A novel fiber optic structure, termed stochastic ordered hole fibers, has been developed that contains an ordered array of six hollow tubes surrounding a hollow core, combined with a nanoporous glass creating a unique fully three dimensional pore/fiber configuration. The objective of this study is to increase the functionality of these stochastic ordered hole fibers, as well as porous clad fibers, by integrating electronic device components such as conductors, and semiconductors, and optically active materials on and in the optical fiber pore structures. Conductive copper pathways were created on/in the solid core fibers using an electroless deposition technique. A chemical vapor deposition system was built in order to attempt the deposition of silicon in on the porous clad fibers. Additionally, conductive poly(3,4-ethylenedioxythiophene)- poly(styrene sulfonate) (PEDOT:PSS) and photoactive polymer blend poly(3- hexylthiophene) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-)6,6)C61 (P3HT: PCBM) were deposited on the fibers using dip coating techniques. Quantum dots of Cadmium Selenide (CdSe) with particle sizes of ranging from 2- 10 nm were deposited in the stochastic ordered hole fibers. SEM and EDS analysis confirm that copper, polymer materials, and quantum dots were deposited in the pore structure and on the surface of the fibers. Finally, resistance measurements indicate that the electrolessly deposited copper coatings have sufficient conductivity to be used as metallic contacts or resistive heating elements. / Master of Science

Magnesium and its alloys are extensively used for various industries such as aerospace, automobile and electronics due to their excellent properties such as low density, high strength and stiffness and electromagnetic shielding. However, the wide spread applications of these alloys are limited due to the undesirable properties such as poor corrosion, wear and creep resistance and high chemical reactivity. These alloys are highly susceptible to galvanic corrosion in sea water environment due to their high negative potential (-2.37 V vs SHE). The effective way of preventing corrosion is through the formation of a protective coating, which acts as a barrier between the corrosive medium and the substrate. Many surface modification methods such as electro/ electroless plating, conversion coating, physical and chemical vapour depositions, thermal spray coating etc., are available currently to improve the corrosion resistance of Mg alloys. Of these methods, the electroless nickel plating has gained considerable importance because of its excellent properties such as high hardness, good wear and corrosion resistance. The properties of binary electroless nickel coating have been further improved by the addition of a third element such as cobalt, tungsten, tin and copper etc. It has been reported that the addition of tungsten as the third element in the Ni-P improves the properties such as hardness, wear and corrosion resistance, thermal stability and electrical resistance. Magnesium alloys are categorized as a “difficult to plate metal”, because of their high reactivity in the aqueous solution. They react vigorously with atmospheric oxygen and water, resulting in the formation of the porous oxide/ hydroxide film which does not provide any protection in the corrosive environment. Further, the presence of this oxide film prevents the formation of a good adhesive bond between the coating and the substrate. The surface treatment process for removal of the oxide layer is very much essential before plating the Mg alloy. Currently two processes such as zinc immersion and direct electroless nickel plating are adopted to plate Mg alloys. Etching in a solution of chromate and nitric acid followed by immersion in HF solution to form a conversion film is necessary for direct electroless nickel (EN) plating of Mg alloy. However, strict environmental regulations restrict their usage because of hazardous nature. Expensive palladous activation treatment is a well-known process as a replacement for chromate-HF pretreatments for Mg alloys. It has been reported that EN plating has been carried out over Mg alloys by using conversion coating followed by HF treatment. Formation of an intermediate oxide layer by electrolytic methods is also one of the ways these toxic pretreatments can be avoided. Microarc oxidation (MAO) is an environment friendly surface treatment technique which provides high hardness, better corrosion and wear resistance properties for the Mg alloys. EN coating has been prepared on MAO layer for improving the corrosion resistance. These MAO/EN composite coatings have been prepared using chromic acid and HF pretreatment process. As the replacement for the chromate-HF pretreatment, SnCl2 and PdCl2 sensitization and activation procedures respectively were adopted over MAO