Efeito da adição de lantânio em catalisadores de Ni/ZrO2 aplicados na reação de reforma a vapor de etanol

The catalytic performance of Ni/ZrO2 catalysts loaded with different lanthanum content for steam reforming of ethanol was investigated. Catalysts were characterized by BET surface area, X-ray diffraction, UV-vis spectroscopy, temperature programmed reduction, and X-ray absorption fine structure techniques. Results showed that lanthanum addition led to an increase in the degree of reduction of both NiO and nickel surface species interacting with the support, due to the higher dispersion effect. The best catalytic performance at 450 ºC was found for the Ni/12LZ catalyst, which exhibited an effluent gaseous mixture with the highest H2 yield.

Modification of the performance of WO3-ZrO2 catalysts by metal addition in hydrocarbon reactions

A study of the different hydrocarbon reactions over Ni doped WO3-ZrO2 catalysts was performed. Ni was found as NiO at low Ni concentration while at high Ni concentrations a small fraction was present as a metal. For both cases, Ni strongly modified total acidity and concentration of strong acid sites. In the cyclohexane dehydrogenation reaction, Ni addition promotes both benzene and methyl cyclopentane production. The hydroconversion activity (n-butane and n-octane) increases with the augment of total acidity produced by Ni. The selectivity to reaction products is modified according to the acid strength distribution changes produced by Ni addition.

Síntesis química, estudios de caracterización y reactividad de un material catalítico a base de ZrO2-H3PW12O40

In this work, the preparation and characterization of materials such as zirconium oxide (ZrO2) and phosphotungstic acid promoted zirconium oxide (ZrO2-H3PW12O40) is presented. Physico-chemical characterization results showed that addition of H3PW12O40 acted as both a textural and chemical promoter of zirconium oxide. The incorporation of phosphotungstic acid into the ZrO2 matrix delayed the sintering of the material and stabilized ZrO2 in the tetragonal phase. ZrO2 acidity was also enhanced, developing strong acid sites on its surface. The Pt/ZrO2-H3PW12O40 catalyst was active for n-pentane isomerization at 250 °C, exhibiting high selectivity to iso-pentane (95%). This result is probably due to its suitable acidity.

SYNGAS PRODUCTION FROM CO2-REFORMING OF CH4 OVER SOL-GEL SYNTHESIZED Ni-Co/Al2O3-MgO-ZrO2 NANOCATALYST: EFFECT OF ZrO2 PRECURSOR ON CATALYST PROPERTIES AND PERFORMANCE

Ni-Co/Al2O3-MgO-ZrO2 nanocatalyst with utilization of two different zirconia precursors, namely, zirconyl nitrate hydrate (ZNH) and zirconyl nitrate solution (ZNS), was synthesized via the sol-gel method. The physiochemical properties of nanocatalysts were characterized by XRD, FESEM, EDX, BET and FTIR analyses and employed for syngas production from CO2-reforming of CH4. XRD patterns, exhibiting proper crystalline structure and homogeneous dispersion of active phase for the nanocatalyst ZNS precursor employed (NCAMZ-ZNS). FESEM and BET results of NCAMZ-ZNS presented more uniform morphology and smaller particle size and consequently higher surface areas. In addition, average particle size of NCAMZ-ZNS was 15.7 nm, which is close to the critical size for Ni-Co catalysts to avoid carbon formation. Moreover, FESEM analysis indicated both prepared samples were nanoscale. EDX analysis confirmed the existence of various elements used and also supported the statements made in the XRD and FESEM analyses regarding dispersion. Based on the excellent physiochemical properties, NCAMZ-ZNS exhibited the best reactant conversion across all of the evaluated temperatures, e.g. CH4 and CO2 conversions were 97.2 and 99% at 850 ºC, respectively. Furthermore, NCAMZ-ZNS demonstrated a stable yield with H2/CO close to unit value during the 1440 min stability test.

KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68%) and selectivity (100%) for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.

