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Zaštita materijala 3. 2011

ZAŠTITA MATERIJALA 2011 52(3) 145-151                             Scientific paper [PDF]


*“Rostislav Kaischew” Institute of Physical Chemistry, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
** Institute of Precious Metals and Metal Chemistry, 73525 Schwäbisch Gmünd, Germany


Effect of electrolyte composition on the electrodeposition of Cu-Sb alloys from methanesulfonate-tartrate electrolytes
Abstract: The electrochemical processes of deposition and dissolution of Cu and Sb separately or together from acid methanesulfonate-tartrate electrolytes are investigated by cyclic voltammetric technique. The influence of different parameters of the electrodeposition process, such as current density, temperature, electrolyte composition and acidity on the antimony content, phase composition and morphology of the coatings is shown. The increase in current density leads to an increase in the antimony content in the alloy, as well as to an increase in the deposition rate of the alloy. The antimony content decreases with the rise in temperature, as expected. The increase in D(-)-tartaric acid concentration in the electrolyte leads to a slight increase in antimony content. The possibility of deposition of compact bright Cu-Sb coatings with up to 52 wt.% Sb and compressive internal stress from the investigated electrolytes is shown.  At high antimony content the deposition of multiphase heterogeneous coatings with ordered spatial distribution of the different alloy phases on the cathodic surface can be observed. The phenomena and the observed structures are very similar to those observed during electrodeposition of some other silver alloys, such as Ag-Sn, Ag-Sb, Ag-Bi and Ag-In.

ZAŠTITA MATERIJALA 2011 52(3) 153-158                       Scientific paper [PDF]


Institute for Multidisciplinary Research, Kneza Višeslava 1a, 11030 Belgrade, Serbia

Electrodeposition and characterization of Ni–Sn alloy coatings as cathode material for hydrogen evolution reaction in alkaline solutions

Abstract: Ni–Sn alloy coatings were deposited from the constant composition pyrophosphate–glycine bath at different current densities. Their morphology, composition and phase composition were investigated by SEM, EDS and XRD techniques. It was shown that the morphology of coatings depends on current density, being rougher and more porous with the increase of deposition current density. EDS analysis of the cross sections revealed that the coating composition varies from the substrate surface towards the coating surface, being richer in Ni close to the substrate surface, while the composition on top of the surface was approximately the same for all samples (50 at.% Ni – 50 at.% Sn). XRD analysis showed the presence of only one phase in all deposits, NiSn2. The increase of Ni-Sn coatings catalytic activity for hydrogen evolution with the increase of deposition current density was shown to be the consequence of their porosity, while the sample with the smooth surface showed lower overvoltage for hydrogen evolution than the commercial De Nora’s electrode (DN), indicating synergetic effect of Ni-Sn alloys.

ZAŠTITA MATERIJALA 2011 52(3) 159-162                                Scientific paper [PDF]

1ICTM – Institute of Electrochemistry, University of Belgrade, Njegoševa 12, Belgrade, Serbia
2Institute for Multidisciplinary Research, Kneza Višeslava 1a, Belgrade, Serbia

Comparison of morphology of powder particles obtained by the constant and periodically changing regimes of electrolysis
Morphologies of copper powder particles obtained by both potentiostatic and pulsating overpotential (PO) regimes of electrolysis were analyzed using the technique of scanning electron microscopy (SEM). The parameters of square waves PO were selected to enable a comparison of the obtained particles with those obtained in the potentiostatic regime from solutions of different CuSO4 and H2SO4 concentrations. It is shown that more solutions of different CuSO4 and H2SO4 concentrations can be replaced by the one solution if the appropriate PC parameters are applied, what can be of high technological significance.