layer for the deposition of Ni-P coating. From the above reported literature, it can be inferred that for the activation of inert MAO layer to deposit electroless nickel coating, the hazardous chromate/HF and highly expensive PdCl2 activation processes were followed. Therefore, there is a need for identifying an alternative simple and cost effective pretreatment process for the deposition of electroless nickel. It is well known that borohydride is a strong reducing agent that has been used for the deposition of Ni-B coatings. In the present study, an attempt has been made to utilize borohydride in the pretreatment process for the reduction of Ni2+ ions over the MAO interlayer, which provides the nucleation sites for the deposition of Ni-P coating. Ni-P and Ni-P/Ni-W-P duplex coatings were deposited from stabilizer free carbonate bath on AZ31B Mg alloy to improve the corrosion resistance of the base substrate. The conventional chromate and HF pretreatment processes were followed for the deposition of electroless nickel coating. In order to improve the corrosion resistance of the duplex coating, post treatments such as heat treatment (4 h at 150°C) and chromate passivation were adopted. EDX analysis of AZ31B Mg alloy showed the presence of 2.8 wt.% of Al and 1.2 wt. % Zn with the balance of Mg for AZ31B Mg alloy. After the chromic acid and HF treatment, the magnesium content was reduced from 90.0 wt % to 54.9 wt%, which could be due to the incorporation of chromium on the surface layer. The surface showed about 17.8 wt. % of F. The alloy exhibited the roughness of about 0.29± 0.01µm after mechanical polishing. The roughness value was significantly changed after the chromic acid treatment processes. The maximum roughness of about 1.28±0.06 µm was obtained after the HF activation. XPS analysis confirmed the existence of chromium in +3 oxidation state after the chromic acid treatment. The Ni-P coating thickness of about 25 microns was obtained in 1 h and 15 min. In the case of duplex coatings, Ni-P plating was done for 45 min. to obtain approx. 17 microns thickness and Ni-W-P plating was done for 1.15 h to obtain a thickness of approx. 10 microns, resulting in a total thickness of 25 ± 5 microns. Ni–P coating exhibited nodular morphology with porosity. The size of these cluster nodules were of about 10 µm in diameter. On the other hand, the duplex coating exhibited a less nodular, dense and smooth appearance. From the compositional analysis it was found that Ni–P coating contained about 6 wt. % P. In the case of duplex coating, the P content was reduced to 3 wt % due to the incorporation of about 2 wt% of tungsten. In corrosion studies, the potentiodynamic polarization data obtained for bare Ni-P coating in 0.15 M NaCl solution exhibited a higher current of about 218 μA/cm2 as compared to the substrate due to the porosity of the coating. However, the Ni-P/Ni-W-P duplex showed 55 times improvement in corrosion resistance, vis-a-vis Ni-P due to the dense nature of the coating. The corrosion resistance of the coatings increased in the following order: Ni-P < bare alloy < duplex < duplex-passivated < duplex-heat treated passivated. In EIS study, the Nyquist plot obtained for the bare substrate and Ni–P coating showed the presence of inductance behavior at the lower frequency region due to the adsorption of electroactive species over the substrate through the porous oxide layer. However, the passivated and duplex passivated coatings exhibited only capacitive behavior due to their compact nature. From the above, it can be concluded that, direct deposition of Ni-P coating over the chosen Mg alloy using chromic acid and HF pretreatment process resulted in porous morphology, which affected the corrosion resistance of the coating. As an alternative strategy, the microarc oxidation conversion coating was developed on Mg alloy and characterized. The MAO coating was developed using silicate electrolyte at three different current densities (0.026, 0.046 and 0.067 A/cm2) for about 15 min. With respect to the MAO coating, an increase in the current density increased the pore diameter and decreased the pore density. The surface of the coating became coarser and rough. The cross-sectional morphology of the coating showed two district layers namely the dense and thin inner layer and a porous thick outer layer. The thickness of the coating increased with increase in current density. MAO coating prepared at an intermediate current density of 0.046 A/cm2 exhibited a higher thickness of about 12 µm and a further increase in current density showed a decrease in thickness, due to the greater rate of dissolution of Mg, relative to the rate of deposition. The surface roughness of the MAO coatings also increased with increase in current density. The Ra value increased from 1.39±0.06 to 3.52±0.17 µm with increase in current density. XRD