Balistički Hibridni Nanokompozitni Materijali Ojačani Neorganskim Fulerenima

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Balistički Hibridni Nanokompozitni Materijali Ojačani Neorganskim Fulerenima UNIVERZITET U BEOGRADU TEHNOLOŠKO-METALURŠKI FAKULTET Danica M. Simić BALISTIČKI HIBRIDNI NANOKOMPOZITNI MATERIJALI OJAČANI NEORGANSKIM FULERENIMA Doktorska disertacija Beograd, 2017. UNIVERSITY OF BELGRADE FACULTY OF TECHNOLOGY AND METALLURGY Danica M. Simić BALLISTIC HYBRID NANOCOMPOSITE MATERIALS REINFORCED WITH INORGANIC FULLERENES Doctoral disertation Belgrade, 2017 MENTOR: ____________________________________ dr Petar Uskoković, redovni profesor, Univerzitet u Beogradu, Tehnološko-metalurški fakultet ČLANOVI KOMISIJE: ________________________________ dr Vesna Radojević, redovni profesor, Univerzitet u Beogradu, Tehnološko-metalurški fakultet _________________________________ dr Aleksandar Kojović, vanredni profesor, Univerzitet u Beogradu, Tehnološko-metalurški fakultet _________________________________ dr Dušica Stojanović, viši naučni saradnik, Univerzitet u Beogradu, Tehnološko-metalurški fakultet ________________________________ dr Zijah Burzić, naučni savetnik, Vojnotehnički institut u Beogradu Datum odbrane: Potpis doktoranda: __________________ __________________________ Danica Simić, dipl.inž. tehnologije ZAHVALNICA Želela bih da izrazim zahvalnost mentoru, prof. dr Petru Uskokoviću, na svesrdno ukazanoj podršci i pomoći prilikom izrade disertacije. Posebno se zahvaljujem višem naučnom saradniku Katedre za konstrukcione i specijalne materijale, dr Dušici Stojanović na podršci, pomoći i korisnim savetima koje mi je pružala tokom planiranja i realizacije eksperimentalnih ispitivanja, kao i tokom pisanja naučnih radova i ove disertacije. Neizmernu zahvalnost dugujem pokojnom profesoru, mentoru i uzoru, dr Radoslavu Aleksiću, koji je vodio izradu ove disertacije u njenom prvom delu i koji je njen idejni tvorac, kao i svom pokojnom ocu, koji me je uvek podsticao da težim ka uspehu i ka boljim rezultatima, a koga bi ova disertacija učinila najsrećnijim čovekom. Zahvalna sam na pomoći i savetima gospodinu Nenadu Ćakiću iz kompanije ''Aleks Armor'' i gospodinu Dušku Vasiliću iz kompanije ''Proizvodnja Mile Dragić''. Ova doktorska disertacija nastala je kao rezultat višegodišnjeg istraživanja na Katedri za konstrukcione i specijalne materijale Tehnološko-metalurškog fakulteta Univerziteta u Beogradu i u laboratorijama Vojnotehničkog instituta. Vojnotehničkom institutu, načelniku Sektora za materijale i zaštitu, naučnom savetniku dr Zijahu Burziću, i Upravi za odbrambene tehnologije Ministarstva odbrane Republike Srbije zahvaljujem se na obezbeđenim sredstvima za realizaciju disertacije. Zahvalnost za pomoć u izvođenju eksperimentalnih ispitivanja dugujem dr Aleksandru Kojoviću, vanrednom profesoru Tehnološko-metalurškog fakulteta, dr Miloradu Zriliću, profesoru u penziji, kao i svojim dragim kolegama iz Vojnotehničkog instituta: docentu dr Saši Brziću, Ljubici Totovski, docentu dr Igoru Radisavljeviću, Mirjani Dimić, Nataši Karišik, Bojani Fidanovski, Ristović Novici, Zorić Bojanu, mr Jeli Galović, Spasov Toši, Bogosavljević Marici, Sirovatka Radoslavu i Mišković Katarini. Ostalim kolegama, pretpostavljenima, svojoj majci, prijateljima, i svim dragim ljudima se zahvaljujem na podršci koju su mi pružili tokom izrade disertacije. Danica Simić i Balistički hibridni nanokompozitni materijali ojačani neorganskim fulerenima Rezime U sredstvima lične balističke zaštite koriste se kompozitni materijali na bazi tkanina velike žilavosti i zatezne čvrstoće, poput aramidnih tkanina impregnisanih polimernim vezivom, uglavnom nekim termoplastičnim ili termoumrežavajućim polimerom. Kompoziti sa nanočestičnim puniocima su perspektivni materijali širokog spektra primene, koji objedinjuju svojstva i prednosti matrice (polimera) i punilaca. Tendencija je da se i u balističkim kompozitnim sistemima postigne maksimum ojačanja, i to uvođenjem nanočestica različitih svojstava i strukture. U ovoj disertaciji ispitana je mogućnost izrade hibridnog nanokompozitnog materijala poboljšane termo-mehaničke i balističke otpornosti, primenom neorganskih fulerenskih nanostruktura volfram disulfida (IF-WS2) i njegovih višeslojnih nanocevi (INT-WS2) kao ojačanja u poli(vinil butiralu), PVB, kojim je impregnisana aramidna tkanina. U različitim istraživanjima u svetu potvrđeno je da upotreba neorganskih nanočestica fulerenske strukture u organsko-neorganskim hibridnim kompozitnim materijalima pruža mogućnost poboljšanja termičkih, mehaničkih, i triboloških svojstava konvencionalnih kompozita. Izradi kompozitnih uzoraka prethodila je detaljna analiza tehnološke procesibilnosti i kompatibilnosti komponenata i materijala korišćenih u istraživanju. Ispitan je efekat upotrebe različitih rastvarača u pripremi nanokompozitnih filmova PVB/IF-WS2 na termo-mehaničko ponašanje