ENGI NEERI NG

MATERI ALS
METAL | CERAMIC | POLYMER
ME T AL S &
C E R AMI C S
CHEMISTRY OF ENGINEERING MATERIALS
CR YS TALLI N I TY AN D
N ON - CR YS TALLI N I TY
FOR CRYSTALLINE SOLIDS, THE NOTION OF CRYSTAL
STRUCTURE IS PRESENTED, SPECIFIED IN TERMS OF A UNIT
CELL. CRYSTAL STRUCTURES FOUND IN BOTH METALS AND
CERAMICS ARE THEN DETAILED, ALONG WITH THE SCHEME
BY WHICH CRYSTALLOGRAPHIC POINTS, DIRECTIONS, AND
PLANES ARE EXPRESSED.
 F U N D AME N TALS
A CRYS TALLINE MATERIAL IS ONE IN WHICH THE ATOMS ARE
SITUATED IN A REPEATING OR PERIODIC ARRAY OVER LARGE
ATOMIC DISTANCES; THAT IS, LONG-RANGE ORDER EXISTS,
SUCH THAT UPON SOLIDIFICATION, THE ATOMS POSITION
THEMSELVES IN A REPETITIVE THREE-DIMENSIONAL
PATTERN, IN WHICH EACH ATOM IS BONDED TO ITS NEAREST-
NEIGHBOR ATOMS.
F U N D AME N TALS
SOME OF THE PROPERTIES OF CRYSTALLINE SOLIDS DEPEND
ON THE CRYS TAL S TRUCTURE OF THE MATERIAL, THE
MANNER IN WHICH ATOMS, IONS, OR MOLECULES ARE
SPATIALLY ARRANGED.

WHEN DESCRIBING CRYSTALLINE STRUCTURES, ATOMS (OR

IONS) ARE THOUGHT OF AS BEING SOLID SPHERES HAVING
WELL-DEFINED DIAMETERS. THIS IS TERMED THE ATOMIC
HARD-S P HERE MODEL IN WHICH SPHERES REPRESENTING
NEAREST-NEIGHBOR ATOMS TOUCH ONE ANOTHER.
F U N D AME N TALS
ATOMIC HARD-SPHERE MODEL

IN THIS PARTICULAR CASE ALL THE

ATOMS ARE IDENTICAL. SOMETIMES
THE TERM LATTICE IS USED IN THE
CONTEXT OF CRYSTAL STRUCTURES;
IN THIS SENSE “LATTICE” MEANS A
THREE-DIMENSIONAL ARRAY OF
POINTS COINCIDING WITH ATOM
POSITIONS (OR SPHERE CENTERS).
 U N I T CE LLS
THE ATOMIC ORDER IN CRYSTALLINE SOLIDS INDICATES THAT
SMALL GROUPS OF ATOMS FORM A REPETITIVE PATTERN. THUS,
IN DESCRIBING CRYSTAL STRUCTURES, IT IS OFTEN CONVENIENT
TO SUBDIVIDE THE STRUCTURE INTO SMALL REPEATING ENTITIES
CALLED UNIT CELLS .

UNIT CELLS FOR MOST CRYSTAL STRUCTURES ARE

PARALLELEPIPEDS OR PRISMS HAVING THREE SETS OF PARALLEL
FACES; ONE IS DRAWN WITHIN THE AGGREGATE OF SPHERES.

