Zastosowanie związków organicznych w wytwarzaniu antyściernych i antykorozyjnych warstw powierzchniowych metodą PAMOCVD

Sobiecki J.R., J.R.

Artykuł - szczegóły

Tytuł artykułu

Zastosowanie związków organicznych w wytwarzaniu antyściernych i antykorozyjnych warstw powierzchniowych metodą PAMOCVD

Autorzy

Sobiecki J.R. J.R.

Identyfikatory

Warianty tytułu

Application of organic compounds in production of antiabrasive and anticorrosive surface layers by the PAMOCVD method

Języki publikacji

Abstrakty

Zwiększenie wymagań stawianych materiałom w zakresie m.in.: właściwości mechanicznych, odporności na zużycie przez tarcie, oddziaływania podwyższonej temperatury, oddziaływania korozyjno-erozyjnego itp., wpłynęło w znacznym stopniu na konieczność ulepszania istniejących i opracowywania nowych materiałów, odznaczających się wysokimi właściwościami eksploatacyjnymi. Techniki inżynierii powierzchni stwarzają szerokie możliwości wytwarzania wyrobów o żądanych właściwościach na bazie istniejących materiałów, przystosowując je do wymagań eksploatacyjnych, co stanowi ich istotną zaletę z ekonomicznego punktu widzenia. Metoda PAMOCVD jest połączeniem metod MOCVD i PACVD. Celem tej metody jest obniżenie temperatury procesu i otrzymywanie twardych, antyściernych i antykorozyjnych powłok na materiałach narzędziowych i konstrukcyjnych. Aktywacja elektryczna środowiska gazowego umożliwia w niskotemperaturowej plazmie wytwarzanie aktywnych cząstek odpowiedzialnych za tworzenie się powłoki. Należy podkreślić, że obok dotychczasowych materiałów podłożowych wykonanych z różnych gatunków stali, powłoki takie są wytwarzane w niskich temperaturach, również na takich materiałach jak tworzywa sztuczne lub ceramika, co jest jednym z perspektywicznych kierunków rozwoju inżynierii powierzchni. Na podstawie doniesień literaturowych oraz rozpoznawczych procesów wytwarzania powłok zaproponowano następującą tezę pracy: Antykorozyjne oraz antyścierne powłoki można wytwarzać metodą PAMOCVD, optymalizując warunki prowadzenia procesu oraz stosując dodatkowe obróbki w warunkach wyładowania jarzeniowego. W celu weryfikacji postawionej tezy zbadano możliwość otrzymania oraz strukturę i właściwości następujących powłok: - kompozytowej typu Al2O3 + NiAl + Ni3Al i AlN + NiAl + Ni3Al, wytworzonej na podłożu niklowym oraz Al2O3 + TiAl + Ti3Al, wytworzonej na stopie tytanu przy udziale związku metaloorganicznego glinu (CH3)3Al - trimetyloglinu; - CrN wytworzonej na materiale modelowym, którym jest żelazo Armco, przy udziale związków metaloorganicznych chromu acetyloacetonianu chromu - (CH3COCH2O)3Cr oraz 2-etyloheksanianu chromu - Cr(OOCCH(C2H5)C4H9)3; - ZrO, wytworzonej na materiale modelowym, którym jest żelazo Armco, przy udziale związku metaloorganicznego cyrkonu Zr(OC4H9)4 - tetrabutyloksycyrkonu; - Ti(N,C,O) wytworzonej na stopie magnezu przy udziale związku organicznego tytanu Ti(i-OC3H7)4 - tetraizopropoksytytanu; - BN wytworzonej na materiale modelowym, którym jest żelazo Armco, przy udziale kompleksu boranowo-pirydynowego - C5H5NBH3. Synteza trudno topliwych, antyściernych i antykorozyjnych azotków i tlenków aluminium, czy też cyrkonu, przebiega dwuetapowo. W pierwszym etapie procesu wytwarzane są powłoki metaliczne. Nieizotermiczna plazma oraz wodór obecny w atmosferze gazowej sprzyja rozerwaniu wiązań węglowych w prekursorach metaloorganicznych, a powstające rodniki węglowodorowe są usuwane w postaci lekkich produktów gazowych ze środowiska reakcji. Tym należy tłumaczyć małą zawartość węgla w powstających powłokach. Aktywne cząstki, głównie jony metali, docierają w pobliże obrabianego detalu i tam ulegają zjawisku chemisorpcji. Etap drugi, polegający na wygrzewaniu powstającej powłoki metalicznej w celu przekształcenia jej w pożądaną fazę azotkową bądź tlenkową nie byłby skuteczny, gdyby nie aktywacja elektryczna środowiska gazowego. W tym właśnie etapie następuje zmiana składu chemicznego wytworzonej powłoki w drodze reakcji chemicznych w fazie stałej, które przebiegają w niższych temperaturach i z większymi prędkościami, niż przy jedynie termicznej aktywacji procesu. Odpowiedzialne za to są cząstki aktywne (jony, atomy, cząstki wzbudzone) o wyższej energii niż wynikałoby to z równowagowego rozkładu energii dla danej temperatury. Dzieje się tak dlatego, że pod działaniem pola elektrycznego nośniki ładunku, zwłaszcza elektrony, mogą uzyskać dużo większą energię od średniej energii cząstek gazu i w zderzeniach z nim przekazać część tej energii. Wynika stąd, że na tworzenie się warstw powierzchniowych w metodzie PAMOCVD można wpływać: - po pierwsze - przez ukierunkowanie reakcji chemicznych w atmosferze gazowej przez zmianę jej składu chemicznego, szybkości przepływu, parametrów prądowo-napięciowych oraz przez odpowiednie przygotowanie warstwy wierzchniej obrabianego detalu w celu kontroli zjawiska chemisorpcji; - po drugie - przez ukierunkowanie reakcji chemicznych w fazie stałej, które zmieniają skład fazowy i chemiczny wytworzonych uprzednio powłok, także kontrolowanych przez wymienione czynniki.

