Volume Fraction Of Block Research Articles

Bulk morphologies of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) triblock terpolymers

The self-assembly of block copolymers in the bulk phase enables the formation of complex nanostructures with sub 100 nm periodicities and long-range order, both relevant for nanotechnology applications. Here, we map the bulk phase behavior of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) (SBT) triblock terpolymers on a series of narrowly distributed polymers with widely different block volume fractions, ϕS, ϕB and ϕT. In dependence of ϕ, we find the lamella–lamella, core-shell cylinder, cylinder-in-lamella and core-shell gyroid morphology, but also a rarely observed cylinder-in-lamella phase. The bulk morphologies are thoroughly characterized by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) and display unusually broad stability regions, i.e. morphologies are observed over a broad range of compositions. We attribute this phase behavior to the asymmetric distribution of block–block incompatibilities, along the SBT block sequence, which are relatively large for S/B and S/T interfaces, but small for B/T. The higher enthalpic penalties at the S/B and S/T interface cause B to preferentially spread on the T microdomain thereby adopting its geometry. The morphological behavior of SBT is thus dominated by the volume ratio of the end blocks, ϕS and ϕT, which reduces the number of potential morphologies to only a few, mostly the core-shell analogue of diblock copolymer morphologies. In general, a simplified terpolymer bulk behavior with large stability regions for morphologies offers straightforward synthetic targeting of specific morphologies that usually only appear in a small parameter space as demonstrated here on the core-shell gyroid.

Sub-10 nm Scale Nanostructures in Self-Organized Linear Di- and Triblock Copolymers and Miktoarm Star Copolymers Consisting of Maltoheptaose and Polystyrene

The present paper describes the sub-10 nm scale self-assembly of AB-type diblock, ABA-type triblock, and A2B-type miktoarm star copolymers consisting of maltoheptaose (MH: A block) and polystyrene (PS: B block). These block copolymers (BCPs) were synthesized through coupling of end-functionalized MH and PS moieties. Small-angle X-ray scattering and atomic force microscope investigations indicated self-organized cylindrical and lamellar structures in the BCP bulks and thin films with domain spacing (d) ranging from 7.65 to 10.6 nm depending on the volume fraction of MH block (ϕMH), Flory–Huggins interaction parameter (χ), and degree of polymerization (N). The BCP architecture also governed the morphology of the BCPs, e.g. the AB-type diblock copolymer (ϕMH = 0.42), the ABA-type triblock copolymer (ϕMH = 0.40), and the A2B-type miktoarm star copolymer (ϕMH = 0.45) self-organized into cylinder (d = 7.65 nm), lamellar (d = 8.41 nm), and lamellar (d = 9.21 nm) structures, respectively.

Crystallization in segregated supramolecular pseudoblock copolymers

Crystallization in polymers under confinement can lead to strong effects, depending on the physical nature of the confining blocks. The present publication addresses crystallization in segregated supramolecular pseudoblock copolymers (SPBCPs, (PCL-Thy)-s-(PS-Tr)) where two constraints are present: one constraint is formed by a hydrogen bonding system connecting two microphase-segregating polymers, the second constraint is formed by the phase boundary of the segregating (PS)-polymer block. Thus mono-functionalized polymers bearing either a thymine end group or 2,4-diaminotriazine end group are prepared and blended together via the association of H-bonding interactions. Thymine functionalized crystallizable poly(ε-caprolactone) (PCL-Thy) and 2,4-diaminotriazine functionalized poly(styrene) (PS-Tr) with molecular weights ranging from 3000g/mol to 6000g/mol and 3000g/mol to 11,000g/mol respectively exhibit complete end group transformation as proven by NMR and MALDI methods. Crystallization studies via DSC experiments show a strong influence on the melting behavior of the PCL crystals upon attaching the PS block. Two distinct Tgs (DSC studies) corresponding to the respective polymers (PCL and PS) are shown for SPBCPs with higher PS block ratio, while ‘cold crystallization’ is shown for samples with nearly equal volume fraction of PCL and PS blocks. In-situ temperature dependent SAXS studies of the SPBCPs indicates a confinement effect of the PS-blocks on the crystallization of PCL, leading to an ordered arrangement of the PCL crystals.

