Unusual finite size effects in the Monte Carlo simulation of microphase formation of block copolymer melts

Extensive Monte Carlo simulations are presented for the Fried-Binder model of block copolymer melts, where polymer chains are represented as self and mutually avoiding walks on a simple cubic lattice, and monomer units of different kind (A, B) repel each other if they are nearest neighbors (ε_AB > 0). Choosing a chain length N = 20, vacancy concentration Φ_v = 0,2, composition ƒ = 3/4, and a L × L × L geometry with periodic boundary conditions and 8 ≤ L ≤ 32, finite size effects on the collective structure factor S(q) and the gyration radii are investigated. It is shown that already above the microphase separation transition, namely when the correlation length ξ(T) of concentration fluctuations becomes comparable with L, a nonmonotonic variation of both S(q) and the radii with L sets in. This variation is due to the fact that the wavelength λ^*(T) of the ordering (defined from the wavenumber q^* where S(q) is maximal at λ^* = 2 π/q^*) in general is incommensurable with the box. The competition of two nontrivial lengths ξ(T), λ^* (T) with L makes the straigthforward application of finite size scaling techniques impossible, unlike the case of polymer blends. Since also the specific heat is found to have a broad rounded peak near the transition only, locating the transition accurately from Monte Carlo simulations remains an unsolved problem.     

X-ray investigation of the nematic and reentrant nematic phases of N-[(4-n-octyloxybenzoyloxy)-salicilidene]-4′-cyanoaniline

We have performed an X-ray scattering study of the nematic-smectic A and reentrant nematic-smectic A phase transitions in N-[(4-n-octyloxybenzoyloxy)-salicilidene]-4′-cyanoaniline (OOBOSCA). A diffractometer with a linear position sensitive detector was used. The results show that the smectic phase in OOBOSCA is of the A_d type with an interlayer spacing incommensurate with the molecular length L; d ∽ 1·2L. In the reentrant nematic phase two types of fluctuation modes were found. One of them corresponds to the monolayer wavevector q ₁ ∽ 2π/L, and the other is due to the partial bilayer fluctuations with the wavevector q ₂ ∽ 0·8q ₁. The temperature dependences of the interlayer spacing, X-ray scattering intensity and longitudinal correlation length for both types of layering in the reentrant nematic phase are presented. The change of the fluctuation regime from S_Ad, to S_Cd type with decreasing temperature in the reentrant nematic phase of OOBOSCA was found. The results are discussed on the basis of models with competing order parameters. The influence of alkyl chain flexibility on the stability of a partial bilayer smectic phase is also considered.     

Dynamics of end-grafted polystyrene brushes in theta solvents

The dynamics of the concentration fluctuations in end-grafted polystyrene brushes in a theta solvent (cyclohexane) are probed by evanescent wave dynamic light scattering at different wavevectors q and temperatures. When the solvent quality changes from marginal to poor, the relaxation function C(q, t) exhibits strong effects as compared with the smooth variation of the brush density profile. From a single exponential above 50 °C, C(q, t) becomes a two-step decay function. The fast decay is still assigned to the cooperative diffusion albeit slower than in the good solvent regime whereas the slow nonexponential and nondiffusive process might relate to microsegragated and/or chain dynamics in the present polydisperse brush. The relaxation function of the present three brushes with different grafting density reveals similarities and disparities between wet brushes and semidilute polymer solutions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3590–3597, 2006     

An analytical method of micropore filling of a supercritical gas

The supercritical gas adsorbed in the micropore having a strong molecular field was presumed to transform into the quasi-vapor to be filled in the micropore (quasi-vaporization adsorption mechanism). The Dubinin-Radushkevitch (DR) equation for micropore filling of vapor was extended to the quasi-vaporized supercritical gas using the quasi-saturated vapor pressureP _{0 q} and the inherent micropore volumeW _L . The reason why the concepts ofP _0q andW _L were introduced was explained with the molecule-pore interaction potential theory which is based on the Lennard-Jones interaction. The extended DR equation was named the supercritical DR equation. TheW _L was evaluated by the Langmuir plot of the adsorption isotherm for a supercritical gas and both ofP _0q andW _L provided the single reduced adsorption isotherms of supercritical NO, N₂, and CH₄ on activated carbon fibers and high surface area carbons were analyzed by the supercritical DR plots. The wide applicability of the reduced adsorption isotherm to these adsorption data was explicity shown. The two phase model of the organized and confined fluids was proposed in order to improve the quasi-vaporization adsorption mechanism.     

