1. Hybrid POSS Lecture 12 Class 2B: Inorganic and organic polymeric phases are mixed and form covalent interactions

2. tin oxides and polymers with carboxylate groups. But not a lot in the literature

3. Cross-linking through fullerenes Used to purify C 60. Did not look at mechanical properties Requires solvent to prepare

4. Cross-linking through fullerenes: my new idea Liquid polymer- no solvent needed

5. Modified organic polymers: Trialkoxysilyl side groups

6. Polybutadiene with side groups

7. Grafted triethoxysilyl groups on polyethylene for moisture crosslinking May also be applied with vinyltriethoxysilane and RF plasma Excellent for moisture curing polyethylene

8. Macromolecules, 2004, 37 (10), pp 3532–3535 Anisotropic Micellar Nanoobjects from Reactive Liquid Crystalline Rod−Coil Diblock Copolymers

9. Modified organic polymers: Trialkoxysilyl end groups

10. Macromolecules 1992,25, 5742-5751 Hydrogenated polybutadiene telechelics with triethoxysilyl groups

11. Triethoxysilyl terminated polysulfone Macromolecules 1991;24:3449–50. Anneal > 200 °CTiO 2 sol in THF Tailorable refractive index 1.6 < n < 1.8

12. Drug delivery hybrid gel Polyethylene glycol Treithoxysilyl group on each end Urea linkage

13. Drug delivery hybrid gel

14. PEO Bridged polysilsesquioxane hybrids Bacteriocide Ag-silsesquioxane coatings Biomacromolecules, 2007, 8 (4), pp 1246–1254 Polymer electrolytes Solid State Ionics, 1999, 116, 197– 209 Coatings for steel. Adv. Technology 2008, 27, 117-126 Electrochemically deposited coatings for stints New J. Chem., 2009, 33, 1596-1604 Luminescent materials J. Non-Crystal Solids 2006, 352, 2292–2295 & Chem. Mater., 2004, 16 (13), pp 2530–2543 Contolled druge release Chem. Mater., 2009, 21 (3), pp 463–467

15. PEO bridged polysilsesquioxanes for polymer electrolytes New J. Chem., 2012, 36, 1218-1223

16. Templating of structures and pores in hybrids, inorganics and organics In templating, you build a material around some molecule, macromolecules or liquid crystal Opals were used as templates for inverse opals and photonic solids (described in an earlier lecture). First we will see polymers phase segregation during sol-gel polymerization generating bone linke structures in hybrids. Then we will look at liquid crystalline surfactant or block copolymer templates

17. Polymer phase separation templation of macropores

18. Using other phase separations to control how particles aggregate Surfactants Polymers Block copolymers Hydrophilic Phase Hydrophobic Phase Monomers are often dissolve in this phase Hydrolyzed monomers and polymers are often dissolve in this phase Polymers are not very soluble in each other and will phase separate like oil and water Larger structures Smaller structures

19. Cited over 10,200 times

21. The Mobil patent was duplicating something already in the literature Somebody did not do a careful literature search!!!!!!

22. Traditional ionic surfactants used in mesoporous materials templation

23. Traditional non-ionic surfactants used in mesoporous materials templation

24. Phase separation: surfactants

25. Pore models of mesostructures with symmetries of (A) p6mm, (B) Ia3 ̄ d, (C) Pm3 ̄ n, (D) Im3 ̄ m, (E) Fd3 ̄ m, and (F) Fm3 ̄ m. MCM-41 FDU-12SBA-16 SBA-1 FDU-2 MCM-48

26. Adv. Mater 1999, Brinker

27. First model for surfactant templating: assumes liquid crystal occupies entire solution A few nanometers in diameter

28. Published in: Avelino Corma; Chem. Rev. 1997, 97, 2373-2420.

29. 1) n-Hexadecyltrimethylammonium bromide (2.5 g, 0.007 mol) was dissolved in deionized water (50 g) 2) To this surfactant solution, 13.2 g of aqueous ammonia (32 wt.%, 0.25 mol) and 60.0 g of absolute ethanol (EtOH, 1.3 mol) were added and the solution was stirred for 15 min (250 rpm). 3) TEOS (4.7 g, 0.022 mol, freshly distilled) was added at one time resulting in a gel. 4) After stirring for 2 h the white precipitate was filtered and washed with 100 ml of deionized water and 100 ml of methanol. 5) After drying overnight at 363 K, the sample was heated to 823 K (rate:1 K min−1) in air and kept at that temperature for 5 h. Synthesis of MCM-41 spheres Microporous and Mesoporous Materials, 1999, 27, 207–216

30. Synthesis of MCM-41 silica spheres Microporous and Mesoporous Materials, 1999, 27, 207–216 X-ray diffraction pattern of an MCM-41 sample prepared in heterogeneous medium with n-hexadecylpyridinium chloride as template.

31. Size of MCM 41 pores can be controlled by process conditions

32. TEM image of the honeycomb structure of MCM-41 and a schematic representation of the hexagonal shaped one-dimensional pores. A close look at the structure shows that it is made of small amorphous silica particles Just like the silica in living sponges > 1 nm in size

33. X-Ray Diffraction (XRD) These materials show peaks at very small angles = larger structures than are typical in crystalline materials

34. formation mechanism of the templated nanoporous silicas New mechanism has individual surfactant molecules and micelles playing a role in developing architecture

35. .Chem. Rev., 2002, 102 (11), pp 4093–4138 Zeolite: silicalite

36. Structure of SBA-1 or SBA-6 observed as an electron density and described either in terms of a clathrate structure or as a surface enveloping the micellar templating agents Nature, 2000, 408, 449 Electron micrographs of SBA-1 and SBA-6 along [100] What are some of these materials and what do they look like (SBA-Santa Barbara.

37. Plane-projection of CDF (a), respective TEM image fragment (b) and its simulation (c).

39. Electronic density maps and bicontinuous cubic structure of MCM-48 Chem. Mater., 1996, 8, 1141

40. HREM images of CMK-4 along the three zone axes [100], [110] and [111] together with a representation of the carbonaceous surface. J. Phys. Chem. B, 2002, 106, 1256

41. Chem. Rev., 2011, 111 (2), pp 765–789 How organic templates can control porosity of materials

42. Liquid crystal forms then monomer enters and reacts Monomer starts reacting and interacting with surfactant as the liquid crystal forms

44. Making Hybrid Materials: Class 2C (Templating) Shown here with block copolymer

45. Tools for hierarchical materials structures Phil. Trans. R. Soc. A 28 April 2009 vol. 367 no. 1893 1587-1605

46. Other challenges Ladder polysilsesquioxanes = super strong materials Pure polyhedral analogs the size of C 60 Fundamentals of particle formation and connectivity at nm length scale Mechanochemical direction of materials-like exercising developing muscles

47. Good-bye Thank you Good Luck I will be here until November 23 & should be back this summer