peaks obtained for the Mg substrates corresponded predominately to magnesium. However, the coated specimens showed the presence of peaks corresponding to Mg2SiO4 along with Mg and MgO. The corrosion measurements for the bare substrate and MAO coatings were carried out in 3.5% NaCl medium (0.6 M). Based on potentiodynamic polarization studies, the MAO coating prepared at 0.046 A/cm2 exhibited a lower corrosion current density with a higher Rp value, which was about five orders of magnitude higher than the bare substrate, due to the dense nature of the coating. In EIS study, MAO coatings were fitted with the two time constants equivalent circuit containing outer porous layer and inner barrier layer. The barrier layer resistance values were higher than that of porous layer resistance, which indicated that the resistance offered by barrier layer was higher than the porous layer. The total resistance value obtained for the coating prepared at 0.046 A/cm2 were higher compared to the other coatings, which attested to its better corrosion resistance. The electrochemical noise measurement was carried out for longer immersion durations upto 336 h in 3.5% NaCl solution. The noise resistance value obtained for the base Mg alloy was about 100 Ω at 1h immersion, whereas for the MAO coating prepared at 0.04 A/cm2 a maximum value of about 34.8 MΩ was achieved and it was retained even after 96 h of immersion. Mott–Schottky analysis showed that the oxide layer on magnesium substrate acted as a n-type semiconductor, whereas the MAO coatings exhibited p-type semiconductor behavior. The MAO coating obtained at an intermediate current density showed a higher acceptor density and the flat band potential, which resulted in the better performance of the coating in corrosive environment. In another set of investigations, the Ni-P and Ni-P/Ni-W-P coatings were deposited on AZ31B Mg alloy with MAO coating as an interlayer. The MAO layer was activated by a simple borohydride pretreatment process. During the pretreatment process, the MAO coating was subjected to mild alkali treatment, immersion in the Ni-P plating solution and finally immersion in borohydride solution. During each pretreatment step, the sample was characterized for their surface morphology and composition. The surface morphology showed the distribution of spherical particles over the surface of MAO coating after immersion in the Ni-P plating solution. EDX analysis showed the presence of 2.4 wt. % of Ni, which confirmed that Ni ions were adsorbed over the surface of the MAO coating during the pretreatment process. XPS analysis carried out after immersion in the Ni-P plating solution indicated that Ni existed in +2 oxidation state. The surface became smooth and uniform with flake- like morphology after the borohydride treatment, which indicated that the surface was etched by the borohydride solution. EDX analysis showed the presence of 1.8 wt.% of Ni after borohydride reduction. XPS analysis confirmed the reduction of nickel to the zero oxidation state. Additionally, MAO/Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were developed on MAO coating after a simple borohydride pretreatment. Ni-P and duplex coatings showed uniform and dense nodular morphology without any defects, which clearly indicated that the borohydride treatment provided a uniform and homogeneous active surface for the deposition of electroless nickel based coatings. Borohydride pretreatment process resulted in excellent bonding between MAO/Ni-P layers in the cross section. Based on potentiodynamic polarization studies, the corrosion current values obtained for MAO/ Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were about 1.44 and 1.42 µA/cm2, respectively. The coating showed about 97 times improvement in corrosion resistance compared to the bare substrate, attesting to the dense nature of the coating. In EIS study, the single time constant equivalent circuit was used for fitting the spectra, which pertained to the coating /electrolyte interface. The single time constant could be attributed to the pore-free dense, uniform coatings developed over the MAO interlayer. For the MAO/Ni-P and MAO/Ni-P-Ni-W-P duplex coatings, the charge transfer resistance of about 15 and 11 kΩcm2 were obtained for duplex and Ni-P coatings, which reinforce the better corrosion protective ability of the coating. The above investigation confirms that MAO coatings have good corrosion resistance in the aggressive chloride medium. Consequently, they can serve as an ideal interlayer for the deposition of the electroless nickel coating. Even if the electroless nickel coating is found to fail in harsh environments, the MAO interlayer can protect the base substrate due to its higher corrosion resistance. It is also noteworthy that the borohydride treatment provides better adhesion between the MAO/Ni-P interlayer.

