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Scholars' Mine Scholars' Mine
Masters Theses Student Theses and Dissertations
1949
A preliminary investigation of the titanium-copper equilibrium A preliminary investigation of the titanium-copper equilibrium
system system
August Robert Savu
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Recommended Citation Recommended Citation Savu, August Robert, "A preliminary investigation of the titanium-copper equilibrium system" (1949). Masters Theses. 4838. https://scholarsmine.mst.edu/masters_theses/4838
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A PRELD1INARY H.JVESTIGATION
OF THE TITANIUM-COPPER
EQUILIBRIUM
SYSTUi
BY
AUGUST SAVU
A
THESIS
submitted to the faculty of the
SCHOOL OF MINES AND ALWRGY OF THE UNIVERSITY OF ISSOURI
in partial fulfillment of the work required for the
Degree of
HASTER OF SCIENCE Ii' }ffiTALllJRGICAL ENGINEERING
Rolla, Missouri
1949
Approved by_---J.:.,.wfl~~~._7.!:~~;!P~Irfl':"'~-:"I=.;::;.;;..'-..----~~:EPPeJ:SheunerProfessor
of Metallurgical Engineering
ACKNOWLEDGEMENT
To Dr. Daniel S. Eppelsheimer and Dr. Albert W. Schlechten
of the Metallurgical Engineering Department of the Missouri School
of Mines and Metallurgy, I wish to express my sincere appreciation
and gratitude for the knowledge and training they have offered to
me through their informative lectures and personal guidance.
ii
TABLE QI CONTENTS
PageAcknowledgement ••••••••••••••••••••••••••••••••• ii
List of Illustrations........................... iv
List of Tables•••••••••••••••••••••••••••••••••• vii
Introduction.................................... 1
Review of Literature............................ 3
A Theoretical Stuqy............................. 5
Preparation of Alloys........................... 8
Chemical Ana~ais••••••••••••••••••••••••••••••• 18
X-Ray AnalYsis•••••••••••••••••••••••••••••••••• 21
Metallographic Technique........................ 23
Specific Gravity Analysis....................... 23
Interpretation of X-Ray Results andCorrelation with Microstructures•••••••••••••• 24
Specific Gravity Stu~.......................... 28
Conclusions••••••••••••••••••••••••••••••••••••• 65
Summa~••••••••••••••••••••••••••••••••••••••••• 66
Bibliography•••••••••••••••••••••••••••••••••••• 67
Vita•••••••••••••••••••••••••••••••••••••.•••••• 68
iii
Fig. Page
iv
A Copper-Titanium Equilbrium Diagram 4a
B Photograph of a 20 Kilowatt Ajax ConverterUnit for the High Frequency InductionFurnace 11
C Photogra.ph of Refractory Materials Usedfor Melting Alloys 12
D Photograph of Apparatus Used 1.3
E Photograph of Apparatus Used 1.3
F Photograph of the Complete Arrangement ofApparatus Used for elting Titanium-Copper Alloys 14
G Chemical Analysis Flowsheet for the Deter-mination of %Ti in Ti-Cu Alloys 19
H Chemical Analysis Flowaheet for the Deter-mination of %Cu in Ti-Cu Alloys 20
1 Microphotometer Tracing of Powder Patternof 28% Ti - 72% Cu Alloy 30
2 Microphotometer Tracing of Powder Patternof 30% Ti - 70% Cu Alloy 31
.3 Microphotometer Tracing of Powder Patternof 40% Ti - 60% Cu Alloy 32
4 Microphotometer Tracing of PoWder Patternof 50% Ti - 50% Cu Alloy 33
5 Microphotometer Tracing of Powder Patternof 60% Ti - 40% Cu Alloy 34
6 Microphotometer Tracing of Powder Patternof 70% Ti - 30% Cu Alloy 35
7 Microphotometer Tracing. of Powder Patternof 80% Ti - 20% Cu Alloy .36
8 Microphotometer Tracing of Powder Patternof 90% Ti - 10% Cu Alloy 37
9 Microphotometer Tracing of Powder Patternof 95% Ti - 5% Cu Alloy 38
g.§! Q.E ILLUSTRATIONS (CaNT I D)
Fig. Page
10 Microphotometer Tracing of Powder Patternof 99.99% Cu 39
II Microphotometer Tracing of Powder Patternof 99.5% Ti 40
Graph #1 Specific Volume As a Function ofComposition 29
12 .Photomicrograph of Ti-Cu AlloY', 28 wt. %Ti,As cast, tched, lOOX 50
13 Photomicrograph of Ti-Cu Alloy, 28 wt. %Ti,Annealed at 850°C for 48 hrs., Etched, lOOX 51
14 Photomicrograph of Ti-Cu Alloy, 28 lit. %Ti,Annealed at 850°C for 48 hra., Etched, 500X 51
15 Photomicrograph of Ti-Cu lloy, 30 wt. ~ Ti,As cast, Etched, 100X 52
16 Photomicrograph of Ti-Cu Alloy, 30 wt. %Ti,As cast, Etched, sOOX 52
17 Photomicrograph of Ti-Cu Alloy, 30 wt. %Ti,Annealed at 850°C for 48 hra., Etched, lOOX 53
18 Photomicrograph of Ti-Cu Alloy, 30 y,"t. %Ti,Annealed at 850°0 for 48 hra., Etched, 500X 53
19 Photomicrograph of Ti-Cu Alloy, 40 wt. %Ti,As cast, Etched, lOOX 54
20 Photomicrograph of Ti-Cu Alloy, 40 wt. %Ti,As cast, Etched, 500X 54
21 Photomicrograph of Ti-Cu Alloy, 40 wt. %Ti,Annealed at 850°C for 48 Urs., Etched, 100l: 55
22 Photomicrograph of Ti-Cu Alloy, 40 wt. %Ti,Annealed at 850°C for 48 hra., Etched, 500X 55
23 Photomicrograph of Ti-Cu Alloy, 50 wt. %Ti,As cast, ~ chad, 100x 56
24 Photomicrograph of Ti-Cu Alloy, 50 wt. %Ti,Annealed at 900°C for 48 hra., Etched, 100X 57
25 Photomicrograph of Ti-Cu Alloy, 50 wt. Ti,Annealed at 900°C for 48 hra., Etched, 500x 57
v
LIST OF ILLUSTRATIONS (CONTI D)
Fig. Page
26 Photomicrograph of Ti-Cu Alloy, 60 wt. %Ti,As cast, "tched, lOOX 58
27 Photomicrograph of Ti-Cu Alloy, 60 wt. %Ti,Annealed at 950°C for 48 hra., tched, lOOX 59
28 Photomicrograph of Ti-Cu Alloy, 60 wt. Ti,Annealed at 950°C for 48 hra., Etched, 500 X 59
29 Photomicrograph of Ti-Cu Alloy, 70 wt. %Ti,s cast, tched, lOOX 60
30 Photomicrograph of Ti-Cu Alloy, 70 wt. %Ti,Aa cast, etched, 500X 60
31 Photomicrograph of Ti-Cu Alloy, 70 wt. %Ti,Annealed at 10000 C for 48 hra., tched, 100X 61
32 Photomicrograph of Ti-Cu Alloy, 70 wt. Ti,Annealed at looooC for 48 hra., Etched, 500X 61
33 Photomicrograph of Ti-Cu Alloy, 80 m. %Ti,Annealed at 11000C for 48 hrs., Etched, lOOX 62
34 Photomicrograph of Ti-Cu Alloy, 80 wt. %Ti,Annealed at 11000C for 48 hra., Etched, 500X 62
35 Photomicrograph of Ti-Cu Alloy, 90 wt. %Ti,Annealed at 12000C for 48 hrs., t.ched, 100X 63
