CRYSTAL STRUCTURES

SCIMATP
X Ray Diffraction
 X Ray Diffraction
• density of electrons within the crystals is
obtained form the measurement of the angles
and intensities
– the mean positions of the atoms in the crystal
– their chemical bonds
– their disorder and various other information.
 RECALL

• Coordination # = 6
(# nearest neighbors)
RECALL

• Coordination # = 8

Adapted from Fig. 3.2,

Callister & Rethwisch 3e.
 RECALL

• Coordination # = 12

Adapted from Fig. 3.1, Callister & Rethwisch 3e.

METALLIC CRYSTAL STRUCTURES

• Atomic bonding in this group is metallic

and thus non-directional
– minimal restriction to the number and
position of nearest neighbor atoms
– Leads to relatively large numbers of
nearest neighbors and dense atomic
packing
METALLIC CRYSTAL STRUCTURES

1. SIMPLE CUBIC
– Rare (Po)

2. BODY-CENTERED CUBIC (BCC)

3. FACE-CENTERED CUBIC (FCC)

4. HEXAGONAL CLOSE-PACKED (HCP)

METALLIC CRYSTAL STRUCTURES
CERAMIC CRYSTAL STRUCTURES

• more complex since they are composed of

different elements
• the bonding in ceramics may range from
purely ionic (nondirectional) to totally
covalent (directional)
 CERAMIC CRYSTAL STRUCTURES

Crystal structure in crystalline ceramics is

influenced by
1. Magnitude of electric charge
• Cation, +
• Anion, -
• Charge Neutrality: Net charge in the ceramic
structure should be zero
» Calcium Fluoride
» Ca 2+, F1-
F-
Ca 2+
CaF2 : cation + anions
F-
 CERAMIC CRYSTAL STRUCTURES

Crystal structure in crystalline ceramics is

influenced by
2. Relative sizes of cations, rc, and anions, ra

rc
1
ra
 CERAMIC CRYSTAL STRUCTURES
To form a stable structure, how many anions can surround
around a cation?
r cation ZnS
Coord #
r anion (zincblende)
< .155 2

.155-.225 3 NaCl
(sodium
.225-.414 4 chloride)

.414-.732 6
Cs Cl
(cesium
.732-1.0 8 chloride)
http://www.chem.ubc.ca/courseware/121/tutorials/exp7A/tetrahedral_hole.gif http://www.math.twsu.edu/history/Images/tetrahedron2.gif
http://www.chem.ubc.ca/courseware/121/tutorials/exp7A/octahedral_hole.gif http://www.luzdegaia.org/alertas/diversos/octahedron-1.gif
 CERAMIC CRYSTAL STRUCTURES

AX-Type Crystal Structures

1. Rocksalt strcuture (NaCl)

rNa = 0.102 nm

rCl = 0.181 nm

rNa/rCl = 0.564

 cations (Na+) prefer octahedral sites

Adapted from Fig. 3.5, Callister & Rethwisch 3e.

 CERAMIC CRYSTAL STRUCTURES

AX-Type Crystal Structures

2. Cesium Chloride Structure (CsCl)

rCs  0.170
  0.939
rCl 0.181

 Since 0.732 < 0.939 < 1.0,

cubic sites preferred
 CERAMIC CRYSTAL STRUCTURES

AX-Type Crystal Structures

3. Zinc Blende/Sphalerite (ZnS)
CERAMIC CRYSTAL STRUCTURES

AmXp-Type Crystal Structures

m and/or p ≠ 1
1. Fluorite (CaF2)
• Cations in cubic sites
CERAMIC CRYSTAL STRUCTURES

AmBnXp-Type Crystal Structures

ceramic compounds with two types of cations
1. Perovskite Crystal Structure
• Ex: Barium Titanate
• FCC
 IONIC LATTICES
• Watch video Clip
– Take note of the following terms:
• Octahedral Holes
• Tetrahedral Holes
Interstitial sites
– locations between the “normal” atoms
or ions in a crystal into which another –
usually different – atom or ion is placed
• Fluorite (CaF2)
• Hallite (NaCl)
• Sphalerite/Zincblende (ZnS)
 COVALENT STRUCTURES

• strength of bonds
throughout the
crystal is non
uniform
• Crystals of low
symmetry and
complex structure
Diamond Structure
 POLYMERIC CRYSTAL STRUCTURES

• No polymer is completely crystalline

– a single polymer chain may be partly in a crystalline
lamella, and partly in the amorphous state
Is this a good thing?
– If you are making PLASTICS, yes
• Crystallinity makes a material strong, but it also
makes it brittle
• A completely crystalline polymer would be too
brittle to be used as plastic
• The amorphous regions give a polymer toughness,
that is, the ability to bend without breaking.
DENSITIES OF MATERIAL CLASSES
• ρmetals > ρceramics >ρpolymers
Graphite/
Metals/ Composites/
Why? Alloys
Ceramics/
Semicond
Polymers
fibers

Metals have... 30
Based on data in Table B1, Callister
20 Platinum *GFRE, CFRE, & AFRE are Glass,
• close-packing (metallic bonding) Gold, W
Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• large atomic mass 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
Ceramics have... Cu,Ni
Steels

3)
Tin, Zinc
• less dense packing (covalent 5
Zirconia

bonding)

 (g/cm
Titanium
4 Al oxide
Diamond
Si nitride
• often lighter elements 3
Aluminum Glass -soda Glass fibers
Concrete
PTFE
Polymers have... 2 Magnesium
Silicon
G raphite
GFRE*
Carbon fibers
CFRE *
Silicone
• poor packing (often amorphous) PVC
PET
Aramid fibers
AFRE *
1 PC
• lighter elements (C,H,O) HDPE, PS
PP, LDPE

Composites have...
0.5 Wood
• intermediate values 0.4
0.3
 References
• http://users.encs.concordia.ca/~woodadam/MECH221/Course_Notes/Crystal%20structure
%20and%20properties.pdf
• cmsweb1.loudoun.k12.va.us/.../lib/.../Atoms_to_Minerals.ppt
• www.ims.uconn.edu/~alpay/Group_Page/.../StructureOfSolids.ppt
• http://www.yourgemologist.com/crystalsystems.html
• http://en.wikipedia.org/wiki/Crystal_system
• CRYSTAL STRUCTURES Lecture. PowerPoint Presentation by Michelle Natividad
(2009)
• Lesson 5. Powerpoint Presentation by Gwendolyne Pascua (2007)
• http://ari.cankaya.edu.tr/~ebiber/ie114/Week-3.ppt
• http://www.ims.uconn.edu/~alpay/Group_Page/Courses/MMAT
%20201/StructureOfSolids.ppt
• http://www.che.yuntech.edu.tw/teacher/lincw/%E9%AB%98%E7%AD%89%E9%AB
%98%E5%88%86%E5%AD%90%E7%89%A9%E6%80%A7/CHAPTER_3_-
_Morphology_and_Order_in_Crystalline_Polymers.pdf
• http://bgu.uniclass.co.il/mate09/uploader.php?file=Chapter_03.ppt&id=2