Chemistry and Physics of Hybrid Organic-Inorganic Materials

Today First hour: Introduction to course: Go over syllabus Introduction to Hybrid Organic Inorganic Materials -10 minute break. Second hour: Quiz Go over quiz answers and discuss (selected students will present their answers to class) Finish introductory material

Instructor: Douglas A. Loy Professor of Chemistry and Biochemistry & Materials Science and Engineering Sabbatical from the University of Arizona in Tucson, Arizona in the United States. Extensive experience with polysilsesquioxanes over 20 years.

Syllabus Five quizs (75 %) – 1 st quiz today Attendance (12.5%) Class participation (12.5%)

Syllabus Day 1: Hour1: Introduction to course and Hybrid Organic-Inorganic Materials Hour2: Quiz 1. To see what students know at the beginning of course. Day 2: Hour1: Hybrid organic-inorganics in nature Hour2: Types of material interactions Day 3: Hour1: Strategies for making hybrids. Hour2: Quiz 2. Hybrids in nature, material interactions, strategies for preparation of hybrids Day 4: Hour1: Class 1A preassembled inorganic phase (particles, fibers) dispersed in organic phase. Hour2: Class 1B: inorganic phase is made in-situ in organic continuous phase.

Day 5: Hour1: Quiz 3. Class 1A-C Hour2: Class 1D: Small organic phase dispersed in continuous inorganic phase Day 6: Class 1E: Phases are formed at same time without covalent attachment - interpenetrating networks Hour2: Class 2A: monomer contains both inorganic and organic components- material is assembled at one time Day 7: Hour1: Class 2A continued Polysilsesquioxanes with pendant groups Hour2: Class 2A Bridged Polysilsesquioxanes. Day 8: Hour1: Quiz 4. Class 1D, 1E, & 2A Hour2: Class 2B & 2C Day 9: Hour1 Class 2D & 2E Hour2: Unanswered questions, remaining challenges, and Holy Grails. Final exam on……

Office hours. Science Building, Room 315 M-F 10 AM –noon & 1 PM – 3 PM. Professor Loy is in Arizona, but will be back in his Harbin office on September 24 th

Course website For lecture slides and other info. Not at HIT website, at Loy research website: Go to loy research group home page and select “courses” on menu at top. Class website “Harbin Institute of Technology, Hybrid Materials Course” is the first entry. Direct url: institute-technology---hybrid-materials- course.html

Resources for course: Sol-gel links at Loy group research website. Sol-Gel Gateway is a website with many tutorials and links. SciFinder or Google Search Applications of hybrid organic–inorganic nanocomposites J. Mater. Chem., 2005,15, J. Mater. Chem., 1996,6, Gelest Website: brary.aspx

The history of humanity follows the development of materials stoneiron copperbronzestoneiron 25°C 600°C1100°CT°C

What are Hybrid Materials? Composite materials mixtures of organic and inorganic components Improvement on either organic or inorganic components Metal oxide network

Best B: Rule of mixtures Bad Why make hybrid materials? Achieve properties not found in either organic or inorganic phase Inorganic: Thermal stability Modulus Strength Porosity Organic: Toughness Elasticity Chromophore Chemical functionality

Applications of hybrid materials Tethers for Bio-molecules Coupling agents For composites Toughened Composites Protective coatings Chromatographic Materials (X-Bridge ®, Waters) Photoresists for Lithography Photographs courtesy of Gelest, Inc. and Waters Co.

More applications of hybrid materials Adhesives Metal Scavenger “resins” Sensor coatings Low  Dielectrics Optical coatings encapsulants Plus ceramic precursors (e.g. SiC)

Hybrid Organic-Inorganic materials are common in nature Nacre Argonite (CaCO 3 ) plates as inorganic with protein (polyamide) as organic Animals Plants phytolith Teeth, spines in echinderms Mussel shells, sponges, diatoms and corals are utilize hybrid organic-inorganic materials Organic phase is biopolymers Carbohydrates are the template and organic phase

Ancient Humans also made Hybrid organic-inorganic materials: Maya Blue L. A. Polette, N. Ugarte, M. José Yacamán and R. Chianelli, Sci. Am. Discovering Archaeology, 2000, July–August, 46 Indigo + white clay palygorskite (Mg,Al) 2 Si 4 O 10 (OH)·4(H 2 O)Al Si OH 2 O (also called Fullers Earth)

Different ways to put hybrids together Class 1: No covalent bonds between inorganic and organic phases Class 2: Covalent bonds between inorganic and organic phases Example: particle filled polymer Monomers in solventGel or dry gel (xerogel) Close-up of hybrid particle

Organic phases Small molecules Macromolecules Dyes Biocides & surfactants Dansylsilane Surface modifiers

Some hybrid monomers: Polymerize by hydrolysis and condensation (sol-gel polymerization) Monomers 2-4 polymerize to class 2 materials But act like class 1 in many cases. Used for many of the other classes as the inorganic component.