Les dispositifs interconnectés moulés (« Molded Interconnected Devices », MID) sont constitués de supports polymères avec des pistes métalliques déposées à leur surface. Les objectifs de la thèse ont été d'optimiser les traitements de surface de polymères d'origine industrielle étudiés dans le contexte des MID pour obtenir des dépôts par métallisation electroless présentant une bonne adhérence. De plus, des procédés innovants de localisation de tels dépôts métalliques ont été développés. Durant ces travaux, la fonctionnalisation par plasma micro-ondes sous différentes atmosphères azotées et sous différentes conditions a été étudiée pour obtenir l'adsorption d'espèces palladiées (catalyseurs universels de la réaction de métallisation electroless). Des plans d'expériences ont été mis en oeuvre pour identifier un protocole type, développé sur PA12, pour obtenir des dépôts adhérents (Ni, Cu). Cette méthode a pu être globalement transposée avec succès sur d'autres polymères d'origine industrielle (ABS/PC, LCP). La seconde partie des travaux a consisté à développer des protocoles originaux basés sur des colloïdes de palladium directement synthétisés en surface d'un tampon en PDMS (lithographie douce) pour la réalisation de motifs métalliques par des procédés « top-down » et « bottomup ». Des analyses de surface AFM, SEM, TEM, XPS, ToF-SIMS et de mouillage ont permis de caractériser les différentes modifications de surface. Ces protocoles ont permis la réalisation de motifs métalliques MID adhérents jusqu'à 15 μm d'épaisseur et des motifs submicrométriques à haute résolution et haute densité avec des caractéristiques non encore obtenues à ce jour via cette technologie / Molded Interconnected Devices (MID) consist in polymer based substrates with metal tracks at their surface. The aim of this thesis was to optimize surface treatments applied to industrial polymers intended for MID applications, in order to obtain electroless metal coatings exhibiting a high practical adhesion. Furthermore, innovative processes to localize these metal coatings were developed. In this work, surface functionalization based on various operating parameters of microwave plasma using various nitrogen-based atmospheres were studied to obtain palladium (universal catalyst for electroless metallization) adsorption. Designs of experiments were used to identify an optimal set of parameters for PA12 surface treatment to obtain adherent metal coatings (Ni, Cu). These conditions were overall successfully transferred to other industrial polymers (ABS/PC, LCP). The second part of this work consisted in the development of innovative processes based on the use of palladium colloids directly synthetized at the surface of PDMS stamps (soft lithography) to achieve localized metallization using bottom-up and top-down approaches. AFM, SEM, TEM, XPS, ToF-SIMS and wettability measurements allowed to characterise the various surface modifications. These processes made possible 15 μm thick MID metal patterns with satisfactory practical adhesion as well as high resolution and high density sub-micrometric patterns with unseen properties for this technology

A reliable and robust diffusion barrier, commonly known as under bump metallisation (UBM), is indispensable in solder interconnects in order to retard the interfacial reaction rate, hence the growth of intermetallic compounds (IMCs). However, electroless Ni-P coatings are not adequate to inhibit interfacial reactions effectively since the formation of columnar structure and voids in the crystalline Ni3P layer in hybrid automotive devices (operating temperature above 300ºC) can significantly deteriorate the mechanical integrity of solder joints. In this thesis, electroless Ni-W-P coatings, as an effective UBM capable to serving under high temperature (up to 450ºC), are developed, characterised and subsequently applied onto the high temperature lead-free solder interconnects.

