Struktur Senyawa dan

Material Anorganik

Minggu 11&12
Program Magister Kimia
Minat Kimia Anorganik dan Material
 Materials
Ceramics (oxides, carbides, nitrides, borides)

Glasses (oxides, fluorides, chalcogenides, metallic)

Metals, Alloys, Intermetallics

Zeolites, Layer and Inclusion Materials (Clays)

Semiconductors (Si, Ge, 13/15, 12/16 compounds)

Composites, Inorganic-Organic Hybrid Materials

Polymers - inorganic, organic, hybrid

Biomimetic Materials, hydroxyapatite

Carbon-based Materials: Fullerenes, Fullerene Tubes, Graphene

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 Properties of Materials
A property = a material trait, the kind and
magnitude of response to a specific stimulus

Properties
Mechanical Electrical
Thermal Magnetic
Optical
Deteriorative (corrosion)
Catalytic
Biocompatibility

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Metals Ceramics Polymers

Strong Strong Usually not strong

Ductile Brittle Very ductile

Electrical Conductor Electrical Insulator Electrical Insulator

Heat Conductor Thermal Insulator Thermal Insulator

Not transparent May be transparent Not transparent

Shiny Heat Resistant Low Densities

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Materials Science:
Studies relationships between the structure and properties of materials

Materials Engineering:
Designing and engineering the structure of a material to produce a
predetermined set of properties

Processing Structure Properties Function

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 Materials Chemistry
Single crystals, defects, dopants, non-stoichiometry Monoliths
Coatings
Thin or thick films - singlecrystalline, polycrystalline, amorphous, epitaxial
Fibers, Wires, Tubes
Powders – primary particles, aggregates, agglomerates polycrystalline,
amorphous, nanocrystalline (1-100 nm)
Porous materials: micropores (< 20 Å), mesopores (20-500 Å),
macropores (> 500 Å)
Micropatterns
Nanostructures – spheres, hollow spheres, rods, wires, tubes, photonic crystals
Self-assembly – supramolecular chemistry: rotaxenes, catenanes, cavitands,
carcerands
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Materials Chemistry Tool Box
Direct reactions of solids – „heat-and-beat“

Precursor methods

Chimie douce, soft-chemistry methods, synthesis of novel

metastable materials, such as open framework phases

Ion-exchange methods, solution, melt

Intercalation: chemical, electrochemical, pressure,

exfoliation-reassembly

Crystallization techniques, solutions, melts, glasses, gels,

hydrothermal, molten salt, high P/T

Vapor phase transport, synthesis, purification, crystal 22

growth, doping
Materials Chemistry Tool Box
Electrochemical synthesis, redox preparations, anodic oxidation,
oxidative polymerization

Preparation of thin films and superlattices, chemical,

electrochemical, physical, self-assembling mono- and multilayers

Growth of single crystals, vapor, liquid, solid phase chemical,

electrochemical

High pressure methods, hydrothermal, diamond anvils

Combinatorial materials chemistry, creation and rapid evaluation of

gigantic libraries of related materials

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Clay Formation
During the weathering process, four
components are released:

• minerals in solution (cations and anions), the

basis of plant nutrition.
• oxides of iron and alumina (sesquioxides Al2O3,
Fe2O3).
• various forms of silica (silicon-oxide compounds).
• stable wastes as very fine silt (mostly fine quartz)
(endapan lumpur) and coarser quartz (sand).
These have no nutritious value for plants.
 Depending on temperature and rainfall, new minerals are formed.
 The oxides of iron and alumina combine with silica to form clay. In
temperate regions a three-layer clay is formed, which is weak,
swells under moisture, and clogs.
 It is able to absorb large amounts of water but is rather heavy on
plant roots, blocking the oxygen the soil organisms need.
 Because clay has a charged surface area, it is able to bind and
retain minerals and nutrients (Cation Exchange Capacity). The
valuable nutrition for plants won't leach away easily in three-layer
clays.
 Two-layer clays are formed in hot, humid tropical regions,
producing arable but easily dried soils.
 These clays are not able to hold much water, or nutrients, but are
still very much better than sand.
 CEC and weathering intensity

Alfisols,
Vertisols, Ultisols Oxisols
Argiudolls*

*remember nomenclature structure = “argi-ud-oll”

Weathering pattern of clay formation
2:1 1:1 Fe/Al Ox

Vertisols Ultisols

Oxisols

Spodosols

Entisols,
Inceptisols Fig 8.16
Silicates are compounds based on the silica tetrahedron,
consisting of a silicon atom surrounded by four oxygens
(Figure 1.11a).
Figure 1.11. The silica tetrahedron and
the structure of silicate minerals.
a. The silica tetrahedron consists of a
central silicon atom bound to 4
oxygens.
b. In orthosilicates such as olivine, the
tetrahedra are separate and each
oxygen is also bound to other metal
ions that occupy interstitial sites
between the tetrahedra.
c. In pyroxenes, the tetrahedra each
share two oxygen and are bound
together into chains. Metal ions are
located between the chains.
d. In sheet silicates, such as talc,
mica, and clays, the tetrahedra each
share 3 oxygens and are bound
together into sheets.
 Clay minerals
‘Weird’, not
1:1 clays 2:1 clays truly 2:1
(one tetrahedral (two tetrahedral
sheet for each sheets for each
octahedral sheet) octahedral sheet)

