PMMA Block Research Articles

Experimental study on influence of air gap on upward flame spread over discrete fuel

In a real fire scenario, the distribution of fire loads may not be continuous. In this paper, PMMA blocks (8 cm × 10 cm × 1 cm) are used as experimental materials to carry out upward flame spread experiments with different air gaps (0–18 cm) to analyze changes in burning rate, flame shape, flame height and pyrolysis front position. It is found that as the air gap increases, the burning rate and flame height both increase first and then decrease, and the turning point of this trend is predicted to be between 6 and 8 cm. In addition, it is founded that the pyrolysis reaction is accelerated due to the additional air entertainment provided by the air gap when the pyrolysis front passes through the air gap. However, this effect becomes insignificant for a larger air gap.

Graphoepitaxy of Symmetric Six-Arm Star-Shaped Poly(methyl methacrylate)-block-Polystyrene Copolymer Thin Film.

The authors perform directed self-assembly based on graphoepitaxy of symmetric six-arm star-shaped poly(methyl methacrylate)-block-polystyrene copolymer [(PMMA-b-PS)6 ] thin film. The affinity between each block and the trench wall is adjusted by using polymer brushes or selective gold (Au) deposition. When the surface of the trench is strongly selective for the PMMA block, (n+0.75)L0 thick (n is the number of the lamellae, L0 is lamellar domain spacing) lamellae parallel to the trench wall are formed at each side, while nanotubes are formed away from the trench wall. However, for a trench grafted with PS brushes, nanotubes are formed beside (n+0.25)L0 thick lamellar layers. By adjusting the trench width (W) and the affinity between the block and the wall, various dual nanopatterns consisting of lines and nanotubes are fabricated. Moreover, when the trench wall is selectively deposited by Au, asymmetric dual nanopattern is formed, where different numbers of lines exist on each side wall, while nanotubes are formed in the middle of the trench. The observed morphologies depending on the commensurability condition between W and L0 are consistent with predictions by self-consistent field theory.

Influence of Osmotic Pressure on Nanostructures in Thin Films of a Weakly-Segregated Block Copolymer and Its Blends with a Homopolymer.

We studied the influence of osmotic pressure on nanostructures in thin films of a symmetric weakly-segregated polystyrene-block-poly (methyl methacrylate), P(S-b-MMA), block copolymer and its mixtures with a polystyrene (PS) homopolymer of various compositions. Thin films were deposited on substrates through surface neutralization. The surface neutralization results from the PS mats, which were oxidized and cross-linked by UV-light exposure. Thus, thermal annealing produced perpendicularly oriented lamellae and perforated layers, depending on the content of added PS chains. Nevertheless, a mixed orientation was obtained from cylinders in thin films, where a high content of PS was blended with the P(S-b-MMA). A combination of UV-light exposure and acetic acid rinsing was used to remove the PMMA block. Interestingly, the treatment of PMMA removal inevitably produced osmotic pressure and consequently resulted in surface wrinkling of perpendicular lamellae. As a result, a hierarchical structure with two periodicities was obtained for wrinkled films with perpendicular lamellae. The formation of surface wrinkling is due to the interplay between UV-light exposure and acetic acid rinsing. UV-light exposure resulted in different mechanical properties between the skin and the inner region of a film. Acetic acid rinsing produced osmotic pressure. It was found that surface wrinkling could be suppressed by reducing film thickness, increasing PS content and using high-molecular-weight P(S-b-MMA) BCPs.

The self-assembly and thermoresponsivity of poly(isoprene-b-methyl methacrylate) copolymers in non-polar solvents

The self-assembly of a series of polyisoprene-block-poly(methyl methacrylate) (PI-b-PMMA) block copolymers, in aliphatic hydrocarbon solvents is reported for the first time. The block copolymers were prepared by a change of mechanism polymerisation (CHOMP) whereby living anionic polymerisation was used to prepare polyisoprene macroinitiators for ATRP (PI-Br), which was in turn used to polymerize MMA. The use of anionic polymerisation ensured optimal control over the molar mass and dispersity of the polyisoprene block, in a synthesis that is readily scaled-up, to enable the production of homologous series of block copolymers by varying only the molar mass of the PMMA block. The block copolymers were subsequently dispersed in n-decane or n-hexane, a selective solvent for the PI block, at high solids content of up to 30 wt%. Analysis of the resulting self-assembled nanostructures using DLS and TEM revealed that the block copolymers self-assemble into varying morphologies (spherical micelles, wormlike micelles or vesicles), dependent upon the molar mass and composition of the block copolymer, enabling the construction of a series of “phase-diagrams”. The resultant self-assembled structures were also found to be thermally responsive and, in some cases, underwent a change in morphology upon heating.