A UNIT CELL IS CHOSEN TO REPRESENT THE SYMMETRY OF THE

CRYSTAL STRUCTURE, WHEREIN ALL THE ATOM POSITIONS IN THE
CRYSTAL MAY BE GENERATED BY TRANSLATIONS OF THE UNIT CELL
INTEGRAL DISTANCES ALONG EACH OF ITS EDGES. THUS, THE UNIT
CELL IS THE BASIC STRUCTURAL UNIT OR BUILDING BLOCK OF THE
CRYSTAL STRUCTURE AND DEFINES THE CRYSTAL STRUCTURE BY
VIRTUE OF ITS GEOMETRY AND THE ATOM POSITIONS WITHIN.
 ME TALLI C
CR YS TAL
S TR U CTU R E
METALLIC CRYSTAL STRUCTURE
THE ATOMIC BONDING IN THIS GROUP OF MATERIALS IS
METALLIC AND THUS NON-DIRECTIONAL IN NATURE.
CONSEQUENTLY, THERE ARE MINIMAL RESTRICTIONS AS
TO THE NUMBER AND POSITION OF NEAREST-NEIGHBOR
ATOMS; THIS LEADS TO RELATIVELY LARGE NUMBERS OF
NEAREST NEIGHBORS AND DENSE ATOMIC PACKINGS FOR
MOST METALLIC CRYSTAL STRUCTURES. ALSO, FOR
METALS, IN THE HARD-SPHERE MODEL FOR THE CRYSTAL
STRUCTURE, EACH SPHERE REPRESENTS AN ION CORE.
THREE RELATIVELY SIMPLE CRYSTAL STRUCTURES ARE
FOUND FOR MOST OF THE COMMON METALS: FACE-
CENTERED CUBIC, BODY-CENTERED CUBIC, AND
HEXAGONAL CLOSE-PACKED.
METALLIC CRYSTAL STRUCTURE
THE FACE-CENTERED CUBIC CRYSTAL STRUCTURE

THE CRYSTAL STRUCTURE

FOUND FOR MANY METALS
HAS A UNIT CELL OF CUBIC
GEOMETRY, WITH ATOMS
LOCATED AT EACH OF THE
CORNERS AND THE CENTERS
OF ALL THE CUBE FACES.
METALLIC CRYSTAL STRUCTURE
THE FACE-CENTERED CUBIC CRYSTAL STRUCTURE
FIGURE 3 .1 A SHOWS A HARD
SPHERE MODEL FOR THE FCC UNIT
CELL, WHEREAS IN FIGURE

3 .1 B THE ATOM CENTERS ARE

REPRESENTED BY SMALL CIRCLES
TO PROVIDE A BETTER
PERSPECTIVE OF ATOM POSITIONS.

THE AGGREGATE OF ATOMS IN

FIGURE 3 .1 C REPRESENTS A
SECTION OF CRYSTAL CONSISTING
OF MANY FCC UNIT CELLS.
 METALLIC CRYSTAL STRUCTURE
THE FACE-CENTERED CUBIC CRYSTAL STRUCTURE
THESE SPHERES OR ION CORES TOUCH ONE ANOTHER ACROSS A
FACE DIAGONAL; THE CUBE EDGE LENGTH A AND THE ATOMIC
RADIUS R ARE RELATED THROUGH

FOR THE FCC CRYSTAL STRUCTURE, EACH CORNER ATOM IS

SHARED AMONG EIGHT-UNIT CELLS, WHEREAS A FACE-CENTERED
ATOM BELONGS TO ONLY TWO. THEREFORE, ONE-EIGHTH OF EACH
OF THE EIGHT CORNER ATOMS AND ONE-HALF OF EACH OF THE
SIX FACE ATOMS, OR A TOTAL OF FOUR WHOLE ATOMS, MAY BE
ASSIGNED TO A GIVEN UNIT CELL.
 NUMBER OF NEAREST-
NEIGHBOR OR TOUCHING
ATOMS
C O O R D I N AT I O N N U M B E R V S
AT O M I C P A C KI N G N U M B E R

SUM OF THE SPHERE VOLUMES OF ALL ATOMS WITHIN A

UNIT CELL (ASSUMING THE ATOMIC HARD- SPHERE MODEL)
DIVIDED BY THE UNIT CELL VOLUME

CRYSTAL STRUCTURE
IMPORTANT CHARACTERISTICS
 FOR FACE- CENTERED CUBICS , THE COORDINATION
NUMBER IS 1 2 . THIS MAY BE CONFIRMED BY
EXAMINATION: THE FRONT FACE ATOM HAS FOUR CORNER
NEARES T- NEIGHBOR ATOMS S URROUNDING IT, FOUR
FACE ATOMS THAT ARE IN CONTACT FROM BEHIND, AND
FOUR OTHER EQUIVALENT FACE ATOMS RES IDING IN THE
NEXT UNIT CELL TO THE FRONT.

