An 11 Blockheizkraftwerken (BHKW) ohne Oxidationskatalysator und an 10 BHKW mit Oxidationskatalysator in Sachsen und Thüringen wurden die Einflussfaktoren auf die Formaldehydemissionen untersucht. Geprüft wurden insbesondere die Motorbetriebsparameter wie z.B. Zylindertemperaturen, Verbrennungsluftverhältnis, die Biogaszusammensetzung und die Biogasfeuchte. Im Ergebnis konnte kein bzw. nur ein geringer Einfluss der untersuchten Parameter auf die Formaldehydbildung festgestellt werden. Ebenfalls ließ sich bei den meisten der untersuchten Anlagen kein Einfluss von Wartungstätigkeiten sowie Ersatzteil- und Betriebsstoffwechseln auf die Formaldehydemissionen feststellen. Sollte der Gesetzgeber künftig einen niedrigeren Formaldehydgrenzwert vorschreiben, werden zusätzliche Technologien zur Biogasaufbereitung z.B. mit Aktivkohlefilter und zur Abgasnachbehandlung z.B. mit Oxidationskatalysator oder Thermoreaktor notwendig. Diese müssen aber noch hinsichtlich ihrer Standzeiten untersucht und optimiert werden.

In this study, a series of denim fiberboards are fabricated using two different resins, malamine urea formaldehyde (MUF) and polymeric methylene diphenyl diisocyanate (pMDI). Two experimental design factors (1) adhesive content and (2) MUF-pMDI weight ratio, were studied. All the denim fiberboard samples were fabricated following the same resin blending, cold-press and hot-press procedures. The physical and mechanical tests were conducted on the fiberboard following the procedures described in ASTM D1037 to obtain such as modulus of elasticity (MOE), modulus of rupture (MOR), internal bond (IB), thickness swell (TS), and water absorption (WA). The results indicated that the MOE was significantly affected by both factors. IB was affected significantly by weight ratio of different glue types, with 17 wt% more MDI resin portion in the core layer of the denim boards, the IB for total adhesive content 15% fiberboard was enhanced by 306%, while for total adhesive content 25% fiberboard, enhanced by 205%. TS and WA, with higher adhesive content used in denim boards' fabrication, and more pMDI portion in the core layer of the boards, the boards' TS and WA was reduced by up to 64.2% and 78.8%, respectively.

Phenol Formaldehyde (PF) and polymeric isocyanate (pMDI) are the two main types of adhesives used in the production of structural wood-based composites. Much is unknown about various aspects of adhesion between these two types of resins and wood. The present research describes the development of techniques which will permit an enhanced understanding of 1.) the extent of cure of PF within a wood based composite, 2.) the scale of molecular level interactions between PF and pMDI and wood, 3.) mechanical performance and durability of wood-adhesive bonds. Correlations were established between conventional methods of characterization of neat PF (thermomechanical analysis, swelling studies) and measurements made using 13C CP/MAS NMR. These correlations were then utilized to characterize PF cured in the presence of wood. The use of 13C labeled PF allowed estimates of relative degrees of resin conversion to be made. The use of 13C and deuterium labeled PF allowed qualitative estimates of resin molecular rigidity to be made. The scale of molecular level interactions between PF and pMDI and wood was probed using NMR relaxation experiments. Evidence was shown to suggest the formation of an interpenetrating polymer network (IPN) morphology existing at both types of wood-resin interphases. The formation of the IPN morphology was strongly influenced by resin molecular weight, cure temperature and the presence of solvent. A new test geometry for the evaluation of the fracture toughness of wood-adhesive bonds was developed. Consistent and reliable results were obtained. It was found that low molecular weight PF possessed enhanced durability over high molecular weight. / Ph. D.