This research presents a novel microfabrication approach and testing methodology for cylindrical ion trap (CIT) microarray tunable for mass- spectrometers. The growing interest in cylindrical ion trap (CIT) mass-spectrometers is primarily due to ease with which cylindrical geometry can be realized as compared to hyperbolic surfaces found in conventional quadrupole ion traps. Also due to the fact that the potential at the center of hyperbolic electrode in quadrupole ion trap and cylindrical electrode in cylindrical ion trap (CIT) does not differ significantly[2]. Since the RF voltage required to eject a given mass-to-charge ion scales as the square of the ion trap radius, a decrease in ion trap dimensions provides a significant reduction in electronics requirements, thereby providing a pathway for overall system miniaturization. The reduction in sensitivity due to reduced ion storage capacity as a result of miniaturization can be improved by employing an array of identically sized ion traps. Microfabrication approach promises excellent uniformity in the fabrication of identically sized holes which in turn leads to low-cost high performance CIT microarray for mass spectrometers[1,2]. The criterion used for the determination of trap diameter was to ensure that the hole to be 1.09 times the wafer thickness to provide optimal potential to trap ions[1]. The end- plates were designed to optimize the electron and ion transmission into and out of the ion trap and provide a high quality electric field definition within each cylindrical ion trap (CIT)[3]. Two different approaches, namely deep reactive ion etching (DRIE) and mechanical drilling using ultrasonic disc cutter were proposed and used for the fabrication of ring-electrode which forms the main body of the ion trap. Excellent uniformity in hole diameter was observed in both the approaches. The end-plates were fabricated using deep reactive ion etching (DRIE) which provided high transmission rigid grid structure for ions and electrons. Standard Bosch process was used for deep reactive ion etching (DRIE). The two electrodes were metallized using electroless plating which provides excellent uniformity of coating even on end-plate structures with 5micro m through holes. CYTOP[trademark], a cyclized perfluoro polymer, was used as an insulation layer and intermediate bonding layer between the ring electrode and end-plates. The breakdown voltage for a released 16 micro m thick CYTOP[trademark] layer was found to be 1.47KV. An assembly for testing miniature cylindrical ion trap (CIT) was designed and built. An electron impact ionization source was used for generation of ions. Mass selective instability scan was used to selectively eject ions with different mass-to-charge ratio. A cylindrical ion trap (CIT) with 4mm diameter was fabricated and tested for analyte gases such as krypton and xenon.

Determination of bio-material by using enzyme, fluorophore or metal-nanoparticles as markers is very important. Generally, gold-nanoparticles have been used frequently as marker for increasing the sensitivity in bio-chemical assay. In this research, gold-nanoparticles were used as marker for immunoassay, DNA sequence assay, and protein analysis. However, the size of gold-nanoparticles affects directly the results of electrochemical detection. For improving the sensitivity of electrochemical method, enlargement of gold-nanoparticles was used in this study. By electroless deposition, Au will be deposited on the surface of gold-nanoparticles. The electrochemical response will thus be increased substantially. In immunoassay and DNA sequence assay, traditional 96-wells microtiter plate was used for immobilizing antibody or oligonucleotide, and the gold-nanoparticles were marked subsequently base on the immunoreaction or protein reaction of streptavidin and biotin. After gold-nanoparticles were enlarged, they were dissolved and transferred to an electrochemical cell for square wave stripping voltammetry¡]SWSV¡^analysis. Under optimal experimental condition, dynamic range of 1 ~ 500 pg/mL and 0.52 ~ 1300 aM were found respectively for RIgG and Target DNA analysis, and a good linear relationship¡]R2 = 0.9975 and 0.9982¡^. The relative standard deviation¡]R.S.D.¡^ of blank were 2.8 % and 2.4 %¡]n = 11¡^for immunoassay and DNA assay, respectively. And the variance was 2.4 %¡]n = 9¡^and 2.4 %¡]n = 12¡^for immunoassay and DNA assay, respectively. The detection limit¡]based on S/N = 3¡^of RIgG and DNA were 0.25 pg/mL and 0.52 aM, respectively. They are very competitive compared with similar results reported in the literature. Additional, a gold nanoelectrode ensemble¡]GNEE¡^coupled microchip system was developed for bio-electrochemical analysis. Due to the difference in mobility of urea and urease were mixed and allowed the enzymatic reaction to proceed in microchannel. The enzymatic product NH4+ was determined by the coupled GNEE at the outlet of the channel. Another experiment of streptavidin conjugated gold-nanoparticles¡]streptavidin-Au¡^, reductant and gold-ion¡]Au3+¡^solution was be applied here, too. The product, NH4+ or Au3+ was passed through downstream of microchannel and detected by GNEE of electrochemical system. Satisfactory linear relationship¡]R2 = 0.9778 and 0.9657¡^were found from 0.1 mM to 50 mM for NH4+ and urea in the range of 0.02 mM to 5.0 mM, respectively. The other satisfactory linear relationship¡]R2 = 0.9842 and 0.9507¡^ were found between 3.75 mg/mL and 3.75 g/mL for Au3+ and streptavidin-Au in the range of 0.2 ng/mL to 100 ng/mL, respectively. Variances of 2.5 %¡]n = 6¡^was found for analysis of with the microchip system.

