MSE3094 (Staley) Test #1 SOLUTIONS

February 13, 2011

This test was an open book and notes take-home assignment, using several different versions of the same fundamental questions. 1) [20 points] Consider a metal that is known to have the following physical properties: density [] = X, electronegativity [EN] = Y, atomic radius [r] = Z, atomic mass [A] = U g/mol, and possible valence of V. Single crystals of this metal exhibit an/isotropic mechanical properties. From this information determine (a) the unit cell volume (in cubic nm) and crystal structure of the metal, (b) whether it is likely to mix with lead [Pb] and if so as what kind of alloy (complete substitutional, incomplete substitutional, or interstitial), and (c) draw the most closely-packed planar arrangement of atoms that would apply for this metal, and indicate on that figure what type of direction dislocations would move most easily in. SOLUTION STRATEGY
(A) UNIT CELL FROM DENSITY FORMULA. MUST FIND (OR CONFIRM) STRUCTURE BY TRIAL & ERROR, + INFO ON ISOTROPIC/ANISOTROPIC MECHANICAL PROPERTIES. (B) CHECK HUME-ROTHERY RULES, DETERMINE SUBSTITUTIONAL ALLOYING. USE LARGE SIZE DIFFERENCE TO PREDICT INTERSTITIAL ALLOYING. (C) CP PLANES ARE RESULT OF XTL STRUCTURE. FAVORED DISLOC MOTION ON PLANE IS LOWEST ENERGY OPTION (DIRECTIONS ON WHICH ATOMS TOUCH).
A) X= 4.403 g/cm , Y=1.2, Z=0.181 nm, U=88.91 g/mol, V=+3 3 a. VC=0.2013 nm , HCP structure determinable from density formula and anisotropic character. b. Follows 1 of 4 alloying rules (radius). Incomplete substitutional c. Top/Bottom Face Plane, along edge directions. 3 B) X= 22.44 g/cm , Y=2.2, Z=0.136 nm, U=192.21 g/mol, V=+2,+3, or +4 3 a. VC=0.0569 nm , FCC structure determinable from density formula and isotropic character. b. Follows 2 of 4 alloying rules (charge & structure). Incomplete substitutional c. Body diagonal Plane, along face diagonal directions. 3 C) X= 3.164 g/cm , Y=1.3, Z=0.161 nm, U=44.96 g/mol, V=+3 3 a. VC=0.1416 nm , HCP structure determinable from density formula and anisotropic character. b. Follows 1 of 4 alloying rules (radius). Incomplete substitutional c. Top/Bottom Face Plane, along edge directions. 3 D) X= 16.69 g/cm , Y=1.5, Z=0.143 nm, U=180.95 g/mol, V=+3, +4, or +5 3 a. VC=0.0360 nm , BCC structure determinable from density formula and isotropic character. b. Follows 1 of 4 alloying rules (EN). Incomplete substitutional c. Face diagonal Plane, along body diagonal directions. 3 E) X= 2.590 g/cm , Y=1.0, Z=0.215 nm, U=87.62 g/mol, V=+2 3 a. VC=0.2249 nm , FCC structure determinable from density formula and isotropic character. b. Follows 2 of 4 alloying rules (charge & structure). Incomplete substitutional c. Body diagonal Plane, along face diagonal directions. 3 F) X= 1.521 g/cm , Y=0.8, Z=0.2475 nm, U=85.47 g/mol, V=+1 3 a. VC=0.1867 nm , BCC structure determinable from density formula and isotropic character. b. Follows 0 of 4 alloying rules, but too big for interstitial. No mixing. c. Face diagonal Plane, along body diagonal directions.
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2) [20 points] The chart below shows axes allowing you to plot natural logarithm of different defect concentrations (ND) as a function of the inverse temperature (1/T), based on the Arrhenius-type behavior that applies for formation of all types of defects. On this figure, qualitatively (i.e., w/o numbers) compare relative concentration vs. temperature relationships you would expect to apply for TWO DIFFERENT GIVEN OPTIONS.

SOLUTION STRATEGY A) PLOTS SHOULD FOLLOW N(D)=N exp(-Q/RT) BEHAVIOR, THEREFORE ALL PLOTS SHOULD LOOK LIKE ABOVE. B) ALL OF THE DIFFERENT OPTIONS SHOULD HAVE PREDICTABLY DIFFT ENERGIES BUT EQUIVALENT INTERCEPTS. C) RELATIVE POSITIONS OF CURVES FOLLOW (SLOPES, INTERCEPTS) FOLLOW FROM (A)&(B). ENERGY COMPARISONS FOR THE GIVEN PAIRS OF DEFECT TYPES Q(Nb in Fe) > Q(Cr in Fe) Q(C in Os) > Q(C in Ti) Q(Frenkel) > Q(Schottky) Q(Mo in Fe) > Q(Cr in V) Q(B in Fe) > Q(C in Fe) Q(self-interstitial) > Q(vacancy)

