A new chemorheological analysis of highly filled thermosets used in integrated circuit packaging

Chemorheology (and thus process modeling) of highly filled thermosets used in integrated circuit (IC) packaging has been complicated by their highly filled nature, fast kinetics of curing, and viscoelastic nature. This article summarizes a more thorough chemorheological analysis of a typical IC packaging thermoset material, including novel isothermal and nonisothermal multiwave parallel-plate chemorheology. This new chemorheological analysis may be used to optimize existing and design new IC packaging processes. (C) 1997 John Wiley & Sons, Inc.

The effects of silica fillers on the gelation and vitrification of highly filled epoxy-amine thermosets

Highly filled thermosets are used in applications such as integrated circuit (IC) packaging. However, a detailed understanding of the effects of the fillers on the macroscopic cure properties is limited by the complex cure of such systems. This work systematically quantifies the effects of filler content on the kinetics, gelation and vitrification of a model silica-filled epoxy/amine system in order to begin to understand the role of the filler in IC packaging cure. At high cure temperatures (100 degreesC and above) there appears to be no effect of fillers on cure kinetics and gelation and vitrification times. However, a decrease in the gelation and vitrification times and increase the reaction rate is seen with increasing filler content at low cure temperatures (60-90 degreesC). An explanation for these results is given in terms of catalysation of the epoxy amine reaction by hydrogen donor species present on the silica surface and interfacial effects.

Phenolic matrices and sisal fibers modified with hydroxy terminated polybutadiene rubber: Impact strength, water absorption, and morphological aspects of thermosets and composites

The aim of the present work was to investigate the toughening of phenolic thermoset and its composites reinforced with sisal fibers, using hydroxyl-terminated polybutadiene rubber (HTPB) as both impact modifier and coupling agent. Substantial increase in the impact strength of the thermoset was achieved by the addition 10% of HTPB. Scanning electron microscopy (SEM) images of the material with 15% HTPB content revealed the formation of some rubber aggregates that reduced the efficiency of the toughening mechanism. In composites, the toughening effect was observed only when 2.5% of HTPB was added. The rubber aggregates were found located mainly at the matrix-fiber interface suggesting that HTPB could be used as coupling agent between the sisal fibers and the phenolic matrix. A composite reinforced with sisal fibers pre-impregnated with HTPB was then prepared; its SEM images showed the formation of a thin coating of HTPB on the surface of the fibers. The ability of HTBP as coupling agent between sisal fibers and phenolic matrix was then investigated by preparing a composite reinforced with sisal fibers pre-treated with HTPB. As revealed by its SEM images, the HTPB pre-treatment of the fibers resulted on the formation of a thin coating of HTPB on the surface of the fibers, which provided better compatibility between the fibers and the matrix at their interface, resulting in a material with low water absorption capacity and no loss of impact strength. (C) 2009 Elsevier B.V. All rights reserved.

Recovery of glass fibre and carbon fibres from reinforced thermosets by batch pyrolysis and investigation of fibre re-using as reinforcement in LDPE matrix

A semi-batch pyrolysis process was used to recover samples carbon fibre and glass fibre from their respective wastes. The mechanical properties of the recovered fibres were tested and compared to those of virgin fibres, showing good retention of the fibre properties. The recovered fibres were then used to prepare new LDPE composite materials with commercial and laboratory-synthesized compatibilizers. Mild oxidation of the post-pyrolysis recovered fibres and the use of different compatibilizers gave significant improvements in the mechanical properties of the LDPE composites; however some of the manufactured composites made from recovered fibres had properties similar to those made from virgin fibres.

The effects of fillers on the chemorheology of highly filled epoxy resins: I. Effects on cure transitions and kinetics

This work examines the effects of level of silica filler (at 0, 10, 30, 50wt%) on the gelation and vitrification of a model silica-filled diglycidyl ether of bisphenol F (DGEBF)/methylenedianiline (MDA) system. An increased filler level is shown to decrease the gelation and vitrification times at low temperatures (below 80degreesC). FTIR cure kinetics show that the reaction rates are increased and the activation energies of gelation are reduced at these temperatures, indicating that network formation is made easier. Entropic and catalytic reasons for this phenomenon are discussed. (C) 2003 Society of Chemical Industry.