Control methods for arc welding power supplies

Welding is one of the most important process of modern industry. Welding technology is used in the manufacture and repair a wide variety of products from different metals and alloys. In this thesis the different aspects of arc welding were discussed, such as stability and control of welding arc, power supplies for arc welding (especially the welding inverters because it is the most modern welding power source). All parameters of power source have influence on the arc parameters and its by-turn influence on quality. The ways of control for arc welding inverter power sources have been considered. Calculations and modeling in Matlab/Simulink were done for PI control method. All parameters of power source have influence on the arc parameters and its by-turn influence on quality.

Structural modelling of liquid ZrO2 and glassy B2O3 by using AB INITIO Molecular Dynamics method

Atomic structure of ZrO2 and B2O3 was investigated in this work. New data under extreme conditions (T = 3100 K) was obtained for the liquid ZrO2 structure. A fractional number of boron was investigated for glassy structure of B2O3. It was shown that it is possible to obtain an agreement for the fractional number between NMR and DFT techniques using a suitable initial configuration.

Laser-TIG–hybridihitsauksen soveltuvuustutkimus

Tässä tutkimuksessa selvitetään ilman hitsauslisäainetta tapahtuvan laser–TIG–hybridihitsausprosessin soveltuvuus 6 mm ja 8 mm paksujen päittäisliitettyjen S355 K2 ja Laser 355 MC rakenneterästen hitsaukseen. Hitsien tarkastelussa huomio kiinnitetään hitsausnopeuteen, hitsien tunkeumaan, liittämistehokkuuteen, hitsien kovuuteen ja hitsausliitoksen ulkonäköön. Muita tutkittavia asioita ovat laser-TIG-hybridihitsattujen levyjen muodonmuutokset ja suuresta hitsausnopeudesta sekä pienestä t8/5 jäähtymisajasta johtuvat mahdolliset kylmähalkeamat. Laser-TIG-hybridihitsejä verrataan robotti-MAG- ja käsin MAG-hitseihin sekä kaarihitsausstandardin SFS-EN ISO 5817 hitsiluokkien mukaisiin raja-arvoihin. Laser-TIG-hybridihitsausprosessissa TIG-valokaari mahdollistaa tasaisen ja lähes roiskeettoman hitsin ja lasersäde aikaansaa syvän tunkeuman sekä tasalaatuisen juurihitsin. Laser-TIG-hybridihitsausprosessilla 6 mm paksut S355 K2 rakenneteräslevyt on mahdollista hitsata levyn yhdeltä puolelta kerralla valmiiksi. Paksummat 8 mm levyt voidaan hitsata levyn yhdeltä tai molemmilta puolilta suoritettavalla laser-TIG-hybridihitsauksella. Laser-TIG-hybridihitsausprosessilla hitsatut hitsit ovat hyvin siistejä ja lähes roiskeettomia. Verrattaessa laser-TIG-hybridihitsausprosessia muihin hitsausprosesseihin sen voidaan todeta olevan erittäin kilpailukykyinen 6 mm paksujen päittäisliitettyjen