THERMAL AND FLAMMABILITY PROPERTIES OF A SILICA-PMMA NANOCOMPOSITE by Alexander B. Morgan, Joseph M. Antonucci, Mark R. VanLandingham, Richard H. Harris, Jr., and Takashi Kashiwagi National Institute of Standards and Technology Gaithersburg, MD 20899 Reprinted from Polymeric Materials Science & Engineering (ACS), Vol. 83, 57, 2000. NOTE: ‘This paper is a contribution of the National Institute of Standards and Technology and is not subject to copyright. Notlonel institute of Standards and Technology‘Thermal and Flammability Properties of Si ‘Nanaeamposite Alesancer 8. Morgan’, Jarph M Antomacet, Mark & VanLandinghom? Richard H. Hari JP. and Tah Kashowag! “re Seience Division, Builng and Fire Research Laboratory lymers Division, Matis Scene and Engineering Latoaory :Dulding Matra Divison, Buldng ond Fan Rese Laboratory see rae en paredetion “The properties of» peer compote materi depend not oly upon By pogens of Be indi! components, mt ater em he pamers fBec apology and inertial popris withthe otc component I te [PBorae metic terween te oo components Sesomes steals Btucr connceraion or eran, Cece of inary npn {Ebminng be overal popes of te compose ati, For example, [iginen fed wih naporcle sca paricee gered a second gs fists fit war much niger tan "hat of se polymer sin Ths eroenon wa accounts fx by he ematon of ight and Host bond [Biren caer wound te price Cer eis eed sn ingen Tse propercr and also sme tmprovenent ema ag? An Efpovemer it Sammi poperie of polymer eng te ence of [Boned increas Inout alent has Geen deans To ey Heooompost™" (nth dy, thease of nanoscale aia parils 1 4 ine scucan sive tm polymer nanacomporte is vesigaed wih {eget provement abot he Rammabliy propecics td te ply ‘Spee of polynety! metas) (PMMA icons, conten Geer are miives, sch at boned comgonc Nye {gqove aby of pols ut tnd to rede psi properties sperimemta PM! metacriate (MMA 99%, inhibied with 10 ppm monomethyl ber of hydroquinone), and 22-dimethoxy-2-ghenslactoghenone (29% DutPa) were prchaced om Aldc, Collotal ea (12mm, 30 nash ‘al ety! Ketone; MEK ST) was donated by Nisan Chemical. A Digit Ermer Dimension 3108 same fre microncope (APM) wat operated in ppg mode in laboratory air conditions using & commercial silicon ‘percanever robe. Manufacuers values forthe probe tip rads and pve spring somatic inte ranges of Sam © 10 am and 29 Nm 0 100 Nim. respecvely. Topographic’ and phase images were obtined aitancusly sing a resonance reavency of approximately 300 Ki forthe debe cicilain, 2 Sean ate of 0.8 Ha, a fee-ocilanon ampline of ‘ypoximatly 30 am, and Setpoint amplitude of approximately 30 nm. Dare inact ae prevented witout any ofeeing, planting, oF karing ‘pled tothe image dats, Bright field taramistion clston misscopy TEM) images of polymethylmethaeryiate (PMMA)-anosiles ‘amcimpoaes nee Give 120 KV, under low-dose condone, ih 3 Alps 4007 elecuon microscope, The PMMA.SiO, nanocomposite was skranicrtored with a diamond knife at 23 °C wo give 70 nm thik sections fhe sectons were tansfened fm Water to carbon-coated Cu grids of 200 test, Thermal gravimetric analysis (TG) data were collected fom 30°C to THO %C se 10 Cin under N cing + TA tates SDT 2960 Preparation of PMMA-Siiea Nanocomposites:" To 1.0 g of the \EK-ST solution was abled 9.0 of MMA The combined solution was lined wie a magne surbar ang'alowed (0 concentrate a 25°C nt the ‘idl misture was approximately 3.0 2 Assuming that most ofthe excess {ety ey Keone had been removed by co-vaporation with te excess of| IMA, the inal eure cnssid of 0.3 ar 10 mash calloial sca ‘ipered in 27 gof MMA. This miarve was placid in 3 clear glass Vial and Ighated fr phoopolymeraaion with 0.7 macs¥= OMPA. The sass vial fomining the activated mixture of MMAISIO, at sealed and alowed 10 Yioepolymerize at 25227 °C fr 6h by exposure aati sunlight cea, ‘Stusotd armed inte Vial wien wal sgeatea and placed in vac veh 1€100°C and a pressure of 27 KPa for 30. The oyindrical composite pg 5 removed by carefully fracturing dhe slas val” AS a como the same Snherztion procedure was conducted on 3.0 g of DMPA-actated MMA ‘sour presence of he MEK. Results and Discussion “Tapping mode atomic fore mieossopy (AFM) images vere taken of & smooth suce of a molded PMMA sample to examine the Gispesion ofthe silica parce ia he PMMA resins 3.00 1.00 ° 1.00 2.00 3.00 Figure 1.” AFM image ofthe PMIMA-SiOy srple: 3 ya x3 jm grea. The olor Sal fom Back wo white representa phate diteence of 30 “The comrast