Komposiittivaipan moderni optimisuunnittelu ja toteutus

Tavoitteena tällä tutkimuksella on soveltaa modernin optimisuunnittelun keinoja komposiittimuovisen nestesäiliön lieriömäisen vaipparakenteen suunnittelemiseksi optimaalisen tyydyttäviksi valmistustekniikan ja kustannusten kannalta. Kuormituksia on kahdenlaisia. Säiliön sisällä on neste, joka tuottaa hydrostaattisen painekuorman ja järjestelmään kytketty puhallin tuottaa ulkoisen ylipaineen. Säiliöt ovat pystysäiliöitä ja ne tukeutuvat alustaan suoran pohjalaatan avulla. FEM- malleissa kuoren alaosat ovat jäykästi kiinnitettyjä ja yläosissa säteensuuntaiset siirtymät ovat estettyjä. Materiaaleiksi kuoreen on valittu kahdella eri menetelmällä lujitetut komposiittimateriaalit. Kantavan kerroksen toimintona on kantaa kuormat. Sulkukerros toimii korroosiosuojana ja sen lujuus on kantavaa kerrosta pienempi. Keinoina käytetään ensin innovatiivista suunnittelua optimaalisten lähtövaihtoehtojen ideoimiseksi ja valitsemiseksi jatkokehittelyä varten. Tavoitteena on asiakkaan tyytyväisyyden maksimointi huomioiden tuotteen kustannukset ja kesto. Yhtenä suunnittelun keinona on käytetty kuoriteoriaa ja komposiittien materiaalimalleja. Kestoehtoina on sovellettu komposiiteille soveltuvia kriteerejä. Toisena keinona käytetään FEM-laskentaa. Elementtityypiksi on valittu kaksiulotteinen kuorielementti, jossa on ortotrooppisen ainemallin mukaiset materiaaliominaisuudet. Jännitystuloksien merkittävyys keston kannalta selvitettiin Tsai-Hillin kriteerillä. Tuloksina saatiin ensin innovoitua rakenteelle kaksi päävaihtoehtoa, joita alettiin optimoida. Valitussa ratkaisussa on huomioitu kokonaisuus ja eri yksityiskohdat, kuten paino, jäykisteet kustannustehokkuus, valmistusnopeus, laatu, hävikit, päästöt, lujuus ja kilpailukykyinen myyntihinta. Yhteenvetona voidaan todeta, että käytetyt keinot ovat hyvin tehokkaita ja niillä voidaan suunnitella ja toteuttaa komposiittirakenteita, jotka tyydyttävät optimaalisesti loppukäyttäjän teknis- taloudelliset vaatimukset. Lisäksi tulokset osoittavat, että standardin ja FEM-laskennan ennustukset ovat lähellä toisiaan sylinterimäisillä kuoriosilla, mutta standardit suosittavat suurempia mittoja itse jäykisteille.

Experimental Studies on Non-Metallic Composite Bone Implants With a Special Reference to Staphylococcal Biofilm Infection

Non-metallic implants made of bioresorbable or biostable synthetic polymers are attractive options in many surgical procedures, ranging from bioresorbable suture anchors of arthroscopic surgery to reconstructive skull implants made of biostable fiber-reinforced composites. Among other benefits, non-metallic implants produce less interference in imaging. Bioresorbable polymer implants may be true multifunctional, serving as osteoconductive scaffolds and as matrices for simultaneous delivery of bone enhancement agents. As a major advantage for loading conditions, mechanical properties of biostable fiber-reinforced composites can be matched with those of the bone. Unsolved problems of these biomaterials are related to the risk of staphylococcal biofilm infections and to the low osteoconductivity of contemporary bioresorbable composite implants. This thesis was focused on the research and development of a multifunctional implant model with enhanced osteoconductivity and low susceptibility to infection. In addition, the experimental models for assessment, diagnostics and prophylaxis of biomaterial-related infections were established. The first experiment (Study I) established an in vitro method for simultaneous evaluation of calcium phosphate and biofilm formation on bisphenol-Aglycidyldimethacrylate and triethylenglycoldimethacrylate (BisGMA-TEGDMA) thermosets with different content of bioactive glass 45S5. The second experiment (Study II) showed no significant difference in osteointegration of nanostructured and microsized polylactide-co-glycolide/β-tricalcium phosphate (PLGA /β-TCP) composites in a minipig model. The third experiment (Study III) demonstrated that positron emission tomography (PET) imaging with the novel 68Ga labelled 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) CD33 related sialic-acid immunoglobulin like lectins (Siglec-9) tracer was able to detect inflammatory response to S. epidermidis and S. aureus peri-implant infections in an intraosseous polytetrafluoroethylene catheter model. In the fourth experiment (Study IV), BisGMATEGDMA thermosets coated with lactose-modified chitosan (Chitlac) and silver nanoparticles exhibited antibacterial activity against S. aureus and P. aeruginosa strains in an in vitro biofilm model and showed in vivo biocompatibility in a minipig model. In the last experiment (Study V), a selective androgen modulator (SARM) released from a poly(lactide)-co-ε-caprolactone (PLCL) polymer matrix failed to produce a dose-dependent enhancement of peri-implant osteogenesis in a bone marrow ablation model.