rakenneterästen hitsaamisessa, mutta se soveltuu myös 8 mm paksujen rakenneterästen hitsaamiseen. Tutkitut hitsit täyttävät kaarihitsausstandardin SFS-EN ISO 5817 B- ja D-hitsiluokkien mukaiset raja-arvot. Vertailukokeet 6 mm paksulla S355 rakenneteräksellä osoittavat, että yhdeltä puolelta suoritettavan laser-TIG-hybridihitsauksen hitsausnopeus on robotti-MAG-hitsaukseen verrattuna yli nelinkertainen ja MAG-käsinhitsaukseen verrattuna yli viisinkertainen. Laser-TIG-hybridihitsauksessa liittämistehokkuus on noin viisinkertainen robotti-MAGhitsaukseen verrattuna. Molemmilta puolilta suoritettavalla laser-TIG-hybridihitsauksella voidaan 8 mm paksulla S355 rakenneteräksellä saavuttaa noin kolminkertainen hitsausnopeus ja liittämistehokkuus robotti-MAG-hitsaukseen verrattuna. Laser-TIG-hybridihitsauksessa TIG-kaaren tuoman lisälämmön ansiosta suurillakin hitsausnopeuksilla (1 m/min) voidaan saavuttaa edulliset kovuusarvot. Kovuusmittausten tulosten perusteella 6 mm ja 8 mm paksujen S355 K2 ja Laser 355 MC rakenneterästen hitsit eivät ylittäneet kaarihitsausstandardin määrittelemää 350 HV kovuuden enimmäisrajaa. Laser-TIG-hybridihitsauksen edullisesta lämmöntuonnista johtuen levyjen pituus- ja poikittaissuuntaiset muodonmuutokset ovat noin 80 prosenttia pienemmät kuin käsin suoritettavassa MAG-hitsauksessa. Laser-TIG-hybridihitsausprosessilla käytetään I-railoa, mutta robotti-MAG- ja käsin MAG-hitsausprosesseilla joudutaan käyttämään V-railoa, jolloin lämmöntuonti ja siitä johtuvat muodonmuutokset ovat suuremmat. Korkea liittämistehokkuus ja edullinen lämmöntuonti merkitsevät vähäisempiä muodonmuutoksia ja siten merkittäviä säästöjä työ-, materiaali- ja energiakustannuksissa. 8 mm ja sitä paksummilla S355 rakenneteräksillä levyn yhdeltä puolelta suoritettava päittäisliitoksen hitsaaminen on laser-TIG hybridihitsauksella haastavaa, koska yli 200 A:n TIG-kaarivirralla suuri metallisula aiheuttaa avaimenreiän sulkeutumisen ja avaimenreiän alaosaan muodostuu kaasukuplia. Tästä voidaan tehdä sellainen johtopäätös, että päittäisliitettävien levyjen ilmarakoa pitäisi kasvattaa niin suureksi, että avaimenreiän sulavirtaus ei pääse estymään. Yli 0,25 mm:n ilmarako edellyttää lasersäteen vaaputusta tai säteen halkaisijan kasvattamista. Ilmaraon kasvattaminen edellyttää myös lisäaineen käyttöä. Tutkimustulosten perusteella laser-TIG-hybridihitsausprosessilla voidaan saavuttaa merkittäviä etuja ja kustannussäästöjä, joten sen hyödyntämistä kannattaa harkita 8 mm ja sitä ohuempien päittäisliitettävien tuotteiden konepaja- ja tehdastuotannossa. Laser-TIGhybridihitsausprosessi soveltuu esimerkiksi seuraavien tuotteiden hitsaamiseen: päittäisliitettävät levyt, palkit, koneenosat, putket, säiliöt ja erilaiset pyörähdyskappaleet.