Computer simulation of brownian motion of a polyelectrolyte molecule (charged bead-spring model)

A Langevin equation of motion for a charged bead-spring statistical chain is written in difference form and the relaxation and equilibrium behavior of the chain is studied by computer simulation. Results are presented for the behavior of end-to-end length h, principal axes of the polymer ellipsoid L₁, L₂, L₃, and chain contour length c in terms of their averages, root mean square values, root mean square fluctuations, orientations, and relaxation strengths and times. The simulation was made with various sets of parameters, bead number N, charge on the bead q, and radius of ion atmosphere around the bead k^?1. It is found that 〈h²〉^1/2 and 〈L₁²〉^1/2 increase more strongly with increasing q and decreasing κ than 〈L₂²〉^1/2, 〈L₃²〉^1/2, and 〈c₁²〉^1/2, indicating that the chain is expanded in three dimensions and at the same time is extended along the end-to-end direction. The relaxation time τ_rot of rotation of the end-to-end vector, which is proportional to N² at q = 0, increases with increasing q and tends to be proportional to N³ for an extended chain, while the relaxation time τ_conf of the magnitude of h is almost independent of q and is always proportional to N². It is concluded that the extended chain possesses a well-defined end-to-end axis and the chain rotates as a whole with a relaxation time τ_rot which is much longer than τ_conf. The complex viscosity of the chain is calculated from the Fourier transform of the time–correlation function of momentum flux and is found to have a frequency spectrum similar to that observed for aqueous solutions of poly(acrylic acid). The dominant mode appearing in the low-frequency range is evidenced to arise from the rotation of the extended chain.     

X-ray study of the nematic and smectic A phases of the cyano-substituted pyridines

We report an X-ray study of lamellar ordering in the nematic and smectic A phases of a homologous series of polar liquid crystals, the 2-(4-alkylphenyl)-5-cyanopyridines (nCP). Experiments were carried out using a diffractometer with a linear position sensitive detector. In the nematic and smectic A phases of the nCP and their mixtures with non-polar 4-n-butyl-4′-methoxyazoxybenzene two types of layering were found. One corresponds to the fluctuations of the smectic density wave with a monolayer wavevector q ₁, and the other is due to the partial bilayer fluctuations with the incommensurate wavevector q ₂ ≠ q ₁/2. The temperature dependences of the X-ray scattering intensity and the longitudinal correlation length for both types of layering in the nematic phase are presented. The critical behaviour in the vicinity of the smectic A-nematic phase transition occurs for a fluctuation mode, either q ₁ or q ₂, depending on the position on the liquid crystal phase diagram. The influence of the molecular structure of cyano-substituted pyridines on the formation of layered structures of different types is also discussed.     

The behavior of xenon dynamic adsorption on granular activated carbon packed bed adsorber

In order to retard radioxenon release into the atmosphere from nuclear power station or to sensitively monitor its concentration to ensure environmental and human safety, it is necessary to know the behavior of xenon dynamic adsorption on granular activated carbon pack bed adsorber. The quantities, including the dynamic adsorption coefficient (k _d), the amount of xenon adsorbed (q), the length of mass transfer zone (L _MTZ) and the length of the unused bed (LUB), used to describe the adsorption behavior, were sorted out and calculated. The factors, including xenon concentrations, pressures and temperatures, to affect these quantities were investigated. The results show that: (1) The values of k _d and q decrease with increasing temperatures, but increase with increasing pressures, (2) The values of L _MTZ and LUB increase with increasing temperatures or pressures, but are independent of concentrations. Knowledge of these quantities is very helpful for packed bed adsorber operation.     

Kinetics of spinodal decomposition in mixtures of low molecular weight liquid crystals and flexible polymers

In this paper, the time-dependent Ginzburg-Landau model for mixtures containing nematogens has been applied to mixtures of low molecular weight liquid crystals and flexible polymers. Dynamic equations for the time evolution of concentration and orientation fluctuations and the structure factors for these fluctuations are given. It is shown that the coupling between concentration and orientation fluctuations is absent in the isotropic spinodal region, thus the evolution of the structure factors for the concentration fluctuations falls into the Cahn-Hilliard classic category and it exhibits no maximum in the structure factors of orientation fluctuations. We should emphasize that, in the anisotropic spinodal region, both concentration and orientation structure factors possess a maximum but not coincide with each other and both are shifting to smaller wave numbers according to the scaling relation, q_max ˜ τ^−α, as time increases. The value of a closely correlates to the interfacial free-energy parameters.     