Phase Behavior of Star-Shaped Polystyrene-block-poly(methyl methacrylate) Copolymers

The phase behavior of 18-arm star-shaped polystyrene-block-poly(methyl methacrylate) copolymers ((PS-b-PMMA)18) with various volume fractions of PMMA block (fPMMA) was investigated by transmission electron microscopy and small-angle X-ray scattering. (PS-b-PMMA)18 was synthesized by atom transfer radical polymerization from α-cyclodextrin (α-CD) having 18 functional groups for the initiation. We also prepared the corresponding linear PS-b-PMMAs by cutting the ester groups connecting α-CD and PS chains in (PS-b-PMMA)18 through the hydrolysis. The microdomains of (PS-b-PMMA)18 changed from body-centered-cubic spheres (BCC), hexagonally packed cylinders (HEX), perforated lamellae (PL), and lamellae (LAM), with increasing fPMMA from 0.3 to 0.8. Interestingly, (PS-b-PMMA)18 with fPMMA of 0.77 showed highly asymmetric lamellar microdomains, while the corresponding linear PS-b-PMMA with the same volume fraction should not have lamellar microdomains. Thus, the microdomains are highly affected by the molecular architecture of block copolymer. The experimental results are discussed with the prediction based on the self-consistent mean-field theory.

Self-Assembly of Flexible–Semiflexible–Flexible Triblock Copolymers

The self-assembly of ABA triblock copolymers comprising flexible amorphous poly(ethyl methacrylate) (PEMA, A block) and semiflexible liquid crystal (LC) polyester (B block) was investigated for amorphous block volume fractions (φ) ranging from 20% to 80%. Two copolymer series with different LC block molecular weights (Mn,LC) were examined. At φ < 55%, block copolymers with Mn,LC = 11 600 formed lamellar microdomains in which LC segments mostly extended along the lamella normal but folded to fit in the lamellae. When φ was augmented, the LC segment fold (Nfold) increased to enhance the interface between the LC and amorphous segments and counterbalanced the increase in amorphous lamella thickness by reducing the LC lamella thickness. When φ > 68%, the LC lamellae were divided into cubes, transforming into spheres in the PEMA matrix. When Mn,LC decreased to 6300, the copolymers showed similar morphology. However, the lamellae adopted zigzag configurations showing a greater tilting angle between the lamella normal to the LC chain axis with increasing φ. Thus, the LC and PEMA segments enhanced their interface by mutually sliding along the chain axis instead of increasing Nfold.

Polymersomes from Polypeptide Containing Triblock Co- and Terpolymers for Drug Delivery against Pancreatic Cancer: Asymmetry of the External Hydrophilic Blocks

Well-defined amphiphilic polymers of the ABA and ABC type are synthesized, where A is poly(L-lysine hydrochloride) (PLL), B is poly(γ-benzyl-(d7) L-glutamate) (PBLG(-d7)), and C is poly(ethylene oxide) (PEO). The two polymers exhibit similar PBLG(-d7) composition, while in the ABC, the volume fraction of PEO block is higher than that of PLL. Both polymers form polymersomes in water. The polymersomes are loaded with doxorubicin or paclitaxel. It is found that in the ABC, due to asymmetry of the two hydrophilic blocks, PEO is always on the outer periphery and the dimensions of the vesicles are smaller. The release of the vesicles is temperature- and pH-dependent. In vivo toxicity tests of the empty vesicles show that they are not toxic. In vitro activity of the loaded vesicles against human pancreatic cancer cell lines reveals comparable activity to Myocet for the ABA loaded with doxorubicin, while lower activity is observed for the ABC.

Attempts to form the 10-nm-order pitch of self-assembled nanodots using PS-PDMS block copolymer