Arc fusion of self-fluxed nickel alloys

Self-fluxed nickel alloys are usually flame fused after thermal spraying. However, due to the practical aspects of high temperatures reached during flame fusing, large structures such as the hydraulic turbines for power generation, can not be efficiently coated. An alternative is to fuse the sprayed coating with a gas tungsten electric arc. In this case, heating is much more intensive and substrate temperature during and after the fusing operation is much lower, thus reducing the possibility that any problem will occur. In this work, coatings of self-fluxed nickel alloy fused by flame and gas tungsten arc were evaluated as protection of hydraulic turbines against cavitational damage. Several tests were performed, including the ASTM ultrasonically vibration-induced cavitation, optical and scanning electronic microscopic metallography, and hardness tests. The results showed that the arc-fused coating presented better cavitation damage resistance, probably due to its finer microstructure. A field application of this new technique is also described. A self-fluxed Ni alloy was flame sprayed in critical regions of Francis-type hydraulic turbine blades and fused by a gas tungsten arc after spraying. The blades will be inspected during the next two years.

Welding current effect on diffusible hydrogen content in flux cored arc weld metal

The application of flux cored arc welding (FCAW) has increased in manufacturing and fabrication. Even though FCAW is well known for its good capability in producing quality welds, few reports have been published on the cause of the relatively high diffusible hydrogen content in the weld metal and its relation with the ingredients used in the wire production and with the welding parameters (mainly welding current). This paper describes experiments where data obtained from weld metal diffusible hydrogen analysis, metal droplet collection, and high-speed recording of metal droplet transfer were used to evaluate the effect of welding current on diffusible hydrogen content in the weld metal. The results from gas chromatography analysis showed that weld metal hydrogen content indeed increased with welding current. A polynomial regressional analysis concluded that hydrogen increase with current was better described by a linear function with proportional constant of approximately 0.7 or 70%. Different from the GMA welding transfer behavior, statistical analysis showed only a small increase in metal droplet size with increasing current. The metal transfer mode remained in the globular range for currents between 100 and 150 A. The most surprising findings were with the high-speed cinematography recording. Observing the high speed movies, it was possible to see that at low current, "unmelted" flux sporadically touched the weld pool but at higher current, the flux remained touching the weld pool during the whole time of droplet formation and transfer. It is believed that since the flux has ingredients that contain hydrogen, hydrogen passes through the arc undisturbed, going to the weld bead intact and increasing the hydrogen content in the weld metal. Another important observation is regarding to droplet size. Droplet size increased with increasing current because forces from decomposed gases from the flux could sustain the droplets, retarding their transfer and allowing them to grow.

NIR-Vis Up-Conversion Luminescence in the Yb3+,Er3+ Doped Y2O2S, ZrO2, and NaYF4 Nanomaterials

Since the discovery of the up-conversion phenomenon, there has been an ever increasing interest in up-converting phosphors in which the absorption of two or more low energy photons is followed by emission of a higher energy photon. Most up-conversion luminescence materials operate by using a combination of a trivalent rare earth (lanthanide) sensitizer (e.g. Yb or Er) and an activator (e.g. Er, Ho, Tm or Pr) ion in a crystal lattice. Up-converting phosphors have a variety of potential applications as lasers and displays as well as inks for security printing (e.g. bank notes and bonds). One of the most sophisticated applications of lanthanide up-conversion luminescence is probably in medical diagnostics. However, there are some major problems in the use of photoluminescence based on the direct UV excitation in immunoassays. Human blood absorbs strongly UV radiation as well as the emission of the phosphor in the visible. A promising way to overcome the problems arising from the blood absorption is to use a long wavelength excitation and benefit from the up-conversion luminescence. Since there is practically no absorption by the whole-blood in the near IR region, it has no capability for up-conversion in the excitation wavelength region of the conventional up-converting phosphor based on the Yb3+ (sensitizer) and Er3+ (activator) combination. The aim of this work was to prepare nanocrystalline materials with high red (and green) up-conversion luminescence efficiency for use in quantitative whole-blood immunoassays. For coupling to biological compounds, nanometer-sized (crystallite size below 50 nm) up-converting phosphor particles are required. The nanocrystalline ZrO2:Yb3+,Er3+, Y2O2S:Yb3+,Er3+, NaYF4:Yb3+,Er3+ and NaRF4-NaR’F4 (R: Y, Yb, Er) materials, prepared with the combustion, sol-gel, flux, co-precipitation and solvothermal synthesis, were studied using the thermal analysis, FT-IR spectroscopy, transmission electron microscopy, EDX spectroscopy, XANES/EXAFS measurements, absorption spectroscopy, X-ray powder diffraction, as well as up-conversion and thermoluminescence spectroscopies. The effect of the impurities of the phosphors, crystallite size, as well as the crystal structure on the up-conversion luminescence intensity was analyzed. Finally, a new phenomenon, persistent up-conversion luminescence was introduced and discussed. For efficient use in bioassays, more work is needed to yield nanomaterials with smaller and more uniform crystallite sizes. Surface modifications need to be studied to improve the dispersion in water. On the other hand, further work must be carried out to optimize the persistent up-conversion luminescence of the nanomaterials to allow for their use as efficient immunoassay nanomaterials combining the advantages of both up-conversion and persistent luminescence.