ZAŠTITA MATERIJALA 2011 52(3) 163-172                                Scientific paper [PDF]


1Corrosion Research Centre, GTN Arts College, Dindigul – 624 005, India
2Department of Physical Sciences, Servite College of Education for Women, Thogaimalai – 621 313, India
3Department of Che-mistry, Yadava College, Madurai, India
4Department of Chemistry, SVN College, Madurai, India
5Department of Chemistry, Chettinad College of Engineering, Karur, India

Inhibition effect of self assembled films formed by adipic acid molecules on carbon steel surface
Abstract: Well-ordered SAMs using adipic acid were formed on the oxide of iron carbon steel surface by immersion method. This leads to ordered, robust monolayers bound to the surface in a tetra dentate manner. Monolayer formation takes place when carbon steel is immersed in an aqueous solution containing 60 ppm of Cl and 50 ppm of adipic acid for 5 minutes, and rinsing the physisorbed molecules in distilled water and heating in a hot air oven. The adipic acid monolayers on iron oxide steel carbon can withstand rinsing with water, concentrated acid and base exposure. Additionally, these monolayers are stable over the course of at least one week. The formation of monolayers were confirmed by AFM study and FTIR spectra. The SAMs were tested by polarization and EIS electrochemical analysis. The results of this study show that adipic acid monolayers adsorbed on metal surface can reduce electrochemical activity on the surface, often the first step in corrosion.


ZAŠTITA MATERIJALA 2011 52(3) 173-180                                 Scientific paper[PDF]


Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Belgrade, Serbia

Electrical contact materials based on silver
Abstract: Composite electrical contact materials based on silver and oxides of different metals have been used for many years in different types of electrical devices for making and breaking of electrical circuit. Ag-CdO materials have been most commonly used over the years as the materials for electrical contacts and other electrical components due to their excellent electrical and mechanical properties, mainly for small and medium-current loads. Recent investigations have led to the development and implementation of new environmentally friendly electrical contact materials in which the toxic CdO is replaced by less harmful metal oxides, while maintaining the good final properties. It was found that the Ag-SnO2 composite material meets most of the required properties. Results of experimental investigations of different technological procedures for obtaining various types of silver based electrical contact materials are presented in this paper through defined technological phases with optimized process parameters. The structural, mechanical and electrical characteristics of the investigated and realized contact materials are presented as well. The examples of materials applications are given and illustrated.

ZAŠTITA MATERIJALA 2011 52(3) 181-188                                Scientific paper [PDF]


1University of Eastern Sarajevo, Faculty of Technology Zvornik, Republic of Srpska
2Univesrity of Belgrade, ICTM – Centre for Electrochemistry, Belgrade, Serbia

 Catalytic effect of sulphuric acid in the process of deposition of chromium coatings
Abstract: This paper analyzes the catalytic effect of sulphuric acid on current efficiency, the coating thickness and the rate of deposition of electrochemical chromium coatings. According to the properties of chrome, there are three types of chrome coatings: decorative, hard and porous. The quantitative composition of baths and working conditions are the factors   which determine which type of a coating will be obtained. The cathodes are made of copper electrolitical plates (99.99%), which are submitted to mechanical smoothing and chemical preparation. Electrochemical chromium coatings were deposited galvanostaticaly from bath I (250 g/dm3 CrO3 + 2.0 g/dm3 H2SO4), are then deposited on the cathodes prepared in this way, also from  bath II (250 g/dm3 CrO3 + 2.5 g/dm3 H2SO4), and from bath III (250 g/dm3 CrO3 + 3.0 g/dm3 H2SO4), at current densities of 10 A/dm2, 15 A/dm2 and 30 A/dm2. Deposition was performed for 5, 10 and 15 minutes intervals in all three baths and for all three current densities. The difference in samples mass before and after electrochemical deposition was measured on the analytical scale.  Cathodic current efficiency, the coating thickness and deposition rate increase with the increase of acid concentration, current density and deposition time. The average deposition rates are approximately the same for baths II and III, for the same deposition time, at the same current densities. This shows that the increase of the concentration of sulphuric acid above 2.5 g/dm3 is not justifiable. The ratio of these parametres, according to the quantity of the sulphuric acid used is the best for bath II, which makes deposition of electrochemical chrome coatings from this bath most profitable, from the aspect of current efficiency, deposition rate, coatings quality and chemicals consumption of bath.

