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Eingeladener Vortrag
- nein (80)
On the thermal behaviour and thermo-oxidative stability of liquid crystalline triphenylene compounds
(1999)
Columnar discotic materials are considered for applications in the area of photoconductivity and light-emitting diodes. A major requirement is their stability at elevated temperatures and in the presence of oxygen. The thermal and thermo-oxidative behaviour of discotic triphenylene derivatives was investigated by us using various methods, in particular by chemiluminescence (CL), UV-vis absorption spectroscopy and in situ thermogravimetry-mass spectroscopy (TG-MS). Various degradation processes are described for increasing temperature, and their influences on functional properties are discussed.
Polarized fluorescence and orientational order parameters of a liquid-crystalline conjugated polymer
(1999)
We report a study of the orientational order of aligned thin films of the liquid crystalline conjugated polymer poly(9,9-dioctylfluorene). Steady state polarized fluorescence measurements were used to determine the orientational order parameter <P2> and <P4>. The influence of intermolecular and intramolecular excitation energy transfer on the degree of polarization is discussed. The role of film morphology is also examined by comparison of the results for glassy and crystalline films.
The thermo-oxidative degradation of a polymeric optical cable is investigated by chemiluminescence, The results are reliable and reproducible. Two distinct processes are reported marked by a peak and a plateau behavior versus the time, respectively. Both processes are ruled by thermally activated processes. Beside the dependencies of temperature and time, the influence of absorbed water is discussed. Chemiluminescence is proposed as a promising candidate for a suitable testing method assessing the thermo-oxidative stability of plastic optical fibers and cables. it requires not more than a simple one-day testing procedure and has the advantage that it can be carried out even within the lo cv temperature ranges of the cables' intended use.
Conjugated polymers based on 1,4-phenylenevinylene units are very promising materials for applications as light-emitting diodes. A major requirement is their stability at elevated temperatures of operation. The thermo-oxidative behaviour of a soluble poly(1,4-phenylenevinylene) derivative, poly[2,5-bis(2-ethylhexyloxy)-1,4-phenylene vinylene], was investigated by using chemiluminescence and UVVis absorption spectroscopy. Extremely sensitive chemiluminescence is successfully applied since even minor chemical changes could lead to a considerable loss of photo- and electro-optical properties. Various degradation processes are described as a function of time and temperature and their influences on functional properties are discussed. The investigated material does not show sufficient thermo-oxidative stability within the temperature range of intended use in contact with air. For industrial application, direct contact with oxygen during processing and operation has to be avoided.
A liquid crystalline mainchain conjugated polymer for polarized electroluminescence applications
(1997)
Polarized fluorescence and orientational order parameters of a liquid crystalline conjugated polymer
(1999)
Photo- and thermo-oxidative stability of aromatic spiro-linked bichromophoric cross-shaped molecules
(2000)
An extensive investigation of the photostability and the thermo-oxidative stability is presented for 2,2,7,7-tetrakis(biphenyl-4-yl)-9,9-spirobifluorene and 2,2,4,4,7,7-hexakis(biphenyl-4-yl)-9,9-spirobifluorene. Both compounds are conjugated fully aromatic systems that are being discussed as active functional materials for a variety of advanced applications. The effect of atmosphere, sample thickness and preparation procedure on photo-oxidative degradation are investigated in detail by absorption and fluorescence spectroscopy. Distinct mechanisms are described in terms of relevant parameters such as the quantum yields of the photo-oxidation and the fluorescence. No oxidative degradation could be detected under nitrogen. In ambient air a strong decrease of the fluorescence performance is found due to effective quenching by defective chromophores. Chemiluminescence investigations were performed to characterise the thermo-oxidative behaviour in the temperature region between 300 and 450 K. It becomes clear that even a stable chemical structure such as the investigated aromatic system does not guarantee sufficient photostability with regard to light emitting properties.
About this Journal
The excitation energy transfer (EET) of a bichromophoric cross-shaped molecule was investigated by stationary polarized fluorescence spectroscopy in the solid state. For this purpose 2,2[prime],7,7[prime]-tetrakis(biphenyl-4-yl)-9,9[prime]-spirobifluorene was embedded in a polymeric bisphenol-A-polycarbonate (PC) matrix. The dependence of the fluorescence on concentration and wavelength was determined. The role of the intermolecular and intramolecular EET is dealt with separately and discussed by means of the degree of polarization. The intermolecular excitation energy transfer is described in terms of a Förster transfer mechanism. The intramolecular transfer is prevented for the zero-point vibrational levels by the molecular cross-shaped structure, but is found for a wide range of wavelength, presumably based on vibrationally excited states.