36 Photomicrograph of Ti-Cu Alloy, 90 wt. %Ti,Annealed at 12000 C for 48 hra., Etched, 500X 63
37 Photomicrograph of Ti-Cu Alloy, 95 wt. %Ti,Annealed at 12500C for 48 hra., Etched, lOOX 64
38 Photomicrograph of Ti-Cu Alloy, 95 wt. %Ti,Annealed at 12500 C for 48 hra., Etched, 500X 64
vi
LIST OF TABLES
Table Page
I Some Physical Constants of Titanium andCopper 9
II Analysis of Granular Titanium 9
III Data for Induction Furnace Preparationof Titanium-Copper Alloys 16
IV Heat Treating Data for the PreparedTitanium-Copper Allo~B 17
V Results of Chemical Analy:ses andPhysical Analysis 22
VI X-Ray Diffraction Data 41
VII X-Ray Diffraction Data for Titanium-Copper Alloys 44
VIII d-Values Assigned to Specific Phases 47
IX Knoop Hardness Numbers Assigned toSpecific Phases 48
X Specific Gravity Data 49
vii
1
INTRODJCTION
Titanium has been used commercially as a doxidizer,
scavenger, hardener, and grain refiner. Its use in the metallic
state for purposes other than those mentioned seems to be wholly
lacking. It is found in great abundance as contained by the
mineral rutile (Ti02) therefore it would seem that there would
be a greater use of this element. It has been estimated
that the occurrence of titanium in nature amounts from 0.3 to
0.45 p rc nt of the earth's crust. It ranks tenth in the list
of the most abundant elements.
The element titanium has a high de ree of chemical activity
at room temperature when in a finely divided condition. In the
massive state this activity is only exhibited at high temperatures.
The pOWdered metal is highly pyrophoric. Titanium forms quite
stable sulphides and carbides, although these are subject to
oxidation at high temperatures. It also forms nitrides. Titanium
being a transitional element forms hydrides with hydrogen which
are stable at ordinary temperatures, but which dissociate at red
heat liberating the hydrogen and leaving the metallic titanium in
a very active state.
(1) F. S. Wartman, U. S. Bureau of nee Confer nee on MetallurgicalResearch, 1940.
2
Alloys are formed with such meta.ls as aluminum, manganese,
(2)iron, cobalt, nickel, copper, zinc, tin and gallium. F. S. Wartman
states that titanium in a.lloying with the other elements tends to
form intenneta1lic compounds that are insoluble in the solid state
or if solid solutions a.re formed the tendency is toward those
which are stable only in the liquid state. Such conditions favor
the formation of brittle alloys of little structural value.
(2) F. S. Wartman, U. S. Bureau of Mines Conference on MetallurgicalResearch, 1940.
REVIEW OF LITERA'IURE
The properties of titanium. are of such a nature that a short
review of what has been found is considered worthy of mention.
W. Kroll (3) found that oxygen-free titanium in a rolled state had
a hardness of Rockwell "C" 20. After melting it in a 99.6% argon
atmosphere the hardness rose to a Rockwell "G" 35 due to the
absorption of small quantities of oxygen and nitrogen. The metal
titanium 1s reported to absorb considerable quantities of both
gases with the probability of suboxide a.nd nitride formation.
These absorbed gases can not be removed by remelting in either
hydrOgen or a vacuum nor ca.n they be removed by deoxidizing with
carbon and thorium. Carbon, like oxygen and nitrogen, makes the
metal very hard and brittle. Titanium has a mean coefficient of
expansion of 97.9 x 10-7 between OOC and 850o
C. It undergoes an
allotropic transformation at 880°C from a hexagonal to a cubic
symmetry. J. D. Fast(4) established the melting point of titanium
oat 1725 C. He also observed the allotropic transformation at
o880 C and noted that the metal titanium absorbed oxygen and nitrogen
upon heating and became brittle as a result.
F. Laves and H. J. Wallbaum( 5) reported that T1Cu) belongs to
the deformed hexagonal type; CuTi was non-existent; CuTi2 was an
isomorphous compound possessing a race-centered cubic structure with
96 atoms per cell.
3
OJ w. Kroll, Metallwirtschart, Vol. 18, (4), 1939, p. 77 - 80.
(4) J. D. Fast, Zeitung Anorg. Chem., Vol. 241 (1), 1939, p. 42 - 56.
(5) F. Laves and H. J. Wallbaum, Naturwlss., Vol. 27, 1939, p. 674 -675.
Data on the Copper-Titanium equilibrium diagram is quite
incomplete. W. Kroll(6) determined the Cu-Ti eutectic composition
to be 24$ Ti and the melting temperature of the eutectic to be 900oC.(7)
F. R. Hensel and E. I. Larsen constructed a tentative equilibrium
diagram from the cooling curves obtained from a thermal analysis.
This is reproduced in Fig. A. Their X-Ray investigations on Cu-Ti
alloys ranging from 0.83% - 27.27% Ti showed that lines belonging
to a face-centered cube were the strongest on all diffraction films.
The 1 ttice constant increased from 3.60 A for pure copper to 3.65 A
for 20.53% titanium alloy. A solid solution of titanium in copper
wal5 indicated with the same space lattice as that of pure copper.
With increasing amounts of titanium new lines corresponded mostly
to pure titanium with the first alloy to show these new lines con
taining 7.72% titanium. Not all lines could be matched with the
titanium structure. Therefore the extra lines may have represented
a copper-titanium compound.
No work has been done on the Ti-Cu equilibrium diagram past
28% Ti and it is hoped that the present research will perhaps
throw a faint light on the possibilities of these alloys.
(6) W. Kroll, Zeit chrift fur Metallkunde, Vol. 23 (33), 1931.
(7) F. R. Hensel and E. I. Larsen, A. I. • M. E., Tech. Pub~.
432, 1931.
4
1000(l
:""'ta • TI (01 T;. Cu CO<l'\DOu~d)
I I
"
4a
200 - ,I
040~ T1Q'!L-....J-_~--'--~--'--~ ........--='=-..-L_"'=---'---;:~~o 5 10 15 20 25 30 'Yo
Titonlum %
Fi).:,A-CllJI~l~r THalllUI11 E uilibriuJI1 l)inJ,{f:un-JlI'Jlstl alld l-orsetl.