Block copolymer (BCP) self-assembly exhibits its ability to form various nanostructures with a size down to 3 nm, which is particularly attractive for emerging technologies such as bit patterned media (BPM). Poly(styrene-b-dimethyl siloxane) (PS-PDMS) has been acknowledged as the most promising block copolymer for self-assembly fabrication due to its possibility to form nanopattern with a fine pitch, high etching selectivity, and its characteristic of robustness for pattern transfer. Here, we attempt to form PS-PDMS self-assembled nanodot array with a 10-nm-order pitch in order to satisfy the demand of low cost technique to form ultrahigh density nanodot array for BPM, which is regarded as the next-generation magnetic recording media, and for quantum devices such as the third-generation quantum dot photovoltaic cell and future battery cell. In this study, self-assembled nanodot array on a large area with pitches of 11 nm ( σ = 2.08 nm) and 10 nm ( σ = 1.61 nm) was formed using PS-PDMS with molecular weights of 5600–1300 g/mol (minority block volume fraction f PDMS = 19.8%) and 4700–1200 g/mol (f PDMS = 21.4%), respectively. In experiments, it was shown that some critical parameters, such as the thickness of PS-PDMS film, the treatment of the substrate surface, and annealing condition, played crucial roles in forming 10-nm-order size of self-assembled nanodot array using PS-PDMS. The relationships between pitches of PS-PDMS nanodot array and the product of the total number of segments and the Flory-Huggins segmental interaction parameter (χN) obtained by calculations and experiments will be discussed. Based on the position of PS-PDMS on mean-field phase diagram for BCP melts, the possibility to form nanodot array with a pitch of less than 10 nm is described. This study promises to open way toward the fabrication of more than 7.45 Tbit/in. 2 storage devices and the application of quantum devices.

Designing block copolymer architectures for targeted membrane performance

Using a combination of block copolymer self-assembly and non-solvent induced phase separation, isoporous ultrafiltration membranes were fabricated from four poly(isoprene-b-styrene-b-4-vinylpyridine) triblock terpolymers with similar block volume fractions but varying in total molar mass from 43 kg/mol to 115 kg/mol to systematically study the effect of polymer size on membrane structure. Small-angle X-ray scattering was used to probe terpolymer solution structure in the dope. All four triblocks displayed solution scattering patterns consistent with a body-centered cubic morphology. After membrane formation, structures were characterized using a combination of scanning electron microscopy and filtration performance tests. Membrane pore densities that ranged from 4.53 × 1014 to 1.48 × 1015 pores/m2 were observed, which are the highest pore densities yet reported for membranes using self-assembly and non-solvent induced phase separation. Hydraulic permeabilities ranging from 24 to 850 L m−2 h−1 bar−1 and pore diameters ranging from 7 to 36 nm were determined from permeation and rejection experiments. Both the hydraulic permeability and pore size increased with increasing molar mass of the parent terpolymer. The combination of polymer characterization and membrane transport tests described here demonstrates the ability to rationally design macromolecular structures to target specific performance characteristics in block copolymer derived ultrafiltration membranes.

Surface pattern based on an azobenzene-containing copolymer thin film and its light-driven morphology modulation

A type of azobenzene-containing block copolymer polymethyl methacrylate-b-poly (n-butylmethacrylate-co-6-(4-(phenylazo) benzoate) hexyl methacrylate) (PMMA-b-(PnBMA-co-PAzoMA)) was synthesized by the atom transfer radical polymerization (ATRP). Macroinitiator polymethyl methacrylate (PMMA) was prepared by ATRP and used to initiate the copolymerization of monomern-butyl methacrylate (nBMA) and azobenzene-based methacrylate monomer (AzoMA). Herein, three block copolymers with different molecular weights and block volume fractions were obtained and spin-coated on a silicon substrate or quartz plate before annealing at 180 °C for 14 h. The surface morphologies in these annealed copolymer films were observed by atomic force microscopy (AFM). Bicontinuous stripe or island patterns with different sizes were formed dependent on the film thickness. These ordered patterns are considered to be formed arising from the dewetting process of the surface layer in the copolymer film. Photoisomerization of azobenzene units in the copolymer films changed the dewetting behaviors of the surface layer of the thin film. Therefore, some copolymer annealed films showed a reversible morphology conversion between bicontinuous stripe and island structure when exposed to UV light and upon being stored in the dark. It was found that the composition of the block copolymer had obvious influences on the photoinduced morphology conversion behaviors in these copolymer thin films. When the volumes of PnBMA and PAzoMA phases in the block copolymer were large enough, the surface morphology could be modulated by UV light irradiation and storage in the dark. This work proposes a new possibility for photoinduced control and design of the dewetting processes of thin films using a linear block copolymer.