On the basis of Wittig-Horner reactions and protection group techniques compound 7 for the core and the components 9a-c and 11a-c for the dendrons were prepared and linked in the final step. The convergent synthesis yielded constitutionally and configurationally pure dendrimers (2a-c, 2a'-c') which consist of distyrylbenzene units. Their thermo-oxidative stability in the presence of air was studied by chemiluminescence and compared to the dendrimers 1 consisting of stilbene units.
Zwischen Chemie, Wirtschaft und Politik - Aus den Aufgaben einer Chemisch-Technischen Bundesanstalt
(1995)
Innovation; Was ist das?
(2005)
Forschen - Prüfen - Beraten; Ressortforschung für Sicherheit und Regelsetzung am Beispiel der BAM
(2005)
Werkstoffe
(2012)
Fast allen deutschen Bundesministerien sind Einrichtungen zugeordnet, die sie in der Erfüllung von Bundesaufgaben auf wissenschaftlicher Grundlage unterstützen. Die Vielfalt sowie die Art und der jeweilige Anteil der Aufgaben (insbesondere der Anteil der Forschung) haben dazu geführt, das es sehr unterschiedliche Typen von Ressortforschungseinrichtungen gibt. Viele dieser Einrichtungen erbringen in bedeutendem Umfang Dienstleistungen für Wirtschaft, Wissenschaft und Gesellschaft; alle stehen den Ministerien für Beratungsaufgaben unmittelbar zur Verfügung. Ihre Kompetenz stützt sich ganz wesentlich auf Forschung und Entwicklung und unterscheidet sie dadurch von anderen Bundesbehörden.
Akkreditierung im Wandel
(2011)
Nanoscience in der BAM
(2011)
If the intramolecular distance between the two isoenergetic chromophores of a bichromophoric compound is much smaller than the Förster radius of excitation energy transfer (EET), the probability to fluoresce is equal for both chromophores, because the EET takes place at a shorter time compared with the nanosecond timescale of the fluorescence lifetime. Then, the fluorescence depolarization of diluted solid solutions of such bichromophoric molecules can be measured with stationary excitation and used to evaluate the orientation between the two chromophores; in the most simple case the angle between their main axes is determined. Model calculations for bichromophoric alkane compounds with various conformational freedom reveal the amount of depolarization and thus the limits of the method. The results are compared to experimental data of 1,3-di(N-carbazolyl)-propane and 1,2-trans-di(N-carbazolyl)cyclobutane.
As far as indicated by the spectra and the fluorescence time decay law, the properties of the
fluorescence of poly(butylene terephthalate) (PBT) are almost identical to those of PET. The groundstate-
stable sandwich dimers in the noncrystalline regions of uniaxially-drawn PBT films were used as chainintrinsic
fluorescent labels for studying the orientation distribution function. The dimers are formed only
in the amorphous regions; concerning the fluorescence signal, "amorphous" includes all the material outaide
perfect crystallites. During deformation, the orientation coefficient <P2>F of the dimers follows approximately a superposition curve of crystallite-like orientation, easily separable in the initial range of stretching ratio λ < 2.5, and of true-amorphous orientation of the affine network type that becomes noticeable at λ > 3. The total fluorescence intensity of PBT, if excited at the proper wavelength, is proportional to the concentration of the dimers; it remains constant in the initial range of stretching, i.e. λ < 1.5. At higher λ, correlated to the increase of amorphous orientation, a strong increase of the dimer concentration, up to a factor of 6, is
observed.
Measurements with linearly polarized exciting and fluorescent light show that the excimerlike fluorescence of pyrenebutyric acid in alkaline solution is polarized. The degree of polarization r depends on temperature and, very pronounced, on the wavelength of excitation. This occurs in the spectral region where the excitation spectrum of the excimer differs from the corresponding monomer spectrum. The value of r, after correction of rotational depolarization, is 0.36 and indicates that single transition moments of absorption and emission coincide nearly in their direction. These results, together with the fluorescence time decay laws, strongly support the conclusion that, at least in an hydrophilic surrounding, not excimers but ground-state stable dimers of pyrene are formed.
