Scholars' Mine
Masters Theses Student Theses and Dissertations
1949
A preliminary investigation of the titanium-copper equilibrium system
August Robert Savu
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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
This thesis is brought to you by Scholars' Mine, a service of the Missouri S&T Library and Learning Resources. This work is protected by U. S. Copyright Law. Unauthorized use including reproduction for redistribution requires the permission of the copyright holder. For more information, please contact [email protected]. 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
fl~~~._7.!:~~;!P~Irfl':"'~-:"I=.;::;.;;..'-..---- Approved by_---J.:.,.w~~:EPPeJ:Sheuner Professor of Metallurgical Engineering ii
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. iii
TABLE QI CONTENTS Page Acknowledgement ••••••••••••••••••••••••••••••••• 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 and Correlation with Microstructures•••••••••••••• 24
Specific Gravity Stu~...... 28 Conclusions••••••••••••••••••••••••••••••••••••• 65
Summa~ ••••••••••••••••••••••••••••••••••••••••• 66 Bibliography•••••••••••••••••••••••••••••••••••• 67 Vita•••••••••••••••••••••••••••••••••••••.•••••• 68 iv
Fig. Page
A Copper-Titanium Equilbrium Diagram 4a
B Photograph of a 20 Kilowatt Ajax Converter Unit for the High Frequency Induction Furnace 11
C Photogra.ph of Refractory Materials Used for Melting Alloys 12
D Photograph of Apparatus Used 1.3
E Photograph of Apparatus Used 1.3
F Photograph of the Complete Arrangement of Apparatus 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 Pattern of 28% Ti - 72% Cu Alloy 30
2 Microphotometer Tracing of Powder Pattern of 30% Ti - 70% Cu Alloy 31
.3 Microphotometer Tracing of Powder Pattern of 40% Ti - 60% Cu Alloy 32
4 Microphotometer Tracing of PoWder Pattern of 50% Ti - 50% Cu Alloy 33
5 Microphotometer Tracing of Powder Pattern of 60% Ti - 40% Cu Alloy 34
6 Microphotometer Tracing of Powder Pattern of 70% Ti - 30% Cu Alloy 35
7 Microphotometer Tracing. of Powder Pattern of 80% Ti - 20% Cu Alloy .36 8 Microphotometer Tracing of Powder Pattern of 90% Ti - 10% Cu Alloy 37
9 Microphotometer Tracing of Powder Pattern of 95% Ti - 5% Cu Alloy 38 v
g.§! Q.E ILLUSTRATIONS (CaNT I D)
Fig. Page
10 Microphotometer Tracing of Powder Pattern of 99.99% Cu 39 II Microphotometer Tracing of Powder Pattern of 99.5% Ti 40
Graph #1 Specific Volume As a Function of Composition 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 vi
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 vii
LIST OF TABLES
Table Page I Some Physical Constants of Titanium and Copper 9 II Analysis of Granular Titanium 9 III Data for Induction Furnace Preparation of Titanium-Copper Alloys 16 IV Heat Treating Data for the Prepared Titanium-Copper Allo~B 17 V Results of Chemical Analy:ses and Physical 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 to Specific Phases 48 X Specific Gravity Data 49 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 Metallurgical Research, 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 Metallurgical Research, 1940. 3
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 o expansion of 97.9 x 10-7 between OOC and 850 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 o at 1725 C. He also observed the allotropic transformation at o 880 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.
