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NASA NTRS2003

Defect, Kinetics and Heat Transfer of CDTE Bridgman Growth without Wall Contact

A detached growth mechanism has been proposed, which is similar to that proposed by Duffar et al. and used to study the current detached growth system. From numerical results, we can conclude that detached growth will more likely appear if the growth and wetting angles are large and meniscus is flat. Detached thickness is dependent on growth angle, wetting angle, and gap width and shape of the fins. The model can also explain why the detached growth will not happen for metals in which the growth angle is almost zero. Since the growth angle of CdZnTe cannot be changed, to promote detached growth, the number density of the fins should be low and the wetting angle should be high. Also, a much smaller gap width of the fins should be used in the ground experiment and the detached gap width is much smaller. The shape of the fins has minor influence on detached growth. An integrated numerical model for detached solidification has been developed combining a global heat transfer sub-model and a wall contact sub-model. The global heat transfer sub-model accounts for heat and mass transfer in the multiphase system, convection in the melt, macro-segregation, and interface dynamics. The location and dynamics of the solidification interface are accurately tracked by a multizone adaptive grid generation scheme. The wall contact sub-model accounts for the meniscus dynamics at the three-phase boundary. Simulations have been performed for crystal growth in a conventional ampoule and a designed ampoule to understand the benefits of detached solidification and its impacts on crystalline structural quality, e.g., stoichiometry, macro-segregation, and stress. From simulation results, both the Grashof and Marangoni numbers will have significant effects on the shape of growth front, Zn concentration distribution, and radial segregation. The integrated model can be used in designing apparatus and determining the optimal geometry for detached solidification in space and on the ground.

Larson, D. J., Jr.↗

NASA NTRS2003

Models of Mass Transport During Microgravity Crystal Growth of Alloyed Semiconductors in a Magnetic Field

Alloyed semiconductor crystals, such as germanium-silicon (GeSi) and various II-VI alloyed crystals, are extremely important for optoelectronic devices. Currently, high-quality crystals of GeSi and of II-VI alloys can be grown by epitaxial processes, but the time required to grow a certain amount of single crystal is roughly 1,000 times longer than the time required for Bridgman growth from a melt. Recent rapid advances in optoelectronics have led to a great demand for more and larger crystals with fewer dislocations and other microdefects and with more uniform and controllable compositions. Currently, alloyed crystals grown by bulk methods have unacceptable levels of segregation in the composition of the crystal. Alloyed crystals are being grown by the Bridgman process in space in order to develop successful bulk-growth methods, with the hope that the technology will be equally successful on earth. Unfortunately some crystals grown in space still have unacceptable segregation, for example, due to residual accelerations. The application of a weak magnetic field during crystal growth in space may eliminate the undesirable segregation. Understanding and improving the bulk growth of alloyed semiconductors in microgravity is critically important. The purpose of this grant to to develop models of the unsteady species transport during the bulk growth of alloyed semiconductor crystals in the presence of a magnetic field in microgravity. The research supports experiments being conducted in the High Magnetic Field Solidification Facility at Marshall Space Flight Center (MSFC) and future experiments on the International Space Station.

Ma, Nancy↗

NASA NTRS2003

Analysis of Surface and Bulk Behavior in Ni-Pd Alloys

The most salient features of the surface structure and bulk behavior of Ni-Pd alloys have been studied using the BFS method for alloys. Large-scale atomistic simulations were performed to investigate surface segregation profiles as a function of temperature, crystal face, and composition. Pd enrichment of the first layer was observed in (111) and (100) surfaces, and enrichment of the top two layers occurred for (110) surfaces. In all cases, the segregation profile shows alternate planes enriched and depleted in Pd. In addition, the phase structure of bulk Ni-Pd alloys as a function of temperature and composition was studied. A weak ordering tendency was observed at low temperatures, which helps explain the compositional oscillations in the segregation profiles. Finally, based on atom-by-atom static energy calculations, a comprehensive explanation for the observed surface and bulk features will be presented in terms of competing chemical and strain energy effects.