COORDINATION NUMBER & ATOMIC P ACKING NUMBER

METALLIC CRYSTAL STRUCTURE

THE FACE-CENTERED CUBIC CRYSTAL STRUCTURE
 FOR THE FCC S TRUCTURE, THE ATOMIC P ACKING FACTOR
IS 0 .7 4 , WHICH IS THE MAXIMUM P ACKING P OS S IBLE FOR
S P HERES ALL HAVING THE S AME DIAMETER. METALS
TYP ICALLY HAVE RELATIVELY LARGE ATOMIC P ACKING
FACTORS TO MAXIMIZE THE S HIELDING P ROVIDED BY THE
FREE ELECTRON CLOUD.

COORDINATION NUMBER & ATOMIC P ACKING NUMBER

METALLIC CRYSTAL STRUCTURE

THE FACE-CENTERED CUBIC CRYSTAL STRUCTURE
METALLIC CRYSTAL STRUCTURE
THE BODY-CENTERED CUBIC CRYSTAL STRUCTURE

ANOTHER COMMON METALLIC CRYS TAL S TRUCTURE ALS O

HAS A CUBIC UNIT CELL WITH ATOMS LOCATED AT ALL
EIGHT CORNERS AND A S INGLE ATOM AT THE CUBE
CENTER.

A COLLECTION OF S P HERES DEP ICTING THIS CRYS TAL

S TRUCTURE IS S HOWN, WHEREAS DIAGRAMS OF BCC
UNIT CELLS WITH THE ATOMS REP RES ENTED BY HARD-
S P HERE AND REDUCED- S P HERE MODELS , RES P ECTIVELY.
METALLIC CRYSTAL STRUCTURE
THE BODY-CENTERED CUBIC CRYSTAL STRUCTURE

CENTER AND CORNER ATOMS TOUCH ONE ANOTHER ALONG

CUBE DIAGONALS , AND UNIT CELL LENGTH A AND ATOMIC
RADIUS R ARE RELATED THROUGH
METALLIC CRYSTAL STRUCTURE
THE BODY-CENTERED CUBIC CRYSTAL STRUCTURE
TWO ATOMS ARE AS S OCIATED WITH EACH BCC UNIT
CELL: THE EQUIVALENT OF ONE ATOM FROM THE EIGHT
CORNERS , EACH OF WHICH IS S HARED AMONG EIGHT-
UNIT CELLS , AND THE S INGLE CENTER ATOM, WHICH IS
WHOLLY CONTAINED WITHIN ITS CELL.

IN ADDITION, CORNER AND CENTER ATOM P OS ITIONS ARE

EQUIVALENT. THE COORDINATION NUMBER FOR THE BCC
CRYS TAL S TRUCTURE IS 8 ; EACH CENTER ATOM HAS AS
NEARES T NEIGHBORS ITS EIGHT CORNER ATOMS .

S INCE THE COORDINATION NUMBER IS LES S FOR BCC

THAN FCC, S O ALS O IS THE ATOMIC P ACKING FACTOR
FOR BCC LOWER— 0 .6 8 VERS US 0 .7 4 .
METALLIC CRYSTAL STRUCTURE
HEXAGONAL CLOSE-PACKED CRYSTAL STRUCTURE
THE TOP AND BOTTOM FACES OF THE UNIT
CELL CONS IS T OF S IX ATOMS THAT FORM
REGULAR HEXAGONS AND S URROUND A
S INGLE ATOM IN THE CENTER.

ANOTHER P LANE THAT P ROVIDES THREE

ADDITIONAL ATOMS TO THE UNIT CELL IS
S ITUATED BETWEEN THE TOP AND BOTTOM
P LANES .