Mesoporous Polystyrenes via Lamellar Block Copolymer Assembly

Block copolymers (BCPs) are well-known to self-assemble into a variety of nanostructures, such as spherical, cylindrical, gyroid-like, and lamellar morphologies, depending on the volume fraction of the block and/or the chain architecture. Organic mesoporous materials applicable to separations, sensors, etc., could be one of the interesting fields using block copolymers. To prepare organic mesoporous materials, block copolymers should consist of chemically inert and labile blocks. A polystyrene-block-polylactide (PS-b-PLA) system is a representative example. The PS block is mechanically and chemically robust, while the PLA block is easily hydrolyzed under basic conditions. In a given morphology, PLA domain structures determine the resulting pore morphology. Among possible pore architectures, one-dimensional cylindrical pores have been intensively studied, perhaps because the morphology exists over a wide range of volume fraction, and also because it consists of confined pores. Recently, a three-dimensionally connected mesoporous structure from a gyroid morphology was also reported. On the other hand, due to its wide volume fraction range near 0.5, a lamellar morphology can be obtained as readily as a cylindrical morphology. Nevertheless, a lamellar morphology has rarely been utilized for preparing organic mesoporous materials. With this in mind, it would be interesting to prepare lamellar mesoporous materials using a lamellar BCP. In this paper, we report a mesoporous material, consisting of PS layers, by a chemical etching of sacrificial PLA layers in a lamellar structure. To obtain the porous material, we first synthesized a block copolymer (PS-b-PLA) using a click reaction of individually prepared PS and PLA blocks. The PS was prepared by the anionic polymerization of styrene. The PS end was functionalized with a hydroxyl group, which was converted into an alkynyl group for the next click coupling (Scheme S1(b)). From the H NMR data, the number average molecular weight (Mn) of the obtained PS was determined to be 14,400 g/mol. The other PLA block was synthesized by a ring opening polymerization (ROP) of D,L-lactide using triethyl aluminum as the catalyst (Scheme S1(c)). For the click coupling with the PS block, the ROP initiator contained an azide end. From the H NMR analysis, the Mn was estimated to be 10,500 g/mol, and the GPC data showed the polydispersity (Mw/Mn) to be 1.06. The click coupling was carried out using Cu(I)Br/PMDETA as the catalyst (Scheme 1). The obtained block copolymer showed a triazolyl hydrogen at 7.39 ppm in the H NMR spectrum (Figure S1), and the polydispersity was 1.04, indicative of its narrow molecular weight distribution (Figure S2). The volume fraction ( f ) of the PS block was calculated to be 0.60. The differential scanning calorimetry (DSC) data of the block copolymer displayed two glass transitions at 51.4 C

Phase diagrams of ABC linear triblock copolymers under nanopore confinements

The phase diagrams of triblock copolymers in cylindrical nanopores are investigated using the real-space self-consistent field theory in a two-dimensional space. We concentrate on pores with neutral surfaces and invariable diameters, whose rich variety of phases are considered to originate from pure geometric frustration. A series of triangular phase diagrams are constructed by varying the volume fractions for several sets of interaction parameters. These diagrams are sorted into three categories according to their interaction parameters. The confined phase diagrams exhibit several characteristic features that differ from those observed in the bulk. First, a rich variety of geometric frustration phases with strong symmetries, such as cylindrical and square, are observed in the triangular phase space because of the symmetry constraint in the geometric boundary. Second, the frustrated phases present some novel and complex features compared with those in the bulk, demonstrating that the confined morphologies much more sensitively depend on the subtle variation in the binary interaction parameters than those in the bulk. Meanwhile, the entropic energies of the symmetric melts with equal end block volume fractions are investigated to further understand the geometric frustration phase behaviors in the triangular phase diagrams. The reasonable formation mechanisms of the frustration phases are also discussed.

Effect of Process Parameters on Microstructures and Mechanical Properties of a Nano/ultrafine Grained Low Carbon Steel Produced by Martensite Treatment Using Plane Strain Compression

In this work, the martensite treatment consisting of cold deformation by plane strain compression and subsequent annealing was used for producing the nano/ultrafine grained structure in a low carbon steel. The equivalent strain was varied from 0.1 to 2, while the annealing process was carried out in the temperature range of 400–600°C for 0–180 min. The microstructural evolution and mechanical properties of the as-deformed and annealed specimens were investigated. The results showed that in the as-deformed specimens, increase in strain intensified the volume fraction of the martensite cell blocks and consequently the strength. Fully equiaxed nano/ultrafine grained ferrite was developed from the martensite cell blocks during the annealing at warm temperature around 500°C for sufficient time lengths. It was concluded that the final multi-phased microstructure composed of ultrafine ferrite grains, block-tempered martensite, and fine cementite precipitates was responsible for the obtained superior mechanical properties.