Ligament-like tough double-network hydrogel based on bacterial cellulose

Using the double-network (DN) method, bacterial cellulose/polyacrylamide (BC/PAAm) DN gels able to sustain not only high elongation but also high compression have been synthesized by combining BC gel as the first network with PAAm as the second network in the presence of N,N′-methylene bisacrylamide (MBAA) as a cross-linker. This DN gel was obtained by modifying the monomer concentration of the second network, acrylamide monomer (AAm) and MBAA, and by controlling the water content of the first network, BC gel. The mechanical properties are discussed in term of the swelling degree (q), which is independent of the concentration of AAm and MBAA. It was found that, for BC/PAAm DN gels with the first network formed from BC gel with high q (BC _q=120), the tensile and compressive modulus (E) scales with q as E μ q ^{- 2} E \propto q^{ - 2} . The tensile fracture stress, σ _F, of this DN gel was almost independent of q, that is s_\textF μ q⁰, \sigma_{\text{F}} \propto q^{0}, but the compressive fracture stress, σ _F, scaled with q as E μ q ^{- 2} E \propto q^{ - 2} . Meanwhile, the tensile and compressive fracture strain (ε _F) of the gel is almost independent of q, which is caused by AAm concentration change, but linearly increased with q, which is caused by MBAA concentration change. Furthermore, by decreasing the water content of the BC gel prior to polymerization of the second (PAAm) network, a ligament-like tough BC/PAAm DN gel could be obtained with tensile strength of 40 MPa.     

Determination of chain stiffness and polydispersity from static light-scattering

Chain stiffness is often difficult to distinguish from molecular polydisperity. Both effects cause a downturn of the angular dependence at large q² (q = (4π/λ)sin θ/2) in a Zimm plot. A quick estimation of polydisperity becomes possible from a bending rod (BR) plot in which lim (c → 0) qRθ/Kc is plotted against q(〈S²〉_z)^1/2 = u. Flexible and semiflexible chains show a maximum whose position is shifted from u_max = 1.41 for monodisperse chains towards larger values as polydispersity is increased, while simultaneously, the maximum height is lowered. Stiff chains display a constant plateau at large q, its value is πM_L where M_L is the linear mass density. Using Koyama's theory, the number of Kuhn segments can be determined from the ratio of the maximum height to the plateau height, if the polydispersity index z = (M_w/M_n ? 1)^?1 is known. Thus, if the weight-average molecular weight M_w, is known, the contour length L_w, the number of Kuhn segments (N_k)_w, the Kuhn segment length l_k and the polydispersity of the stiff chains can be determined. The influence of excluded volume is shown to have no effect on this set of data. The reliability of this set can be cross-checked with the mean-square radius of gyration 〈s²〉_z which can be calculated from the Benoit-Doty equation for polydisperse chains. Rigid and slightly bending rods exhibit no maximum in the BR plot, and the effect of polydispersity can no longer be distinguished from a slight flexibility if only static scattering techniques are applied.     

Investigations by electrochemical quartz crystal impedance system-electrodeposition of silver and polyaniline

An electrochemical quartz crystal impedance system (EQCIS) which allows rapid and simultaneous measurements of admittance spectra of piezoelectric quartz crystal resonance during electrochemical processes was developed by combining an HP 4395A Network/Spectrum/Impedance analyzer with an EG & G M283 potentiostat. Non-linear least square regression analyses of simultaneously acquired conductance and susceptance data were discussed in detail, giving that R_m, C_s, 1/C_m (or L_m) and of as estimation parameters is the best choice among various fitting routines. Equivalent electrical circuit parameters of quartz crystal resonance during electrodeposition of silver and polyaniline and electrochemical processes of the deposits were obtained and discussed according to changes in electrode mass, electrode surface roughness and film conductivity etc. The significant changes of motional resistance R_m and static capacitance C, observed in the silver case was believed to result mainly from changes in electrode surface roughness and the linear relationship between them was well explained by the following equation, C_s = C_q+ C_e = ε_qA_q/ h_q + ε_ek²R_m/[h_e(ωρ_Lη_L]1/2.     

