Self-repair ability of evolved self-assembling systems in cellular automata

Self-repairing systems are those that are able to reconfigure themselves following disruptions to bring them back into a defined normal state. In this paper we explore the self-repair ability of some cellular automata-like systems, which differ from classical cellular automata by the introduction of a local diffusion process inspired by chemical signalling processes in biological development. The update rules in these systems are evolved using genetic programming to self-assemble towards a target pattern. In particular, we demonstrate that once the update rules have been evolved for self-assembly, many of those update rules also provide a self-repair ability without any additional evolutionary process aimed specifically at self-repair.     

Synthesis and properties of acrylonitrile-CR-methyl methacrylate graft copolymer

Graft copolymerization of acrylonitrile (AN) and methyl methacrylate (MMA) onto polychloroprene (CR) was carried out using benzoyl peroxide as initiator. The effects of mole ratio of AN to MMA, reaction temperature, reaction time, solvent, and initiator concentration on the graft copolymerization were examined. It was found that the thermal stability and weatherability of the AN—CR—MMA graft copolymer (ACM) were considerably better than those of CR.     

Copolymerizations of ethylene with 1–decene over various ansa–metallocene complexes combined with Al( i-Bu) 3/ [CPh 3] [B(C 6F 5) 4] cocatalyst

Copolymerizations of ethylene with 1-decene were carried out with a series of stereospecific metallocene compounds, rac–(EBI)Zr(NMe₂)₂ [ 1, EBI = ethylene–1,2–bis( 1–indenyl)], rac–(EBI)Hf(NMe₂ (2), rac–Me₂Si( 1–C₅H₂–2–Me–4– ^t Bu)₂Zr(NMe₂)₂ (3), ethylidene(cyclopentadienyl)(9-fluorenyl)ZrMe2 [4, Et(Flu)(Cp)ZrMe2] and isopropylidene(cyclopentadienyl)(9–fluorenyl)ZrMe₂ [5, iPr(Flu)(Cp)ZrMe₂], combined with Al(i–Bu)₃/[CPh₃] [B(C₆F₅)₄] cocatalyst. All catalyst systems showed very high copolymerization rates and the 1–decene reactivity decreased in the order of 2 > 5 > 1 4 > 3. The reactivity product of ethylene and 1–decene (r _E x r _D) was below 1 except 3 catalyst, corresponding to random copolymer structures with an alternating character. The melting point (T_m), crystallinity (X_C), intrinsic viscosity ([] and density of the 1–decene/ethylene copolymers decreased markedly with an increase in the 1–decene content, regardless of the type of catalytic system.     

Syntheses and biological activities of polymers containing methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid or 5‐fluorouracil

A series of novel copolymers, poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalic acid) [poly(MTCA‐co‐ETAc)], poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐hydrogenethyl‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalate) [poly(MTCA‐co‐HEET)], and poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐α‐ethoxy‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthaloyl‐5‐fluorouracil) [poly(MTCA‐co‐EETFU)], were prepared from corresponding monomers by photopolymerizations at 25°C for 48 h. The polymers were identified by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopies. The number‐average molecular weights of the fractionated polymers determined by GPC were in the range from 9400 to 14,900 and polydispersity indices were 1.2–1.4. The in vitro IC₅₀ values of polymers against mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines and mouse liver cells (AC2F) as a normal cell line were much higher compared to that of 5‐fluorouracil (5‐FU). The in vivo antitumor activities of monomers and polymers against mice bearing sarcoma 180 tumor cell line were better than those of 5‐FU. The inhibition of DNA replication and antiangiogenesis activities of MTCA and copolymers were better compared to those of 5‐FU. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 57–64, 2004     

Unusual swelling behavior of polymer-clay nanocomposite hydrogels

The swelling behavior and the elastic properties of nanocomposite hydrogels have been investigated. The hydrogels were prepared by free-radical polymerization of the monomers acrylamide (AAm), N,N-dimethylacrylamide (DMA), and N-isopropylacrylamide (NIPA) in aqueous clay suspensions at 21 °C. Laponite with a radius of gyration in distilled water of 20 nm was used as clay particles in the hydrogel preparation. The reactions with AAm monomer were carried out in the presence of the chemical crosslinker N,N′-methylenebis(acrylamide) (BAAm). It was found that the volume of nanocomposite hydrogels immersed in water rapidly increases and attains a maximum value after about one day. Surprisingly, further increase in the swelling time results in the deswelling of the gels until they reach a limiting swelling ratio after about 5 days. This unusual swelling behavior is observable only when the clay concentration in the hydrogel is above the overlap threshold c^∗. Swelling measurements combined with the elasticity tests show that the effective crosslink density first decreases, but then increases with increasing time of swelling of the hydrogels. The results were explained in terms of the rearrangements of the highly entangled polymer chains and clay particles during the gel volume change.     