THE ATOMS IN THIS MIDP LANE HAVE AS

NEARES T NEIGHBORS ATOMS IN BOTH OF THE
ADJ ACENT TWO P LANES .
 METALLIC CRYSTAL STRUCTURE
HEXAGONAL CLOSE-PACKED CRYSTAL STRUCTURE
THE EQUIVALENT OF S IX ATOMS IS CONTAINED IN
EACH UNIT CELL; ONE- S IXTH OF EACH OF THE 1 2
TOP AND BOTTOM FACE CORNER ATOMS , ONE-
HALF OF EACH OF THE TWO CENTER FACE ATOMS ,
AND ALL THREE MIDP LANE INTERIOR ATOMS .

THE COORDINATION NUMBER AND THE ATOMIC

P ACKING FACTOR FOR THE HCP CRYS TAL
S TRUCTURE ARE THE S AME AS FOR FCC: 1 2 AND
0 .7 4 , RES P ECTIVELY.
 SAMPLE PROBLEM
CALCULATE THE VOLUME OF AN FCC UNIT CELL IN
TERMS OF THE ATOMIC RADIUS R.
 DENSITY OF METALS
A KNOWLEDGE OF THE CRYS TAL S TRUCTURE OF A
METALLIC S OLID P ERMITS COMP UTATION OF ITS
THEORETICAL DENS ITY THROUGH THE RELATIONS HIP
 SAMPLE PROBLEM
COP P ER HAS AN ATOMIC RADIUS OF 0 .1 2 8 NM, AN
FCC CRYS TAL S TRUCTURE, AND AN ATOMIC WEIGHT
OF 6 3 .5 G/ MOL. COMP UTE ITS THEORETICAL DENS ITY
AND COMP ARE THE ANS WER WITH ITS MEAS URED
DENS ITY.
 CE R AMI C
CR YS TAL
S TR U CTU R E
CERAMIC CRYSTAL STRUCTURE
FOR THOS E CERAMIC MATERIALS FOR WHICH THE
ATOMIC BONDING IS P REDOMINANTLY IONIC, THE
CRYS TAL S TRUCTURES MAY BE THOUGHT OF AS BEING
COMP OS ED OF ELECTRICALLY CHARGED IONS INS TEAD
OF ATOMS . THE METALLIC IONS , OR CATIONS , ARE
P OS ITIVELY CHARGED, BECAUS E THEY HAVE GIVEN UP
THEIR VALENCE ELECTRONS TO THE NONMETALLIC
IONS , OR ANIONS , WHICH ARE NEGATIVELY CHARGED.

TWO CHARACTERIS TICS OF THE COMP ONENT IONS IN

CRYS TALLINE CERAMIC MATERIALS INFLUENCE THE
CRYS TAL S TRUCTURE: THE MAGNITUDE OF THE
ELECTRICAL CHARGE ON EACH OF THE COMP ONENT
IONS , AND THE RELATIVE S IZES OF THE CATIONS AND
ANIONS .
CERAMIC CRYSTAL STRUCTURE
WITH REGARD TO THE FIRS T CHARACTERIS TIC, THE CRYS TAL
MUS T BE ELECTRICALLY NEUTRAL; THAT IS , ALL THE CATION
P OS ITIVE CHARGES MUS T BE BALANCED BY AN EQUAL NUMBER
OF ANION NEGATIVE CHARGES . THE CHEMICAL FORMULA OF A
COMP OUND INDICATES THE RATIO OF CATIONS TO ANIONS , OR
THE COMP OS ITION THAT ACHIEVES THIS CHARGE BALANCE.

THE S ECOND CRITERION INVOLVES THE S IZES OR IONIC RADII OF

THE CATIONS AND ANIONS , RC AND RA, RES P ECTIVELY.
BECAUS E THE METALLIC ELEMENTS GIVE UP ELECTRONS WHEN
IONIZED, CATIONS ARE ORDINARILY S MALLER THAN ANIONS ,
AND, CONS EQUENTLY, THE RATIO RC/ RA IS LES S THAN UNITY.
EACH CATION P REFERS TO HAVE AS MANY NEARES T- NEIGHBOR
ANIONS AS P OS S IBLE. THE ANIONS ALS O DES IRE A MAXIMUM
NUMBER OF CATION NEARES T NEIGHBORS
CERAMIC CRYSTAL STRUCTURE
WITH REGARD TO THE FIRS T CHARACTERIS TIC, THE CRYS TAL
MUS T BE ELECTRICALLY NEUTRAL; THAT IS , ALL THE CATION
P OS ITIVE CHARGES MUS T BE BALANCED BY AN EQUAL NUMBER
OF ANION NEGATIVE CHARGES . THE CHEMICAL FORMULA OF A
COMP OUND INDICATES THE RATIO OF CATIONS TO ANIONS , OR
THE COMP OS ITION THAT ACHIEVES THIS CHARGE BALANCE.