The considerable interest in nanomaterials and nanotechnology over the last decade is attributed to Industry's desire for lower cost, more sophisticated devices and the opportunity that nanotechnology presents for scientists to explore the fundamental properties of nature at near atomic levels. In pursuit of these goals, researchers around the world have worked to both perfect existing technologies and also develop new nano-fabrication methods; however, no technique exists that is capable of producing complex, 2D and 3D nano-sized features of arbitrary shape, with smooth walls, and at low cost. This in part is due to two important limitations of current nanofabrication methods. First, 3D geometry is difficult if not impossible to fabricate, often requiring multiple lithography steps that are both expensive and do not scale well to industrial level fabrication requirements. Second, as feature sizes shrink into the nano-domain, it becomes increasingly difficult to accurately maintain those features over large depths and heights. The ability to produce these structures affordably and with high precision is critically important to a number of existing and emerging technologies such as metamaterials, nano-fluidics, nano-imprint lithography, and more. Summary To overcome these limitations, this study developed a novel and efficient method to etch complex 2D and 3D geometry in silicon with controllable sub-micron to nano-sized features with aspect ratios in excess of 500:1. This study utilized Metal-assisted Chemical Etching (MaCE) of silicon in conjunction with shape-controlled catalysts to fabricate structures such as 3D cycloids, spirals, sloping channels, and out-of-plane rotational structures. This study focused on taking MaCE from a method to fabricate small pores and silicon nanowires using metal catalyst nanoparticles and discontinuous thin films, to a powerful etching technology that utilizes shaped catalysts to fabricate complex, 3D geometry using a single lithography/etch cycle. The effect of catalyst geometry, etchant composition, and external pinning structures was examined to establish how etching path can be controlled through catalyst shape. The ability to control the rotation angle for out-of-plane rotational structures was established to show a linear dependence on catalyst arm length and an inverse relationship with arm width. A plastic deformation model of these structures established a minimum pressure gradient across the catalyst of 0.4 - 0.6 MPa. To establish the cause of catalyst motion in MaCE, the pressure gradient data was combined with force-displacement curves and results from specialized EBL patterns to show that DVLO encompassed forces are the most likely cause of catalyst motion. Lastly, MaCE fabricated templates were combined with electroless deposition of Pd to demonstrate the bottom-up filling of MaCE with sub-20 nm feature resolution. These structures were also used to establish the relationship between rotation angle of spiraling star-shaped catalysts and their center core diameter. Summary In summary, a new method to fabricate 3D nanostructures by top-down etching and bottom-up filling was established along with control over etching path, rotation angle, and etch depth. Out-of-plane rotational catalysts were designed and a new model for catalyst motion proposed. This research is expected to further the advancement of MaCE as platform for 3D nanofabrication with potential applications in thru-silicon-vias, photonics, nano-imprint lithography, and more.