Evaluation of fracture resistance and color stability of innovative esthetic crowns for primary posterior molars

Abstract: Purpose: To evaluate color stability and fracture resistance of CAD/CAM and manually fabricated tooth colored materials as crowns on primary molars. Methodology : Eighty epoxy replicas (Vertex- Dental B.V., The Netherlands) of minimally prepared primary molar were constructed to receive a tooth colored crown. Replicas were assigned into 4 groups (n=20) according to crown material used: CAD/CAM PMMA blocks (Telio Cad, Ivoclar Vivadent AG, Liechtenstein) [CC], self-polymerizing temporary resin material [SP] (Snap, Parkell, NY 11717 USA), auto-mix temporary resin material [AT] (Telio CS CB SP (∆E =5.4 ± 1.6), AM (∆E =6.7 ± 1.2) and TP (∆E =4.4 ± 2.5). On the other hand, CC crowns demonstrated high color stability (∆E=1.7 ± 0.2). CAD/CAM crowns demonstrated significantly higher fracture resistance (1417.9 ± 62 N) compared to manually fabricated crowns (SP=1096 ± 50, AM=989 ± 41 and TP=1297 ± 45). Conclusions: CAD/CAM PMMA crowns revealed superior fracture resistance and color stability properties suitable for long-term clinical performance within the primary molars.

Co-Nonsolvency Effect in Solutions of Poly(methyl methacrylate)-b-poly(N-isopropylacrylamide) Diblock Copolymers in Water/Methanol Mixtures

The self-assembly of the thermoresponsive amphiphilic diblock copolymer PMMA21-b-PNIPAM283 is studied in different water/methanol mixtures. It consists of a short hydrophobic poly(methyl methacrylate) block and a long thermoresponsive poly(N-isopropylacrylamide) block. Adding methanol as a cosolvent causes the PNIPAM block, which is soluble in both pure water and pure methanol, to collapse due to the so-called co-nonsolvency effect. Meanwhile, the addition of methanol reduces the incompatibility of the PMMA block with water. By means of turbidimetry and differential scanning calorimetry, the solvent-composition-dependent phase diagram is constructed. Dynamic light scattering and synchrotron radiation-based small-angle X-ray scattering provide structural information at 20 °C in dependence on the solvent composition. In water-rich solvent mixtures, self-assembled spherical core–shell micelles are formed. The internal structure of the micelles is adjusted by the solvent compositions in two ways: methanol softens the PMMA micellar core, while it causes the shrinkage of the PNIPAM micellar shell. In methanol-rich solvent mixtures beyond the miscibility gap, the copolymers are molecularly dissolved chains. They are collapsed near the coexistence line, while they become random coils as the methanol content increases. We propose that the internal morphology of the micelles and the conformation of the dissolved chains depend strongly on the solvent composition, as a consequence of the superposed co-nonsolvency effect of PNIPAM and the overall enhanced solvation of PMMA when adding methanol.

Buried Structure in Block Copolymer Films Revealed by Soft X-ray Reflectivity.

Interactions between polymers and surfaces can be used to influence properties including mechanical performance in nanocomposites, the glass transition temperature, and the orientation of thin film block copolymers (BCPs). In this work we investigate how specific interactions between the substrate and BCPs with varying substrate affinity impact the interfacial width between polymer components. The interface width is generally assumed to be a function of the BCP properties and independent of the surface affinity or substrate proximity. Using resonant soft X-ray reflectivity the optical constants of the film can be controlled by changing the incident energy, thereby varying the depth sensitivity of the measurement. Resonant soft X-ray reflectivity measurements were conducted on films of polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) and PS-b-poly(methyl methacrylate) (PS-b-PMMA), where the thickness of the film was varied from half the periodicity (L0) of the BCP to 5.5 L0. The results of this measurement on the PS-b-P2VP films show a significant expansion of the interface width immediately adjacent to the surface. This is likely caused by the strong adsorption of P2VP to the substrate, which constrains the mobility of the junction points, preventing them from reaching their equilibrium distribution and expanding the observed interface width. The interface width decays toward equilibrium moving away from the substrate, with the decay rate being a function of film thickness below a critical limit. The PMMA block appears to be more mobile, and the BCP interfaces near the substrate match their equilibrium value.