Bozzolo, Guillermo↗

NASA NTRS2004

Identification and Control of Gravity Related Defect Formation During Melt Growth of Electro-Optic Single Crystals Bismuth Silicate(Bi12SiO20)

A research carried out under Award Number NAG8-1487 was aimed at to the design, conduct and analysis of experiments directed at the identification and control of gravitational effects on crystal growth, segregation and defect formation in the Sillenite system: bismuth silicate (Bi(12)SiO(20)). Correlation analyses was conducted in order to establish the influence of gravity related defects introduced during crystal growth on critical, application specific properties. Achievement of the states objective was conducted during the period from Feb. 01, 1998 to Dec. 31, 2003 with the following anticipated milestones: 1. Establishment of capabilities for (a) reproducible Czochralski and Bridgman-type growth of BSO single crystals and (b) for comprehensive analysis of crystalline and chemical defects as well as for selective property characterization of grown crystals (year 1). 2. Design and execution of critical space growth experiment(s) based on analyses of prefatory space results (experiments aimed at establishing the viability of planned approaches and procedures) and on unresolved issues related to growth, segregation and defect formation associated with conventional growth in Bridgman geometries. Comparative analysis of growth under conventional and under mu-g conditions; identification of gravity related defect formation during conventional Bridgman growth and formulation of approaches for their control (years 2 and 3). Development of charge confinement system which permits growth interface demarcation (in a mu-g environment) as well as minimization of confinement related stress and contamination during growth; design of complementary mu-g growth experiments aimed at quantitative mu-g growth and segregation analyses (year 4). 3. Conduct of quantitative mu-g growth experiments directed at: (a) identification and control of gravity related crystalline and chemical defect formation during single crystal growth of Bi(12)SiO(20) and at (b) defect engineering -the development of approaches to the controlled generation during crystal growth of specified point defects in homogeneous distribution (year 5). The proposed research places focus on a class of materials which have outstanding electrical and optical properties but have so far failed to reach their potential, primarily because of our inability to control adequately their stoichiometry and crystal defect formation as well as confinement related contamination and lattice stress.

Becia, Piotr↗

NASA NTRS2005

A Model for Siderophile Element Distribution in Planetary Differentiation

Planetary differentiation begins with partial melting of small planetesimals. At low degrees of partial melting, a sulfur-rich liquid segregates by physical mechanisms including deformation-assisted porous flow. Experimental studies of the physical mechanisms by which Fe-S melts segregate from the silicate matrix of a molten H chondrite are part of a companion paper. Geochemical studies of these experimental products revealed that metallic liquids were in equilibrium with residual metal in the H chondrite matrix. This contribution explores the geochemical signatures produced by early stages of core formation. Particularly, low-degree partial melt segregation of Fe-S liquids leaves residual metal in the silicate matrix. Some achondrites appear to be residues of partial melting, e.g., ureilites, which are known to contain metal. The metal in these achondrites may show a distinct elemental signature. To quantify the effect of sulfur on siderophile element contents of residual metal we have developed a model based on recent parametrizations of equilibrium solid metal-liquid metal partitioning experiments.

Humayun, M.↗

NASA NTRS2017

Core Formation on Asteroid 4 Vesta: Iron Rain in a Silicate Magma Ocean

Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft, suggest that Vesta resembles H chondrites in bulk chemical composition, possibly with about 25% of a CM-chondrite like composition added in. For this model, the core is 15% by mass (or 8 volume %) of the asteroid. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. Melting in the Fe-Ni-S system begins at a cotectic temperature of ~940 deg. C. Only about 40% of the total metal phase, or 3-4 volume % of Vesta, melts prior to the onset of silicate melting. Liquid iron in solid silicate initially forms isolated pockets of melt; connected melt channels, which are necessary if the metal is to segregate from the silicate, are only possible when the metal phase exceeds about 5 volume %. Thus, metal segregation to form a core does not occur prior to the onset of silicate melting.

Kiefer, Walter S.↗

DOE OSTI2019

Characterization techniques for TRU waste from the Analytical Laboratory Hot Cells at Idaho National Laboratory