ZAŠTITA MATERIJALA 2011 52(3) 189-193                               Scientific paper [PDF]


1Institute for Technology of Nuclear and Other Mineral raw materials, 86 F. d’Esperey St., Belgrade, Serbia
2University of Belgrade, Faculty of Agriculture, 6 Nemanjina St., Belgrade, Serbia

The copper biosorption using unmodified agricultural waste materials
Abstract: The rapid increase in global industrial activities has lead to the serious environmental pollution that requires systematic and sustainable approach in order to protect environment and biodiversity. Special concern is accented on heavy metal pollution because of their high toxicity, persistence and bioaccumulation tendency. The conventional methods for their removing are often either too expensive or create a large quantities of toxic sludge, so the other technologies, cheaper and more effective should be employed. Biosorption is one of the recently employed promising technologies that use biomaterials as sorbents for different type of pollution. Thanks to their active surface groups, biosorbents pose wider operational spectrum than mono functional ion exchangers. Agricultural waste materials have proved to be highly efficient, low cost and renewable source of biomass that can be exploited for heavy metal remediation, which leads to increase of their life cycle and also solve their disposal problem. The purpose of this paper is investigation of possible application of wasted untreated biomass from ”Vino Župa” Company as potential biosorbent that can be used for copper removal from water solutions. For this purpose, several type of biomass have been examined and the preliminary results presented in this paper have showed that this wasted untreated materials can bee used as promising and cheap adsorbents for copper removal from water solutions, but also that further physical and chemical modifications should be done in order to increase their biosorption capacity.

ZAŠTITA MATERIJALA 2011 52(3) 195-200                      Originalni naučni rad [PDF]


Univerzitet u Sarajevu, Prirodnomatematički fakultet, Sarajevo, BiH


Određivanje fosfora u čelicima, indirektno, mjerenjem koncentracije bizmuta odnosno molibdena u bizmut fosfomolibdatnom kompleksu metodom AAS

Izvod: Pored poželjnih elemenata u čeliku se u većim ili manjim količinama nalaze i nepoželjani elementi kakav je fosfor. Pri sadržaju fosfora od 0,2 % i na niskim temperaturama žilavost čelika praktično pada na nulu. Iz tih razloga poznavanje sadržaja fosfora u čeliku  je od izuzetne važnosti. Fosfor u čelicima najčešće je određivan spektrofotometrijski kao fosfomolibdat u redukovanom ili neredukovanom obliku. Iako je puno korištena, ova metoda ima svojih nedostataka, tako da se nastoji iznaći nove metode za određivanje fosfora u čeliku. AAS se nameće kao dobro rješenje, međutim direktna metoda ne može biti primjenjena za određivanje fosfora, zbog rezonantnih linija koje se nalaze u UV području na talasnim dužinama: 177,5; 178,3 i 178,8 nm. U ovom radu, za određivanje fosfora razvijena je indirektna metoda-AAS, bazirana na formiranju bizmut-fosfomolibdatnog kompleksa, i njegovoj ekstrakciji sa metil-izobutil ketonom. Bizmut, odnosno molibden koji se u ovom kompleksu nalaze u poznatom stehiometrijskom odnosu sa fosforom određivani su AAS.

ZAŠTITA MATERIJALA 2011 52(3) 201-206                       Originalni naučni rad [PDF]


Sveučilište u Zagrebu, Fakultet strojarstva i brodogradnje, Zagreb, Hrvatska
Zaštita ugljičnog čelika vodorazrjedivim premazima