Welding of additively manufactured stainless steel parts: Comparative study between sheet metal and selective laser melted parts

Additive manufacturing is a fast growing manufacturing technology capable of producing complex objects without the need for conventional manufacturing process planning. During the process the work piece is built by adding material one layer at a time according to a digital 3D CAD model. At first additive manufacturing was mainly used to make prototypes but the development of the technology has made it possible to also make final products. Welding is the most common joining method for metallic materials. As the maximum part size of additive manufacturing is often limited, it may sometimes be required to join two or more additively manufactured parts together. However there has been almost no research on the welding of additively manufactured parts so far, which means that there has been very little information available on the possible differences compared to the welding of sheet metal parts. The aim of this study was to compare the weld joint properties of additively manufactured parts to those of sheet metal parts. The welding process that was used was TIG welding and the test material was 316L austenitic stainless steel. Weld joint properties were studied by making tensile, bend and hardness tests and by studying the weld microstructures with a microscope. Results show that there are certain characteristics in the welds of additively manufactured parts. The building direction of the test pieces has some impact on the mechanical properties of the weld. Nevertheless all the welds exhibited higher yield strength than the sheet metal welds but at the same time elongation at break was lower. It was concluded that TIG welding is a feasible process for welding additively manufactured parts.

Narrow Gap flux-cored arc welding of high strength shipbuilding steels

This thesis is part of the Arctic Materials Technologies Development –project. The research of the thesis was done in cooperation with Arctech Helsinki Shipyard, Lappeenranta University of Technology and Kemppi Oy. Focus of the thesis was to study narrow gap flux-cored arc welding of two high strength steels with three different groove angles of 20°, 10° and 5°. Welding of the 25 mm thick E500 TMCP and 10 mm thick EH36 steels was mechanized and Kemppi WisePenetration and WiseFusion processes were tested with E500 TMCP steel. EH36 steel test pieces were welded without Wise processes. Shielding gases chosen were carbon dioxide and a mixture of argon and carbon dioxide. Welds were tested with non-destructive and destructive testing methods. Radiographic, visual, magnetic particle and liquid penetrant testing proved that welds were free from imperfections. After non-destructive testing, welds were tested with various destructive testing methods. Impact strength, bending, tensile strength and hardess tests proved that mechanized welding and Wise processes produced quality welds with narrower gap. More inconsistent results were achieved with test pieces welded without Wise processes. Impact test results of E500 TMCP exceeded the 50 J limit on weld, set by Russian Maritime Register of Shipping. EH36 impact test results were much closer to the limiting values of 34 J on weld and 47 on HAZ. Hardness values of all test specimens were below the limiting values. Bend testing and tensile testing results fulfilled the the Register requirements. No cracking or failing occurred on bend test specimens and tensile test results exceeded the Register limits of 610 MPa for E500 TMCP and 490 MPa for EH36.

Percent body fat is a better predictor of cardiovascular risk factors than body mass index

The objective of the present study was to evaluate the predictive values of percent body fat (PBF) and body mass index (BMI) for cardiovascular risk factors, especially when PBF and BMI are conflicting. BMI was calculated by the standard formula and PBF was determined by bioelectrical impedance analysis. A total of 3859 ambulatory adult Han Chinese subjects (2173 males and 1686 females, age range: 18-85 years) without a history of cardiovascular diseases were recruited from February to September 2009. Based on BMI and PBF, they were classified into group 1 (normal BMI and PBF, N = 1961), group 2 (normal BMI, but abnormal PBF, N = 381), group 3 (abnormal BMI, but normal PBF, N = 681), and group 4 (abnormal BMI and PBF, N = 836). When age, gender, lifestyle, and family history of obesity were adjusted, PBF, but not BMI, was correlated with blood glucose and lipid levels. The odds ratio (OR) and 95% confidence interval (CI) for cardiovascular risk factors in groups 2 and 4 were 1.88 (1.45-2.45) and 2.06 (1.26-3.35) times those in group 1, respectively, but remained unchanged in group 3 (OR = 1.32, 95%CI = 0.92-1.89). Logistic regression models also demonstrated that PBF, rather than BMI, was independently associated with cardiovascular risk factors. In conclusion, PBF, and not BMI, is independently associated with cardiovascular risk factors, indicating that PBF is a better predictor.