Synthesis and characterization of chiral liquid crystal polymers containing donor–acceptor group

A series of new chiral side-chain liquid crystalline polymers with electron donor–acceptor action were prepared containing chiral monomer with donor group and nematic LC monomer with acceptor group. All polymers were synthesized by graft polymerization using polymethylhydrosiloxane as backbone. The mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), thermogravimetric analyses (TGA), and X-ray diffraction measurements (XRD). The chemical structures of monomers and polymers were confirmed by Fourier transform infrared (FTIR), proton nuclear magnetic resonance spectra (¹H NMR and ¹³CNMR). M ₁ did not show liquid crystalline phase and M ₂ turned out nematic phase on heating and cooling cycle. Polymers P ₂ –P ₇ were cholesteric phase. Cholesteric phase and low glass temperature liquid crystalline polymers have been obtained, which offered the possibility of application. Experimental results demonstrated that the glass-transition temperatures rose and isotropization temperatures decreased and the ranges of the mesophase temperature reduced with increasing the content of chiral agent. All of the obtained polymers showed high thermal stability.     

Optical characterization of a new donor–acceptor type conjugated polymer derived from 3,4-diphenylthiophene

A new donor–acceptor type poly{2-(3,4-didecyloxythiophen-2-yl)-5-[3,4-diphenyl-5-(1,3,4-oxadiazol-2-yl)thiophen-2-yl]-1,3,4-oxadiazole} (P1) has been designed and synthesized starting from thiodiglycolic acid, 1,2-diphenylethane-1,2-dione, and diethyl oxalate through multi-step reactions using precursor polyhydrazide route. The charge-transporting and linear optical property of the polymer has been investigated by cyclic voltammetric, UV–visible, and fluorescence emission spectroscopic studies. The UV–visible absorption spectrum of polymer in thin film form showed maxima at 420 nm. The polymer displayed bluish-green fluorescence both in solution and thin film form. The optical band gap is determined to be 2.27 eV. Third-order nonlinear optical property of the new polymer has been investigated at 532 nm using single beam Z-scan and degenerate four wave mixing (DFWM) techniques with nanosecond laser pulses. The absorptive nonlinearity observed for the polymer P1 is of optical limiting type, which arises due to an “effective” three-photon absorption (3PA) process. The third-order nonlinear optical susceptibility (χ⁽³⁾) of the polymer is found to be 0.831 × 10^–12 esu. Both linear and nonlinear optical studies revealed that the new polymer (P1) is a promising material for applications in photonic devices.     

Multifunctional donor–acceptor conjugated polymers containing isoindigo and benzothiadiazole moieties for electrochromic,photoelectric sensor, 2,4,6-trinitrophenol detection and resistance memory device

Journal of Materials Science - Six novel donor–acceptor conjugated polymers were designed and synthesized by the Stille coupling reaction of triarylamine derivatives as donor units with...     

Electrochemical and optical properties of a new donor–acceptor type conjugated polymer derived from 3,4–didodecyloxythiophene

In this communication, we report the synthesis and characterization of a new donor–acceptor type conjugated polymer carrying alternate 3,4-didodecyloxythiophene and (1,3,4-oxadiazol-yl)pyridine moieties and evaluation of its optical and electrochemical properties. The polymer was synthesized through precursor polyhydrazide route. It has well defined structure, stability and it shows good solubility in common organic solvents. Optical and electrochemical properties were studied by UV-visible, fluorescence spectroscopy and cyclic voltammetric studies, respectively. It displays bluish-green fluorescence both in solution and in film state. Cyclic voltammetric studies showed that the polymer P1 possesses a HOMO energy level of −6·01 and LUMO energy level of −3·34 eV. The preliminary studies clearly reveal that the new polymer can have potential application in the fabrication of light emitting diodes. The studies on its device application are in progress.     