Characterization techniques for TRU waste from the Analytical Laboratory Hot Cells at Idaho National Laboratory Since the first reactor went hot in 1942, there has been a never ending desire to improve the nuclear reactor and the fuel that it burns. The Idaho National Laboratory has been a key player in reactor and fuel development. As more research projects begin, the spectrum of waste parameters grows. Over the years, the Analytical Laboratory (AL) at the Materials and Fuels Complex (MFC) at Idaho National Laboratory (INL) has supported a large range of various research projects. Each project brings its own challenge and analytical technique that, in turn, yields its own unique waste parameters. The AL Hot Cells at INL consist of 6 small cells that can support around 12 different fuel research projects at a time along with infrastructure and environmental samples. Each different project yields different levels of transuranic (TRU) material, RCRA constituents, dose, and contamination levels. The waste parameters from each project dictate a path forward for the waste Low-Level Waste (LLW), Contact Handled TRU (CH-TRU), Mixed Contact Handled TRU (M-CH-TRU), Remote Handled TRU (RH-TRU), or Mixed Remote Handled TRU (M-RH-TRU). With visual examination techniques and process knowledge as an aid, there have been waste handling methods developed that allow debris and sample material to be segregated. Unique characterization mechanisms have been applied for each debris and sample material that are generally more accurate than smear and surface contamination data. For debris found in the Hot Cells, analytical data is gathered and conservatively summarized for each fuel type and research method. This consists of data from Quadrupole Inductively Coupled Plasma Mass Spectrometry (Q-ICP-MS), Gamma Spectroscopy, and some data verification through Thermal Ionization Mass Spectrometry (TIMS) and Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). This data gives a range of TRU isotope concentrations. Fuel age is taken into account to determine the dominant TRU activity isotopes. Cesium concentrations are also gathered. Each parameter/fuel type then ties a measured Cesium number to TRU content based on historical analytical data. Debris in the hot cells is segregated by project and packaged in individual 2 gallon metal paint cans. Each can is counted by gamma spectroscopy in a calculated and measured geometry. Using process knowledge to determine the fuel or project type, newly counted cesium numbers can be applied to the historic analytical data and TRU content can be estimated. The TRU content allows waste debris to be segregated between CH-TRU and RH-TRU. Packaging techniques can allow for the minimization if RH-TRU waste. Sample material received into the AL must be dissolved into a liquid matrix in order to be analyzed in most cases. When analysis is complete, these liquids go through a consolidation, complexation, neutralization, and solidification process where real time analytical data can be used to calculate TRU content and RCRA constitutes. These calculations allow for no further analytical data to be gathered. The waste matrix is considered stable and acceptable by all AK [define AK] documents. The unique techniques used in characterizing and handling the Analytical Laboratories Hot Cell waste can be applied to various situations and various laboratories. They allow for more accurate data for waste constituents and also for the minimization of RH-TRU waste.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2019

Developing Waste Characterization Capabilities in Support of the Near Surface Disposal Facility - 19245

Upon approval from the Canadian Nuclear Safety Commission, Canadian Nuclear Laboratories (CNL) Proposed Near Surface Disposal Facility (NSDF) to be constructed at CNL's Chalk River Laboratories will be the first permanent disposal facility in Canada for the disposal of low level radioactive waste. The NSDF is currently in the approval process and as such, a preliminary Waste Acceptance Criteria (WAC) has been implemented for the proposed facility. Waste currently generated at CNL is being characterized to verify that it meets the WAC and will be 'disposal ready' once the NSDF is operational. A robust waste characterization program is required for the following reasons: 1. Improved waste segregation to support waste minimization and recycling to ensure non-radioactive waste is reliably segregated and removed from radioactive waste streams destined for the NSDF. This includes characterization and discrimination of Naturally Occurring Radioactive Material (NORM) and anthropogenic radioactive material. 2. To ensure low level waste (LLW) is properly characterized as per the limits stipulated within the WAC to ensure criteria is met for NSDF packaging requirements 3. To ensure intermediate level waste is reliably segregated from NSDF destined wastes streams The purpose of this paper is to provide a review of the development of a waste characterization program strategy at Chalk River Laboratories and applicability of various waste streams; including consideration of important factors such as measurement methods, techniques, and the management of data. Emphasis is necessarily placed on non-destructive gamma spectrometry systems which are central to CNL's approach. A review of near-term developments is also provided. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2019

Characterization Techniques for TRU Waste from the Analytical Laboratory Hot Cells at Idaho National Laboratory - 19610