A THEORETICAL sruDY- -OF .QEcl! ALWYS
The extent of the solid solubility of one element in another
is generally conceded to depend on several factors which include:
(1) the relative lattice types and the atomic sizes of the solute
and the solvent metals; (2) the chemical affinity of one for the
other; (3) the relative valency effect. Titanium occurs in two
allotropic forms, the alpha modification at room temperature is
hexagonal close packed and the beta fo~ is body-centered cubic at
8BOoC. Copper ls, of course, face-centered cubic. Thus a dissimilar
crystal. structure exists between the two elements. The atom size
factor consideration shows titanium and copper to differ by about
13% 1n their atomic radii (8) so that this points toward a border-
line condition for solubility. Titanium appears on the left side
of the first long period of the periodic table included in the
group of the so-called transition elements and which are considered
electropositive. Copper also occurs in the first long period of
the periodic table but is to the right of titanium and therefore
electronegative with respect to it. Thus a difference exists in
the two elements as in regards to their chemical affinity since the
more electropositive the solute and the more electronegative the
solvent, or vice versa, the greater is the tendency to restrict
solid solubility and to form intermetallic compound.
(8) L. Pauling, "Journal of Amer. Chem. Soc.", Vol. 69 #3, 1947,p.542.
5
6
A metal of lower valency tends to dissolve a metal. of higher
valency more readily than vice versa. In the case of copper it
dissolves decreasing amounts of a solute as the valency of the
solute increases. Titanium is considered tetravalent and as such
its solubility in copper therefore can be expected to be limited.
Considering the reverse of this or the solubility of copper in
titanium it would appear that even less copper would dissolve in
titanium than vice versa. The general rule that in a binary-
system the solubility in a higher melting metal is greater than
in a low melting metal ~uld thus appear to be an exception in
this case as well. Thus a. strong tendency is indicated to form
stable intermediate compound at the expense of primary solid
solutions. Titanium being strongly electropositive with respect
to copper would thus be expected to exhibit this tendency. The
formation of a stable compound normally restricts solid solubility
and therefore the solubility limit of the restricted solid solution
increases with t perature. This rule appeare to be followed in
the copper-titanium system since the solid solubility of titanium
in copper increases from a minimum of about O.40~ Ti at room
temperature to ms.ximum of about 4.5% Ti at 878o
C. A minimum
in the liquidus curve shows the formation of a eutectic which
according to Kroll exists at a 2-4% titanium concentration. Laves
and Wallbaum report that there are compounds CU3Ti and CuTi2 present.
7
The former corresponds to an epsilon phase with an electron atom
ratio of 7:4, while the CuTi2 which suggests a gamma phase does
not correspond to an electron atom ratio of 21: 13 according to(9)
Hume-Rothery's rule • If these compounds do exist J then the
equilibrium diagram certainly needs modification to include them.
(9) W. Hume-Rothery, Structure of Metal and Alloys, 1947, p. 110 - 113.
PREPARATION ill: A.LWYS
The most feasible manner of alloying titanium ~nd copper was
to use the induction furnace method, that is, the melting of
metallic titanium and copper in a high frequency induction furnace.
Induction Furnace Method:
The melting points of titanium and copper differ by 717°C, but
the boiling point of copper is 5000C greater than the melting point
of titanium. It thus seems logical, that alloys of these two metals
can be prepared by melting the constituent metals together in spite
of the great difference in the melting points. Some of the physical.
constants of copp r and titanium are given in Table I.
Copper analyzing 99.99% copper was used in the meltH with
granular titanium. See Table II for the analysis of the titanium
used.
The most suitable crucibles used for these melts were made of
graphite. Although, it is generally conceded that titanium is a
strong carbide stabilizer, no apparent amount of titanium carbide
was formed from contact \od..th the graphite. Heat was 8Upplled bY' the
induction heating of the graphite as well as of the charge.
Melting of the constituent metals was carried out under an
inert atmosphere. A pressure of 100 microns of mercury was obtained
to offer protection from nitride and oxide formations.
8
TABLE I
SOME PHYSICAL CONSTANTS(lO)
OF TITANnJlIIf AND COPPER
9
A.t. No. A.t. wt. M. P. Sp. G.
Copper
Titanium
29
22
63.57
47.90
TABLE II
ANALYSIS OF GRANULAR
TITANIUM(U)
Titanium.
T1
99.5%
Fe
0.1% 0.2%-0.1%
81
less 0.1%
(10) Handbook of Chemistry and Physics, 30th Ed., ChemicalRubber Publishing Co., 1947, p. 306, p. 287.
(11) R. S. Dean and B. Silkes, I. C. 7381, U. S. Bureau ofnes, 1946, p. 5 - 6.
A tank of helium was introduced after evacuating the furnace to
100 microns of mercury. The pressure of helium was maintained
during the melting and until after the alloys had cooled to
room temperature.
The furnace used for the preparation of these alloys was
an Ajax 20 KW high frequency induction furnace operating on
frequencies between 20,000 and 30,000 cycles. A photograph of
a 20 KW Ajax eonv rter unit for the high frequency induction
furnace is shown in Fig. B. 'l'he water cooled vacuum head was
used to seal the fused qua.rtz furnace tube. More insulation
was obtained by placing another qu rtz inner sleeve inside con
taining the graphite crucible with the cbarge. A photograph of
the refractory materials used is shown in Fig. C. Silica sand
of 20 mesh was placed in the bottom of the fused quartz furnace
tUbe to protect the tube in case of run outs. Photographs of
the furnace setup tor the induction heating method of preparing
the titanium and copper alloys are shown in Fig. D, Feg. • and
Fig. F.
The granular titanium and pure copper shavings were pressed
into one inch diameter compacts in a single-plunger dies with a
pressure of 50 T. S. I. supplied by a universal testing machine.
The compacta which weighed 100 grams were placed in the graphite
crucibles and melted.
10
FIG. D - FRONT VIEW
FIG. E - SIDE VIEW
FRONT AND SIDE VIEWS OF APPARATUS USED SHOWING:
VAClJUM PUMP AND CONNECTIONS
HELIUM TANK
PRESSURE GAUGE
REBREATHER AND CONNECTIONS
VACUUM HEAD AND COOLING WATER HOSE
QJ ARTZ FURNACE TUBE
HIGH FREQUENCY FURNACE COIL
13
15
Melting data are given in Table III. After proper melting
had taken place, all samples were allowed to furnace cool.
T1?-ree to four hours were usually required for the temperature
to come down to room temperature.
The titanium, which floated to the top of the molten bath,
was the last material to fuse, so when the surface began to
ripple because of the agitation by the magnetic field, all the
metallic charge was assumed to have fused. A soaking period of
5 minutes before cooling was begun. No temperature measurements
were made.
Heat Treatment: The alloy specimens for heat treatment were sealed
in evacuated quartz tubes. The heat treating furnaces used were:
(1) A Burrell Glo-bar type with a built in calibrated
Pt-PtRh thennocouple.