Inorganic Phases Metal Oxide Networks Organically modified Metal Oxide Networks

Inorganic Phases Silica Particles Preformed inorganic clusters Ti 12 O 16 (OPr i ) 16 Ti 17 O 24 (OPr i ) 20 Ti 18 O 22 (OBu n ) 26 (Acac) 2 Ti(OR) 4-x (acac) x POSS

Inorganic Phases Isolated metal atoms in polymeric architectures (organometallic polymers)

Inorganic Phases Carbon Buckeyballs, nanotubes and graphene Nature Materials 9, 868–871 (2010)

Making Hybrid Materials: Class 1A (pre-formed particles and fibers) Physical mixing or particles

Making Hybrid Materials: Class 1B (in situ particle growth) No Solvent except for monomer(s) Generally uses low t g organic polymers or in polymer melts (< 100 °C).

Making Hybrid Materials: Class 1C (Polymerizing in pores) Porous metal oxide Liquid monomer (no solvent) UV, heat, radiation Non-porous composite material

Making Hybrid Materials: Class 1D (encapsulation of small organics) Polymerize metal oxide around organic pores must be small or leakage will occur Solid state dye lasers, filters, colored glass © Asahi- Kirin

Making Hybrid Materials: Class 1E (Interpenetrating network) Both organic and inorganic phases grow simultaneously Timing is more difficult Reproducibility is a challenge May need to use crosslinking organic monomers to ensure solid product

Making Hybrid Materials: Class 2A (Covalent links at molecular level) Organic group is attached to network at molecular level Pendant or bridging monomers Bridging groups can be small or macromolecule This class also includes the organometallic polymers

Making Hybrid Materials: Class 2B (Covalent links at polymer level) ligands attached to polymer Reaction rates slow unless in sol. or melt

Making Hybrid Materials: Class 2C (Templating) Shown here with block copolymer Heat polymer then cool or cast from solvent

Making Hybrid Materials: Class 2C (Templating) Shown here with block copolymer PEO, Al 2 O 3 and RSiO 1.5 polyisoprene Block copolymer Sol-gel system Multiple phases created by varying size of blocks

1. Davis, H. T., Bodet, J. F., Scriven, L. E., Miller, W. G. Physics of Amphiphilic Layers, 1987, Springer-Verlag, New York Templating with surfactants First prepare two phase surfactant system Add monomer. Sol- gel monomers move into aqueous phase with hydrolysis Filter precipitate remove surfactant by calcining or extraction Many different phases can be accessed

Surfactant templating to make hierarchical materials

Surfactant templating Benzene-silica hybrid material with 3.8 nm pore diameter (Inagaki, Nature, 2002).

Classes 2D &E Covalent coupling agents Class 2E: Attaching inorganic group onto organic polymer For tough electrical wire coating & shrink fit wrap Class 2D: Attaching organic group onto inorganic material

Summary Outline for course. Step by step practical review of hybrid materials syntheses, structure, properties, and applications Five quizes, no final exam Attendance is required Lecture notes available at under courses.

Quiz1: 20 minutes to take quiz 1 Your name (pin yin) and student number and today’s date at top Then we will go over answers to quiz

Quiz 1: Write your name, and ID number at top of page. Then write the answers to 1-8 in English. 1) What is your major (for example, chemistry or chemical engineering or physics)? 2) What is the two letter symbol for the element silicon? 3) Molarity is a measure of what quantity? What are SI units of Molarity? 4) What scientific instrument does the acronym "NMR" stand for? (please write our its full name). 5) How much would 0.2 moles of 3-(trimethoxysilyl)propyl methacrylate weigh? 6) What is a polymer? 7) If the rate, R, of a reaction was shown to have a simple, first order dependence on water concentration and a first order dependence on the reactant concentration, write the reaction rate equation. 8) According to the scientific method, what should a researcher do once she has made a hypothesis to explain some of her observations?

Answers to quiz1 Do not show to students until after quizes turned in.

Quiz 1 Problem 1: What is your major (for example, chemistry or chemical engineering or physics)?

2) What is the two letter symbol for the element silicon?

2) What is the two letter symbol for the element silicon? Si

3) Molarity is a measure of what quantity? What are SI units of Molarity?

3) Molarity is a measure of what quantity? Concentration What are SI units of Molarity? Moles/Liter

4) What scientific instrument does the acronym "NMR" stand for? (please write our its full name).

4) What scientific instrument does the acronym "NMR" stand for? (please write our its full name). Nuclear Magnetic Resonance

5) How much would 0.2 moles of 3- (trimethoxysilyl)propyl methacrylate weigh?

5) How much would 0.2 moles of 3- (trimethoxysilyl)propyl methacrylate weigh? # g = 0.2 moles x g/mole = 49.7 g

What is a polymer?

A polymer is a macromolecule (a very large molecule) composed of many small molecules (monomers) covalently bonded together in some fashion. Generally, greater in molecular weight than 10K g/mole.

7) If the rate, R, of a reaction was shown to have a simple, first order dependence on water concentration and a first order dependence on the reactant concentration, write the reaction rate equation.

Rate = k[H 2 O][reactant]

8) According to the scientific method, what should a researcher do once she has made a hypothesis to explain some of her observations?

Design and conduct experiments to test hypothesis by trying to disprove it.