Self-organization of random copolymers to nanopatterns by localized e-beam dosing

Strategic electron beam (e-beam) irradiation on the surface of an ultrathin (<100 nm) film of polystyrene–poly(methyl methacrylate) (PS-PMMA) random copolymer followed by solvent annealing stimulates a special variety of dewetting, leading to large-area hierarchical nanoscale patterns. For this purpose, initially, a negative (positive) tone of resist PS (PMMA) under weak e-beam exposure is exploited to produce an array of sites composed of cross-linked PS (chain-scissioned PMMA). Subsequently, annealing with the help of a developer solvent engenders dewetted patterns in the exposed zones where PMMA blocks are confined by the blocks of cross-linked PS. The e-beam dosage was systematically varied from 180 μC cm−2 to 10 000 μC cm−2 to explore the tone reversal behavior of PMMA on the dewetted patterns. Remarkably, at relatively higher e-beam dosing, both PMMA and PS blocks act as negative tones in the exposed zone. In contrast, the chain scission of PMMA in the periphery of the exposed regions due to scattered secondary electrons caused confined dewetting upon solvent annealing. Such occurrences eventually lead to pattern miniaturization an order of magnitude greater than with conventional thermal or solvent vapor annealed dewetting. Selective removal of PMMA blocks of RCP using a suitable solvent provided an additional 50% reduction in the size of the dewetted features.

Erosion of CAD/CAM restorative materials and human enamel: An in vitro study

This in vitro study used the same frequency and duration of acid contact as a previous in situ/in vivo study to evaluate the effect of erosion on CAD/CAM restorative materials and human enamel and to compare the effects of in vitro and in situ/in vivo acid challenges on CAD/CAM restorative materials and human enamel. The CAD/CAM restorative materials (IPS e.max CAD, Lava Ultimate, and PMMA block) and human enamel were eroded by immersion in 150 ml of cola drink for 14 days (4 × 5 min/day). The surface microhardness and surface roughness of the specimens were measured at baseline (T1), day 7 (T2), and day 14 (T3). The substance losses were measured at T2 and T3. The data were statistically analyzed using repeated measures ANOVA and Bonferroni's test (α = 0.05). Erosion significantly decreased the surface microhardness of the CAD/CAM restorative materials and human enamel (all P < 0.001). The overall percentage of surface microhardness loss (%SMHl) of the PMMA block and enamel due to in vitro erosion was significantly higher than that due to in situ/in vivo erosion (P = 0.02 and P < 0.001, respectively). Consistent with in situ/in vivo erosion, the surface roughness and profile of the tested restorative materials remained unchanged after in vitro erosion. A significant increase in the surface roughness and substance loss was observed for enamel after in vitro erosion (all P < 0.001). The overall substance loss of enamel due to in vitro erosion was significantly higher than that due to in situ/in vivo erosion (P < 0.001). In conclusion, erosion decreased the surface microhardness of the CAD/CAM restorative materials and human enamel. Moreover, erosion negatively influenced the substance loss and surface roughness of human enamel. For the substance loss of enamel and %SMHl of PMMA block and enamel, the in vitro erosive effects were approximately 1–2 times greater than the in situ/in vivo effects. However, for the surface roughness and profile of the CAD/CAM restorative materials, no significant difference was found between in vitro and in situ/in vivo erosion.

Comparing Fracture Resistance of Provisional Restorations of 3-Unit Fixed Partial Dentures: An in Vitro Study of CAD/CAM versus Indirect Technique

Objective: To compare the indirect and CAD/CAM techniques and using acrylic and composites resins onthe fracture resistance of provisional 3-unit fixed partial dentures (FPDs).Materials and Methods: In in vitro setting, thirty samples were divided into three groups included 10FPDs manufactured indirectly and made of composite based bis-acryl (Protemp 4) resin, 10 FPDs indirectlymilled with polymethyl methacrylate resin (PMMA) and 10 FPDs fabricated by CAD/CAM PMMA blocks.Fracture resistance was measured using universal testing machine (UTM). The master model was made ofNiCr-alloy which designed using CAD/CAM technology.Results: FPDs fabricated using CAD/CAM PMMA blocks showed the highest fracture resistance valuesfollowed by Protemp 4 and then PMMA using indirect method. Statistically significant difference wasfound between the three groups (P=0.001). Bonferroni test was applied for pair wise comparison, in whichthe statistically significant difference was observed between FPDs fabricated by CAD/CAM which madeof PMMA blocks and Protemp 4 and between CAD/CAM PMMA blocks and indirect/PMMA FPDs andbetween indirect/Protemp 4 FPDs and indirect/PMMA FPDs. Hence this suggested that PMMA significantlyhas minimum value of fracture resistance when compared to both CAD/CAM and Protemp 4.Conclusion: This study proved the superiority of CAD/CAM PMMA blocks for fabricating 3-unit FPDsover Protemp 4 and PMMA using indirect method, and the superiority of Protemp 4 over PMMA in termsof fracture resistance using indirect methods

