Solution‐processable and electroactive aromatic polyamides with 3,5‐bis(trifluoromethyl)triphenylamine moiety

New fluorine‐containing, triphenylamine‐based diamine and dicarboxylic acid monomers, namely 3,5‐bis(trifluoromethyl)‐4′,4″‐diaminotriphenylamine and 3,5‐bis(trifluoromethyl)‐4′,4″‐dicarboxytriphenylamine, were synthesized and polymerized with commercially available aromatic dicarboxylic acids and diamines, respectively, leading to two series of aromatic polyamides, 5a–h and 7a–e . Most of the polyamides were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent, flexible and strong films with good mechanical properties. The polyamides had useful levels of thermal stability associated with high glass transition temperatures of 273–305 °C and 10% weight‐loss temperatures in excess of 500 °C. Cyclic voltammograms of films of polymers 5a–h on indium–tin oxide‐coated glass substrates exhibited reversible oxidation redox couples with E_1/2 around 1.15 V versus Ag/AgCl in tetrabutylammonium perchlorate/acetonitrile solution, accompanied by a color change from colorless neutral state to reddish brown oxidized state. The 7 series polymers displayed a higher oxidation potential and less electrochemical stability as compared to the 5 series analogues. © 2017 Society of Chemical Industry     

Experimental determination of NH<Subscript>4</Subscript>NO<Subscript>3</Subscript>-KNO<Subscript>3</Subscript> binary phase diagram

The solid-state phase transitions in ammonium nitrate (AN)-potassium nitrate (KN) system, and the equilibrium AN-KN phase diagram have been determined by using differential scanning calorimetry and high-temperature in situ x-ray diffractometry. Sample preparation was performed in a special “dry room” with very low humidity. A single phase region (AN III) with no phase transitions to 373 K was observed in the composition range 5 to 20% KN; this is critical for use in air bag gas generators. The high-temperature KN phase (KN I) has a wide range of stability from 20 to 100 wt.% KN. There are one eutectic, two eutectoid, three peritectoid, and one congruent transformations in this phase diagram. Two new nonstoichiometric phases were found at lower temperatures in the mid-composition range between the AN and KN terminal solid solutions. Details of the phase equilibria are presented.     

IDENTIFICATION OF TRANSFER FUNCTION MODELS FROM THE RELAY FEEDBACK TEST

A MIMO process is considered to be composed of several single-input-multi-output (SIMO) processes. In this article, a method for identifying such SIMO process is devised. To identify each SIMO process, a single run of relay feedback experiment on a particular input is required. For each of such experiments, models of FOPDT (First-Order-Plus-Dead-Time) or of SOPDT (Second-Order-Plus-Dead-Time) are identified. Estimation of the parameters is carried out one-by-one and does not involve least square minimization. Direct application of these SIMO identification to MIMO processes is thus illustrated. The accuracy of each estimated gain can be controlled within one single run of experiment. A sufficient condition for the experiments to ensure robustness of the resulting model is presented. Thus, this proposed method can be applied to some MIMO processes even they are ill-conditioned.     

Simulation of a mold‐cooling process for gas‐assisted injection molded parts designed with a top rib on the gas channel

The same CAE model used for the filling and packing stage in the gas‐assisted injection molding (GAIM) process simulation was also applied to simulate the cooling phase. This was made possible by using the line source method for modeling cooling channels. The cycle‐averaged and cyclic transient mold cavity surface temperature distribution within a steady cycle was calculated using the three‐dimensional modified boundary element technique similar to that used in conventional injection molding. The analysis results for GAIM plates of a semicircular gas channel design attached with a top rib are illustrated and discussed. It was found that the difference in cycle‐averaged mold wall temperatures may be as high as 10°C, and within a steady cycle, part temperatures may also vary by about 15°C. The conversion of the gas channel into equivalent circular pipe and further simplification into two‐node elements using the line source method not only affects the mold wall temperature calculation very slightly but also reduces the computer time by 93%. This indicates that it is feasible to achieve an integrated process simulation for GAIM under one CAE model, resulting in great computational efficiency for industrial application.     