Synthesis, characterization, and nonlinear optical properties of donor–acceptor conjugated polymers and polymer/Ag nanocomposites

Two new donor–acceptor (D–A) conjugated polymers P1 and P2 containing 3,4-didodecyloxythiophene and 1,3,4-oxadiazole units are synthesized via Wittig reaction methodology. Cyclic voltammetry studies reveal that the polymers are both p and n dopable, and possess low-lying LUMO energy levels (?3.34?eV for P1 and ?3.46?eV for P2) and high-lying HOMO energy levels (?5.34?eV for P1 and ?5.27?eV for P2). The optical band gap of the polymers is in the range of 2.25–2.29?eV, calculated from the onset absorption edge. The polymers emit orange to yellow light in the film state when irradiated with a UV light. The synthesized polymers are used to prepare polymer nanocomposites with different wt% of silver nanoparticles. The polymer nanocomposites are characterized by UV–Vis absorption spectroscopy, field emission scanning electron microscopy, and thermogravimetric analysis. Both polymers and polymer/Ag nanocomposites show good thermal stability with onset decomposition temperature around 300?°C under nitrogen atmosphere. The nonlinear optical properties of polymers and polymer/Ag nanocomposites are measured by Z-scan technique. Both polymers and polymer nanocomposites show a good optical limiting behavior. Nearly five times enhancement in the nonlinear optical properties is observed for polymer/Ag nanocomposites. The value of effective two-photon absorption coefficient (β) is in the order of 10^?10–10^?11?m/W. These results indicate that the synthesized polymers (P1 and P2) and their Ag nanocomposites are expected to be good candidates for application in photonic devices.     

Novel thieno[3,4-c]pyrrole-4,6-dione-based conjugated copolymers with donor–acceptor structures

A series of novel copolymers with alkylthiophene/alkoxythiophene and the thieno[3,4-c]pyrrole-4,6-dione moieties were synthesized by Sonogashira cross-coupling reactions. The structures and properties of these copolymers were characterized using FT–IR, ¹H NMR, UV–Vis, thermal gravimetric analysis, different scanning calorimetry, and cyclic voltammetry (CV). All of the copolymers possess adequate thermal stability, and exhibit good solubility in common organic solvents such as THF, chloroform, and toluene. The electrochemical and photophysical properties were investigated, and the results show that the spectral response of these copolymers are extended up to 700, 750, and 640 nm for P ₁ , P ₂ , and P ₃ , respectively. CV studies reveal that the band gaps of these copolymers range from 1.51 to 1.97 eV, implying that the resulted polymers may be promising candidates for solar cells.     

A two-dimensional electron gas in donor–acceptor doped backward heterostructures

We propose a backward-diode heterostructure modified by a built-in acceptor-doped layer that forms an additional potential barrier decreasing the transverse transport of hot electrons to the substrate. According to calculations, this structure is characterized by (i) an energy difference between dimensional quantization levels that is several times the optical phonon energy in GaAs and (ii) increased linearity of transfer characteristics.     

Structure–property relationships in biaxially deformed polypropylene nanocomposites

Semi-solid forming processes such as thermoforming and injection blow moulding are used to make much of today’s packaging. As for most packaging there is a drive to reduce product weight and improve properties such as barrier performance. Polymer nanocomposites offer the possibility of increased modulus (and hence potential product light weighting) as well as improved barrier properties and are the subject of much research attention. In this particular study, polypropylene–clay nanocomposite sheets produced via biaxial deformation are investigated and the structure of the nanocomposites is quantitatively determined in order to gain a better understanding of the influence of the composite structure on mechanical properties. Compression moulded sheets of polypropylene and polypropylene/Cloisite 15A nanocomposite (5 wt.%) were biaxially stretched to different stretching ratios, and then the structure of the nanocomposite was examined using XRD and TEM techniques. Different stretching ratios produced different degrees of exfoliation and orientation of the clay tactoids. The sheet properties were then investigated using DSC, DMTA, and tensile tests .It was found that regardless of the degree of exfoliation or orientation, the addition of clay has no effect on percentage crystallinity or melting temperature, but it has an effect on the crystallization temperature and on the crystal size distribution. DMTA and tensile tests show that both the degree of exfoliation and the degree of orientation positively correlate with the dynamic mechanical properties and the tensile properties of the sheet.     