Hierarchical Self-Assembly of Thickness-Modulated Block Copolymer Thin Films for Controlling Nanodomain Orientations inside Bare Silicon Trenches.

We study the orientation and ordering of nanodomains of a thickness-modulated lamellar block copolymer (BCP) thin film at each thickness region inside a topological nano/micropattern of bare silicon wafers without chemical pretreatments. With precise control of the thickness gradient of a BCP thin film and the width of a bare silicon trench, we successfully demonstrate (i) perfectly oriented lamellar nanodomains, (ii) pseudocylindrical nanopatterns as periodically aligned defects from the lamellar BCP thin film, and (iii) half-cylindrical nanostructure arrays leveraged by a trench sidewall with the strong preferential wetting of the PMMA block of the BCP. Our strategy is simple, efficient, and has an advantage in fabricating diverse nanopatterns simultaneously compared to conventional BCP lithography utilizing chemical pretreatments, such as a polymer brush or a self-assembled monolayer (SAM). The proposed self-assembly nanopatterning process can be used in energy devices and biodevices requiring various nanopatterns on the same device and as next-generation nanofabrication processes with minimized fabrication steps for low-cost manufacturing techniques.

Inverted Cylindrical Microdomains by Blending Star-Shaped and Linear Block Copolymers

We investigated the morphology formed in the binary blend of six-arm star-shaped (poly(methyl methacrylate)-block-polystyrene)6 copolymer [(PMMA-b-PS)6] and PMMA-b-PS linear diblock copolymer by varying their molecular weights as well as volume fractions of the blocks. When the molecular weight of PMMA-b-PS is much larger (> ∼4) than that of one arm of (PMMA-b-PS)6, PMMA-cylindrical microdomains are formed even though the volume fraction of PMMA (fPMMA) in both (PMMA-b-PS)6 and PMMA-b-PS is nearly symmetric (fPMMA ∼0.5). On the other hand, when the ratio of molecular weights between these two copolymers is not large, lamellar morphology is observed in the blend as expected. Very interestingly, we found that even for a binary blend with the overall volume fraction of the PMMA block (f̅PMMA) as large as 0.71, the major PMMA blocks still aggregate into cylindrical microdomains, and thus, “inverted cylinders” are formed, although PS-cylinders are observed in the neat (PMMA-b-PS)6 and PMMA-b-PS melts. This interesting inverted cylinder is mainly stabilized by two factors. On the one hand, the long linear diblock copolymer swells the domain significantly, thus preventing the short (PMMA-b-PS)6 star copolymer from forming the favorable bridging configurations in order to avoid the high stretching energy. As long as the bridging configurations are prohibited, the PMMA-core blocks of (PMMA-b-PS)6 prefer to stay inside the curvature, amplifying the tendency of forming a spontaneous curvature toward PMMA-blocks. On the other hand, the radial distribution of the long PMMA-block of the diblock and the short PMMA-block of the star increases the spontaneous curvature. The experimental results as well as the formation of the inverted cylinders have been verified by self-consistent field theory (SCFT).

Self-Assembled Micelles from Thermoresponsive Poly(methyl methacrylate)-b-poly(N-isopropylacrylamide) Diblock Copolymers in Aqueous Solution

The temperature-dependent phase behavior and self-assembly behavior in aqueous solution of the thermoresponsive amphiphilic diblock copolymer PMMA21-b-PNIPAM283 made of a short permanently hydrophobic poly(methyl methacrylate) block and a long thermoresponsive poly(N-isopropylacrylamide) are studied. Turbidimetry, dynamic light scattering (DLS), and synchrotron small-angle X-ray scattering (SAXS) provide temperature-dependent structure information. A lower critical solution temperature (LCST) behavior with a cloud point TCP = 31.1 °C in dilute solution is observed. Below TCP, spherical core–shell micelles are present, having a small PMMA core and a hydrated PNIPAM shell with a radial gradient of water content. Below TCP, the micelles are interpenetrated and show a weak correlation with each other. As the temperature approaches TCP, the micellar core shrinks and thus, the aggregation number decreases, revealing that the PMMA blocks are still mobile. Moreover, the micellar shell dehydrates above TCP and the micelles notably contract. They form clusters, which grow and transform into large compact aggregates as temperature is raised far above TCP.