(2) A Glo-bar electric kiln with a calibrated Pt-PtRh
thennocoup1e.
(3) An electric multiple unit furnace with a calibrated
iron-constantin thennocouple.
The heat treating data are given in Table IV.
TAiLE III
DATA FOR THEINDUCTION FURNACE
PREPARATION OF T1-Cu ALLOYS
Estimated Wt. ofRun No. %T1 Charge Melting Date
1 30 100 gInS. 5 KW for 5 min.10 KW for 10 min.20 KW for 10 min.25 KW for 10 min.Furnace Off
2 40 100 gms. Same as Run No. 1
45 100 gms. 5 KW for 5 min.10 KW for 5 min.15 for 5 min.20 KW for 20 min.Furnace Off
4 55 100 gInS. Same as Run No. 3
5 60 100 gillS. Same as Run No. 3
6 65 100 ginS. Same as Run No. 3
7 70 100 gIna. Same as Run No. 3
S 80 100 gms. 5 KW for 5 min.10 KW for 5 min.20 KW for 10 min.25 KW for 15 min.Furnace Off.
9 90 100 gms. Same as Run No. 8
10 95 100 gma. Same as Run No. 8
16
TABLE IV
HEAT TREATING DATA
FOR THE PREPARED Ti-Cu ALLOYS
Sample Ho. %Ti Annea1ins Temp. Annealing Period
* 850°C1 28 48 hrs.
2 30 850°C 48 hra.
3 40 900°C 48 hrs.
4 45 900°C 48 hre.
** 900°C5 50 48 hrs.
6 60 950°C 48 hrs.
7 70 10000 C 48 hr••
8 80 11000 C 48 MS.
9 90 12000 C 48 hra.
10 95 12500C 48 hrs.
* Alloy Prepared by Metal Hydrides Inc., Beverly, SSe
** Alloy Prepared by Metal Hydrides Inc., Beverly, 8S.
17
EXAMIN TION OF Ti-Ou ALLOYS
Chemical Analysis:
Titanium is rapidly attached by concentrated H2SO4, con
centrated HOI, and concentrated HN03
, but the samples of
titanium and copper went into solution in these acids only with
great difficulty. A combination of mixed acida of 3 parts of
concentrated HzS04, 1 part of concentrated HN03
, and 2 parts of
concentrated HCl was used in putting the titanium into solution.
Heating was necessary to obt~n complete solution in an optimum.
length of time (i hr.). All of the samples used were -200
mesh, and the grinding wa performed wet under alcohol in an agate
mortar. The alcohol was volatilized later. All of the samples
used were 0.500 gram in weight.
The basic chemical principle involved is the precipitation
of the titanium as the hydroxide by ammonium hydroxide in an
ammoniacal solution. Fig. G. gives a flowaheet of the steps in-
valved in the chemical analysis of the alloys for the percentages
of titanium..
The copper percentages of the alloys were also determined in
order to run a check on the titanium determinations. The copper
anal.yeis used was the potassium. cyanide method(12). Fig. H gives
a flowsheet of the steps involved in the chemical analysis of the
alloys for the percentages of copper. The subtraction of copper
determinations from 100% gave a close check against the titanium
percentages deter.mined experimental~.
(12) Scott's Standard Methods of Analysis, 5th Ed., Vol. 1, 1939,pp. 373 - 374.
18
Fig. G - CHEMICAL ANALYSIS
.FLOWSHEET FOR %T1 in T1-Cu ALWY
Weigh out 0.500 gm. sample in a 6"porcelain evaporating dish
~Dissolve in a mixture of 15 m1. H2SO4,
5 rol. of conc. HN03, and 10 ml.of cone. HCl
¥Evaporate to fumes of
S03~
Cool and boil with 50 - 60 ml. ofdistilled H20 and 5 - 10 ml. of conc.
HC1.f
Filter into a 500 mI. beakerJt
Wash the residue with hot H20Jt
Save the filtrate for a Cu an~sis
itAdd 15 ml. of cone. HCl and 200 ml.
of hot H20it
Boil and add NH40H until it isammoriiacal
VFilter and wash clean
VDry residue at 110°C
Ignite at 2000°: to constantweight
%Ti _ wt. of Ti02 x 0.5995 x 1000.500
lleagent 6 Used:
1. Mixed Acids: 1 part HN03, 2 parts HC1, 3 parts H2SO4
2. Concentrated NH40H
3. Concentrated HC1
4. Concentrated HN03
5. Concentrated H2So4
6. Litmus
19
I 0.5ml. KCN soln.
\Fig. H - CHEMICAL ANALYSIS
fLOWSHEET FOR %Cu in Ti-Cu ALWYS
Standard Potassium Cyanide Solution:35 ginS. of the salt dissolvedin H20, and diluted to 1000 ml.
Standardization:
~~igh out 0.5~0 gm. of pure Cu.
Di,ssolve in a naak with 10 ml.of dilute HNO).
J,Boil to expel nitrous fumes •
.vNeutralize the solution.
VD~lute and titrate as directed,
under Procedure.
Wt. of Cu/ml. of standard KCN solution.
Procedure:
Solutio containing eu is neutralized withNa2C03 or NaOH, the reagent is added until
a slight precipitate forms.~
1 ml. of NH40H is added.i-
Titrate solution with standard KCN solution
color changes: blue~pink:colorless.
20
ml. of KCN x factor/ml. = Wt. of Cu
%au =;(t. of Cu x 1000.500
Reagents Used:
1. KeN salt
2. Pure Cu
3. Dilute HN03
4. NabH
Results of chemical an&l.yses and physical analysis of the titanium
copper alloys are given in Table V. Graph #1 illustrates the rel
ationship between the specific volume and the composition of
titanium.
X-Ray Analysis:
The prepared alloys of titanium-copper were investigated by
X-ray diffraction. A North American Phillips X-Ray Spectrometer
was used with a copper target and a mckel filter. The recording
device consisted of a Geiger-Muller Counter with its output
operating a recording potentiometer.
Powder samples were prepared by grinding under alcohol in
an agate mortar. All powder samples were ground to -200 mesh.
The powdere were annealed as specified. The -200 mesh po\«ler
specimen was mixed with collodion and molded into a plastic sample
holder.
The information in Table VI was used in interpreting the I-ray
patterns and micrographs of the prepared titanium-eopper alloys.
Table VII contains the X-ray data obtained for the prep red
titanium-copper alloys.
Photostatic reductions of the microphotometer tracings of the
powder patterns of the prepared titanium-copper allOy8 were also
made.