“Order from chaos”: A field-based estimate on bulk rheology of tectonic mélanges formed in subduction zones

Many tectonic HP–LT mélanges exhibit block-in-matrix structures. In contrast to the pervasively deformed matrix, the blocks of various lithologies and PT-histories usually appear undeformed. If we accept that an HP–LT mélange reflects persistent high strain deformation in a deep (>30km) subduction channel, the record of these rock associations can provide insight into stress state, rheology, and flow patterns along a plate interface. The bulk rheology of a block-in-matrix structure is controlled by (a) the dominant deformation mechanism of the matrix, (b) the volume fraction of blocks engulfed in that matrix and (c) the geometry of the blocks. The microstructures of the matrix indicate distributed deformation by dissolution–precipitation creep (DPC), while crystal plastic deformation is subordinate. DPC is grain size sensitive, controlled by the type of interfaces, and requires an aqueous pore-fluid at quasi-lithostatic pressure. The rheology of a rock body undergoing deformation by DPC is believed to be Newtonian viscous. Matrix viscosities are estimated to be on the order of ~1019Pas or less. Here, we explore the effect of rigid blocks embedded in a weak matrix on the bulk rheology. Using stereology, we determine the block size distributions as well as the total block volume fractions for block-in-matrix structures from several regions. The volume fractions are found to range from 2 to 70% with typical values between ~5 and 50%. Using published mixing laws, we model the subduction channel as a suspension of rigid spheres with a linear viscous matrix and predict that for the typical values of 5 to 50%, the viscosity increase is less than one order of magnitude. Consequently, the influence of blocks on the bulk viscosity of a subduction channel is minor. Instead, bulk rheology is primarily controlled by the deformation behaviour of the matrix material.

Disorder-to-Order Transition of Triblock Comb Copolymer Am+1(BC)m

The disorder to order transition of comb copolymer Am+1(BC)m is investigated by the self-consistent field theory. The interaction parameters between the three different blocks are considered by varying the composition of the comb triblock copolymer with the side chain number m = 1 and 3. As the side chain number m increases, the Flory–Huggins interaction parameter of disorder to order transition (DOT) increases and the lowest DOT occurs when the volume fractions of blocks A, B, and C are approximately equal. When one component is the minority, the disorder-to-order transition curve is similar to binary Am+1Bm comb copolymer. The influence of the side chain density on phase transition is also discussed. The comb copolymer is more difficult to phase separate with larger side chain number m and shorter side chain.

The influence of volume fractions on the phase behaviors of linear A(BC)nBA′ multiblock terpolymers

The phase behaviors of A(BC)(n)BA' linear multiblock terpolymers are investigated using the pseudo-spectral method of self-consistent field theory by varying the volume fractions of different blocks. The relative stability among the lamellae-in-lamellae structures with different BC internal layers is tuned by the volume fraction of the two long tails. A larger A volume fraction favors the formation of structures with fewer BC thin layers. When the volume fraction of A is increased further, a hierarchical cylinder phase can be formed because of the effect of the spontaneous curvature and vice versa. The separation between B and C significantly reduces the phase regime of the cylinder, especially for the case of small A volume fraction.

Microstructure – Properties Relationships in Carbide-free Bainitic Steels

We elaborated two carbide-free bainitic steels with different microstructures through specific alloy design and austempering process. Microstructural characterizations were performed by means of EBSD analysis and in-situ high energy synchrotron diffraction in order to evaluate the phase fractions and the carbon content in the retained austenite, as well as the microtextures. These microstructural features were correlated to the tensile properties. Both steels exhibited an excellent compromise between high strength (above 1250 MPa), good ductility (uniform elongation up to 14%) and high fracture strain (reduction of area up to 46%). The volume fraction of MA blocks (blocks of retained austenite partially transformed into fresh martensite during the final cooling at room temperature) was a key relevant parameter that strongly influenced the work-hardening at the expense of the damaging processes at high strain.

