Spin-1 Ising–Heisenberg Model in the Mean-Field Approximation: a New Approach

Thermodynamic properties of the mixed spin-1 and spin-1/2 Ising–Heisenberg model are studied on a honeycomb lattice using a new approach in the mean-field approximation to analyze the effects of longitudinal D_z and transverse D_x crystal fields. The phase diagrams are calculated in detail by studying the thermal variations of the order parameters, i.e., magnetizations and quadrupole moments, and compared with the literature to assess the reliability of the new approach. It is found that the model yields both second-and first-order phase transitions, and tricritical points. The compensation behavior of the model is also investigated for the sublattice magnetizations, and longitudinal and transverse quadrupolar moments. The latter type of compensation is observed in the literature but its possible importance is overlooked.     

Critical properties of mixed spin-1 and spin-5/2 with equal and unequal crystal fields

The effects of assuming equal or unequal crystal fields (CF) on the phase diagrams of a mixed spin-1 and spin-5/2 system are investigated in terms of the recursion relations on the Bethe lattice (BL). The equal CF case was considered for the coordination numbers q=3, 4, and 6, while for q=3 the unequal CF case was also studied. It was found that for the equal CF case, the model exhibits second-order phase transitions and two compensation temperatures for all q, the reentrant behavior for q=4 and first-order phase transitions and tricritical point (TCP) for q=6. In the unequal CF case for q=3, the system yields first- and second-order phase transitions, TCP's, and three compensation temperatures. In addition, the TCP's in a very short range are classified as the stable and unstable ones depending on their free energies.     

Dynamic phase transitions in the kinetic spin-1 Blume-Capel model on the Bethe lattice

The stationary states of the kinetic spin-1 Blume-Capel (BC) model on the Bethe lattice are analyzed in detail in terms of recursion relations. The model is described using a Glauber-type stochastic dynamics in the presence of a time-dependent oscillating external magnetic field (h) and crystal field (D) interactions. The dynamic order parameter, the hysteresis loop area and the dynamic correlation are calculated. It is found that the magnetization oscillates around nonzero values at low temperatures (T) for the ferromagnetic (F) phase while it only oscillates around zero values at high temperatures for the paramagnetic (P) phase. There are regions of the phase space where the two solutions coexist. The dynamic phase diagrams are obtained on the (kT/J,h/J) and (kT/J,D/J) planes for the coordination number q=4. In addition to second-order and first-order phase transitions, dynamical tricritical points and triple points are also observed.     

Spin-1 Blume–Capel model with random crystal field effects

The random-crystal field spin-1 Blume–Capel model is investigated by the lowest approximation of the cluster-variation method which is identical to the mean-field approximation. The crystal field is either turned on randomly with probability p$p$ or turned off with q=1−p$q=1-p$ in a bimodal distribution. Then the phase diagrams are constructed on the crystal field (Δ$\Delta$)–temperature (kT/J)$(kT/J)$ planes for given values of p$p$ and on the (kT/J,p$kT/J,p$) planes for given Δ$\Delta$ by studying the thermal variations of the order parameters. In the latter, we only present the second-order phase transition lines, because of the existence of irregular wiggly phase transitions which are not good enough to construct lines. In addition to these phase transitions, the model also yields tricritical points for all values of p$p$ and the reentrant behavior at lower p$p$ values.     

The Bethe lattice treatment of sound attenuation for a spin- 3/2 Ising model

The sound attenuation phenomena is investigated for a spin- 3/2 Ising model on the Bethe lattice in terms of the recursion relations by using the Onsager theory of irreversible thermodynamics. The dependencies of sound attenuation on the temperature (T$T$), frequency (w$w$), Onsager coefficient (γ$\gamma$) and external magnetic field (H$H$) near the second-order (_Tc)$\left(T_c\right)$ and first-order (_Tt)$\left(T_t\right)$ phase transition temperatures are examined for given coordination numbers q$q$ on the Bethe lattice. It is assumed that the sound wave couples to the order-parameter fluctuations which decay mainly via the order-parameter relaxation process, thus two relaxation times are obtained and which are used to obtain an expression for the sound attenuation coefficient (α)$\left(\alpha \right)$. Our investigations revealed that only one peak is obtained near _Tt$T_t$ and three peaks are found near _Tc$T_c$ when the Onsager coefficient is varied at a given constant frequency for q=3$q=3$. Fixing the Onsager coefficient and varying the frequency always leads to two peaks for q=3,4$q=3,4$ and 6 near _Tc$T_c$. The sound attenuation peaks are observed near _Tt$T_t$ at lower values of external magnetic field, but as it increases the sound attenuation peaks decrease and eventually disappear.     