THE S ECOND CRITERION INVOLVES THE S IZES OR IONIC RADII OF

THE CATIONS AND ANIONS , RC AND RA, RES P ECTIVELY.
BECAUS E THE METALLIC ELEMENTS GIVE UP ELECTRONS WHEN
IONIZED, CATIONS ARE ORDINARILY S MALLER THAN ANIONS ,
AND, CONS EQUENTLY, THE RATIO RC/ RA IS LES S THAN UNITY.
EACH CATION P REFERS TO HAVE AS MANY NEARES T- NEIGHBOR
ANIONS AS P OS S IBLE. THE ANIONS ALS O DES IRE A MAXIMUM
NUMBER OF CATION NEARES T NEIGHBORS
CERAMIC CRYSTAL STRUCTURE
S TABLE CERAMIC CRYS TAL S TRUCTURES FORM WHEN THOS E
ANIONS S URROUNDING A CATION ARE ALL IN CONTACT WITH
THAT CATION
CERAMIC CRYSTAL STRUCTURE
THE S IZE OF AN ION WILL DEP END ON S EVERAL FACTORS . ONE
OF THES E IS COORDINATION NUMBER:

• IONIC RADIUS TENDS TO INCREAS E AS THE NUMBER OF

NEARES T- NEIGHBOR IONS OF OP P OS ITE CHARGE INCREAS ES .
• THE CHARGE ON AN ION WILL INFLUENCE ITS RADIUS .
 SAMPLE PROBLEM
S HOW THAT THE MINIMUM CATION- TO- ANION RADIUS
RATIO FOR THE COORDINATION NUMBER 3 IS 0 .1 5 5 .
CERAMIC CRYSTAL STRUCTURE
AX-TYPE CRYSTAL STRUCTURES

THES E ARE OFTEN REFERRED TO AS AX COMP OUNDS ,

WHERE A DENOTES THE CATION AND X THE ANION.

THERE ARE S EVERAL DIFFERENT CRYS TAL

S TRUCTURES FOR AX COMP OUNDS ; EACH IS
NORMALLY NAMED AFTER A COMMON MATERIAL THAT
AS S UMES THE P ARTICULAR S TRUCTURE.
 AX-TYPE CRYSTAL STRUCTURES
R O CK S A L T S T R U CT U R E

P ERHAP S THE MOS T COMMON AX

CRYS TAL S TRUCTURE IS THE S ODIUM
CHLORIDE (NACL), OR ROCK S ALT, TYP E.
THE COORDINATION NUMBER FOR BOTH
CATIONS AND ANIONS IS 6 , AND
THEREFORE THE CATION– ANION RADIUS
RATIO IS BETWEEN AP P ROXIMATELY
0 .4 1 4 AND 0 .7 3 2 .
 AX-TYPE CRYSTAL STRUCTURES
CES I UM CHLORI DE S TRUCTURE
THE COORDINATION NUMBER IS 8 FOR
BOTH ION TYP ES . THE ANIONS ARE
LOCATED AT EACH OF THE CORNERS OF
A CUBE, WHEREAS THE CUBE CENTER IS
A S INGLE CATION. INTERCHANGE OF
ANIONS WITH CATIONS , AND VICE
VERS A, P RODUCES THE S AME CRYS TAL
S TRUCTURE. THIS IS NOT A BCC
CRYS TAL S TRUCTURE BECAUS E IONS OF
TWO DIFFERENT KINDS ARE INVOLVED.
 AX-TYPE CRYSTAL STRUCTURES
ZI NC BLENDE S TRUCTURE

