Passivity of titanium with special reference to hydrochloric acid solutions

126 Pages·010.849 MB·English

by  Schlain, David

David Schlain, Ph.D., 1951
Title of Thesis: Passivity of Titanium with Special
Reference to Hydrochloric Acid Solution
Thesis and Abstract Approved
Associate Professor,
Dept, of Chem. Png.
A Civil O' VLEDG-EIT PITT $
rmh-e author Pishes to express his sincere ug.orGciatian
to Dr. Joseph. P. Dmatko for his vein stole sue pest ions and
constant encouragement throughout this investimation and. to
Dr. v’ilbert J. TTuf£ for his interest and advice. is .also
~T-e
grateful to Dr. Paul V. • Ambrose, Chief of Diner a Is Technology
Division, "Region Dili, IT.C'# bureau of Dines and to Dr. J. R. I onp ,
formerly Chief of Physical metallurgy Section, U.C. bureau
of ?'±nos, College dark, Maryland. for their support and h o le
in carrying out this pork. Aclmour lodgements ere also due the
various members of the staff of the bureau of Dines for
their assistance.
PASSIVITY OP TITANIUM WITH SPECIAL REFERENCE
TO HYDROCHLORIC ACID SOLUTIONS
by
David Schlain
Thesis submitted to the Faculty of the
Graduate School of the University of Marvla&d
ia partial fulfillment of the requirements for
the degree of Doctor of* Philosophy
UMI Number: DP71090
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TABLE 01- CONTENTS
Page
XNTKODUCTION ........... 1
DEVELOPMENT OF METALLIC TITANIUM . . . . . . . . 3
PROPERTIES Of' TITANIUM METAL ............... 8
come Chemical Properties 8
Corrosion Properties . . . . . 10
Physical Properties ............... . 16
POTENTIAL USES FOR TITANIUM ....... 19
A LEW ELEMENTS OF COHHOSION ......... . 22
PASSIVITY ............. . 29
Various Types ........................ 29
Theories of Passivity ............. . 36
ELECTLOLE POTENTIALS . . . . . . . . . . . . . . 42A
Definition 42A
Measurement . . . . . . . . . . . . . . . * 42B
Significance of Electrode Potential . . . . . 42F
PRESENT INVESTIGATION ......... ........... . 43
PRELIMINARY EXPERIMENTAL WORK ............... 44
Single Electrode Potentials of Titanium in
Various Electrolytes • . 45
single Electrode Potentials of a Few Common
Metals In Three Percent Sodium Chloride and
In 1.1 N Sulfuric A c i d .................. 51
Galvanic Couples in Three Percent Sodium
Chloride Solution • • • • • • ....... * . 54
PASSIVITY OP TITANIUM IN HYDROCHLORIC ACIP,
ELECTRODE POTENTIAL MEASUREMENTS . ......... 62
General Method 62
Effect of Air .................. 64
Exploratory Experiments on the Effect of I.;is-
solved Metals ........................ 69
Effect of Various 1 issolved Metals....... . 72
Effect of Copper In Various Concentrations of
Hydrochloric Acid ............. . 76
Effect of Various Concentrations of Copper t # .
PASSIVITY 01 TITANIUM IN HYDROCHLORIC ACID, COR­
ROSION -TESTS..................................
ADDITIONAL EXPERIMENTS ON PASSIVITY OP TITANIUM . .
Stagnant Solutions of Hy urochloric Acid . . .
Effect of Copper Ions in Sulfuric Acid Solution
Hydrogen Atmosphere .......................
Melted Titanium . .........................
EFFECT OF PASSIVITY ON GALVANIC CORROSION .......
CONCLUSIONS . .................* . .
SUMMARY AND
REFERENCES ......... .....................
LIST OF TABLES
Tabid
1* Proparties of Metallic Titanium * * * * * * * *
2* Summary of Single Electrode Potentials of
Titanium in Various Electrolytes at Hoorn
Temperature
# * » # « « * • • * # * • « * # • •
2A Single Electrode Potentials of Titanium in
Various Electrolytes at Boos Temperature# * * ♦
3* Single Electrode Potentials of Metals in 2$
Sodium Cnloride Solution# # # *
4 Single Electrode Potentials of Metals in 1*1 n
*
sulfuric Acid solution#
* * # # # # # # # . # # 1#
5, Galvanic Couple Tests, Titanium and Other
Metals in 3T" Sodium Chloride Solution, Air* * »
6# Galvanic Couple Tests, Ti**Al, in 3$ Sodium