Creep recovery of acrylate urethane oligomer/acrylate networks. 2. Investigation of different modes of molecular motion

The creep recovery and dynamic mechanical properties of acrylate urethane oligomer/acrylate networks were investigated. The retardation spectra L_CR obtained from the creep recovery experiments were significantly different from the corresponding retardation spectra L_DMA obtained from the dynamic mechanical measurements. The reduced frequency ω^* dependence of L_DMA and the relaxation spectra H_DMA in the higher ω^* region were approximately represented as L_DMA ∝_ω^*−p and H_DMA ∝_ω^*q, although L_CR decreased faster than L_DMA with an increase in ω^*. The exponents q were close to ½ characterizing the Rouse modes in the systems containing an acrylate urethane oligomer of M_w = 5000 but less than ½ in the system containing an acrylate urethane oligomer of M_w = 12,000. For the latter systems, significant thermorheological complexity was observed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2543–2550, 1997     

Studies on nickel(II) complexes of N-aryl thioureas

The preparation and properties of the crystalline compounds of the type NiL ₄Cl₂, NiL ₂Cl₂ and NiLCl₂ (L=N-aryl thioureas) are described. Analytical, conductometric, magnetic and spectral data (infrared and electronic)_show that complexes of the type NiL ₄Cl₂ possess octahedral structure and those of NiL ₂Cl₂ and NiLCl₂ are characterised as distorted octahedral in solid state. The ligand field parametersD _q ,B and calculated from electronic spectral data, suggest a weak field for all the ligands. Metal sulphur bonding for all ligands is adduced from infrared and far infrared spectral studies.

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Untersuchungen an Nickel(II) Komplexen von N-Aryl-thioharnstoff Derivaten

Zusammenfassung Darstellung und Eigenschaften der kristallinen Verbindungen vom Typ NiL ₄Cl₂, NiL ₂Cl₂ und NiLCl₂ (L=N-Arylthioharnstoff) werden beschrieben. Magnetische Eigenschaften, Leitfähigkeitsmessungen, analytische und spektroskopische Daten beweisen, daß die Komplexe vom Typ NiL ₄Cl₂ oktaedrische Struktur besitzen; die Komplexe vom Typ NiL ₂Cl₂ und NiLCL₂ weisen eine verzerrt oktaedrische Geometrie auf. Die Ligandenfeld-ParameterD _q ,B und , die aus Elektronenanregungsspektren berechnet wurden, zeigen ein schwaches Feld für alle untersuchten Liganden an Aus Untersuchungen der Spektren des IR und fernen IR folgt, daß die Komplexe eine Metall—Schwefel-Bindung aufweisen.

     

Über die Meß-Strategie bei der Untersuchung der Röntgen-Kleinwinkelstreuung verdünnter Lösungen von Biopolymeren, 2. Mitt.

Zusammenfassung Der maximale Abstand der Meßpunkte bei der Registrierung von Röntgen-Kleinwinkelstreukurven ist durch die Beziehung b=(2L)^–1 gegeben.L ist der größte Durchmesser der untersuchten Objekte. Falls keine obere Schranke fürL vor der Messung bekannt ist, können Schranken für die Größe vonL mittles Ungleichungen aus dem ermittelten StreumassenradiusR _s abgeschätzt werden. Zu diesem Zweck wird für verschiedene Modellformen der Formfaktorq ₇₆=L (R _s)^–1 berechnet.

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Techniques of small-angle X-ray measurements in studies of diluted solutions of biopolymers, II

The largest distance between the sampling points by recording of the small-angle x-ray scattering is given as b= =(2L)^–1.L is the largest diameter of the objects of examination. If no upper limit ofL is known before of the measuring, one can estimate limits for the value ofL with help of unbalanced equations by means of the measured radius of gyrationR _s. For this end is the shape factorq ₇₆=L (R _s)^–1 calculated for different typs of particles.