The photophysical behavior of poly(p-phenylphenylenevinylene) (PPPV) and several oligomeric
model compounds in isotropic and anisotropic samples is investigated by means of polarized fluorescence
spectroscopy. As long as excitation energy transfer and mutual alignment are considered, the behavior of
PPPV can be modeled by a chain consisting of a distribution of independent oligomeric segments. The
results of fluorescence polarization, e.g., the nonzero value of r in isotropic PPPV, cast doubt on the application
of the semiconductor band model but favor an interpretation of spectroscopic properties in terms of molecular
transitions. The orientation coefficients of the oligomers and of PPPV in stretched polyethylene are determined.
The change of fluorescence spectra of oriented PPPV in stretched polyethylene demonstrates directly that
conformational changes of the macromolecule influence the pathway of energy transfer.
Polarized fluorescence spectroscopy is used to investigate the photophysical behavior of poly(p-phenylphenylenevinylene) (PPPV) in polystyrene matrix in comparison with oligomeric model compounds. For this purpose PPPV is modeled by a chain consisting of a distribution of independent oligomeric segments. Excitation energy transfer (EET) between the segments depends on the wavelength of excitation, not only for transfer along an isolated polymer chain, but also for intermolecular transfer at high concentration of PPPV. The spatial range of EET, as indicated by fluorescence depolarization, is reduced for excitation at the long wavelength edge of the absorption spectrum ("red-edge-effect").
Bei elektrisch isolierenden Polymeren kann durch Beimischung leitfähiger Partikel eine Leitfähigkeit erreicht werden. Polymere mit einem strukturell geordneten, ungesättigten Polymerkörper besitzen bereits eine intrinsische Leitfähigkeit. Dünne Polymerschichten, wie sie mit Plasmaverfahren erzeugt werden, unterscheiden sich ganz wesentlich in ihrer Struktur von den klassischen Polymeren. So besitzen Plasmapolymerschichten aus leitfähigen Polymeren nur sehr geringe Leitfähigkeiten. Diese kann durch eine Dotierung mit Jod bei erhöhter Temperatur verbessert werden. Da eine Dotierung während des Plasmaprozesses mit elementarem Jod schwierig ist, wurde am Fraunhofer-Institut für Angewandte Materialforschung ein neues Plasmaverfahren entwickelt und in einer Laboranlage erprobt. Die Anlage arbeitet mit einem Argon-Mikrowellenplasma, dem jodhaltige aromatische Monomere (2-lodthiophen) zugesetzt wird. Die elektrische Leitfähigkeit der erzeugten Plasmapolymerschicht ist gut; ihr Aufbau und molekulare Struktur wurden mit ESCA und IR-Spektroskopie untersucht.
Polyolefin surfaces (polyethylene and polypropylene) were exposed to haloform (CHX3) plasmas for introduction of monosort halogen groups. Bromoform and chloroform plasmas produced selectively C-Br (100 Br/100 C) and C-Cl (200 Cl/100 C) groups in high yields. The bromoform plasma showed 1-3 and the chloroform plasma 2-7 post-plasma introduced O-functionalities per 100 C. The polyolefin C-Br groups were grafted wet-chemically or by exposure to the vapour of amines, diols and glycols. Thus, spacer molecules could be covalently bonded to maximal 15 spacer molecules per 100 C for the smallest grafted molecules and 1.2 molecules/100 C for larger molecules as octaaminophenylene-POSS. After metal evaporation the end groups of these polymer-bonded spacer molecules formed also covalent bonds to the metal. Thus, flexible, hydrophobic and barrier elements were introduced into the polymer-metal interfaces for high-impact, high-durable and water-resistant metal-polymer composites as measured by means of peel strengths.
Intrinsically conductive plasma polymers were formed in a 2.45 GHz microwave low pressure plasma. The electrical conductivity and structure of the polymeric films were compared with those of electrochemically polymerized polythiophene. A new method of doping was tested using the iodine-containing monomer 2-iodothiopene. Films with high electrical conductivity (10-1 down to 10-6 S cm-1) could be produced, and their chemical structure was studied by X-ray photoelectron spectroscopy and Fourier transform IR spectroscopy. The IR spectra give a strong indication that the chemical structure of these films is comparable with that of electrochemically deposited polythiophene. Optical emission spectroscopy was used to give in-situ information about the fragmentation mechanism in the plasma.