rezultujućeg materijala. Tri tipa PVB praha, odnosno tri različite molekulske mase, najpre je rastvarano u različitim organskim rastvaračima, a nakon otparavanja rastvarača dobijenim uzorcima u vidu tankog filma diferencijalnom skenirajućom kalorimetrijom (DSC) određena je temperatura ostakljivanja (Tg) i to pri različitim režimima zagrevanja uzoraka. Nakon što je na ovaj način odabrana optimalna molekulska masa PVB i režim analize DSC, pristupilo se ispitivanju efekta dodatka nanočestica i njihove koncentracije na svojstva materijala. PVB optimalnog kvaliteta je rastvaran u etanolu, 2-propanolu, n-butanolu, 3- metilbutanolu, etilacetatu i metiletilketonu. IF-WS2 nanočestice su inkorporirane u ii rastvore PVB različitim tehnikama deaglomeracije i disperzije, i ponovo su izrađeni uzorci u obliku tankog filma, koji su podvrgnuti analizi DSC, nanoindentacije, tribološkim ispitivanjima, SEM mikroskopiji, EDS analizi. Kada se stekao uvid u kvalitet uzoraka dobijenih različitim tehnikama disperzije i deaglomeracije nanočestičnog punioca i u efekat rastvarača na svojstva kompozitnih filmova, u odabranim optimalnim rastvaračima je ispitana raspodela veličine nanočestica i kompatibilnost PVB i nanočestica mikrokalorimetrijskom analizom. Primenom dinamičko mehaničko termičke analize (DMTA) ispitana su termo-mehanička svojstva filmova pri dinamičkom opterećenju, prateći modul sačuvane energije, modul izgubljene energije, kao i mehanički faktor gubitaka u funkciji temperature. Stekavši jasnu sliku o uticaju koji nanočestice imaju na PVB, nakon ove podrobne preliminarne analize pristupilo se izradi makroskopskih uzoraka laminiranih kompozitnih struktura koje čine presovani slojevi aramidne tkanine, odnosno preprega aramidne tkanine s fenolformaldehidnom smolom, impregnisani sistemom PVB/rastvarač/IF-WS2/INT- WS2. Definisani su parametri procesiranja: temperatura, pritisak i vreme presovanja na hidrauličnoj presi, kako bi se formirali kvalitetni laminirani kompozitni uzorci za dalja ispitivanja. Kvalitet impregnacije aramidne tkanine sa PVB/WS2, kao i disperzija i deaglomeracija nanočestica u PVB matrici analizirani su pomoću skenirajućeg elektronskog mikroskopa (SEM). FTIR analizom potvrđeno je da nema hemijske reakcije između WS2 i PVB, a potvrđena je hemijska reakcija između fenolformaldehidne smole i PVB. Uticaj prisutnih nanočestica i nanocevi volfram disulfida na mehaničke karakteristike kompozita ispitan je na DMTA uredjaju, Šarpijevom klatnu i univerzalnoj kidalici. Karakteristike određene ovim metodama su modul sačuvane energije, modul izgubljene energije i mehanički faktor gubitaka u funkciji temperature i frekvencije naprezanja, prividna energija aktivacije, udarna žilavost, zatezna čvrstoća, modul elastičnosti. Na kraju, balistička ispitivanja uspešno su sprovedena: pripremljeni kompoziti su testirani gađanjem sa dva različita kalibra, u skladu sa standardom NIJ 0101.06, a testirana je i otpornost na ubod nožem prema standardu NIJ 0115.00. Potvrđen je ojačavajući efekat ispitivanih nanočestičnih punilaca. Pokazalo se da IF-WS2 i INT-WS2 imaju povoljan uticaj na termo-mehaničku i balističku otpornost dobijenih kompozitnih materijala, što otvara mogućnost njihove iii primene kako u materijalima za balističku zaštitu, tako i u drugim oblastima, u kompleksnim sistemima gde su potrebne izuzetne performanse. Ključne reči: Nanokompoziti, balistička zaštita, poli(vinil butiral), fulerenske nanočestice, nanocevi, volfram disulfid, termo-mehanicka otpornost, hibridni kompoziti Naučna oblast: Tehnološko inženjerstvo Uža naučna oblast: Inženjerstvo materijala iv Ballistic hybrid nanocomposite materials reinforced with inorganic fullerenes Abstract In the means of personal ballistic protection, composite materials based on fabric of high toughness and tensile strength are used, such as aramid fabrics, impregnated with polymeric binder, mainly some thermoplastic or thermosetting polymer. Composites with nanoparticle fillers are promising materials for a wide range of applications, which combine the properties and benefits of matrix (polymer) and fillers. There is also a tendency in ballistic composite systems to achieve maximum reinforcement by introducing nanoparticles of different properties and structures. In this thesis a possibility is investigated of making hybrid nanocomposite materials of improved thermo-mechanical and ballistic resistance, with the application of inorganic fullerene-like nanostructures of tungstendisulfide (IF-WS2) and its multi- layer nanotubes (INT-WS2) as the reinforcement in the poly (vinyl butyral), PVB, as impregnation on aramid fabric. Various studies in the world have confirmed that the use of inorganic nanoparticles of a fullerene structure in organic-inorganic hybrid composite materials provides the possibility of improving the thermal, mechanical, and tribological properties
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