Structure and rheology of twin liquid crystalline polymers

Addition of short mesogenic segments at the ends of flexible chains alters the mechanical properties by orders of magnitude. Twin liquid crystalline polymers (TLCPs) were synthesized from 4-[(4′-alkoxybenzoyl)oxy]-benzoyl chloride and ,ω-dihydroxy-telechelic polytetrahydrofuran (PTHF) of different molecular weights. With increasing temperature, four equilibrium states of these TLCPs, i.e. crystalline state, phase separated state with mesogenic domains in isotropic PTHF matrix, phase separated amorphous state, and single phase isotropic state, have been observed by dynamic mechanical measurements, differential scanning calorimetry and polarizing microscopy. In the phase separated state, mesogenic domains function as physical crosslinks which give rise to unusually high viscoelastic properties at small strains. Disturbing this state by large amplitude shear resulted in very pronounced shear thinning and slow recovery of structure. At increased temperature, the mesogenic domains become isotropic and their effect as physical crosslinks was significantly reduced, as shown by lower viscoelasticity and weak shear thinning. In the single phase isotropic state above the coexistence temperature T_s, the TLCPs behaved like a common homopolymer of low molecular weight. T_s decreased as the weight ratio of PTHF spacer increased in the experimental range (50–82% PTHF).     

Solubility and agronomic effectiveness of partially acidulated phosphate rocks as influenced by their iron and aluminium oxide content

Partially acidulated phosphate rock (PAPR) has been shown to be an effective source of P for plants grown on acid soils. Less information in available, however, regarding the effect of the phosphate rock (PR) source on the solubility and agronomic effectiveness of PAPR.The effect of Fe₂O₃ + Al₂O₃ content in PR on the quality of PAPR produced was investigated in this study. Nine sources of PR from Africa, Latin America, and the United States, representing a range of Fe₂O₃ + Al₂O₃ from 0.7% to 12.4%, were used. In a single-step process, the finely ground PRs were partially acidulated with H₂SO₄ at the 30% or 50% acidulation level and granulated (–3.35 + 1.18 mm or –6 + 14 mesh). It was found that the water-soluble P content in PAPR decreased with increasing Fe₂O₃ + Al₂O content in the PR used. Apparently, the presence of Fe₂O₃ + Al₂O₃ resulted in a reversion of some of the water-soluble P to citrate-soluble P and sometimes even to citrate-insoluble P.A short-term (6 weeks) greenhouse study was conducted to evaluate crop response to PAPRs and single superphosphate (SSP); maize, the test crop, was grown on an acid soil (pH 4.5)—Hartsells silt loam (Typic Hapludults). The agronomic effectiveness of PAPRs with respect to SSP (in terms of dry-matter yield of maize) decreased with increasing Fe₂O₃ + Al₂O₃ content in PRs. Phosphorus uptake by maize from PAPRs was found to correlate well with water solubility but not with citrate solubility. The results obtained in this study show that the detrimental effect of Fe₂O₃ + Al₂O₃ content on the solubility and P availability of PAPR should be considered when selecting a PR for PAPR production.     

Polymer precursor synthesis of high Tc superconductors

Summary Free standing oxygen deficient perovskite Y₁Ba₂Cu₃O_X has been synthesized from polymer precursors. As prepared the material is comprised of crystallites of uniform and extensively interconnected morphology. The decrease of resistivity with temperature is perfectly linear, the onset of T_C occurs at 92.4 K and T_C (90%-10%) is ca. 1K. This precursor method of synthesis requires much lower temperature and shorter time than the usual ceramic techniques. Both free standing films and fibers can be obtained which is not possible otherwise.     