Chloride Solution * « * • * » • # « • * » » * •
7* Galvanic Couple Tests, Ti-Mg, in 3^ Sodium
Chloride Solution, Linear Velocity 75 feet
per Minute • • • • # * « • * * » • * * « * • * •
o
O • Electrode Potentials of Titanium in Hydrochloric
ix c id a # * # * # # * # * # # # * # * # # * # # ' #
D * Electrode Potentials of Titanium in 1 H HC1
Containing 0*003 mole of Dissolved Metals
per liter, Helium Atmosphere, Titanium
Polished* . • • * * * • * » • « « » * * * * * *
10 Electrode Potentials of Titanium in 1 N HOI
*
Containing 0*003 mol© of Dissolved Metals per
liter, Air Atmosphere, Titanium Polished# * * *
lit .Electrode Potentials of Titanium in 1 N KC1
Containing 0*003 mole of Dissolved Metals per
liter, Air or Helium Atmosphere, Titanium
Unpolished* + * • * • • » « * « • * • * » • * •
12# Electrode Potentials of Titanium Specimen® In
HC1 Solutions Containing 200 milligrams Copper
per liter, ndlum $ « # * » $ * • * # * « * * #
fable Peg©
13* Electrode Potentials of Titanium Specimens
in I1CX Solutions Containing 200 milligrams
Copper per liter. Air * # * * # # # * * ♦ # # 80
14* Effect of Copper Concentration in 1 1 HCl*
Helium sad Air* * * . * * * » • * « * » * » » 84
15* Effect of Copper Concentration in 5 If HCl*
Helium and Air# » • • « * # • * « • » • • # * 85
16* Effect of Copper Concentration in 10 N HCl*
Helium and Air* # « » • » « • • * * * * * # # 86
17# Effect of Copper on Corrosion of Titanium in
HCl Solutions, Air* * * • • « # » # • • « * » 89
18# Effect of Copper on Corrosion ©f titanium in
HCl Solutions, Helium * • « # * » » * * • * * 90
19# Passivity of Titanium in Stagnant Hydrochloric
Acid Solutions * • * • » • • * « * * # * • # » 93
20* Galvanic Couple Experiments, Titanid»*Copper« 99
21# Galvanic Couple Experiment a f Tit&niuia-Copper* 100
22# Passivity and Corrosion of Titanium * * * # * 104
LIST OF FIGURES
Figure Pag©
1 Current in Corrosion Cell • • » » • « « » 26
2 Effect of Inhibitors on Corrosion « • - • 33
3 Electrode Potential of Metal .......... 42H
4 Electrode Potentials of Titanium versus
Immersion Time ............... • • • 46
5 Electrode Potentials of Titanium in Pure
Hydrochloric Acid Solutions ......... 66
6 Electrode Potentials of Titanium In
Hydrochloric Acid, 200 milligrams Copper
per liter, Air ...................... * 81
7 Electrode Potentials of Titanium in
Hydrochloric Acid, 200 milligrams Copper
per liter, Helium » 82
INTRODUCTION
According to Clark®, titanium makes up 0.62 percent of
the lithosphere and is the tenth moat abundant element.
Only three structural metals, aluminum, iron, and magnesium
are more abundant than titanium and it Is more abundant than
copper, lead, and zinc. Titanium is widely dispersed in the
earth's crust and is generally present In igneous rocks and
in the sedimentary material derived from them. Out of 800
igneous rocks analyzed in the laboratories of the united
States Geological Survey, 7^4 contained titanium. It occurs
most often as tItacit®, ilsaenite, rutile and perofsteite and
Goes not occur free. The chief commercial mineral, ilmonite^
{FeTiQj), is found in many widely distributed deposits
amenable to concentration, large domestic deposits are
available in York, Wyoming Virginia, Arkansas, and
Hew ,
Florida. Substantial deposits of rutlie (TiOg) have been
located in Virginia.
The use of titanium oxide in pigments is several decades
old and has Increased in recent years.*7 a new development
is the electric smelting of ilmenite to produce pig iron and
a. slag with high, recoverable titanium dioxide content. 5^.
Titanium, compounds also have minor industrial applica-
tiorig~>3$ 52and the tetrachloride has been used as a military
smoke screen. But in spite of the availability of titanium
compounds, the utilisation of the metal as a structural
material is Just beginning. The high melting point of