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. 4
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. 4a
1000 "
(l
:a""'t • TI (01 T;. Cu CO 200 - , I 040~ T1 Q'!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. 5 -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. 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 o temperature to ms.ximum of about 4.5% Ti at 878 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 existJ then the equilibrium diagram certainly needs modification to include them. (9) W. Hume-Rothery, Structure of Metal and Alloys, 1947, p. 110 - 113. 8 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 0 the boiling point of copper is 500 C 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. 9 TABLE I SOME PHYSICAL CONSTANTS(lO) OF TITANnJlIIf AND COPPER A.t. No. A.t. wt. M. P. Sp. G. Copper 29 63.57 Titanium 22 47.90 TABLE II ANALYSIS OF GRANULAR TITANIUM(U) T1 Fe 81 Titanium. 99.5% 0.1% 0.2%-0.1% less 0.1% (10) Handbook of Chemistry and Physics, 30th Ed., Chemical Rubber Publishing Co., 1947, p. 306, p. 287. (11) R. S. Dean and B. Silkes, I. C. 7381, U. S. Bureau of nes, 1946, p. 5 - 6. 10 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. 11 FIG. B-A 20 KILOWATT AJAX CONVERTER UNIT FOR THE HIGH ~ENCY INIlJCTION FURNACE 12 FIG. C- LEFT TO RIGHT: QJARTZ FURN CE TUBE QJARTZ INNER SLEEVE GRAPHITE MELTING CRICIBLE 13 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 QJARTZ FURNACE TUBE HIGH FREQUENCY FURNACE COIL 14 FIG. F- COJ.'iPLETE ARRANGEMENT OF APPARAWS USED 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. 16 TAiLE III DATA FOR THE INDUCTION FURNACE PREPARATION OF T1-Cu ALLOYS Estimated Wt. of Run 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 17 TABLE IV HEAT TREATING DATA FOR THE PREPARED Ti-Cu ALLOYS Sample Ho. %Ti Annea1ins Temp. Annealing Period 1* 28 850°C 48 hrs. 2 30 850°C 48 hra. 3 40 900°C 48 hrs. 4 45 900°C 48 hre. 5** 50 900°C 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. 0 10 95 1250 C 48 hrs. * Alloy Prepared by Metal Hydrides Inc., Beverly, SSe ** Alloy Prepared by Metal Hydrides Inc., Beverly, 8S. 18 EXAMIN TION OF Ti-Ou ALLOYS Chemical Analysis: Titanium is rapidly attached by concentrated H SO , con 2 4 centrated HOI, and concentrated HN0 , but the samples of 3 titanium and copper went into solution in these acids only with great difficulty. A combination of mixed acida of 3 parts of concentrated HzS0 , 1 part of concentrated HN0 , and 2 parts of 4 3 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. 19 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. of distilled H20 and 5 - 10 ml. of conc. HC1 .f Filter into a 500 mI. beaker Jt Wash the residue with hot H20 Jt Save the filtrate for a Cu an~sis it Add 15 ml. of cone. HCl and 200 ml. of hot H20 it Boil and add NH40H until it is ammoriiacal V Filter and wash clean V Dry residue at 110°C Ignite at 2000°: to constant weight %Ti _ wt. of Ti02 x 0.5995 x 100 0.500 lleagent6 Used: SO 1. Mixed Acids: 1 part HN03, 2 parts HC1, 3 parts H2 4 2. Concentrated NH40H 3. Concentrated HC1 4. Concentrated HN03 Concentrated H 5. 