3) [20 points] Consider the four proposed polymers listed below, described in terms of their primary and secondary structures. Repeat units and abbreviations for polymer names are given in Appendix D. (a) Which of these structures would actually be possible? Briefly explain your reasoning for all four cases. (b) Draw one of the structures that could actually happen, showing all of the listed features in the same figure by using multiple repeat units arranged together in the appropriate way. SOLUTION STRATEGY (A) DETERMINE POSSIBLE STRUCTURES FROM FEATURES OF CHAIN CONFIGURATION, ISOMERISM, & XTLLIZATION FOR DIFFERENT MERS (B) DRAWING SHOULD LOOK LIKE SECONDARY STRUCTURE FIGS IN CH.4. NEED NOT DRAW LEVEL OF CRYSTALLINITY (EXTRA CREDIT).
STRUCTURES THAT ARE POSSIBLE Partly-crystalline isotactic branched polyvinyl fluoride Networked amorphous melamine. Crosslinked amorphous trans-polyisoprene Amorphous networked phenyl-formalydehyde Amorphous branched atactic poly(vinyl acetate) Partly-crystalline branched isotactic poly(acrylonitrile) Mostly-crystalline linear isotactic trans-polyethylene Partly-crystalline linear trans-poly(butadiene) Partly-crystalline alternating polyethylene-polystyrene copolymer Mostly-crystalline linear syndiotactic polypropylene Amorphous isotactic branched PMMA (BUT UNLIKELY!) STRUCTURES THAT ARE IMPOSSIBLE (WITH REASONS) Partly-crystalline atactic polyisobutylene (cant be atactic) Amorphous isotactic linear PPO (cant be isotactic) Partly-crystalline branched cis-PTFE (cant be cis) Networked amorphous polyacrylonitrile (cant network) Mostly crystalline linear isotactic polyisobutylene (cant be isotactic) Amorphous networked cis-polychloroprene (cant network) Partly-crystalline linear PET-PEEK random copolymer (cant crystallize) Amorphous linear isotactic polyvinyl alcohol (wont be amorphous) Amorphous crosslinked trans-polyisoprene (cant be trans) Amorphous linear cis-poly(styrene) (cant be cis) Mostly-crystalline branched atactic poly(vinyl chloride) (wont crystallize) Partly-crystalline crosslinked syndiotactic polybutadiene (cant be syndio-) Mostly-crystalline linear trans-PMMA (cant be trans)

4) [20 points] Combinations of X with Y and Z with W will form compounds whose crystal structures can be predicted using the information given below. Using this data, determine (a) predictions for the cation and anion coordination numbers for these two structures; (b) whether there are any reasons why these predictions might not really apply; and (c) whether either of these compounds might have special ease or difficulty in forming anion Frenkel defects, cation Frenkel defects, or Schottky defects (briefly explain your reasoning).
SOLUTION STRATEGY GIVEN CHARGES AND RADII OF IONS (A) PREDICT CN(+) & CN(-) FROM RADIUS RATIO & STOICHIOMETRY. NON-1:1 COMPOUNDS WILL HAVE PREDICTABLY DIFFERENT VALUES FOR THE TWO CNS. (B) CHECK %IONICITY TO SEE IF IONIC PREDICTION SHOULD REALLY APPLY. (C) ANION FRENKEL EASY IF ANION SIZE < CATION, OR ESPECIALLY FOR OPEN ANION SITES; OTHERWISE DIFFICULT. CATION FRENKEL EASY IF CATION SIZE < ANION, OR ESPECIALLY FOR OPEN CATION SITES; OTHERWISE DIFFICULT. SCHOTTKY DEFECTS HARDER FOR NON 1:1 COMPOUNDS. NONE ARE POSSIBLE IF THE COMPOUND IS COVALENT RATHER THAN IONIC.
Compound Na2S Radius ratio .554 CN+ 3 CN6 %ionic & effect 47% Problem 93% OK 82% OK 22% Problem 91% Okay 18% Problem 59% Likely OK 15% Problem 86% OK 55% Likely OK 15% Problem 22% Problem Cation Frenkel Anion Frenkel Easy (empty sites) Easy (small anion) Schottky Difficult (3 atoms)

CsF RaO

.78 .92

8 8

8 8

TiC

.265

Covalent wouldnt do any (no special character otherwise) Easy Easy Difficult (empty sites) (small anion) (3 atoms) Covalent wouldnt do any (no special character otherwise) Easy Difficult (empty (5 atoms) sites) Covalent wouldnt do any (no special character otherwise) Easy (small anion, empty sites) Difficult (3 atoms)

RaF2 MgTe

0.88 .34

8 4

4 4

Cr2O3 CdS

.45 .52

6 6

4 6

Cs2O (TYPO IN PROBLEM) CaBr2 CdS

.82

4 (8 ok) 6 6

.51 .52

3 6

Easy Difficult (empty sites) (3 atoms) Covalent wouldnt do any (no special character otherwise) Covalent wouldnt do any (but missing sites for cation Frenkel, & 3 atoms in Schottky)

MnI2

.31

5) [20 points] Consider the solid materials listed below. For each of these, list all of the specific types of primary & secondary bonding that you think will significantly contribute to the materials behavior. Show any work/reasoning involved in these determinations. SOLUTION STRATEGY SIMPLY NOTE EXPECTED METALLIC, IONIC, COVALENT, INDUCED DIPOLE, PERMANENT DIPOLE, & HYDROGEN BONDING. Version A Matl A Fe-Mo Metallic Matl B CH4 Covalent, Induced dipole Matl C B-C Covalent, (perm dipole?) GeO2 Covalent Matl D Nylon Covalent, H bond

C D E F

Ca-S Ionic & Covalent Ti-Mn Metallic BaF2 Ionic Cu-Ag Metallic KBr Ionic (some Covalent

Mg-Pb Metallic & Ionic Br2 Covalent, Induced dipole K-Cd Metallic & ionic C6H6 Covalent Induced dipole Ca-Zn Metallic & ionic

Fe-C Covalent Ionic InAs Covalent Cr2O3 Covalent Ionic Cu2S Covalent

PMMA Covalent, H bond PVA Covalent, H bond Polyimide Covalent (H bond?) Polycarbonate Covalent, H bond PVC Covalent & perm dipole (H bond?)