Izvod: Mnoge antikorozivne prevlake nisu ekološki prihvatljive zbog povećane emisije organskih otapala u zrak. Za zaštitu materijala trebale bi se koristiti prevlake dobrih zaštitnih svojstava, ali i smanjenog štetnog utjecaja na okoliš. Velik broj istraživača pokušava pronaći  pravu formulaciju takve prevlake. Jedan od važnijih smjerova razvoja je primjene  antikorozivnih premaza kao što su vodorazrijedivi premazi  kojiimaju niski sadržaj hlapivih organskih spojeva te ne sadrže toksične elemente (kroma i olova), a mogu se koristiti za zaštitu metalnih materijala u različitim sredinama. U ovom radu ispitana su zaštitna svojstva epoksidnih vodorazrjedivih premaza  elektrokemijskim metodama. Također, provedeno je i ubrzano ispitivanje u QUV komori. Dobiveni rezultati pokazuju da se vodorazrjedivi premazi imaju dobra zaštitna svojstva  te se mogu koristiti za zaštitu metalnih materijala u mnogim granama industrije.

ZAŠTITA MATERIJALA 2011 52(3) 207-212                                    Stručni rad [PDF]


Tehnički fakultet »Mihailo Pupin«, Đure Đakovića bb, Zrenjanin

Razvoj i primena postupka boriranja u funkciji produženja radnog veka mašinskih delova
Izvod: Autori su u radu pokušali da sistematizuju znanja i prikažu važnost upotrebe boriranja kao termodifuzionog postupka na uvećanje veka trajanja mašinskih elemenata, u zavisnosti od konstrukcije, odnosno tipa i radnih uslova. U radu su opisane osnovne zakonitosti za postupak boriranja koji se primenjuje prvenstveno u cilju povećanja otpornosti prema abrazivnom mehanizmu trošenja. Pored napred navedenog, autori su ukazali na sadašnje stanje i perspektive razvoja postupka boriranja, navodeći pri tom karakteristične primere njegove primene na sadašnjem nivou znanja. Autori su takođe ukazali na veliku razliku između naučnog istraživanja i industrijske prakse, što je posebno izraženo u inostranstvu, gde se radi toga organizovano podupiru i iniciraju projekti dopunskog obrazovanja o razvoju inženjerstva površina. Time se podupire primena, ne samo boriranja, već i ostalih postupaka modifikovanja, čijom se upotrebom postižu višestruka povećanja postojanosti i trajnosti metalnih mašinskih elemenata, što doprinosi značajnom povećanju kvaliteta tretiranog dela i ekonomičnosti proizvodnje. Dobijeni rezultati ukazuju na celishodnost proizvodnje boriranih elemenata, koji nisu jako dinamički napregnuti i koji tokom rada ne trpe naprezanje na istezanje, za primenu u uslovima koji zahtevaju ekstremnu otpornost na habanje.


ZAŠTITA MATERIJALA 2011 52(3) 213-217                                        Stručni rad [PDF]


1Fakultet zaštite na radu u Nišu
2Visoka tehnička škola strukovnih studija Požarevac
3Zavod za preventivnu medicinsku zaštitu u Nišu
4Tehnološki fakultet u Leskovcu

Redizajniranje tretmana otpadnih voda tehnološkog procesa galvanizacije
Izvod: Tehnološki proces galvanizacije, prema kvalitativno-kvantitativnim karakteristikama, predstavlja jedan od najkompleksnijih zagađivača otpadnih voda. Veliki broj zagađujućih materija (joni metala, cijanidi, kiseline, baze, masti i ulja, organski rastvarači, površinski aktivne materije, fosfati i dr.), koji se nalaze u galvanskim otpadnim vodama, prečišćavaju se konvencionalnim metodama (hemijska oksidacija i redukcija, neutralizacija, taloženje, koagulacija i flokulacija). Uvođenje nekonvencional-nih sistema za prečišćavanje otpadnih voda (elektohemijska oksidacija i redukcija, jonska izmena, kao i membranski procesi, reverzna osmoza, ultrafiltracija i elektrodijaliza) osnovni je preduslov za re-dizajn tehnološkog sistema, a sve u cilju ostvarivanja apsolutnih tehnologija. To podrazumeva de-toksikaciju cijanida, regeneraciju teških metala i njihovo vraćanje u tehnološki proces proizvodnje i recirkulaciju vode koja se ponovo koristi za ispiranje metalnih delova u galvanizaciji.