Since the first reactor went hot in 1942, there has been a never ending desire to improve the nuclear reactor and the fuel that it burns. The Idaho National Laboratory has been a key player in reactor and fuel development. As more research projects begin, the spectrum of waste parameters grows. Over the years, the Analytical laboratory (AL) at the INL Materials and Fuels Complex (MFC) has supported a large range of various research projects. Each project brings its own challenge and analytical technique that, in turn, yields its own unique waste parameters. The AL Hot Cells at INL consist of 6 small cells that can support around 12 different fuel research projects at a time along with infrastructure and environmental samples. Each different project yields different levels of transuranic (TRU) material, RCRA constituents, dose, and contamination levels. The waste parameters from each project dictate a path forward for the waste as Low-Level Waste (LLW), Contact Handled TRU (CH-TRU), Mixed Contact Handled TRU (M-CH-TRU), Remote Handled TRU (RH-TRU), or Mixed Remote Handled TRU (M-RHTRU). With visual examination techniques and process knowledge as an aid, there have been waste handling methods developed that allow debris and sample material to be segregated. Unique characterization mechanisms have been applied for each debris and sample material that are generally more accurate than smear and surface contamination data. For debris found in the Hot Cells, analytical data is gathered and conservatively summarized for each fuel type and research method. This consists of data from Quadrupole Inductively Coupled Plasma Mass Spectrometry (Q-ICP-MS), Gamma Spectroscopy, and some data verification through Thermal Ionization Mass Spectrometry (TIMS) and Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). This data gives a range of TRU isotope concentrations. Fuel age is taken into account to determine the dominant TRU activity isotopes. Cesium concentrations are also gathered. Each parameter/fuel type then ties a measured Cesium number to TRU content based on historical analytical data. Debris in the hot cells is segregated by project and packaged in individual 2 gallon metal paint cans. Each can is counted by gamma spectroscopy in a calculated and measured geometry. Using process knowledge to determine the fuel or project type, newly counted cesium numbers can be applied to the historic analytical data and TRU content can be estimated. The TRU content allows waste debris to be segregated between CH-TRU and RH-TRU. Packaging techniques can allow for the minimization of RHTRU waste. Sample material received into the AL must be dissolved into a liquid matrix in order to be analyzed in most cases. When analysis is complete, these liquids go through a consolidation, complexation, neutralization, and solidification process where real time analytical data can be used to calculate TRU content and RCRA constitutes. These calculations allow for no further analytical data to be gathered. The waste matrix is considered stable and acceptable by all Acceptable Knowledge (AK) documents. The unique techniques used in characterizing and handling the Analytical Laboratories Hot Cell waste can be applied to various situations and various laboratories. They allow for more accurate data for waste constituents and also for the minimization of RH-TRU waste. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Alloying induces directionally-dependent mobility and alters migration mechanisms of faceted grain boundaries

Faceted grain boundaries exhibit unusual segregation and migration tendencies. To gain a deeper understanding of how solute atoms interact with faceted interfacial structures during migration, this study probes the migration behavior of a faceted Σ11 boundary in Cu doped with Ag atoms. Furthermore, the solutes are found to segregate to the facet with more free volume and strongly reduce boundary velocity in one migration direction, but not the other, due to the presence of a directionally-dependent motion mechanism that can escape solute pinning and therefore speed up migration. Hence, a new mechanism of chemically-induced anisotropy in grain boundary mobility is uncovered by these simulations.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Effects of Remelting Current on Structure, Composition, Microsegregation, and Inclusions in Inconel 718 Electroslag Remelting Ingots

The macro- and microstructures, chemical compositions, microsegregations, and nonmetallic inclusion characteristics at different positions of the as-cast IN718 ingots produced by a laboratory-scale electroslag remelting (ESR) furnace under four remelting currents (150, 200, 250, and 300 A) were compared and investigated comprehensively. The results indicate that the average melting rate increases with the increasing remelting current, and the molten pool tends to be deeper. Thus, at the same position of the ESR ingots, the volume fraction of the segregated phase, the degree of elemental segregation, and the secondary dendrite arm spacing have the same tendency to increase with the increasing remelting current and show an increasing trend from the bottom to the top along the height of each ingot. If the current is set relatively low, the oxygen and nitrogen levels in the ingots increase, the conditions that make the contents and distributions of Al and Ti become unstable. In addition, the major nonmetallic inclusions in the IN718 ESR ingots are MgO·Al{sub 2}O{sub 3} complex oxide inclusions with a three-layer structure and (Nb,Ti)N nitrides. The volume fractions and mean equivalent diameters display a downward trend with the increasing remelting current. The size and quantity of these inclusions are always larger in the upper portions of the ingots than those in the lower portions.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Doping Effects on the Ductility of a Lightweight Refractory High-Entropy Alloy: Grain Boundary and Bulk Lattice Aspects