2So4 6. Litmus 20 \Fig. H- CHEMICAL ANALYSIS fLOWSHEET FOR %Cu in Ti-Cu ALWYS Standard Potassium Cyanide Solution: 35 ginS. of the salt dissolved in 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 • .v Neutralize the solution. V D~lute, and titrate as directed under Procedure. I 0.5 Wt. of Cu/ml. of standard KCN solution. ml. KCN soln. Procedure: Solutio containing eu is neutralized with Na2C03 or NaOH, the reagent is added until a slight precipitate forms. ~ 1 ml. of NH 0H is added. 4 i- Titrate solution with standard KCN solution color changes: blue~pink:colorless. ml. of KCN x factor/ml. = Wt. of Cu %au =;(t. of Cu x 100 0.500 Reagents Used: 1. KeN salt 2. Pure Cu 3. Dilute HN03 4. NabH 21 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. 22 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 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 11r Loss 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. " 0.8" aDD ~pocii'ic Volt~ As A Function of CompOB iti on aZi 0.2Do o/~ 0.180 0.110 § O./iJO oJ r-I 0 :::. ....0 t:)./fO ....'H 0 8- (J./¥o Ul f:)./~O 0./20 0-110 a. k:)O c. .., /0 au Ti w"rft ., .. ~"""'Jaor"ll""~ .uo ...... UMt lolA(Mte -..u I. • ••• ~.~ ...... a.. ~.., Q. o o o ...... po o... po Co"" ~I> 1e.-r..T ~ • , 1&. 1 IIlcropllGt_ter ~"'1Jll;tII,, 1'cMl&erJ'lat birD or 2S n - 12l' eu • Alloy 01 sa.p1.------2~1-12$tyTube 811 t-----.". Date------Deo. 29 Tube "00(0 ----1<> Jad1Ation--eu a.1!:8r sl1t-}le ...... ;;OH~"O • c..n. ~. • • • c II) II) 10 II) T. c... CO"~Ol/tG .. .,.CiT.'. l') ~ q M o &--t' LT ..r r .If N ~ l'It ~ til l'It N 32 L 2 ; :_..1. Jj r~t-'f'~-I I 0 ;. ·f I I ., I I I I ! : ., i "' • L • • I· I j::lj~~~' ~ I• ~ .... ! Q 'J I Jj' I. ~ ~ l~ r': ..I~ I e ~ ~ -'f I s"0°3 ;: ~e~ i!iri : 'J c ~ I to ~ q~ i j I ..S po L g t' ".. f· ! I II' trt;, ,- I 1..1 q 10 ...... li .. .B~3 :t• ... 1~·8'il3 ! ! ... F. ~ I ~ ~ ..~ !~. t~· QL ~ , ~ • .. I Sl'.... , ~ i .... t ~~ ~ ~ ... §• l:l • t ~ • e t' C , ~ ~ ~ 1~1tQ~1K4 ~ U ...... OII ...... -.cJIwnl ...... Y:If ...... n ...... tla.L..... "'MOW_ .... " ..... 1 "-M... ""'O.:J ...... ow ...... , e_Of'tpw,. Q -'1 o ... , .. .; ? • ~"lr • - r1~.' W.cr~r Tr&Clnc of TIW Pa.!.er PlLt_rD of 60%T1 - &OJ'eu at • All"" ,a----6O!'T1-5O)I:Ca TUbe 8lit---'tu:. DKte------Deo. 29 Tube .d~---h liOIlia1;io~-eu Goi~rSlit--ltHl. rUter---:1 Gei~orWod,e--12 TUbe CUTr.";"6.l_ ~l1tud.. ---1G Cll • Volta,o---:lZkY DuipiDt------e • ...... :- ... • • 10 OwPIH/4 o,flCPOlIN» II) '(',..T.: J II) II) '! c...r.:! To: . - 40 c. r.: .. .. It I") ~ Ne~ liN II 1.1 .I, .. " %7" " If ... 6 ~ ..... " ... .. I .... .,~...,.... -=t ...... - -.u. oUt ...... OIIt ...... to looee ~M' ..nit...... ,.~ ... tuMC)H ..... tIW"-anlloW 00 ...... n...... -oIfe .. LI A ...0 .. -- ~ ~ ~r~t.r ;. ... b& of The I ...... - p-.er hi 'a.JC'• l • ... ,...... • CI co to to to 10 3.5 • J I I I ~ P rI I } ; I~ e 9 L lil .. t . •• I 1 • I' I! II I" • 9 ~ 2.-_ 0_.__-- ~~- ~ .... \I• ~~ • I ~ I ! t Q 1" ~ ! ..... ~ e •1-· i= I:~ I_ "... I ~~. ! ~ ~ 8 I C~· I, t • ~ ~ " e I .".. n ·w. ~t--..ltO"""I'"00 UdlltlMlUwt N.-oer. Mot..I. "'..... , .&.H...... O, "._1-"ON a~lof:) o Q o o ...... Fia:;. 7 1I1"l'o~teT TT... !.D&of :rJw PowdeT Paii:.e,.. of aof, T1 - 20% Cu • llloy III III 5~::Iple----~i-20';CU Tube 511\.---1"". Date.------Dec. 29 TIl',. ""c1r;e----17 !lad bction---::u Ce1 -er Slit--- t&l~. Fi1ttlr---- .1 Gei,."r Wedr.--1 fD ~iJaC\.;.rrexr.-o.L... .lJIpl1cu 0---- CI III ·J~lta - e----S2kv Dupi ------1 e.1'410""S> ,~,.<, .".. "" "" "" .