Characterization of cationic water-soluble polyacrylamides

Copolymers of poly(acrylamide-co-acryloyloxyethyltrimethylammonium chloride or AM–CMA) and poly(acrylamide-co-methacryloyloxyethyltrimethylammonium chloride or AM–CMA) prepared by inverse emulsion polymerization were characterized by different analytical techniques. The chemical composition of the copolymers was estimated by elemental analysis and by nuclear magnetic resonance spectroscopy (NMR). NMR spectroscopy and computer simulation were further used for investigating the polymers' sequence distribution. The poly(AM–CMA) copolymers are chemically more homogeneous than are the poly(AM–CMA). The configurational propagation of dyads and triads for the homopolymers obeys Bernouilli's statistics. For the copolymers, the chemical sequences distribution is governed by Markov's first-order statistics.     

Advanced underfill for high thermal reliability

The key to the success of flip‐chip technology lies in the availability of sucessful underfill materials. However, the reliability of flip‐chip technology using current underfill materials is generally found to be lower than that of conventional wire‐bond connection packaging materials such as epoxy molding compound (EMC) because of the high coefficients of thermal expansion (CTE) and moisture absorption of cured underfill material. In this study desbimide (DBMI), which has a low melting point (about 80°C), was used in the underfill materials as a cohardener. As a result, DBMI‐added underfill can show excellent thermal reliability, which is due to the superior properties of the CTE, the elastic modulus, and water resistance. When the properties of a 2 wt % DBMI‐added underfill were compared with those of a typical underfill (epoxy/anhydride), the CTE value was reduced to less than one‐half at the solder reflow temperature (about 200°C), the elastic modulus was reduced to less than one‐half in the temperature region below the glass‐transition temperature, and the water resistance was improved twofold. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2617–2624, 2002     

Hydrodesulfurization of model diesel using Pt/Al2O3 catalysts prepared by supercritical deposition

Pt/Al₂O₃ catalysts with Pt loadings ranging from 0.5 to 11 wt.% were synthesized by supercritical carbon dioxide (scCO₂) deposition method. Transmission electron microscopy (TEM) images showed that the synthesized catalysts contained small Pt nanoparticles (1–4 nm in diameter) with a narrow size distribution, no observable agglomeration, and uniformly dispersed on the alumina support. The catalysts were found to be active for hydrodesulfurization of dibenzothiophene (DBT) dissolved in n-hexadecane (n-HD) without sulfiding the metal phase. The reaction proceeded only via the direct hydrogenolysis route in the temperature range 310–400 °C and at atmospheric pressure. The activity increased with increasing the metal loading. Increasing [H₂]₀/[DBT]₀ by either increasing [H₂]₀ or decreasing [DBT]₀, increased the DBT conversion. At a fixed weight hourly space velocity and feed concentration, conversion did not increase with increasing temperature beyond 330 °C. The presence of toluene inhibited the catalyst activity presumably due to competitive adsorption between DBT and toluene. Under the operating conditions, the reaction was far from equilibrium.     

Polypropylene photostabilization by hindered amines in the presence of acidic species

Some volatile acids were found to dramatically reduce the effectiveness of additives based on 2,2,6,6-tetramethylpiperidine as photostabilizers for polypropylene films. Strong acids such as HCl, HBr, and HNO₃ had the largest effect with sulfurous acid somewhat less detrimental. Weak organic acids did not impair the effectiveness of the hindered amine light stabilizers. The role of acid concentration and contact time were explored for the HCl–piperidyl additive system. Secondary and tertiary amines were included in the study as well as oligomeric additives and an N-oxyl derivative. The latter is less basic than the free amines, and it was correspondingly less effected by acid exposures. The possibilities for acid exposure during the compounding, fabrication, and use of stabilized polyolefin articles is discussed as well as the effects of acids in terms of proposed stabilization mechanisms for the hindered amines.     

Fully aliphatic polyimides from adamantane‐based diamines for enhanced thermal stability,solubility, transparency,and low dielectric constant

We have synthesized a series of fully aliphatic polyimides (APIs) from bicyclo[2,2,2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BOCA) and various aliphatic diamines, including linear aliphatic, flexible alicyclic, and rigid adamantyl diamines. We performed the polymerization reactions using one‐step syntheses in m‐cresol at elevated temperatures without the isolation of poly(amic) acid. The chemical composition and structure of the polymers were characterized by nuclear magnetic resonance (NMR) and infrared (IR) spectrometry. The characterization data are reported from analyses using gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), and wide‐angle X‐ray diffraction (WXAD) measurements. The polyimides are also subjected to solubility, solution viscosity, tensile strength, transparency, and dielectric constant measurements. The resultant polyimides possess well‐controlled molecular weight, reasonable intrinsic viscosity, good transparency, enhanced solubility, low dielectric constants, and high glass transition temperature, together with marginal thermal and mechanical stability. These properties were enhanced in copolyimides containing equimolar amounts of rigid and flexible moieties. These rigid‐rod APIs derived from the alicyclic dianhydride and aliphatic diamines are promising candidates as advanced materials for future applications in micro‐ and photoelectronic devices. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3316–3326, 2006