Effect of cosolvent on the rheological properties and self-assembled structures from telechelic polyampholytes

A triblock copolymer with hydrophobic end blocks and a polyampholytic middle block is investigated in a mixture of water and acetone with a focus on the dependence of the rheological properties and of the micellar structure and correlation on the content of acetone. The polymer under study is PMMA86-b-P(DEA190-co-MAA96)-b-PMMA86, where PMMA stands for poly(methyl methacrylate) and P(DEA-co-MAA) for poly(2-(diethylamino) ethyl methacrylate-co-methacrylic acid). The pH is chosen at 3. Rheological measurements reveal a transition from a viscoelastic solid over a viscoelastic liquid to a freely flowing liquid upon addition of 5 or 10 wt% of acetone to a 3 wt% aqueous polymer solution, respectively. Using small-angle neutron scattering on 0.5 wt% polymer solutions in water/acetone with the content of the latter ranging between 0 and 30 wt%, significant structural changes are observed as well, such as a decrease of the distance between the PMMA cross-links and of the size of the network clusters upon increasing acetone constant. These changes are attributed to the reduction of the dielectric constant by the addition of the cosolvent acetone, enhancing the flexibility of the middle blocks and their tendency to backfolding, as well as to the decrease of the solvent selectivity, inducing significant exchange rate enhancement of the core-forming PMMA blocks.

Dispersity effects on phase behavior and structural evolution in ultrathin films of a deuterated polystyrene-block-poly(methyl methacrylate) diblock copolymer

We report the unique phase behavior and structural transitions in thin films of a distorted network (DNW) nanostructure, which is an equilibrium phase contained in the bulk of a nearly-symmetric deuterated polystyrene-block-poly (methyl methacrylate), dPS-b-PMMA, block copolymer. The DNW is due to a broad dispersity for the PMMA block. Grazing incidence small-angle X-ray scattering, neutron reflectometry, atomic force microscopy and transmission electron microscopy techniques were used to characterize thermally-annealed dPS-b-PMMA ultrathin films with neutral boundaries at both the free surface and substrate interface. Brief thermal annealing imposed on the ultrathin films leads to perpendicular lamellae (L⊥). Upon increasing the duration of thermal annealing, the dPS-b-PMMA ultrathin films exhibit thickness dependence of phase transition kinetics and different irreversible routes of phase transition. As a result, the protracted thermal annealing of the thin films of various thicknesses produces either hexagonal arrays of perpendicular PMMA cylinders (HEX-C⊥) or disordered PMMA nanostructures (DIS). The phase transition routes and kinetics in ultrathin films suggest various possibilities to obtain diverse nanoscale patterns via thin film self-assembly.

Tailored inclusion of semiconductor nanoparticles in nanoporous polystyrene-block-polymethyl methacrylate thin films

Nanoporous/nanocomposite thin films with controlled morphology at nanoscale were prepared onto transparent and conductive indium tin oxide (ITO) supports by exploiting the self-assembly of a lamellar polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) block copolymer (BCP). A perpendicular orientation of PS and PMMA lamellar nanodomains was achieved by grafting a random PS-r-PMMA copolymer to the ITO supports and successive thermal annealing. Stable and reproducible nanoporous morphologies, characterized by PS lamellar nanodomains of width equal to ≈20 nm alternating to nanochannels of width equal to ≈8 nm, were obtained by irradiating the samples with an appropriate UV-C dose able to fix the relative arrangement of PS domains through activation of cross-linking reactions and selective removal of PMMA blocks. Nanoporous hybrid composites with a stable morphology were obtained either by applying the UV irradiation protocol to BCP nanocomposites characterized by selective inclusion of zinc oxide (ZnO) nanoparticles (NPs) in the PS domains (nanocomposite first/nanopores after) or by selective infiltration of cadmium selenide (CdSe) NPs in the nanochannels left free by PMMA removal through UV irradiation (nanopores first/nanocomposite after), demonstrating the strenght of the approach.