Fabrication of superhydrophobic silica‐based surfaces with high transmittance by using polypropylene and tetraeyhoxysilane precursors

Preparation of superhydrophobic silica‐based surfaces via sol–gel process by adding polyethylene glycol (PEG) polymer into the precursor solution has been developed. Surface roughness of the films was obtained by removing the organic polymer at 500°C and then the hydrophobic groups bonded onto the films were obtained by self‐assembly modification with a monolayer. Characteristic properties of the as‐prepared films were analyzed by contact angle measurements, scanning electron microscopy, atomic force microscopy, UV–vis scanning spectrophotometer, and X‐ray photoelectron spectrophotometer. The experimental parameters were varied by the type of silane species, the R ratio, the hydrolysis time of the precursor solution, the molecular weight of PEG, the pH value of mixing solution, and the different reagents for modification. The results showed that optimum ratio of TEOS/H₂O/ethanol in the sol–gel process for precursor solution was set to 1/10/4. The better contact angles of the films can be obtained by the acid catalyst reaction, especially the pH value of mixing solution was adjusted to 0. When the as‐prepared rough films were modified with (tridecafluoro‐1,1,2,2‐tetrahydrooctyl) dimethylchlorosilane (TFCS), the contact angle of the film can be promoted to 150.4°, and the transmittance of the films in the visible light region was greater than 94.5%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of organosoluble polyimides derived from 2,2′‐dibromo‐ and 2,2′,6,6′‐tetrabromo‐4,4′‐oxydianilines

Two new aromatic diamines, 2,2′‐dibromo‐4,4′‐oxydianiline (DB‐ODA 4 ) and 2,2′,6,6′‐tetrabromo‐4,4′‐oxydianiline (TB‐ODA 5 ), have been synthesized by oxidation, bromination, and reduction of 4,4′‐oxydianiline (4,4′‐ODA). Novel polyimides 6a–f and 7a–f were prepared by reacting DB‐ODA ( 4 ) and TB‐ODA ( 5 ) with several dianhydrides by one‐step method, respectively. The inherent viscosities of these polyimides ranged from 0.31 to 0.99 dL/g (0.5 g/dL, in NMP at 30°C). These polyimides showed enhanced solubilities compared to those derived from 4,4′‐oxydianiline and corresponding dianhydrides. Especially, polyimides 7a , derived from rigid PMDA and TB‐ODA ( 5 ) can also be soluble in THF, DMF, DMAc, DMSO, and NMP. These polyimides also exhibited good thermal stability. Their glass transition temperatures measured by thermal mechanical analysis (TMA) ranged from 251 to 328°C. When the same dianhydrides were used, polyimides 7 containing four bromide substituents had higher glass transition temperatures than polyimides 6 containing two bromide substituents. The effects of incorporating more polarizable bromides on the refractive indices of polyimides were also investigated. The average refractive indices (n_av) measured at 633 nm were from 1.6088 to 1.7072, and the in‐plane/out‐of‐plane birefringences (Δn) were from 0.0098 to 0.0445. It was found that the refractive indices are slightly higher when polyimides contain more bromides. However, this effect is not very obvious. It might be due to loose chain packing resulted from bromide substituents at the 2,2′ and 2,2′,6,6′ positions of the oxydiphenylene moieties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structural Basis for the Improved Potency of Peroxisome Proliferator‐Activated Receptor (PPAR) Agonists

The need to develop safer and more effective antidiabetic drugs is essential owing to the growth worldwide of the diabetic population. Targeting the PPAR receptor is one strategy for the treatment of diabetes; the PPAR agonists rosiglitazone and pioglitazone are already on the market. Here we report the identification of a potent PPAR agonist, 15 , whose PPARγ activation was more than 20 times better than that of rosiglitazone. Compound 15 was designed to incorporate an indole head with a carboxylic acid group, and 4‐phenylbenzophenone tail to achieve a PPARγ EC₅₀ of 10 nM . Compound 15 showed the most potent PPARγ agonist activity among the compounds we investigated. To gain molecular insight into the improved potency of 15 , a structural biology study and binding energy calculations were carried out. Superimposition of the X‐ray structures of 15 and agonist 10 revealed that, even though they have the same indole head part, they adopt different conformations. The head part of 15 showed stronger interactions toward PPARγ; this could be due to the presence of the novel tail part 4‐phenylbenzophenone, which could enhance the binding efficiency of 15 to PPARγ.