Phenol-furfural resins to elaborate composites, reinforced with sisal fibers - Molecular analysis of resin and properties of composites

Resol type resins were prepared in alkaline conditions (potassium hydroxide or potassium carbonate) using furfural obtained by acid hydrolysis of abundant renewable resources from agricultural and forestry waste residues. The structures of the resins were fully determined by H-1, C-13, and 2D NMR spectrometries with the help of four models compounds synthesized specially for this study. MALDI-Tof mass spectrometry experiments indicated that a majority of linear oligomers and a minority of cyclic ones constituted them. Composites were prepared with furfural-phenol resins and sisal fibers. These fibers were chosen mainly because they came from natural lignocellulosic material and they presented excellent mechanical microscopy images indicated that the composites displayed excellent adhesion between resin and fibers. Impact strength measurement showed that mild conditions were more suitable to prepare thermosets. Nevertheless, mild conditions induced a high-diffusion coefficient for water absorption by composites. Composites with good properties could be prepared using high proportion of materials obtained from biomass without formaldehyde. (c) 2008 Wiley Periodicals, Inc.

Biobased composites from glyoxal-phenolic resins and sisal fibers

Lignocellulosic materials can significantly contribute to the development of biobased composites. In this work, glyoxal-phenolic resins for composites were prepared using glyoxal, which is a dialdehyde obtained from several natural resources. The resins were characterized by (1)H, (13)C, (2)D, and (31)P NMR spectroscopies. Resorcinol (10%) was used as an accelerator for curing the glyoxal-phenol resins in order to obtain the thermosets. The impact-strength measurement showed that regardless of the cure cycle used, the reinforcement of thermosets by 30% (w/w) sisal fibers improved the impact strength by one order of magnitude. Curing with cycle 1 (150 degrees C) induced a high diffusion coefficient for water absorption in composites, due to less interaction between the sisal fibers and water. The composites cured with cycle 2 (180 degrees C) had less glyoxal resin coverage of the cellulosic fibers, as observed by images of the fractured interface observed by SEM. This study shows that biobased composites with good properties can be prepared using a high proportion of materials obtained from natural resources. (C) 2009 Elsevier Ltd. All rights reserved.

Sisal Fibers Treated with NaOH and Benzophenonetetracarboxylic Dianhydride as Reinforcement of Phenolic Matrix

In this work, composites based on a phenolic matrix and untreated- and treated sisal fibers were prepared. The treated sisal fibers used were those reacted with NaOH 2% solution and esterified using benzophenonetetracarboxylic dianhydride (BTDA). These treated fibers were modified with the objective of improving the adhesion of the fiber-matrix interface, which in turn influences the properties of the composites. BTDA was chosen as the esterifying agent to take advantage of the possibility of introducing; the polar and aromatic groups that are also present in the matrix structure into the surface of the fiber, which could then intensify the interactions occurring in the fiber-matrix interface. The fibers were then analyzed by SEM and FTIR to ascertain their chemical composition. The results showed that the fibers had been successfully modified. The composites (reinforced with 15%, w/w of 3.0 cm length sisal fiber randomly distributed) were characterized by SEM, impact strength, and water absorption capacity. In the tests conducted, the response of the composites was affected both by properties of the matrix and the fibers, besides the interfacial properties of the fiber-matrix. Overall, the results showed that the fiber treatment resulted in a composite that was less hygroscopic although with somewhat lower impact strength, when compared with the composite reinforced with untreated sisal fibers. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 269-276, 2010

Characterization of cure of carbon/epoxy prepreg used in aerospace field

Carbon/epoxy 8552 prepreg is a thermoplastic toughened high-performance epoxy being used in the manufacture of advanced army material. Understanding the cure behavior of a thermosetting system is essential in the development and optimization of composite fabrication processes. The cure kinetics and rheological behavior were evaluated using a differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and a rheometer. Values of the kinetic parameters were obtained from dynamic DSC scans using an nth order reaction model. Rheological measurements as a function of temperature and time were made for the prepreg system. The manufacturer's recommended cure cycle was evaluated and considered adequate to consolidated the studied system.

Propriedades de materiais nanoestruturados do sistema epoxídico DGEBA/TETA modificado com um éster de silsesquioxano

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Tailored norbornene-based copolymer with systematic variation of norbornadiene as a crosslinker obtained via ROMP with alternative amine Ru catalysts

Copolymers of norbornene (NBE) with norbomadiene (NBD) were obtained via ROMP with [RuCl2(PPh3)(2)(L)] type complexes as initiators (1 for L = piperidine and 2 for L = 3,5-Me(2)piperidine). The reactions were performed using a fixed quantity of NBE (5000 equivalents/[Ru]) for different concentrations of NBD (500, 1000, 1500 and 2000 equivalents/ [Ru]) in CHCl3, initiated with ethyl diazoacetate at room temperature. The presence of NBD in the NBE chains was characterized by H-1 and C-13 NMR. Whereas the copolymer microstructure was influenced neither by the NBD quantity nor by the initiator type, the N-n and PDI values were improved when increasing the NBD quantity in the medium. When raising the NBD amount, DMA results indicated increased cross-linking with increasing T-g and E ' storage modulus, as well as the fact that SEM micrographs indicated decreased pore sizes in the porous isolated copolymers. (C) 2011 Elsevier Ltd. All rights reserved.