Doping elements in small amounts often segregate to grain boundaries (GBs) in alloys and can significantly impact mechanical properties and performance. Refractory high-entropy alloys (RHEAs) are known for their poor ductility, especially at low temperatures. Promoting GB cohesion through segregation can be an effective approach to mitigate embrittlement. Here, in this study, first-principles density functional theory (DFT) calculations were performed to examine the effects of important interstitial dopants (O, B, C, and N) and substitutional dopants (Cr, Y, La, and Ce) on the Σ5(310) [001] tilt GB of a lightweight RHEA Nb 32.5 Ti 27.5 Mo 22.5 Ta 12.5 Hf 2.5 Zr 2.5 . The DFT calculations reveal that certain dopants, such as B, C, Cr, N, and Y, exhibit favorable GB strengthening effects by improving bonding interactions with the bulk alloy. The impact of doping on the ductility parameter of the bulk lattice, defined as the ratio of surface energy to unstable stacking fault energy for the {110} <111> slip system, was also studied; and the results show that doping reduces the intrinsic ductility of the alloy, decreasing the D-parameter from 2.90 to 2.55, depending on the specific dopant. The present findings provide a foundational understanding at atomic level of the effect of representative dopants on mechanical properties of RHEAs and can be used to guide future alloy design for improved mechanical properties.

deformation charge density↗

DOE OSTI2025

Tailoring mechanical properties of a multi-principal element alloy through a multi-length-scale approach

In this study, a multi-length-scale strengthening approach was used to tailor the microstructure and the mechanical properties of a NiCoCr-based multi-principal element alloy (MPEA). Grain size refinement, severe lattice distortion, and stacking fault energy (SFE) reduction with Mo addition (up to 10 at.%) enhance yield strength by 85% with only 10% reduction in ductility in as-annealed MPEAs. A pronounced increase in the strain hardening rate was observed with the addition of Mo, which is ascribed to the promotion of complex stacking fault (SF) interaction and intersection, accompanied by Lomer-Cottrell (L-C) and Hirth locks inhibiting dislocation motion and substantial increase in the accumulation of back stress. To push the limit of the yield strength further, the Suzuki segregation phenomenon was manipulated by a careful control of SF density by pre-straining and a subsequent 500 °C heat treatment. The stress-strain responses of the pre-strained and heat treated MPEAs showed an obvious SF density and Mo concentration dependence. Furthermore, the yield strength of the pre-strained Mo-added MPEAs with subsequent heat treatment was increased up to true stress of 2.3 GPa with a corresponding fracture elongation of 12% true strain. SFs formed during pre-straining served as Cr segregation sites during subsequent heat treatment, which substantially varies the local SFE within the SF, presenting a roughened landscape and frustrating the dislocation dynamics.

mechanical properties↗

DOE OSTI2020

Analysis of chemical stress and the propensity for cracking during the vertical Bridgman growth of BaBrCl:Eu

Computational models are employed to analyze residual chemical stresses arising from compositional variations in europium-doped BaBrCl crystals grown by the vertical Bridgman method. We find that significant chemical stress is produced by radial segregation of Eu in this system. In particular, the distribution of normal stresses is set by the radial concentration gradient, whose changing sign produces surface states in tension or compression. Additionally, crack opening from surface flaws will be promoted or suppressed by tensile or compressive surface stresses, respectively. Thus, crystal growth processing strategies that change the radial dopant concentration gradients are posited to affect the propensity for cracking. For this system, surface stresses are changed from states of tension to compression when the growth rate is increased, thus improving the chances to avoid cracking—a strategy that defies classical wisdom that dictates slower growth to improve outcomes. Similar strategies affecting segregation may prove beneficial to tailor chemical stress fields to reduce cracking in other crystal growth systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Local damage in grain boundary stabilized nanocrystalline aluminum