21
TABLE V
RESULTS OF CHEf/tiCAL ANALYSES
AND PHYSICAL ANALYSIS
Sample No. %Ti (tCu Spa Gravity
1 28.60 72.00 7.65
2 30.,36 70.00 7.57
3 40.00 59.76 7.16
4 44.74 45.45 7.08
5 50.40 50.30 6.71
6 59.76 48.22 6.42-
7 70.80 29.95 5.67
8 79.99 19.97 5.48
9 89.80 10.18 -4.95
10 95.00 5.02 4.70
22
23
Metallographic Technique:
The samples were mounted in lucite and bakelite. They were
ground flat on a belt grinder. Preliminary polishing was per-
formed on a horizontal belt grinder using 80, and 120 abrasive
belts. The intermediate polishing was performed in tlllO stages:
First stage: The first polishing wheel was covered with 8 to 12-
oz. canvas duck to which was applied FF Turkish emery, No. 500
carborundum or grades of alundum No. 400 and finer. Second stage:
The second polishing wheel was covered with '1«)01 broadcloth and
uses abrasive called tripoli. The final polishing wheel was
covered with a fine grade wool and a water suspension of levigated
alumina 'was used in conjunction 'With this operation.
All polishing wheels were kept wet during use by a water drip
and the specimens, between steps, were kept wet and were thoroughJ.y
rinsed free of abrasives. After removal from the final wheel, the
specimens were immediately rinsed in alcohol and quickly dried
prior to etching.
S,.pecific Gravity Analysis: The Westphal balance method for the
detennination of the specific gravities of the prepared Ti-Cu alloys
was used. This method is based upon the following equation:
Specific Gravity. Weight in 11rLoss of Weight in lrlater
The data for the determination of specific graviti~8 of the prepared
Ti-Cu alloys 1s found in Table X.
Interpretation of X-Ray Results
And Correlation with Microstructures:
From the theoretical study of titanium-copper alloys,
(see page 5) the lattice structure of copper in the copper
solution is not distorted to the same degree as in the
titanium lattice in the titanium solid solution. It seems
logical, therefore, that the solid solubility of copper in the
titanium is greater than that of the titanium in the copper.
Ti-Cu Alloy. 28 me %T1: It appears that from the
photomicrographs shown in Fig. 12, Fig. 13, Fig. 14 that this
alloy consists of a coarse eutectic structure which might be made
up of solid solution and a compound. The microphotometer tracing of
the powder pattern of this alloy (see Fig. 1) shows the intense peaks
for the d-values of pure copper, which is typical for a eutectic, and
peaks for new d-values, that could correspond to an unknown compound.
The tukon hardness results (see Table IX) for this possible compound
corresponds to a knoop hardness number of 560. The probable solid
solution has a knoop hardness number of 317.
Ti-Cu AlloY', 30 wt. %T1: Photomicrographs shown in Fig. 15,
Fig. 16, Fig. 17, and Fig. 18 reveal that this alloy consists of a
eutectic structure which might consist of solid solution plus compound,
and compound. X-Ray analysis (see Table VIII) indicates the continued
presence of a possible compound. The microphotometer tr cing of the
powder pattern ot this alloy (see Fig. 2) shows more intense peaks
for copper and less intense peaks for the compound, as compared to the
28% Ti - 72% Cu alloy.
.25
The tukon hardness results (see Table IX) for the compound
correspond to a Knoop hardness nwnber of 565. The eutectic
has a Knoop hardness number of 325.
Ti-Cu Alloy, 40 wt. %Ti: Photomicrographs shown in Fig. 19,
Fig. 20, Fig. 21, and Fig. 22 reveal that this alloy consists
of a eutectic structure which might consist of solid solution plus
compound, and compound. X-Ray analysis (see Table VIII) indicates
the presence of a possible compound. The microphotometer tracing of the
powder pattern of this alloy (see Fig. 3) shows less intense peaks
for the copper and greater intensity peaks for the compound. The
tukon hardness results (see Table IX) showed a greater Knoop hardness
number of 795 for the compound. The eutectic had a Knoop hardness
number of 325.
Ti-Cu Alloy, 50 wt. %T1: Photomicrographs shown in Fig. 23,
Fig. 24, and Fig. 25 reveal a minimum amount of eutectic, possibly
consisting of solid solution plus compound, and a maximum amount
of compound. X-Ray analysis (see Table VIII) indicates the possible
presence of compound. The microphotometer tracing of the powder
pattern of this alloy (see Fig. 4) shows the greatest intensity
peaks for the compound. The tukon hardness results (see Table IX)
show a maximum Knoop hardness number of 1052 for the compound. The
eutectic had a Knoop hardness number of 319.
26
Ti-Cu Alloy. 60 wt.. %Ti: Photomicrographs shown in Fig. 26,
Fig. 27, and Fig. 28 reveal small areas of eutectic in a matrix of
compound. -Ray analysis (see Table III) indicates the presence of
both the titanium and a possible compound. The microphotometer trac
ing of the powder pattern of this alloy (see Fig. 5) shows the peaks tor
titanium that have the same d-values as for pure titanium. Less intense
peaks which could be compound can also be observed. The tukon hard
ness results (see Table IX) 5how a Knoop hardness number of 1050 for the
compound. The eutectic had a Knoop hardness number of 792.
Ti-eu Alloy. 70 wt. %Ti: Photomicrographs show in Fig. 29,
Fig. 30, Fig• .31, and Fig• .32 reveal white areas of a compound and
a. large amount of eutectic. X-Ray analysis (see Table VIII) indi
cates the presence of titanium and a possible compound. The
microphotometer tracing of the powder pattern of this alloy ( see
Fig. 6) shows less intense peaks for both the titanium and compound.
The tukon hardness reaults (see Table IX) show a Knoop hardn as number
of 1048 for the compound and a Knoop hardness number of 760 for the
eutectic.
Ti-Cu Alloy. 80 wt. %Ti: Photomicrographs shown in Fig• .3.3
and Fig. 34 reveal white dendrites of titanium in a matrix ot what
appears to be a fine eutectic. X-Ray analysis (see Table VIII)
indicates the presence of both the titanium and a possible compound.
27
he microphotometer tracing of the powder pattern of this alloy (see
Fig. 7) shows the intensity peaks for both the titanium and compound
are markedly decreased. The t on hardness results (see Table IX)
show a Knoop hardness number of 925 for the compound and a Knoop
hardness of 592 for the matrix.
Ti-Cu Alloy. 90 wt. %Ti: Photomicrographs shown in ig. 35
and Fig. 36 reveal large white dendrites of titanium in a matrix of
what appears to be a fine eutectic. X-Ray analysis (see Table VIII)
indicates the presence of both the titanium and a possible compound.
The microphotometer tracing of the powder pattern of this alloY' (see
Fig. 8) shows a marked increase in the intensitY' peaks for both the
titanium and compound, as compared to the 80% Ti - 20% Cu alloY'. The
tukon hardness results (see Table IX) show a Knoop hardness number of
841 for titanium and a Knoop hardness number of 487 for the matrix.
Ti-Cu Alloy. 95 wt. Ti: Photomicrographs shown in Fig. 37
and Fig. 38 reveal white areas of titanium and what appears to be
a eutectic. X-Ray analysis (see Table VIII) indicates the presence
of both the titanium and a possible compound. The microphotometer
tracing of the powder pattern of this alloy (see Fig. 9) shows a
maximum decrease in the intensity of the peaks for both the titanium
and compound. Th tukon hardness results (see T ble IX) sbow a
Knoop hardness number of 692 for the titanium and a Knoop hardness
number of 371 for the apparent eutectic.