Pulsed laser deposition film of a donor–acceptor–donor polymer as possible active layer in devices

A molecule having a ketone group between two thiophene groups was synthesized. Presence of alternating electron donating and accepting moieties gives this material a donor–acceptor–donor (DAD) architecture. PolyDAD was synthesized from DAD monomer by oxidative polymerization. Device quality films of polyDAD were fabricated using pulsed laser deposition technique. X-ray photoelectron spectroscopy (XPS) and fourier transform infrared spectra (FTIR) data of both as synthesized and film indicate the material does not degrade during ablation. Optical band gap was determined to be about 1.45 eV. Four orders of magnitude increase in conductivity was observed from as synthesized to pulsed laser deposition (PLD) fabricated film of polyDAD. Annealing of polyDAD films increase conductivity, indicating better ordering of the molecules upon heating. Rectifying devices were fabricated from polyDAD, and preliminary results are discussed.     

Synthesis and characterization of Y-shape electron donor–acceptor type organic dyes for dye-sensitized solar cells

Three Y-shape organic dyes, (Z)-3-(5-(3,5-bis(4-(9H-carbazol-9-yl)styryl)-4-methoxyphenyl)thiophen-2-yl)-2-cyanoacrylic acid (OD-1), (Z)-3-(5′-(3,5-bis(4-(9H-carbazol-9-yl)styryl)-4-methoxyphenyl)-2,2′-bithiophen-5-yl)-2-cyanoacrylic acid (OD-2) and (Z)-3-(5′-(3,5-bis(4-(9H-carbazol-9-yl)styryl)-4-methoxyphenyl)-3,4′-4″-trithiophenyl-5-yl)-2-cyanoacrylic acid (OD-3) were synthesized and used as sensitizers in nanocrystalline dye-sensitized solar cells (DSSCs). The introduction of the bis(carbazolylstyryl) units as an electron donor group and oligothiophene units as a both electron donors and π-spacers increased the conjugation length of the sensitizers and thus improved their molar absorption coefficient and light harvesting efficiency. DSSCs with the configuration of SnO₂:F/TiO₂/organic dye/liquid electrolyte/Pt devices were fabricated using these OD-1, OD-2 and OD-3 as a sensitizers. Among the devices, the DSSC composed of OD-3 exhibited highest power conversion efficiency of 3.03% under AM1.5G (100 mW cm⁻²).     

Synthesis and photovoltaic properties of benzotriazole-based donor–acceptor copolymers

Two new D–A copolymers containing benzotriazole (BTz) acceptor unit and different donor units of benzodithiophene (BDT) and 2,7-carbazole, PBDT-DTBTz and PC-DTBTz, were synthesized for the application as donor materials in polymer solar cells (PSCs). By changing the donor units, the band gaps and the highest occupied molecular orbital (HOMO) energy levels of the copolymers could be finely tuned. PC-DTBTz exhibited the lower HOMO energy level of ?5.34 eV, and the lower HOMO energy level can lead to a higher open-circuit voltage (V _oc) of 0.73 V in PC-DTBTz-based devices. The PCEs of the PSCs based on PBDT-DTBTz and PC-DTBTz blends with [6,6]-phenyl-C₆₁ butyric acid methyl ester (PC₆₁BM) were 1.55 and 1.33 %, respectively, under the illumination of AM1.5, 100 mW/cm².     

Structure–property relationships in isotactic polypropylene/multi-walled carbon nanotubes nanocomposites

In this work, the influence of multi-walled carbon nanotubes (MWCNT) on electrical, thermal and mechanical properties of CNT reinforced isotactic polypropylene (iPP) nanocomposites is studied. The composites were obtained by diluting a masterbatch of 20 wt.% MWCNT with a low viscous iPP, using melt mixing. The morphology of the prepared samples was examined through SEM, Raman and XRD measurements. The effect of MWCNT addition on the thermal transitions of the iPP was investigated by differential scanning calorimetry (DSC) measurements. Significant changes are reported in the crystallization behavior of the matrix on addition of carbon nanotubes: increase of the degree of crystallinity, as well as appearance of a new crystallization peak (owing to trans-crystallinity). Dynamic mechanical analysis (DMA) studies revealed an enhancement of the storage modulus, in the glassy state, up to 86%. Furthermore, broadband dielectric relaxation spectroscopy (DRS) was employed to study the electrical and dielectric properties of the nanocomposites. The electrical percolation threshold was calculated 0.6–0.7 vol.% MWCNT from both dc conductivity and dielectric constant values. This value is lower than previous mentioned ones in literature in similar systems. In conclusion, this works provides a simple and quick way for the preparation of PP/MWCNT nanocomposites with low electrical percolation threshold and significantly enhanced mechanical properties.     