Cheminio variavimo tirpalai bei cheminio variavimo procesai tiriami jau nuo XX a. vidurio iki šių dienų, ieškant vis efektyvesnių parametrų dangų funkcinėms bei dekoratyvinėms savybėms pagerinti. Pastaruoju metu vis didesnis dėmesys krypsta ne tik į nusodinamų dangų funkcionalumą, bet ir į ekologiškai nekenksmingus ar mažiau kenksmingus technologinius procesus, pzv., vykdoma ekologiškai nekenksmingų ligandų paieška. Kaip alternatyva šiuo metu siūlomos dvi cheminių junginių klasės t.y. alditoliai (polihodroksiliai alkoholiai) ir hidroksikarboksirūgštys. Pagrindinis darbo tikslas: ištirti cheminio variavimo sistemas ir jose vykstančius procesus, vario(II) jonų ligandais naudojant ekologiškai nekenksmingas citrinų ir vyno rūgštis. Cheminio variavimo sistemose panaudoti du nauji Cu(II) jonų ligandai t.y. citrinų rūgštis ir vyno rūgšties D-izomeras. Atliktų tyrimų duomenys rodo, kad minėti ligandai sėkmingai gali būti naudojami cheminio variavimo sistemose, kur reduktoriumi naudojamas formaldehidas. Nustatyta, kad 2-hidroksipropan-1,2,3-trikarboksirūgštis (citrinų rūgštis) ir 2,3-dihidroksibutano-1,4-dirūgštis (vyno rūgštis) šarminėje terpėje sudaro pakankamai patvarius kompleksus su vario(II) jonais ir yra tinkamas ligandas vario(II) kompleksinimui šarminiuose (pH > 12) cheminio variavimo tirpaluose. Ištirta vario(II)-citrato ir Cu(II)-D-, L- ir DL-tartratų kompleksų redukcija hidratuotu formaldehidu, apibūdintos gautosios vario dangos. Optimaliomis proceso vykdymo sąlygomis... [toliau žr. visą tekstą] / Electroless metal coating technique is one of the elegant ways of metal coating by controlling the temperature and pH of the plating bath in which there is no usage of electric current. The industrial electroless copper plating solution containing formaldehyde as reducing agent are known from the middle of the last century and are widespread in the practice up to now. However many chemical compounds used in such kind technological processes are hazardous for total environment, therefore the efforts are made to displace those substances with less hazardous or purely harmless compounds. Generally two classes of chemical compounds were proposed as EDTA alternative, namely alditols (polyhydroxylic alcohols) and hydroxypolycarboxylic acids. The aim of the work was to investigate peculiarities of formaldehyde containing alkaline electroless copper deposition systems using environment friendly hydroxycarboxylic acids as Cu(II) ligands. Two new Cu(II) ligands, namely citric acid and D-isomer of tartaric acid, were applied for the systems of electroless copper deposition. The results of the investigations show that the ligands mentioned can be successful applied in the processes of electroless copper deposition using formaldehyde as reducing agent. Citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid) and different isomers of tartaric acid (2,3-dihydroxybutanedioic acid), namely L- and D-tartrate, and their racemic mixture DL-tartrate, forming sufficiently stable complexes with... [to full text]

Electroless metal coating technique is one of the elegant ways of metal coating by controlling the temperature and pH of the plating bath in which there is no usage of electric current. The industrial electroless copper plating solution containing formaldehyde as reducing agent are known from the middle of the last century and are widespread in the practice up to now. However many chemical compounds used in such kind technological processes are hazardous for total environment, therefore the efforts are made to displace those substances with less hazardous or purely harmless compounds. Generally two classes of chemical compounds were proposed as EDTA alternative, namely alditols (polyhydroxylic alcohols) and hydroxypolycarboxylic acids. The aim of the work was to investigate peculiarities of formaldehyde containing alkaline electroless copper deposition systems using environment friendly hydroxycarboxylic acids as Cu(II) ligands. Two new Cu(II) ligands, namely citric acid and D-isomer of tartaric acid, were applied for the systems of electroless copper deposition. The results of the investigations show that the ligands mentioned can be successful applied in the processes of electroless copper deposition using formaldehyde as reducing agent. Citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid) and different isomers of tartaric acid (2,3-dihydroxybutanedioic acid), namely L- and D-tartrate, and their racemic mixture DL-tartrate, forming sufficiently stable complexes with... [to full text] / Cheminio variavimo tirpalai bei cheminio variavimo procesai tiriami jau nuo XX a. vidurio iki šių dienų, ieškant vis efektyvesnių parametrų dangų funkcinėms bei dekoratyvinėms savybėms pagerinti. Pastaruoju metu vis didesnis dėmesys krypsta ne tik į nusodinamų dangų funkcionalumą, bet ir į ekologiškai nekenksmingus ar mažiau kenksmingus technologinius procesus, pzv., vykdoma