Computer simulations on double hydrophobic PS-b-PMMA porous membrane by non-solvent induced phase separation

The formation of porous membrane of double hydrophobic Polystyrene-b-Poly (methyl methacrylate) (PS-b-PMMA) block copolymer is studied by dissipative particle dynamics (DPD) simulations with the non-solvent induced phase separation (NIPS) method. It is also the first time to investigate the mechanism for double hydrophobic copolymer to form porous membrane. Results show that polymer concentration has the most significant effect on the membrane morphology. Different polymer concentrations lead to diversified morphologies. For the double hydrophobic PS-b-PMMA system, although PS and PMMA are both hydrophobic, due to their relative difference in hydrophobicity, the polymer and non-solvent undergo micro-phase separation. Channel membrane could be observed among the polymer concentration range of 30~40%. The block ratio influences the distribution of PS and PMMA block; meanwhile, block ratio has certain effect on the pore size. Effects of two different good solvents, dimethylacetamide (DMAC) and tetrahydrofuran (THF), on the membrane morphologies are also studied, the results exhibit that the block copolymer PS25-b-PMMA25 dissolved in both DMAC and THF could form channel pore, but the pore size is bigger for the DMAC system.

Supertough Poly(lactic acid) and Sustainable Elastomer Blends Compatibilized by PLLA-b-PMMA Block Copolymers as Effective A-b-C-Type Compatibilizers

A series of poly(L-lactic acid) (PLLA)-b-poly(methyl methacrylate) (PMMA) block copolymers with well-defined chemical structures were synthesized by ring-opening polymerization followed by atom-tra...

Erosion of CAD/CAM restorative materials and human enamel: An in situ/in vivo study

This in situ/in vivo study aimed to evaluate the effects of erosion on the surface microhardness, substance loss, and surface roughness of CAD/CAM restorative materials and human enamel. This study used a 2-treatment (14 days each) crossover design with 8 healthy volunteers. Each volunteer wore an intraoral appliance containing 3 CAD/CAM restorative material specimens [IPS e.max CAD, Lava Ultimate CAD/CAM Restorative, and a poly (methyl methacrylate) (PMMA) block for CAD/CAM] and 1 human enamel specimen. The specimens were subjected to in vivo erosion cycles by rinsing with 150 ml of cola drink (4 × 5 min/day) for 14 days. The surface microhardness, substance loss, and surface roughness of the specimens were measured at baseline (T1), day 7 (T2) and day 14 (T3). The data were statistically analyzed using repeated measures ANOVA and Tukey's test (α = 0.05). After erosion, significant increases in substance loss and surface roughness were observed for enamel, though the surface roughness and substance profile of the tested restorative materials remained unchanged. Erosion significantly decreased the surface microhardness of all materials. For IPS e.max and Lava Ultimate, a significantly higher percentage of surface microhardness loss (%SMHl) was found at T3 than at T2, while no significant difference was found between T2 and T3 for enamel and the PMMA block. In conclusion, CAD/CAM restorative materials showed smaller changes in surface roughness and the surface profile than human enamel after in situ/in vivo erosion. However, CAD/CAM restorative materials and human enamel showed similar changes in surface microhardness after in situ/in vivo erosion.

Tunable Assembly of Block Copolymer Tethered Particle Brushes by Surface-Initiated Atom Transfer Radical Polymerization.

A strategy to synthesize SiO2-g-PMMA/PMMA-b-PS mono- and bimodal block copolymer particle brushes by surface-initiated atom transfer radical polymerization (SI-ATRP) from silica particles is presented. First, PMMA blocks were prepared by normal ATRP with controlled degree of polymerizations and grafting density. In a second step, the PS block was synthesized through a chain extension using low parts per million of Cu catalyst. Variation of the SiO2-g-PMMA-Br macroinitiator concentration had a pronounced effect on the modality of the chain extension product. In the limit of small concentration, partial termination resulted in bimodal brush architectures, while more uniform brush architectures were observed with increasing concentration of macroinitiator. Brush nanoparticles with bimodal architectures assembled into string-like aggregates that bore a resemblance to structures found in systems comprised of sparse (homopolymer) brush particles. The unexpected effect of modality on structure formation points to opportunities in controlling microstructures in brush particle materials.