The excess free volume in grain boundaries of pure nanocrystalline aluminum leads to the grain coarsening, which degrades their desirable mechanical properties. The preferential segregation of dopants to the grain boundaries has been proposed to enhance the stability of the nanostructure. Here, to shed light on the stabilization mechanisms, we present results from virtual mechanical tests on nanocrystalline aluminum samples with similar grain sizes but different magnesium dopant contents. The segregation of magnesium decreases the excess free volume within the grain boundaries and prohibits the nucleation and growth of intergranular cracks.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Direct Structural Evidence for Interfacial Gradients in Asymmetric Polymer Nanocomposite Blends

Understanding the complex structure of polymer blends filled with nanoparticles (NPs) is key to design their macroscopic properties. In this work, the spatial distribution of hydrogenated (H) and deuterated (D) polymer chains asymmetric in mass is studied by small-angle neutron scattering. Depending on the chain mass, a qualitatively new large-scale organization of poly(vinyl acetate) chains beyond the random-phase approximation is evidenced in nanocomposites with attractive polymer–silica interactions. The silica is found to systematically induce bulk segregation. Only with long H-chains, a strong scattering signature is observed in the q range of the NP size: it is the sign of interfacial isotopic enrichment, that is, of contrasted polymer shells close to the NP surface. A quantitative model describing both the bulk segregation and the interfacial gradient (over ca. 10–20 nm depending on the NP size) is developed, showing that both are of comparable strength. In all cases, NP surfaces trap the polymer blend in a non-equilibrium state, with preferential adsorption around NPs only if the chain length and isotopic preference toward the surface combine their entropic and enthalpic driving forces. This structural evidence for interfacial polymer gradients will open the road for quantitative understanding of the dynamics of many-chain nanocomposite systems.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Learning from Imperfections: Predicting Structure and Thermodynamics from Atomic Imaging of Fluctuations

In materials characterization, traditionally a single experimental sample is used to derive information about a single point in the composition space, while the imperfections, impurities, and stochastic details of material structure are deemed irrelevant or complicating factors in the analysis. Here we demonstrate that atomic-scale studies of a single nominal composition can provide information about microstructures and thermodynamic response over a finite area of chemical space. Using the principles of statistical inference, we develop a framework for incorporating structural fluctuations into statistical mechanical models and use it to solve the inverse problem of deriving effective interatomic interactions responsible for elemental segregation in a La 5/8 Ca 3/8 MnO 3 thin film. Here, the results are further analyzed by a variational autoencoder to detect anomalous behavior in the composition phase diagram. This study provides a framework for creating generative models from a combination of multiple experimental data and provides direct insight into the driving forces for cation segregation in manganites.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Exploring Microphase Separation in Semi-Fluorinated Diblock Copolymers: A Combined Experimental and Modeling Investigation

We report the combined experimental and theoretical study of the bulk self-assembly behavior of polystyrene-blockpoly( 2,3,4,5,6-pentafluorostyrene) diblock copolymers. These block copolymers were designed to create highly antagonistic blocks (with a high Flory−Huggins interaction parameter, χ) with minimum disruption to the molecular construct (i.e., only replacing five hydrogen atoms with five fluorine atoms). A large library of diblock copolymers (41 samples) was synthesized by reversible addition− fragmentation chain transfer (RAFT) polymerization to map out a major portion of the phase space. All block copolymers exhibited narrow molecular weight distributions with dispersity (D) values between 1.07 and 1.32, and subsequent thermal annealing revealed phase separation into well-defined nanoscale morphologies depending on their molecular composition, as determined from small-angle X-ray scattering and transmission electron microscopy analyses, with an experimental phase diagram being constructed. The χ value at 25 °C for this block copolymer was estimated to be 0.2 using strong segregation theory, based on trends in phase-separated domain spacing and interfacial width. When applying theoretical approaches, the majority of the domain spacing data trends were captured by a coil−coil diblock copolymer model; however, a better fit to the data for samples with shorter fluorinated blocks was obtained with a rod−coil model, indicating that the chains in these fluorinated blocks likely have a higher inherent stiffness and were thus rod-like. This observation demonstrates that, due to the very high value of χ, a transition from coil−coil to rod−coil behavior can be obtained purely by reducing the length of the stiffer of the two blocks and without varying temperature or the chemical composition of the polymers. Here, this work showcases the presence of strong microphase separation within AB diblock copolymers despite the relatively similar chemical composition of the constituent “A” and “B” units, with a clear transition from rod−coil to coil−coil segregation behavior.

RAFT polymerization↗