28
Intexoretation of Seecific Volume
Versus Composition in Cu-Ti Alloys:
The specific gravity of an alloy composed of a conglomerate of two
kinds of crystallites is not proportional to the specific gravity of
each cr,ystallite present. But the reciprocal of the specific gravity;
that is, the specific volume is quite closely so proportional. The
specific volume "VII of a given alloy containing "n" per cent by volume
of A (Ti) crystallites, and (100 - n) per cent by volume of B (Cu)
crystallites is equal to
v (alloy) .. n YeA) + (100 - n ) V(B)
The reciprocal of this sum giv 8 the specific gravity of the alloy
considered.
This same rule holds very closely for solid solution series,
although there may be a slight contraction in volume (less than
0.5 per cent) causing a lower value than calculated. The specific
volumes of the copper-titanium alloys are shown in Graph # 1.
The specific volumes of intermetallic compounds deviate some-
what from this rule. (13).
Graph #1 shows that the end portions have all points for the
specific volumes falling on a continuous straight line. Therefore,
one may state that there might be the possible existence of two solid
solutions , namely, a copper solid solution, and a titanium solid
solution. The irregularities or deviations i8 indicative of the
possible existence of a compound which may be present in different
relative amounts.
(1.3) D. M. Liddell and G. E. Doan, The Principles of Metallurgy,First Ed., 193.3, pp. 511 - 519.
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TABLE VI
X-RAY DIFFRACTION OAT *(Cu Ka Radiation)
Substance 1/11 d in AO
Ti 1.00 2.230.2.7 2.540.2.0 2.340.1.3 1.72.0.13 1.4700.13 1..3.300.11 1.2480.05 1.2..300.01 1.2.75
Cu 1.00 2.080.53 1.810•.3.3 1.2770•.3.3 1.0890.09 1.04.30.03 0.905
TiC l.00 2.150.75 2.490.50 1.520.25 1.3000.10 1.2450.09 0.9650.05 0.9900.05 0.8810.03 1.0790.02 0.8.31
Ti02 (anatase) 1.00 .3.520.40 1.880.28 1.700.24 2•.370.24 1.660.2.4 1.4800.11 1.262O.OS 1.3620.00 1.335
* J. D. Hanawalt, Rinn, H. W., and Frevel, L. K., Indu trialand Engineering Chemistry, Anal. Ed., Vol. 10, No.9, 1938.
41
TABLE VI (CONT'D),d in AOSubstance III1
Ti02 (anatase) 0.06 1.1640.03 1.0450.02 0.9500.02 0.9130.02 0.894
Ti02 (rutile) 1.00 1.690.80 3.240.60 2.490.30 2.190.30 1.620.30 1.3550.20 1.4850.20 1.4490.12 2.050.08 1.1700.08 1.0910.08 1.0400.08 0.8900.04 2.290.04 1.2450.04 1.1470.04 0.9640.04 0.8750.04 0.8320.04 0.8220.02 0.9030.02 0.843
TiO 1.00 2.120.80 2.450.80 1.4980.60 1.2770.60 1.2220.60 0.9470.60 0.8640.60 0.8150.40 1.0580.40 0.972
TABLE VI (CONTID)!
Substance 1/11 din 0
TiN 1.00 2.201.00 1.5551.00 0.9841.00 0.8981.00 0.8470.70 2.540.70 1.3270.70 1.2700.50 1.1000.50 1.009
TiH21.00 2.620.27 2.260.24 1.580.19 1.350.08 1.28
43
TABLE VII
X-RAY DIFFRACTION DATA
FOR ANNEALED
Ti-Cu AlJ.i)YS
(Cu KaRadiation)
•Observed Angle
Substance Intensity 0 d Identity
Rn No. 1 102 21.80 2.07 Copper28% Ti) 45 25.35 1.80 II
30 37.15 1.27 "22 44.85 1.13 "
132 20.95 2.15 Compound67 22.90 1.97 "39 35.55 1.30 "22 18.40 2.43 "12 29.40 1.55 "
Run No. 2 49 21.65 2.09 Copper(30% Ti) 18 25.20 1.80 "
19 37.10 1.27 II
12 44.85 1.04 "80 20.90 2.15 Compound19 22.80 1.97 "21 35.45 1.29 "39 18.25 2.46 II
25 29.50 1.51 II
Run No. 5(40% Ti 36 21.70 2.07 Copper
12 25.40 1.79 "35 37.45 1.26 "16 44.80 1.13 "
UB 20.95 2.15 C p~und
34 23.55 1.96 II
32 35.40 1.32 II
69 18.25 2.45 II
7 29.45 1.57 II
44
TABLE VII (CONTID)Observed Angle
Substance Intensity 0 d Identity
Run No.4 82 21.75 2.07 Copper(50% Ti) 38 25.30 1.80 II
24 37.10 1.27 11
24 44.85 1.13 "145 21.00 2.14 Compound
42 22.95 1.97 "43 35.60 1.32 "35 18.25 2.45 11
12 29.30 1.57 "Run No. 5 105 20.95 2.15 Compound
(60% Ti) 31 22.90 1.97 11
29 35.60 1.32 "12 18.30 2.45 "9 29.25 1.57 "
28 19.75 2.24 Titanium5 17.50 2.54 II
15 19.30 2.33 II
13 27.12 1.69 "9 31.85 1.46 II
13 38.55 1.23 If
Run No.6 60 21.00 2.14 Compound(70% Ti) 31 22.95 1.99 11
8 35.55 1.32 "44 18.00 2.48 II
32 29.15 1.58 "4 19.15 2.34 Titanium
11 27.05 1.69 II
8 31.65 1.46 "12 38.00 1.21 II
Run No.7 49 21.40 2.10 Compound(80% Ti) 7 35.10 1.34 II
28 18.30 2.45 11
24 30.65 1.51 "17 20.25 2.22 Titanium10 19.6 2.29 "
5 26.50 1.72 "5 31.40 1.47 "9 38.10 1.24 11
45
TABLE VII (CONT' D)Observed Angle
Substance Intensity 0 d Identity
Run No.8 56 21.20 2.12 Compound(90% Ti) 46 18.15 2.47 II
30 30.60 1.50 II
31 19.90 2.26 Titanium8 26.95 1.70 II
18 36.60 1.29 II
10 38.10 1.24 II
15 38.55 1.23 II
Run No. 9 19 20.95 2.14 Compound(95% Ti) 14 18.05 2.49 II
11 30.35 1.52 II
22 19.95 2.25 Titanium13 19.10 2.35 II
6 26.35 1.73 II
10 35.15 1.336 "7 38.10 1.24 II