inthe image (Figure 1) is likely caused by repulsive tp- sample interactions for the nanos, eeting 3 piv pane tha hoe ‘Ups bight and an atvacte tip-sampe intcraction fr the PMMA, esulng in a negative phase tha shows up as dark In the figure, many small seglomerszs of perhaps buoneen 2 ad 6 paces ate ubneved any wi what appear to be single patiles with Gameters of appoxiately 12 Note tht the AFM image is ofthe sample sutace and the hgh phase contrast indicates tera potions of snoslca a ery near he sre, Figure. TEM image of PMMA-SiO, sample The TEM aalyss ofthe PMMA-SiO, material at high magnification shows the 12 am sca spheres clearly (Figure 2), but algo shows ares of Polym, Mater. Sei. Eng. 2000, 83, 57, 7yeu sca concetration. This image, combined wih the broader area alysis tom AFM (Figure 1) indicaes thatthe PMMAS(O, nanocomposite ‘as Some non-nirmityof SiO; dispersion, Figure 3. TGA and defvitive TOA (STGA): curves for PMMA’ + SiO aoconpsits. Starard deviation forthe wi ley at 700°C 0.167 for PMMA*Si0, 19 for PMMA, ‘The TGA data (Figure 3) show thatthe PMMAYSIO: nanocompenite has ahighe esidue yield (abou 15% of esidue mass ~ 10% sca mass = shout 6% organ residuetchay) and higher thermal stability When compe tothe conrol PMMA sample. The observed thre peaks at about 210°C (a 2houlee instead of » pe). 200 °C, and 366 °C appar #0 be insta By Seisions of fheadso-head linkages, by seissions st te, chan-nd tom vinlidene ends, and by random session within. the polymer hain, especialy" The peak heign of the Seca peak Of he PIMATSION anovomposite i let than that of the sowgol PMMA sample and the tid peak is shied toward higher temperance by about 7 °C fhe the ‘ancomposite sample compared to he contol PMMA Sample. This indicates, that the bound polymer chans near silica particles might have higher thermal ability ovand the nanaiice way be pring a baler at pores release of evolved degradation products, thus Tapping the produc which ‘recombine w fem thermally stable residurichar“Sioce the thermal stabi Of polymere materials have. significant iafluece on ther famabiliy properties, it que feasible that the Mammablicy properties of the anoonmpetite sample wid he signieanty improved compared with thowe ofthe conto! sample, ‘Scaled up preparaons of tiese pes of nanocomposes ae under way to improve the dpersion ofthe nanoscale silica paces in PMMA and tobe the to make lager samples forthe measiement of flammability properties, ‘Tae esas wil be presented ae meeting Conclusions “The feasibility ofthe preparation of «nanocomposite saple consisting of PMMA and nanoscale ica patles was demonsrated wing 2 flatly Simple procedure of photopolymenzation of MMA wih the colo silica ‘The resionably good dispersion ofthe particles was confimmed by AFM and ‘TEM oxcepe ina few seas where significant agglomeration it observed ‘TGA data Show an improvement in thermal aby and enhanced formation of organic resiueschar for the nanocomposite sample compared 1 he Soutcl PMMA sample. The popuatine of er mone Mih wel ‘dspesed nanosliza files to give their somesponding nanocomposites by ‘mpl ambien polymeraaon methods also shouldbe fsbe ‘Ackaowledgement. We tar Nisan Chemical Corp. fr the donation of a colloidal sien sample ia MEK, We woul6 algo like to task {Be Cathey Incheon of NIST-MSEL for asztance withthe TEM werk and fur ese ofthe TEM facts inthe Polymers DWvision (1) This work was carried ou by the Natal Instn of Stands “Technology (NIST), an agency ofthe U.S. government, and Is ot sbjet to copright the United State. () Novak, BM, acy Maer 1993, 5.422 (2) Teagaopouics, Cand Esenber, A, Macromoleculer 1995, 28, (3) Tsagaropouios. 0. ana Eisenberg, Macromolecules 1993, 2, @) Landy. C.-T, Coliain, BK, Lando, MR, Fitzgerald, 1 Long VK. Sacromelecner 1993, 25,37 (9) Hail, P David C, Gerad, 1, Pacau, JP. and Visi, G, Se Part B1999, 37,3172 (6) Heiue, GH, Ko, 91, Huang, ¥-P, and Jeng, Ri, Pole 3 28 (2) Giancelis, ey, Morr 1996, 5,29, (8) Guan, 3. and Kashiwagl. T. SAM¢PE J. 1997, 33,40 (9) Gilman, 1, Applied Clay Sei 1999, 15,31 (2) Certain’ eommecrint equipment, intraments, mattis, serv ‘companies az iene in is paper in oder to specify adequa fexpermetal procedure, This im 90 way implies endosen (10) Takahashi, FE; Amonuci, J Stunsbury, J Wang, F. Polym 4997, 380,183, (1) Kashivag. Inaba, A, Brown, LE, Hatda, K, Katayama, Masud, E Nacrometecules 1986, 19,2160. (1) Kang” Te Twenty-Four Symporim Combustion 1984, 183, (temations