In films of poly(para-phenylphenylenevinylene) a photoreaction has been observed. The significant feature is a decrease of the fluorescence emission intensity during irradiation. It is assumed that a cycloaddition between C=C- double-bonds leads to crosslinks in the material.
Under similar conditions of excitation a photoreaction has not been observed in poly(p-phenylenevinylene) prepared via the precursor-route.
A method is developed to determine orientational order parameters <P2> and <P4> of films by steady state fluorescence polarization in a spectrometer with 90° angle between excitation and emission beam. This is the geometry usually found in commercial fluorescence spectrometers. The method includes the determination of the fundamental molecular anisotropy rM of the fluorescent chromophore (doped or intrinsic) in stretched and unstretched films and the determination of instrumental correction coefficients from an isotropic film. As an example, the method is applied to orientation analysis of polyethylene and polystyrene films doped with fluorescent molecules of repetitive styrene units. It is concluded that in uniaxially stretched polyethylene-films orientation of these molecules is dominated by their molecular shape; in polystyrene films orientation is influenced by additional interactions.
Stationary polarized fluorescence spectra of poly(1,4-phenylene-1-phenylvinylene), poly(1,4-phenylene-1,2-diphenylvinylene) and poly[1,4-phenylene-1,2-bis(4-phenoxyphenyl)vinylene] in tetrahydrofuran solution and in polystyrene films were recorded at room temperature. In these matrices, different behaviour is found concerning the Stokes shift, the degree of polarization and the quantum yield; it is interpreted as a viscosity induced effect. The commonly accepted model of a conjugated polymer chain to consist of independent segments of various length should not be applied to the poly(phenylene-arylvinylene)s studied in this work.
Measurements of polarized excitation and fluorescence spectra were carried out with thin films of PPV and with films of oligomer model compounds in a polystyrene matrix. The degree of fluorrescece polarization r and its spectral dependence are discussed with respect to the transfer of excitation energy and the mutual alignment of the flurophores. In contrast to the behaviour of conventional aromatic polymers, the value of r is non-zero in isotropic PPV and depends on preparation (up to r = 0.25 at λexc = 460 nm and λflu = 555 nm). r can be nearly as high as in the dilute solid solution of the oligomers. This is easily understood if the PPV segments are highly aligned in the distance range of energy transfer.
Plasma polymer films of vinyltrimethylsilane (VTMS) were deposited by radiofrequency (RF. 13.56 MHz) or Microwave (MW, 2.45 GHz) discharges in two reactors of the same volume and geometry. — The polymer films were characterized by electron spectroscopy for chemical analysis (ESCA) and infrared spectroscopy (FTIR). It turned out, that the RF — and the MW — polymers had almost the same Si/C-composition ratio of 1/5 in the entire range of RF-and MW-power (60-150 W). Although the Si/C film-composition remains almost constant, the binding states of Si-and C-atoms in the respective ESCA-spectra are changing. While the CSi part of the C1s-peak increases with the RF-or MW-power, the C-H/C-C part of the peak decreases, indicating a loss of hydrogen in the polymer films. — Obviously the fragmentation of the VTMS-monomer is quite different for the two types of plasma discharges. While films of the RF-plasma clearly show strong contributions of the methyl and vinyl groups, these groups are completely missing for the MW-plasma polymers. — From these results structure models of the plasma polymers have been developed.
Structural investigations of electrical conducting plasma polymerized films from 2-iodothiophene
(1993)
Thin plasma polymerized films were produced in a microwave (2.45 GHz) plasma discharge using 2-iodothiophene as the initial monomer. The structure of these electrically conducting films (10-6-10-1 S/cm), the chemical state of the doping element iodine and the elemental homogeneity at the surface and in the films have been investigated by XPS, FTIR and AES. An interesting relationship was found that indicates some similarity to conventional polythiophene, prepared by electrodeposition. Besides covalently bound iodine, considerable amounts of I 3- and I 5- were detected and also a small number of O-I bonds were identified.
Chemie
(2008)
Über Innovation
(2007)