Multicompartment micelles from A2-star-(B-alt-C) block terpolymers in selective solvents

The ability of multiblock ABC terpolymers to self-assemble into multicompartment micelles in an A-selective solvent is of great current interest. We have used dissipative particle dynamics (DPD) to explore the morphologies adopted by a particular block terpolymer architecture, A2-star-(B-alt-C), where the two A blocks form the micelle corona and the alternating B and C blocks segregate within the core. Parameters of interest include the strength of the pairwise interactions among A, B, and C, the relative length of the A blocks compared to B + C, and the relative selectivity of the solvent towards B and C. A rich suite of structures are observed, including those with either spherical or wormlike cores, and with internally segregated B and C domains. Within the spherical micelle family, the B and C domains adopt various packings, including concentric layers, the “hamburger” motif (B–C–B layers and C–B–C layers), and a bicontinuous network. For wormlike micelles, the B and C domains are arranged as stacked alternating disks, or as intertwined helices. The choice of morphology is rationalized in terms of the relative block volume fractions and interaction energies. The DPD algorithm is a promising approach to screen ABC terpolymer architectures for the ability to produce potentially useful hierarchical structures.

Microcapsules with Tailored Nanostructures by Microphase Separation of Block Copolymers

Colloidal microcapsules of thin nanoshell membranes were prepared by the evaporation-induced self-assembly of poly(styrene)-block-poly(butadiene)-block-poly(styrene) (SBS) triblock copolymers inside the oil phase of a water-in-oil-in-water (W/O/W) double emulsion, which was prepared via a two-step sequential emulsification process. To see the nanoconfinement effect, the shell thickness was kept very thin and comparable to the feature scale of self-organized nanostructure. By exploiting the density mismatch between the microcapsules and the continuous medium, single-cored microcapsules with thin shells were selectively separated from mixtures of multicored microcapsules or thick-shelled microcapsules. The internal morphology of the membrane could be modulated by controlling the volume fractions of styrene and butadiene blocks, which was achieved simply by adding polystyrene homopolymer of relatively low molecular weight. By varying the amount of homopolymer, various morphologies were produced in the microcapsule membranes, including lamellae, perforated lamellae, and cylindrical and spherical phases. Moreover, the addition of polystyrene homopolymer could be used to control the mechanical characteristics of the microcapsules.

Broadband Antireflection Coating Covering from Visible to Near Infrared Wavelengths by Using Multilayered Nanoporous Block Copolymer Films

Broadband antireflection (AR) covering from visible light to near infrared (NIR) wavelengths (400-2000 nm) was obtained by using three sequential spin-coatings of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) copolymers with different volume fractions of PMMA block (f(PMMA)) on a glass. PS-b-PMMA having the lowest PMMA volume fraction (f(PMMA) approximately 0.3) among three PS-b-PMMAs was first spin-coated on a glass substrate. After spin-coating, the film was irradiated by ozone to prevent dissolution during the next spin-coating process. Then PS-b-PMMA with the next larger volume fraction of PMMA block (f(PMMA) approximately 0.46) was spin-coated and irradiated again by ozone. Finally, PS-b-PMMA with the largest volume fraction of PMMA block (f(PMMA) approximately 0.69) was spin-coated. After three sequential spin-coatings, the entire film was irradiated under UV followed by rinsing with acetic acid, which removed PMMA blocks. This process allowed us to have the triple layers with spongelike nanoporous structures where the refractive index increases from the top to the bottom of the film. The morphology of the triple-layered nanoporous block copolymer films was investigated by scanning electron microscopy. The nanoporous film exhibited excellent broadband AR at wavelengths from 400 to 2000 nm. The measured reflectance curves are in good agreement with the calculation from the characteristic matrix theory. This AR coating would be used for the development of solar cells with high power convergence efficiency.

Amorphous Diblock Copolymers with a High Organometallic Block Volume Fraction: Synthesis, Characterization and Self-Assembly of Polystyrene-block-Poly(ferrocenylethylmethylsilane) in the Bulk State

The preparation of polystyrene-b-poly(ferrocenylethylmethylsilane) diblock copolymers (PS-b-PFEMS) with a high volume fraction of the organometallic block (ϕPFEMS = 0.69−0.87) has been achieved via the sequential living anionic polymerization of styrene and ethylmethylsila[1]ferrocenophane. High molecular weights (Mn = 50000 to 250000 g/mol) and narrow molecular weight distributions (PDI = 1.05−1.17) were achieved. As both of the blocks are amorphous, the resulting diblock copolymers undergo predictable self-assembly in the bulk and well-ordered microdomains are reported. The data described complement previous results on analogous block copolymers with a low PFEMS volume fraction and a morphology diagram for PS-b-PFEMS is described.