ekologiškai nekenksmingų ligandų paieška. Kaip alternatyva šiuo metu siūlomos dvi cheminių junginių klasės t.y. alditoliai (polihodroksiliai alkoholiai) ir hidroksikarboksirūgštys. Pagrindinis darbo tikslas: ištirti cheminio variavimo sistemas ir jose vykstančius procesus, vario(II) jonų ligandais naudojant ekologiškai nekenksmingas citrinų ir vyno rūgštis. Cheminio variavimo sistemose panaudoti du nauji Cu(II) jonų ligandai t.y. citrinų rūgštis ir vyno rūgšties D-izomeras. Atliktų tyrimų duomenys rodo, kad minėti ligandai sėkmingai gali būti naudojami cheminio variavimo sistemose, kur reduktoriumi naudojamas formaldehidas. Nustatyta, kad 2-hidroksipropan-1,2,3-trikarboksirūgštis (citrinų rūgštis) ir 2,3-dihidroksibutano-1,4-dirūgštis (vyno rūgštis) šarminėje terpėje sudaro pakankamai patvarius kompleksus su vario(II) jonais ir yra tinkamas ligandas vario(II) kompleksinimui šarminiuose (pH > 12) cheminio variavimo tirpaluose. Ištirta vario(II)-citrato ir Cu(II)-D-, L- ir DL-tartratų kompleksų redukcija hidratuotu formaldehidu, apibūdintos gautosios vario dangos. Optimaliomis proceso vykdymo sąlygomis... [toliau žr. visą tekstą]

Electroless plating is a metal deposition technique widely used in the coating industry. It is the method of choice to plate substrates with complex geometries and nonconductive surfaces, such as polymers and ceramics, since it is based on a chemical reduction in solution rather than on an external electrical energy source like the electroplating method. Among others, examples of well-established applications are the electroless deposition of decorative metal coatings such as gold and silver, wear and corrosion resistant nickel coatings, particularly to coat drive shafts, rotors, and bathroom fixtures, as well as the electroless deposition of copper in electronic devices as diffusion barriers and conductive circuit elements. In the academic research, electroless plating is extensively used thanks to its low cost, simple equipment and versatility that allow rapid prototyping. Two common applications are the coating of small particles and the selective plating of flat surfaces. Metal coated ceramic particles are of enormous interest in many scientific fields, e.g. fluorescent diagnostics in biochemistry, catalysis, and fabrication of photonic crystals. Metal coated ceramic nanoparticles and microparticles are also gaining attention as potential candidates in the fabrication of higher quality metal matrix Composites, which is one of the applications addressed by this work. Metal coated ceramic particles are easier to integrate in metal matrix composites, avoiding aggregation caused by the low wettability of the particles by the matrix metal, and are potentially shielded from oxidation and undesired chemical reactions that take place at the interface between the particles and the metal Matrix. Electroless plating is an autocatalytic process, meaning that the deposited metal atoms catalyze the deposition of further metal. In order to achieve the first stable metal seeds on a surface, the latter has to be functionalized. Without this functionalization the metal ions in the electroless plating bath are not reduced or are simply reduced to metal nanoparticles in solution. The traditional activation step for nonconductive surfaces is performed by immersion of the substrate in palladium based solutions, which is very time-consuming and extremely expensive. In particular for nanoparticles, previous work showed that at least 1015 Pd atoms/cm2 are required for a uniform activation of a surface, meaning that in the case of nanoparticles with a surface area of about 100 m2/g are necessary 6.4 g of palladium for each gram of substrate. Assuming a price of about 150 €/g (laboratory scale) for palladium nanoparticles and palladium precursors used for surface activation, it results that the activation of 1 g of nanoparticles costs around 1000 €. Such costs are suboptimal considering the typical production scale, and therefore alternative functionalization methods are desired. In this work, new organic-based functionalization methods based on (3-mercaptopropyl)triethoxysilane to functionalize oxide particles, 3-aminopropylphosphonic acid to activate carbide particles and a substrate-independent method based on the bioinspired polydopamine are developed and investigated in detail, together with the respective electroless plating baths, which often have to be specifically tailored regarding the different reactivity of the different molecules and substrates. Furthermore, in the fabrication of metallic patterns on substrates by electroless plating, new, simple, and cost-effective activation and metal deposition processes are desired. In this work, two new methods are presented, one based on the printing of (3-mercaptopropyl)triethoxysilane by microcontact printing, the other based on the capillary force lithography of polymethylmethacrylate.