What determines the mobility of charge carriers in conjugated polymers?

In a conjugated polymer, the mobility of charge carriers is not a well-defined coefficient of a particular material as it is in an inorganic crystalline semiconductor but depends on the time domain of detection. On a time-scale of typically 100 fs, the on-chain mobility is ultra-high and controlled by the electronic band width of the polymer chain. When a carrier hits a chain imperfection, subsequent mesoscopic on-chain motion is retarded and controlled by intrachain disorder to which the chain environment contributes. Macroscopic transport commences after a time when interchain carrier jumps become rate limiting. It is routinely probed by time-of-flight experiments and can be rationalized in terms of random walk within a rough energy landscape. Experimental signatures of the various modes of transport are discussed.     

Structure–property relationships in intercritical heat affected zone of low-carbon microalloyed steels

Abstract

The conditions for martensite formation in the intercritical heat affected zone (HAZ) of two low-carbon microalloyed steels have been investigated using optical and transmission electron microscopy. Based on Charpy V-notch testing of a large number of thermally cycled specimens, it is concluded that embrittlement within the intercritical HAZ of such steels is closely related to the development of twinned martensite during the weld cooling cycle. The reduced HAZ toughness probably arises from the associated stress concentrations developed in the surrounding ferrite matrix, which give rise to the initiation of brittle fracture in the ferrite.

MST/634     

Synthesis,characterization, and photovoltaic properties of acceptor–donor–acceptor organic small molecules with different terminal electron-withdrawing groups

Two soluble acceptor–donor–acceptor (A–D–A) type organic small molecules, 2,2′-(5,5′-(1E,1′E)-2,2′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(ethene-2,1-diyl)bis(3,4-dihexylthiophene-5,2-diyl))bis(methan-1-yl-1-ylidene)dimalononitrile (BvT-DCN) and 2,2′-(3,3′-(1E,1′E)-2,2′-(5,5′-(1E,1′E)-2,2′-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(ethene-2,1-diyl)bis(3,4-dihexylthiophene-5,2-diyl))bis(ethene-2,1-diyl)bis(5,5-dimethylcyclohex-2-ene-3-yl-1-ylidene))dimalononitrile (BT-C6), were synthesized by Knoevenagel condensation reaction based on benzothiadiazole, thiophene, and different terminal electron-withdrawing groups. The acceptor group benzothiadiazole and donor group thiophene inside the molecules are connected by all-trans double bonds, which ensures the benzothiadiazole and thiopene groups are in the same plane and makes the molecules have a relative narrow band gap and absorb sunlight in the long wavelength. The terminal electron-withdrawing groups, malononitrile and 2-(5,5-dimethylcyclohex-2-en-1-ylidene)malononitrile (DCM), are symmetrically introduced into the molecules, respectively, to tune the energy level and extend the absorption of the molecules. The UV–Vis absorption spectrum and cyclic voltammetry measurements indicated that BT-C6 has a lower energy band gap (1.60 eV) than BvT-DCN (1.71 eV), which arises from the stronger electron-withdrawing ability of DCM group in BT-C6 than that of malononitrile group in BvT-DCN. And BvT-DCN and BT-C6 have nearly the same highest occupied molecular orbital energy level, ?5.74 eV for BvT-DCN and ?5.72 eV for BT-C6 due to the same electron–donor group of the two compounds. Bulk heterojunction photovoltaic devices were fabricated using BvT-DCN or BT-C6 as donor and (6,6)-phenyl C₆₁-butyric acid methyl ester as acceptor. The device based on BT-C6 has a higher (~8 times) short circuit current and power conversion efficiency than the device based on BvT-DCN, resulting from the wider solar light absorption of BT-C6 and smaller phase separation dimension of the active layer based on BT-C6.