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Mit 1 Abbildung     

Cylindrical molecular brushes with a loose grafting density

A cylindrical molecular brush with a low graft density was synthesized by two steps. Firstly, free radical alternating copolymerization of styrene (St) and N‐[2‐(2‐bromoisobutyryloxy)ethyl] maleimide (BiBEMI) gave a macroinitiator where pendant initiating sites for atom transfer radical polymerization (ATRP) being positioned along the backbone with an interval of four C? C bonds. The backbone‐to‐be with an alternating sequence was verified by elemental analysis (EA). Secondly, grafting poly(tert‐butyl acrylate) chains from the macroinitiator by ATRP produced the novel molecular brush. Size exclusion chromatography, static light scattering (SLS), and ¹H NMR and atomic force microscopy (AFM) were used to characterize the macroinitiator and the molecular brush. The results show that the backbone contains an average 730 repeat units (1 repeat unit = a pair of St and BiBEMI) and the absolute molecular weight of the brush, M_w,SLS, was 4.88 × 10⁶ Da. The brush reveals a number average length L_n to be 96 nm under AFM observation on carbon coated mica, corresponding to the length per main chain monomer unit (L_unit) of 0.066 nm, indicating a less extended conformation due to the low grafting density. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5527–5533, 2009     

Length scale hierarchy in sol,gel, and coacervate phases of gelatin

Length scale hierarchy in gelatin sol, gel, and coacervate (induced by ethanol) phases, having same concentration of gelatin in aqueous medium (13% w/v), has been investigated through small angle neutron scattering and rheology measurements. The static structure factor profile, I(q) versus wave vector q, was found to be remarkably similar for all these samples. This data could be split into three distinct q‐regimes: the low‐q regime, I_ex(q) = I_ex(0)/(1+q²ζ²)² valid for q < 3R_g^?1; the intermediate q‐regime, I(q) = I(0)/(1+q²ξ²) for 3R_g^?1 < q < ξ^?1; and the asymptotic regime, I(q) = (c/q) exp(?R_c²q²/2) for q > ξ^?1. Consequently, three distinct length scales could be deduced from structure factor data: (a) inhomogeneity of size, ζ = 20 ± 1 nm for all the three phases; (b) average mesh size, ξ₀ = 2.6 ± 0.2 nm for sol and gel, and smaller mesh size, ξ_os = 1.2 ± 0.2 nm for coacervate; and (c) cross section of gelatin chains, R_c = 0.35 ± 0.04 nm. In addition, the structure factor data obtained from coacervating solution analyzed in the Guinier region, I(q) = exp(?q²R_g²/3), yielded value of typical radius of gyration of clusters, R_g ≈ 69 nm that indicated existence of triple‐helices of length, L ≈ 239 nm; (d) Frequency and temperature sweep measurements conducted on coacervate samples revealed two other length scales: (e) viscoelastic length, ξ_ve = 14 ± 2 nm and (f) correlation length at melting, ξ_T = 500 ± 70 nm. Thus, existence of six distinct length scales, (a–f), ranging from 1.2 to 500 nm has been established in the coacervate phase of gelatin–ethanol–water system. Results are discussed within the framework of Landau‐Ginzburg treatment of dynamically asymmetric systems (Prog Theor Phys 1977, 57, 826; Phys Rev A 1991, 44, R817; J Phys II (France) 1992, 2, 1631). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1653–1667, 2006     

Characteristic lengths and the structure of salt free polyelectrolyte solutions. A small angle neutron scattering study

We have studied salt free semi dilute polyelectrolyte solutions by small angle neutron scattering. Specific labelling associated with an extrapolation method has allowed the separation of the form factor of a single polyelectrolyte chainS ₁(q) and the structure factorS ₂(q). Two lengths are deduced from these two factors: the persistence lengthb _t which characterizes the electrostatic interactions along the chain by a fitting ofS ₁(q) with calculation of the scattering function for a wormlike chain, and fromS ₂(q),q _m ^–1 which characterizes the interactions between chains. These two lengths vary in the same way with the concentration of polyions (b _t C _p ^–1/2 ,q _m ^–1 C _p ^–1/2 ) and a constant relation exists between them: only one length is then necessary to describe the structure of polyelectrolyte soltuion on this semidilute concentration range.Laboratoire Commun CEA-CNRS.     