Multicritical behaviors of the antiferromagnetic Blume–Emery–Griffiths model with the external magnetic field on the Bethe lattice

The antiferromagnetic Blume–Emery–Griffiths model in an external magnetic field is studied by using the exact recursion relations on the Bethe lattice for arbitrary values of biquadratic and for negative values of bilinear interactions. We have studied the thermal variations of two-sublattice magnetizations belonging to spin-1 BEG model to obtain the phase diagrams on the (H/|J|,kT/|J|)$(H/|J|,\mathit{kT}/|J|)$ plane. As a result, we have found that the system presents second- and first-order phase transitions, therefore, tricritical points for appropriate values of K/|J|$K/\left|J\right|$, D/|J|$D/\left|J\right|$ and q  . We have also found that the second-order phase transition lines exhibit reentrant phenomena in temperature, besides it also shows reentrant phenomena for the first-order phase lines in external magnetic field for q=4$q=4$ and 6.     

An exact formulation of the Blume-Emery-Griffiths model on a two-fold Cayley tree model

A two-fold Cayley tree graph with fully q-coordinated sites is constructed and the spin-1 Ising Blume-Emery-Griffiths model on the constructed graph is solved exactly using the exact recursion equations for the coordination number q = 3. The exact phase diagrams in (kT/J, K/J ) and (kT/J, D/J) planes are obtained for various values of constants D/J and K/J, respectively, and the tricritical behavior is found. It is observed that when the negative biquadratic exchange (K) and the positive crystal-field (D) interactions are large enough, the tricritical point disappears in the (kT/J, K/J) plane. On the other hand, the system always exhibits a tricritical behavior in the phase diagram of (kT/J, D/J) plane. Received 8 June 2001 and Received in final form 28 September 2001     

Thermal entanglement in two-qutrit spin-1 anisotropic Heisenberg model with inhomogeneous magnetic field

The thermal entanglement of a two-qutrit spin-1 anisotropic Heisenberg XXZ chain in an inhomogeneous magnetic field is studied in detail. The effects of the external magnetic field (B), a parameter b which controls the inhomogeneity of B, and the bilinear interaction parameters J_{x=Jy≠Jz on the thermal variation of the negativity are studied in detail. It is found that negativity N decreases when the values of magnetic field, inhomogeneity b and temperature are increasing. In addition, N remains at higher temperatures for higher values of Jz and lower values of B and b.}     

Lyotropic Liquid Crystal to Soft Mesocrystal Transformation in Hydrated Salt–Surfactant Mixtures

Hydrated CaCl₂, LiI, and MgCl₂ salts induce self‐assembly in nonionic surfactants (such as C₁₂H₂₅(OCH₂CH₂)₁₀OH) to form lyotropic liquid‐crystalline (LLC) mesophases that undergo a phase transition to a new type of soft mesocrystal (SMC) under ambient conditions. The SMC samples can be obtained by aging the LLC samples, which were prepared as thin films by spin‐coating, dip‐coating, or drop‐casting of a clear homogenized solution of water, salt, and surfactant over a substrate surface. The LLC mesophase exists up to a salt/surfactant mole ratio of 8, 10, and 4 (corresponding to 59, 68, and 40 wt % salt/surfactant) in the CaCl₂, LiI, and MgCl₂ mesophases, respectively. The SMC phase can transform back to a LLC mesophase at a higher relative humidity. The phase transformations have been monitored using powder X‐ray diffraction (PXRD), polarized optical microscopy (POM), and FTIR techniques. The LLC mesophases only diffract at small angles, but the SMCs diffract at both small and wide angles. The broad surfactant features in the FTIR spectra of the LLC mesophases become sharp and well resolved upon SMC formation. The unit cell of the mesophases expands upon SMC transformation, in which the expansion is largest in the MgCl₂ and smallest in the CaCl₂ systems. The POM images of the SMCs display birefringent textures with well‐defined edges, similar to crystals. However, the surface of the crystals is highly patterned, like buckling patterns, which indicates that these crystals are quite soft. This unusual phase behavior could be beneficial in designing new soft materials in the fields of phase‐changing materials and mesostructured materials, and it demonstrates the richness of the phase behavior in the salt–surfactant mesophases.