This work reports the elucidation of the structure of a copolymer generated by the cross- catalyzed reactions of PF and pMDI prepolymers.  The electronic behavior of phenolic monomers as perturbed by alkali metal hydroxides in an aqueous environment was studied with 1H and 13C NMR.  Changes in electronic structure and thus reactivity were related to solvated ionic radius, solvent dielectric constant, and their effect on ion generated electric field strength. NMR chemical shifts were used to predict order of reactivity for phenolic model compounds with phenyl isocyanate with good success.  As predicted, 2-HMP hydroxymethyl groups were more reactive than 4-HMP in forming urethane bonds under neutral conditions and 2-HMP hydroxymethyl groups were more reactive than 4-HMP in forming urethane bonds under alkaline conditions. The structure of the reaction products of phenol, benzyl alcohol, 2-HMP, and 4-HMP with phenyl isocyanate were studied using 1H and 13C NMR under neutral organic and aqueous alkaline conditions.  Reactions in THF-d8 under neutral conditions, without catalyst, were relatively slow, resulting in residual monomer and the precipitation of 1,3-diphenyl urea from the carbamic acid reaction.  The reactions of phenol, 2-HMP, and 4-HMP in the presence of TEA catalyst favored the formation of phenyl urethanes (PU). Reactions with benzyl alcohol, 2-HMP, and 4-HMP in the presence of DBTL catalyst favored the formation of benzyl urethanes (BU).  Reactions of 2-HMP and 4-HMP led to formation of benzylphenyldiurethane (BPDU).  DBTL catalysts favored formation of BDPU strictly by a benzyl urethane pathway, while TEA favored its formation mostly via phenyl urethane, although some BU was also present.  Under aqueous alkaline conditions, 2-HMP was more reactive than 4-HMP, exhibiting an enhanced reactivity that was attributed to intramolecular hydrogen bonding and a resulting resonance stabilization of the phenolic aromatic ring. ATR-FTIR spectroscopic studies generated real time structural information for model compound reactions of the cross-catalyzed system, differentiating among reaction peaks generated by the carbamic acid reaction, PU and BU formation.  ATR-FTIR also permitted monitoring of propylene carbonate hydrolysis and accelerated alkaline PF resole condensation.  ATR-FTIR data also showed that the overall reaction stoichiometry between the PF and pMDI components drove copolymer formation.  Benzyl urethane formation predominated under balanced stoichiometric conditions in the presence of ammonium hydroxide, while phenyl urethane formation was favored in its absence.  Accelerated phenolic methylene bridge formation became more important when the PF component was in excess in the presence of sufficient accelerator.  A high percentage of free isocyanate was present in solid copolymer formed at ambient temperature. The combination of ammonium hydroxide and tin (II) chloride synergistically enhanced the reactivity of the materials, reducing the residual isocyanate. From 13C CP/MAS NMR of the copolymer, the presence of ammonium hydroxide and tin (II) chloride and the higher PF concentration resulted in substantial urethane formation.  Ammonium hydroxide favored formation of benzyl urethane from the 2-hydroxymethyl groups, while phenyl urethane formed in its absence.  The low alkalinity PF resole with ammonium hydroxide favored benzyl urethane formation.  Comparison of these results with the 13C NMR model compound reactions with phenyl isocyanate under alkaline conditions confirmed high and low alkalinity should favor phenyl and benzyl urethane formation respectively.  These cross catalyzed systems are tunable by formulation for type of co-polymer linkages, reactivity, and cost. / Ph. D.

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No description available.

This research took place in 3 stages. In the first stage, lignin graphene (LG) was synthesized using a catalytic thermal conversion process. In stage 2, the time and temperature correlations for polyvinyl acetate (PVAc) and phenol resorcinol formaldehyde (PRF) adhesives were found and PRF showed stronger correlation when doped with carbon nanomaterials. Stage 3 evaluated the effect of the nanomaterials on radio frequency (RF) heating time and adhesive strength. It was found that all versions of the PRF adhesive resulted in higher shear strength values when cured in room temperature for 24 hours or in an oven at 170 °F for 30 minutes. The combination of PRF + 0.5 % LG and 120 s RF heating resulted in significantly higher block shear strengths when compared to the other RF heating durations. Pine lumber was selected as it is the single most important commercial/structural species in North America, by volume. A substantial portion of pine is directed to glue-laminated timber and cross-laminated timber. Both industries use or can use RF curing and as such both may benefit from improvements developed herein.

No description available.

<p> High molecular weight poly(ethylene oxide) (PEO) is used in conjunction with a cofactor such as phenol formaldehyde resin (PFR) as flocculants for newsprint manufacture. The objectives of the work described in this thesis were to prepare flocculants superior to PEO and to determine the flocculation mechanism. A series of novel comb copolymers consisting of a polyacrylamide backbone with short pendant poly(ethylene glycol) (PEG) chains was prepared and characterized. Additionally, polymerization conversion curves and reactivity ratios were measured. An interesting finding was that the reactivity of the macromonomer in free radical copolymerization decreased with PEG chain length. </p> <p> Flocculation results with both model latex dispersions and commercial wood pulp suspensions showed that copolymer chain length was the most important variable ; molecular weights greater than 3 million were required for good flocculation. On the other hand, the PEG pendant chains could be as short as 9 ether repeat units. Also, only 1 to 2 PEG chains for every 100 acrylamide backbone moieties were required. </p> <p> No published flocculation mechanisms could predict all the behaviors of the PEO or copolymer system. A new mechanism called complex bridging was proposed. According to this mechanism PEO or copolymer chains aggregate in the presence of cofactor to form colloidally dispersed polymer complex which heteroflocculates with the colloidal particles. </p> <p> Given in this work is the first explanation of the requirement for extremely high PEO or copolymer molecular weights for flocculation. It is proposed that polymer chains with molecular weights less than 106 collapse in the presence of PFR to an inactive precipitate before flocculation can occur whereas complexes based on very high molecular weight PEO collapse slowly enough to permit flocculation. </p> <p> Published mechanistic studies are hindered by the fact that PFR has poorly defined structures. It is shown for the first time in this work that welldefined, linear, poly(p-vinyl phenol) (PVPh) is an effective cofactor. </p> / Thesis / Doctor of Philosophy (PhD)

No description available.