Kaolinite, Smectites Micas Vermiculites Chlorites

nacrite, dickite,
halloysite, etc. Montmorillonite, Illite, Tri- or di- Cookeite,
beidellite, muscovite, vermiculite chamosite,
saponite, etc. biotite, etc. etc.
Visual comparison of common silicate clays’ structure

more strongly held

than in smectite

illite “2:1:1”
montmorillonite
 Isomorphous substitution
equal shape/size

• The replacement of one ion for another of

similar size within the crystalline structure of
the clay
• Often results in change in net charge
• takes eons – doesn’t change rapidly
Substitution in tetrahedral sheet

Si2O4 SiAlO4
+4, +3, -8 (-2*4)
neutral negative

Tetrahedral sheet
 Substitution in octahedral sheet

(OH)2Al2O2 (OH)2AlMgO2
-2, +3, +2, -4
neutral negative

Octahedral sheet
 1:1 Silicate Clays
• Layers composed of one tetrahedral
sheet bound to one octahedral sheet
• Kaolinite: one of the most widespread
clay minerals in soils; most abundant in
warm moist climates
• Stable at low pH, the most weathered of
the silicate clays
• Synthesized under equal concentrations
of Al3+ and Si4+
 Kaolinite
• A 1:1 clay
• Little or no isomorphous substitution
• “nutrient poor”
• No shrink-swell (stable ‘cuz of H-
bonding between adjacent layers)
• A product of acid weathering (low pH,
common in soils of the SE USA
 Structure of Kaolinite
NO ISOMORPHOUS SUBSTITUTION!!!

Sheets of silicon tetrahedra and aluminum octahedra

linked by shared oxygen atoms.
 Kaolinite under low pH

Al—OH + H+  Al—OH2+
No charge positive charge
 2:1 Silicate Clays
• Two silica tetrahedral sheets linked to
one aluminum octahedral sheet
• Three key groups:
– Smectites (e.g., montmorillonite)
– Vermiculites
– Micas (e.g., illite)
• And one “2-1-1” (chlorites)
 Montmorillonite (2:1, a Smectite)
• Layer charge originates from the
substitution of Mg2+ for Al3+ in the
octahedral sheet
• Unstable (weathers to something else)
under low pH and high moisture
• Most swelling of all clays
• “Nutrient rich”
 Structure of Montmorillonite

Al

Structure of montmorillonite (a smectite): it is built of two sheets of silicon

tetrahedra and one sheet of aluminum octahedra, linked by shared
oxygen atoms.
Structure of Montmorillonite
Causes cations to
move into the
interlayer space,
where they can
be replaced by
other cations

Isomorphous
substitution here, in
the octahedral sheet

= Mg
 Vermiculites (2:1)
• Alteration product of micas (rock form)
• Formed from loss of K+
• Interlayer K+ of mica replaced with Mg2+
• Limited shrink-swell …
 Vermiculites (cont.)
• High layer charges: BOTH tetra and
octa
• “nutrient rich!”
• Stable under moderate to low soil pH,
high Mg, Fe
• Common in midwestern US
Structure of Vermiculite

Lots of
charge
imbalance,
both sheets:
High
nutrient
supply
capacity

= Al = Fe = Mg
 Illite (2:1, a Mica)
• Al3+ substitution for Si4+ on the tetrahedral
sheet
• Strong surface charge
• “fairly nutrient poor”
• Non-swelling, only moderately plastic
• Stable under moderate to low pH, common
in midwestern US
Structure of Illite
 Structure of Illite
1. Isomorphous
substitution is in
K+ K+ the tetrahedral
sheets

2. K+ comes into
the interlayer
space to satisfy the
charge and “locks
up” the structure
 Chlorites (2:1:1)
• Hydroxy octahedral sheet in the
interlayer space
• Restricted swelling
• “Nutrient poor”
• Common in sedimentary rocks and the
soils derived from them
 Structure of Chlorite

Mg-Al 1. Iron-rich
hydroxy sheet 2. “locked”
Mg-Al structure
hydroxy
sheet 3. Low
nutrient
supply
capacity

= Al = Fe = Mg
Factors affecting mineral stability
• Number and type of base cations in the
structure (base cations are soluble…)
• Number of silica tetrahedra that are linked
(more sharing of oxygens = more stable)
• Al3+ proxy for Si4+ (more proxy = less stable)
• Presence of Fe (more Fe = less stable)
• Kinds of bonds
– Ionic are heat tolerant
– Covalent generally stronger ‘cuz shared electrons
between atoms, but not heat tolerant
Where to find different clays
Modification of clay
2. Synthesis and characteristics of clay composites with various modifications

• 2.1. Clay composites modified with carbon materials

2.1.1. Activated carbon-clay composites
2.2. Clay composites
modified with organic
compounds
• small organo-montmorillonite
Large organo-montmorillonite
Inorganic modifiers modified montmorillonite

I
inorganic modifiers modified
M
montmorillonite
t
inorganic and organic modifiers modified montmorillonite
• One approach for safely disposal of the spent Mt after the uptake of
heavy metal cations (e.g., Cd2+, Cu2+) and radioactive nuclides (e.g.,
Lu3+, La3+, UO2 2+) is to in-situ sequestrate the adsorbed contaminants
by thermal treatment.
Preparation of graphene-like carbon
Carboxy-methyl-cellulose (CMC) modified Bentonite
CMC-Ben for adsorption of
Pb(II) and CR
Modifikasi Bentonit
Pengaruh soa abu pada swelling
Sinergitas soda abu dan CMC
Terimakasih