Growing requirements that must be met by materials in terms of, among others, their mechanical properties, resistance to wear by friction, impact of higher temperatures, corrosion/erosion interaction etc., have had a considerable influence on the necessity of improvement of existing materials and development of new materials that would be characterized by high operating properties. Surface engineering technologies create wide possibilities of making products of the requested properties on the basis of existing materials by adapting them to the specific operating properties, which is their substantial merit from the economic point of view. The PAMOCVD method is a combination of MOCVD and PACVD methods in order to decrease process temperature and produce hard antiabrasive and anticorrosive layers on tool and constructional materials. Electrical activation of the gas environment enables low-temperature plasma to create active particles responsible for coating production. It should be stressed that apart from the to-date substrate materials made of various grades of steel, these coatings are produced in low temperatures also on such materials as plastics or ceramics, which is one of prospective directions of surface engineering development. On the basis of literature investigations and recognizable processes of coating production, the following hypothesis was proposed. Anticorrosive and antiabrasive coatings may be produced with the PAMOCVD method with process conditions optimization and with the use of additional treatment in glow discharge conditions. In order to verify the hypothesis, the possibility of producing the following coatings as well as their structure and properties have been examined: - Composite coatings of Al2O3 + NiAl + Ni3Al and AlN + NiAl + Ni3Al type produced on nickel and Al2O3 + TiAl + Ti3Al substrate produced on titanium alloy with the use of organometallic aluminium compound (CH3)3Al - trimethylaluminium. - CrN coating produced on model material like Armco iron with the use of organometallic compounds of chromium: chromium acetylacetonate - (CH3COCH2O)3Cr and chromium 2-ethylhexanoate - Cr(OOCCH(C2H5)C4H9)3. - ZrO2 coating produced on model material like Armco iron with the use of organometallic compound of zirconium Zr(OC4H9)4 - zirconium tetra-tertiary butoxide. - Ti(N,C,O) coating produced on magnesium alloy with the use of organic compound of titanium Ti (i-OC3H7)4 - titanium tetraisopropoxide. - BN coating produced on model material like Armco iron with the use of pyridine-borane complex - C5H5NBH3. Synthesis of infusible, antiabrasive and anticorrosive nitrides and aluminium oxides or zirconium occurs in two stages. In the first stage of the process, metallic coatings are produced. Non-isothermal plasma and hydrogen present in the gas atmosphere facilitate cleavage of carbon bonds in organometallic precursors and the arising hydrocarbon radicals are removed from the reaction environment in the form of light gas products. This explains Iow content of carbon in produced coatings. Active particles, mainly metal ions, get close to the processed detail where they undergo the phenomenon of chemical adsorption. The second stage, consisting in heating of the created metallic coating in order to convert it into the desired nitride or oxide phase, would not be effective if it were not for the electric activation of the gas environment. At this stage, a change of the chemical compound of the created coating by means of chemical reactions in the solid phase takes place. The chemical reactions occur at lower temperatures and faster than in case of process thermal activation only. These are active particles (ions, atoms, induced particles) of higher energy than it would result in balanced energy distribution for a given temperature that is responsible for this phenomenon. It happens so because charge carriers, especially electrons may get much higher energy under the influence of electric field than average energy of gas particles and transmit some energy in collision with it. It appears from the above that obtaining surface layers by the PAMOCVD method may be influenced by: - first of all, by orientation of chemical reactions in the gas atmosphere through a change of its chemical composition, flow speed, current-voltage parameters and through an appropriate preparation of the surface layers of the processed detail in terms of chemisorption phenomenon control, - second of all, by orientation of chemical reactions in the solid phase that change phase and chemical composition of previously produced coatings, also controlled by the above-mentioned factors.

Słowa kluczowe

inżynieria materiałowa inżynieria powierzchni związki organiczne warstwa powierzchniowa warstwa antyścierna warstwa antykorozyjna metoda PAMOCVD

materials engineering surface engineering organic compounds surface layer antiabrasive layer anticorrosive layer PAMOCVD method

Wydawca

Oficyna Wydawnicza Politechniki Warszawskiej

Czasopismo

Prace Naukowe Politechniki Warszawskiej. Inżynieria Materiałowa

Rocznik

2010

Tom

z. 23

Strony

3--131

Opis fizyczny

Bibliogr. 283 poz., tab., rys., wykr.

Twórcy

autor

Sobiecki J.R. J.R.

Wydział Inżynierii Materiałowej, Politechnika Warszawska

Bibliografia

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