A THIRD AX S TRUCTURE IS ONE IN

WHICH THE COORDINATION NUMBER IS
4; THAT IS , ALL IONS ARE
TETRAHEDRALLY COORDINATED. THIS IS
CALLED THE ZINC BLENDE, OR
S P HALERITE, S TRUCTURE, AFTER THE
MINERALOGICAL TERM FOR ZINC
S ULFIDE (ZNS ).
CERAMIC CRYSTAL STRUCTURE
AMXP - TYPE CRYSTAL STRUCTURES

IF THE CHARGES ON THE

CATIONS AND ANIONS ARE NOT
THE S AME, A COMP OUND CAN
EXIS T WITH THE CHEMICAL
FORMULA AMXP , WHERE M
AND/ OR P ≠ 1 .

AN EXAMP LE WOULD BE AX2 ,

FOR WHICH A COMMON CRYS TAL
S TRUCTURE IS FOUND IN
FLUORITE (CAF2 ).
 CERAMIC CRYSTAL STRUCTURE
AMBNXP - TYPE CRYSTAL STRUCTURES
IT IS ALS O P OS S IBLE FOR
CERAMIC COMP OUNDS TO
HAVE MORE THAN ONE TYP E
OF CATION; FOR TWO TYP ES
OF CATIONS (REP RES ENTED
BY A AND B) , THEIR
CHEMICAL FORMULA MAY BE
DES IGNATED AS AMBNXP

BARIUM TITANATE ( BATIO3 ) ,

HAVING BOTH BA2 + AND TI4 +
CATIONS , FALLS INTO THIS
CLAS S IFICATION.
 SAMPLE PROBLEM
ON THE BAS IS OF IONIC RADII, WHAT CRYS TAL
S TRUCTURE WOULD YOU P REDICT FOR FEO?
 DENSITY OF CERAMICS
IT IS P OS S IBLE TO COMP UTE THE THEORETICAL
DENS ITY OF A CRYS TALLINE CERAMIC MATERIAL FROM
UNIT CELL DATA IN A MANNER S IMILAR TO THAT
DES CRIBED IN METALS . IN THIS CAS E THE DENS ITY
MAY BE DETERMINED US ING A MODIFIED FORM OF
EQUATION FORM METALS , AS FOLLOWS :
 SAMPLE PROBLEM
ON THE BAS IS OF CRYS TAL S TRUCTURE, COMP UTE THE
THEORETICAL DENS ITY FOR S ODIUM CHLORIDE. HOW
DOES THIS COMP ARE WITH ITS MEAS URED DENS ITY?
POLYMORPHISM AND ALLOTROPY
S OME METALS , AS WELL AS NONMETALS , MAY
HAVE MORE THAN ONE CRYS TAL S TRUCTURE, A
P HENOMENON KNOWN AS P OLYMORP HIS M.

WHEN FOUND IN ELEMENTAL S OLIDS , THE

CONDITION IS OFTEN TERMED ALLOTROP Y.

THE P REVAILING CRYS TAL S TRUCTURE DEP ENDS

ON BOTH THE TEMP ERATURE AND THE
EXTERNAL P RES S URE.
CR YS TALLI N I TY AN D
N ON - CR YS TALLI N I TY
FOR A CRYSTALLINE SOLID, WHEN THE PERIODIC AND
REPEATED ARRANGEMENT OF ATOMS IS PERFECT OR
EXTENDS THROUGHOUT THE ENTIRETY OF THE SPECIMEN
WITHOUT INTERRUPTION, THE RESULT IS A S INGLE CRYS TAL.
ALL UNIT CELLS INTERLOCK IN THE SAME WAY AND HAVE THE
SAME ORIENTATION.

MOST CRYSTALLINE SOLIDS ARE COMPOSED OF A

COLLECTION OF MANY SMALL CRYSTALS OR GRAINS; SUCH
MATERIALS ARE TERMED POLYCRYS TALLINE. VARIOUS
STAGES IN THE .SOLIDIFICATION OF A POLYCRYSTALLINE
SPECIMEN