Run No. 10(99.99% Cu) 132 21.7 2.08 Copper
77 25.3 1.80 II
52 37.2 1.275 "35 44.85 1.09 "
Run No. 11 26 19.75 2.25 Titanium(99.5% Ti) 14 34.8 1.34 "10 37.7 1.25 "
9 26.2 1.74 "8 18.75 2.37 II
7 17.3 2.58 II
6 31.0 1.20 II
TABLE VIII
d-VAllJES ASSIGNED TO
SPECIFIC PHASES
47
Run NumbersIf! #2 #3 #4 #5 #6 #7 #8 #9
28% 30% 40% 50% 60% 70% 80% 90% 95% PurePhase Ti Ti Ti Ti Ti Ti Ti Ti T1 Phase
Copper 2.07 2.03 2.07 2.07 2.081.80 1.79 1.79 1.80 1.801.27 1.27 1.26 1.27 1.2771.13 1.09 1.13 1.13 1.089
Compound 2.15 2.15 2.14 2.15 2.14 2.10 2.12 2.14 2.141.97 1.93 1.96 1.97 1.97 1.99 1.971.30 1.33 1.32 1.32 1.32 1.32 1.34 1.322.43 2.37 2.45 2.45 2.45 2.48 2.45 2.47 2.49 2.451.55 1.58 1.57 1.57 1.57 1.5S 1. 51 1.50 1.52 1.55
Titanium - 2.24 - 2.22 2 26 2.25 2.232.54 -- 2.542.33 2.34 2.29 2.35 2.341.69 1.69 1.72 1.70 1.73 1.721.46 1.46 1.47 1.471.23 1.21 1.24 1.24 1.24 1.248
1.23 1.231.29 1.336 1.330
TABLE IX
TUKON HARDNESS TESTS RESJLTS
48
%Ti
phases 28 .30 40 50 60 70 80 90 95
~ CopperKnoop Hardness .317 .325 .325 319Solid -- --- ---
~ Solution R "C" II .30 32 .32 30.5 --- ---Eutectic (
'f CompoundKnoop Ha.rdness 560 565 795 1052 1050 1048 - -- -or
~~mpounds R UC" " 52 53 65.5 Ofr Scal ----- -- ---
Knoop Hardness 792 760 592 487 .371Eutectic R "C" II 65 6.3 54 46 36
Titanium. Knoop Hardness 850 841- 692or R "ell II 70 69 60
Ti solidsolution
49
TABLE X
SPECIFIC GRAVITY DATA
%Cu %Ti eight in Air Loss of Weight in H2o Sp. G.
*100 0 ------- -------- 8.9•
72 28 4.50 ginS. 0.59 gms. 7.65
70 30 4.58 gms. 0.60 gms. 7.57
60 40 4.58 gina. 0.64 gms. 7.16
55 45 1.70 gms. 0.24 gms. 7.08
50 50 56.68 gms. 8.74 gms. 6.71
40 60 4.75 gms. 0.74 gms. 6.42
30 70 2.44 gms. 0.43 gms. 5.67
20 80 2.85 gms. 0.52 gms. 5.48
10 90 21.36 gms. 4.32 ginS. 4.95
5 95 69.26 gma. 1.4.74 gInS. 4.70
4.50 *0 100 ----- ------
See Graph o. 1, page 29.
* Handbook of Chemistry and Physics, 30th d., Chemical RubberPublishing Co., 1947, p. 306, p. 287
Figure 12 l00xTitanium-Copper alloy, 28 wt. %Ti, as cast,etched in NH~OH:H20: H202; FeC13• WidmanstattenStructure. Dark portions of eutectic.White matrix which appears to be compound.
50
51
Figure 13 '1001Titanimn-Copper alloy, 28 wt. %Ti, as annealedat 850°C for 48 hra. 5 sec. etch in 4% HF. CoarseEutectic Structure. Black areas are polishingpits.
Figure 14 500xTitanimn-Copper alloy, 28 wt. %Ti, as annealedat 850°C for 48 hrs. 5 sec. etch in 4% HF. CoarseEutectic Structure.
Figure 15 lOOXTitanium-Copper alloy, 30 wt.% Ti, as cast,etched in NH40H: H20: H202; FeCl~. White areaof compound and eutectic. Bla~k areas arepolishing pits.
F;1.gure 16 SOOXTitanium-Copper alloy, 30 wt. %Ti, as cast,etched in NH40H:H20:H202; FeC13• White areasof compound and eutectic.
52
53
'Figure 17 lOOXTitanium-Copper alloy, 30 wt. %Ti, as annealedat 850°C for 48 hra. Etched in NHl&.0H:H20 ~02;FeC13• White areas of Compound and eutectic.
Figure 18 500XTitanium-Copper alloy, 30 wt. %Ti, as annealedat 850°C for 48 hra. Etched in NH~OH:H20:H202; Fee13•White areas of compound and eutect~c.
Figure 19 1100XTitanium-Copp1er alloy, 40 wt.% Ti, as cast,etched in NH40H:H20:H202; FeC13• White areasof compound and eutectic.
,Figure 20 500XTitanium-Copper alloy, 40 wt. %Ti, as cast,etched in NH40H:H20:H202; FeC13" White areasof compound 8..1'1d eutectic.
54
. -:r
55
'Figure 21 lOOXTitanium-Copper alloy, 40 wt. %Ti, as annealedat 850°C for 48 hrs. 10 sec. etch in 4% HF.Shaded areas of eutectic. Matrix of compound.Dark areas are polishing pits•
Figure 22 500XTitanium-Copper alloy, 40 wt. %Ti, as annealedat 850°C for 48 hrs. 10 sec. etch in 4% HF.Shaded areas of eutectic in a matrix of compound.
!Figure 23 lOOXTitanium-Copper alloy, 50 wt. %Ti, as cast,etched in NH40H:H20:H202} FeCl~. Islands andstringers of eutectic in a mat~ix of compound.
56
57
Figure 24Titanium-Copper alloy, 50 wt. %Ti, as annealedat 900°C for 48 hrs. 10 sec. etch in 5% HF.Islands of eutectic in a matrix of compound,.
Figure 25 SOOX~itanium-eopper alloy, 50 wt. %Ti, as annealedat 9000C for 48 hrs. 10 s c etch in 5% HF.Dark portions of eutectic in a matrix of compound.
.Figure 26 lOOXTitanium-Copper alloy, 60 wt.. %Ti, a8 cast,et.ched in NHl&.0H: H20: H202; FeCl). Dark areasof eut.ectic in a matrix of compound.
58
59
.Figure 27 lOOXTitanium-Copper alloy, 60 wt. %Ti, as annealedat 950°C for 48 hra. 15 sec. etch in5% Hr.Islands of eutectic in a. matrix of compound.Black areas are polishing pits.
Figure 28 .,OOXTitanium-Copper alloy, 60 wt. %Ti, as annealedat 950°C for 48 hra. 15 sec. etch in 5% HF.Shaded portions of eutectic in a matrix of compound.