Static and dynamic light scattering studies of the critical behaviour of polymer mixtures

Critical fluctuations were studied in polymer mixtures of poly(dimethylsiloxane) and poly(ethylmethylsiloxane), which exhibit an upper critical temperature at T_c ⋍ 57 °C. The measurements were performed in a broad temperature range at three compositions in the miscible region close to the coexistence line. The temperature dependence of the static structure factor S(q=0) can be described by a mean field behaviour except for temperatures in the range of 6 K above T_c. There, a turnover to an Ising behaviour is observed according to a modified Landau-Ginzburg criterion. The mean field spinodal temperature T_s was determined by extrapolation of S(0)⁻¹ to zero. From the Ornstein-Zernike representation of the angular dependence of S(q), the correlation length ζ of the concentration fluctuations can be determined and leads to a critical amplitude ζ₀ = lim ζ(T→∞) = 20.5 Å. The interdiffusion dynamics described by the mutual diffusion constant D has been measured by quasielastic light scattering. It shows for the critical composition ϕ_c a critical slowing down as T approaches the critical temperature T_c. Furthermore, the q² scaling of the relaxation rate of the interdiffusion dynamics changes to q³ behaviour close to T_c according to the mode coupling theory by Kawasaki.     

CPS GL 799

The effect of illumination on transport of sulfonated bisazo direct dyes, CI Direct Yellow 12, and CI Direct Yellow 4, into a cellulose membrane has been studied at various temperatures. Transport of CI Direct Yellow 12, which exhibits photoinduced reversible trans-cis isomerism in aqueous solution into a cellulose membrane, was influenced by illumination. It is likely that the transport was influenced by transisomerization of the photoisomeric dye and the diffusivity was controlled by surface diffusion rather than by pore diffusion under both light and dark conditions.Notations C Concentration of dye in the pores (mol/dm³) - C _E Concentration of electrolyte in the bulk solution (mol/dm³) - C _o Concentration of dye in the bulk solution (mol/dm³) - D _p Pore diffusivity (m²/s) - D _s Surface diffusivity (m²/s) - [M] Mean concentration of dye in membrane (mol/dm³) - [M] _L Local concentration of dye in membrane (=q+ _p C) (mol/dm³) - [M] Mean concentration of dye in membrane (mol/kg) - [M] _L Local concentration of dye in membrane (=q/V+ _p C) (mol/dm³) - F Fractional attainment of equilibrium - l Thickness of membrane (m) - q Concentration of dye adsorbed on pore wall (mol/dm³) - q _o Adsorbed concentration of dye in equilibrium withC _o (mol/dm³) - q Concentration of dye adsorbed on pore wall (mol/kg) - q _o Adsorbed concentration of dye in equilibrium withC _o (mol/kg) - t Time (s) - V Volume of membrane swollen with water per unit dry cellulose (dm³/kg) - x C/C _o - y q/q _o - z Distance that the dye diffused in the membrane (m) - q _o / _o C _o - D _s /D _p - Coefficient of the Freundlich isotherm - _p Pore void fraction - z/l - _p D _p t/l ² - _s D _s t/l ²     

Deformation of a Polymer Brush Immersed in a Binary Solvent

An analog of the Alexander‐De Gennes box model is used for the theoretical investigation of an external deformation of polymer brushes in a mixture of two solvents. The basic solvent A and the admixture B are assumed to be highly incompatible (Flory‐Huggins parameter χ_AB = 3.5). The thermodynamics of a polymer in the solvents A and B is described by parameters χ_A and χ_B, χ_A > χ_B. The brush behavior under deformation is investigated with regard to solvent composition and polymer‐solvent interactions. It is shown that in a pre‐binodal range of the solvent composition Φ_B < Φ_B⁰ in the bulk (here Φ_B⁰ is a binodal value) there is such a value of Φ_B = Φ _B* that deformation does not affect solvent composition inside the brush. This invariant quantity Φ _B*, being a function of only thermodynamic parameters, is independent of the brush characteristics, such as grafting density. It is shown that two types of the first‐order phase transitions can arise in the system considered: a compositional phase transition induced by a change in the solvent composition in the bulk, and a deformational phase transition caused by an external deformation of the brush. The value of Φ _B* defines a borderline concentration of the admixture in the bulk; the brush behavior in the ranges 00 ⪇ Φ_B ⪇ Φ _B* and Φ _B* ⪇ Φ_B < Φ_B⁰ are different. If no compositional phase transition occurs in the system, the deformational phase transition should arise under stretching at Φ _B* ⪇ Φ_B. If the compositional phase transition exists, it is realized in the range Φ_B < Φ _B* and causes the deformational phase transition in this concentration range, not only under stretching, but also under compression. Microphase segregation inside the brush is demonstrated for both phase transitions despite overestimation of the brush homogeneity in the box model.