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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. B - A 20 KILOWATT AJAX CONVERTERUNIT FOR THE HIGH ~ENCY INIlJCTION FURNACE

11

12

FIG. C - LEFT TO RIGHT: QJARTZ FURN CE TUBE

QJARTZ INNER SLEEVE

GRAPHITE MELTING CRICIBLE

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

14

FIG. F - COJ.'iPLETE ARRANGEMENT OF APPARAWSUSED FOR MELTING TITANIUM-COPPER ALLOYS

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.

68

ugust Saw was born in St. Louis, Mis ouri on October 17,

1921. entary and Secondary Schooling was received in

St. Louis, and a Bachelor of cience degree in Metallurgical

Engineeri g was obtained in June 1944 from the School of Mines

and Metallurgy, University of ssouri at Rolla, Missouri.