~igure 29 lOOXTitanium-Copper alloy, 70 wt. %Ti, as cast,etched in NH40H:H20:H202; FeC1J • White portionsof compound and eutectic•
.Figure 30 ,500xTitanium-Copper alloy, 70 wt. %Ti, as east,etched in NH40H:H20:H202; FeelJ" White portionsof compound and eutectic.
60
61
Figure 31 100xTitanium-Copper alloy, 70 wt. %Ti, as annealedat 1000°0 for 48 brs. 15 sec. etch in 5% HF.White areas of compound and eutectic.
n~e~ ~~Titanium-Copper alloy, 70 wt. %Ti, as annealedat 1oo00 C for 48 hra. 15 sec. etch in 5% HF.Shaded 'areas of eutectic. White areas of compound.
Figure 33 lOOXTitanium-Copper alloy, 80 wt. %Ti, a s annealedat ll000 C for 48 bra. 15 Sec. etch in 5% HF.White dendrites of titanium in a matrix of whatappears to be eutectic.
Figure 34 500xTitanium-Copper alloy, 80 wt. %Ti, as annealedat llOOoC for 48 hre. 15 sec. etch in 5% HF.White dendrites of titanium in a matrix of whatappears to be eutectic.
62
'\ ~..,. ,1.,· .•..,.. "'''r~ .,'. _', , ~'. ; ~Qc~" . ".;':' ...~
i/:0.'''. , 'j' , .. ~ "","0' '~.
"l '!J " ~ • I .,. :""it',," ',,:, • '" I '~,,~~'
'. > 1':, • ", " ''''L,', 'l,' ... ~ ,,"~.',i ", I '",
' '-:, T' '., ~,,', ... .; "': ,/ l '.
'~, .,.- 'IIiJI' ," ',"I'l : :,-:'; • ~t:. .: '" :"~ ,:: .... ':':.' '" '"
:. :,. ,l' .. '\. ~~ '.'~.. ,/,'.. 0 • , 0- to .... .. .... I; , ,1,. ..
iii' • ·~t..,~~x.. ~"O: .. '" 0".,:,.""I .\ ',,":' ", .~ .' ... . .--.. ~ ""'\', "'. ....,.., , " ' " ,.. ,,", '-'• , " , ; . ,'i -" ,', '",
.,/, , >; • ,'" ~"'''''" ''',';." '~, ", 1 '''1.1 ••.••, '.','.: _.>'« ~ . ,~, ' .. ' . ".¢!.. ; ~"t;'.$~.,,: .::- ....:, ~ .."-!Iv, . 'Y-~ ...'.. , ..• " ..•. I J ,
.... lJ t- • '. t" .. ~ ',' " ."\.~ ,
'.. .1..... ~...\' I .\..>f)' •."J . -1: -:--'~"
-'\1." \ ~
Figure 35 100XTitanium-Copper alloy, 90 wt. %Ti, as annealedat 12000 C for 48 bra. 15 sec. etch in 5% HF.White dendrites of titanium in a matrix of '\toIhata.ppears to be eutectic.
63
n~re36 ~~Titanium-Copper alloy, 90 wt. %Ti, as annealedat 12000C tor 48 br • 15 sec. etch in 5% HF.White dendrites ot titanium and a matrix thatappears to be eutectic.
---
64
Figure 37 lOOXTitanium-Copper alloy, 95 wt. %Ti, as annealedat 12500 C for 48 hra. 15 sec. etch in 5% 1iF.White areas of titanium in a matrix of what appearsto be eutectic.
Figure 38 500XTitanium-Copper alloy, 95 wt. %Ti, as annealedat 12500C tor J.J3 hrs. 15 sec. etch in 51> HF.White areas of Titanium in a matrix of what appearsto be eutectic.
65
CONCWSIONS
1. Titanium-Copper alloys can best be prepared by the
Induction Furnace method.
2. From the foregoing preliminary wrk a nd a study
of the work of other investigators, plus theoretical con
siderations, the following statements can be made about the Ti-Cu
system:
a. A copper solid solution which consists of a
substitutional solid solution of titanium atoms in the copper
lattice.
b. A eutectic exists in the copper rich portion of the
g,ystem. W. Kroll determined the eutectic composition to be 24% Ti.
Metallographic examination of a 28% Ti alloy (see Fig. 12) shows
a structure that may be a little beyond the eutectic.
c. Metallographic examinations indicate the possibility
that a eutectic exists in the titanium rich portion of the system.
There appears to be a maximum amount of eutectic at 80% Ti.
d. The presence of a solid solubility curve in t e
copper rich end of the Ti-Cu binary system indicates the possibility
of age-hardening some of these alloys. This was established by the
work of other investigators.
e. X-Ray analyses, hardness determinations, and specific
volume measurements indicate the presence of one or more intermetallic
compounds in the system.
66
SUMMARY
A number of 8l..1oys of titanium and copper were prepared by the
Induction Furnace elting method.
The predictions made from the theoretical study (see page 5 - 6)
were partially correct since it appears that:
(1) A complete series of solid solutions does not exist.
(2) At each end of the system, a phase is shown which could
be a solid solution.
(3) At least one intennetallic compound exists.
The titanium-copper alloys prepared were studied by X-Ray
diffraction and metallography. Certain d-values obtained were
not listed in the Ti-Cu binary system in the Hannewalt Tables*.It seems probable that these d-values belong to a new phase.
A study of the specific volumes of the titanium-copper alloys
prepared might indicate the possibility of t he presence o"f a copper
solid solution, a titanium solid solution, and a compound.
It can be stated that until a more complete study 0 f the alloys
in this series is made, positive identification of these new phases
can not be assured nor accepted without reservation.
* See Reference on Page 41.
67
BIBLIOGRAPHY
1. Wartmann, F. S., U. S. Bureau of Mines Conference onMetallurgical Research, 1940.
2. Wartmann, F. S., U. S. Bureau of Mines Conference onetallurgical Research, 1940.
3. Kroll, ., etallwirtschaft, Vol. 18, (4), 1939,pp. 77 - 80.
4. Fast, J. D., Zeitung Anorg. Cham., Vol. 241, (1),1939, pp. 42 - 56.
5. Laves, F., and Wal1baum, H. J., Naturwiss., Vol. 27,1939, pp. 674 - 675.
6. Kroll, W. Zeitschrift fur Meta1lkunde, Vol. 23, (33),1931.
7. Hensel, F. R., and Larsen, E. I., .I.M.M.E., Tech.Pub1. 432, 1931.
8. Pauling, L., "Journal of Amer. Chern. Soc.", Vol. 69,#3, 1947, pp. 542 - 553.
9. Hume-Rothery, ., The tructure of l-1etals and Alloys,The Institute of Metals MOnograph and eport SeriesNo.1, 1947, pp. 110 - 113.
10. Dean, R. S., and Silkes, B., I.C. 7381, U. S. Bureauof Mines, 1946, pp. 5 - 6.
ll. Liddell, D. ., and G. E. Dean, The Principles of Metallurgy,First Ed., 1933, pp. 511 - 519.