- CI • CI II 00 ~ , - III '\Il III to , 10 e.... PoII~, ~Cf ...... - ...... JI ...... I • .""".... J ., ~ ., f'» I't ..... ¥vIvI- tA ~ C) e ----"'"r{ ~ .N .u .z.s- Z7 J.! .V ..IJ d ~ JI : ' . N N fit fit - N 31 J. iii f; l; 0 0\- I'" I I. 1.-1'.'1 I I .I I I 1 L I I I I I ,I .1 ! I - L ~ • • ~ ~ ;~~~~~ ~ ",. '"" ,.. II I I 1/ : Q ~<". l~~ill '" ~ ;l .. i '.. S". 's ;iJ~~j- t. ~~! 1 g !'8f~ ~ .. ! ... ~ 0 f~ • • ':l' Itt=~· i ~~': !.~ II§' '8"~u "i II IIII ~! I '.l: :i! 1 :;l"o I; j ai'.sI'..... ~ ~ lt 0 •I ... - ... - - . r'~-.... .- " \:! i- ~ .... i~ ~ .... ~ ~ t 41 TABLE VI X-RAY DIFFRACTION OAT * (Cu Ka Radiation) O Substance 1/11 d in A Ti 1.00 2.23 0.2.7 2.54 0.2.0 2.34 0.1.3 1.72. 0.13 1.470 0.13 1..3.30 0.11 1.248 0.05 1.2..30 0.01 1.2.75 Cu 1.00 2.08 0.53 1.81 0•.3.3 1.277 0•.3.3 1.089 0.09 1.04.3 0.03 0.905 TiC l.00 2.15 0.75 2.49 0.50 1.52 0.25 1.300 0.10 1.245 0.09 0.965 0.05 0.990 0.05 0.881 0.03 1.079 0.02 0.8.31 Ti02 (anatase) 1.00 .3.52 0.40 1.88 0.28 1.70 0.24 2•.37 0.24 1.66 0.2.4 1.480 0.11 1.262 O.OS 1.362 0.00 1.335 * J. D. Hanawalt, Rinn, H. W., and Frevel, L. K., Indu trial and Engineering Chemistry, Anal. Ed., Vol. 10, No.9, 1938. ,TABLE VI (CONT'D) Substance III1 d in AO Ti02 (anatase) 0.06 1.164 0.03 1.045 0.02 0.950 0.02 0.913 0.02 0.894 Ti02 (rutile) 1.00 1.69 0.80 3.24 0.60 2.49 0.30 2.19 0.30 1.62 0.30 1.355 0.20 1.485 0.20 1.449 0.12 2.05 0.08 1.170 0.08 1.091 0.08 1.040 0.08 0.890 0.04 2.29 0.04 1.245 0.04 1.147 0.04 0.964 0.04 0.875 0.04 0.832 0.04 0.822 0.02 0.903 0.02 0.843 TiO 1.00 2.12 0.80 2.45 0.80 1.498 0.60 1.277 0.60 1.222 0.60 0.947 0.60 0.864 0.60 0.815 0.40 1.058 0.40 0.972 43 TABLE VI (CONTID) ! Substance 1/11 din 0 TiN 1.00 2.20 1.00 1.555 1.00 0.984 1.00 0.898 1.00 0.847 0.70 2.54 0.70 1.327 0.70 1.270 0.50 1.100 0.50 1.009 1.00 TiH2 2.62 0.27 2.26 0.24 1.58 0.19 1.35 0.08 1.28 44 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 Copper 28% Ti) 45 25.35 1.80 II 30 37.15 1.27 " 22 44.85 1.13 " 132 20.95 2.15 Compound 67 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 Compound 19 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 45 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 Titanium 5 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 Titanium 10 19.6 2.29 " 5 26.50 1.72 " 5 31.40 1.47 " 9 38.10 1.24 11 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 Titanium 8 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 Titanium 13 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 47 TABLE VIII d-VAllJES ASSIGNED TO SPECIFIC PHASES Run Numbers If! #2 #3 #4 #5 #6 #7 #8 #9 28% 30% 40% 50% 60% 70% 80% 90% 95% Pure Phase Ti Ti Ti Ti Ti Ti Ti Ti T1 Phase Copper 2.07 2.03 2.07 2.07 2.08 1.80 1.79 1.79 1.80 1.80 1.27 1.27 1.26 1.27 1.277 1.13 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 2.14 1.97 1.93 1.96 1.97 1.97 1.99 1.97 1.30 1.33 1.32 1.32 1.32 1.32 1.34 1.32 2.43 2.37 2.45 2.45 2.45 2.48 2.45 2.47 2.49 2.45 1.55 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 2.23 2.54 2.54 2.33 2.34-- 2.29 2.35 2.34 1.69 1.69 1.72 1.70 1.73 1.72 1.46 1.46 1.47 1.47 1.23 1.21 1.24 1.24 1.24 1.248 1.23 1.23 1.29 1.336 1.330 48 TABLE IX TUKON HARDNESS TESTS RESJLTS %Ti phases 28 .30 40 50 60 70 80 90 95 ~ Copper Solid Knoop Hardness .317 .325 .325 319 ------~ Solution R "C" II .30 32 .32 30.5 ------Eutectic ( 'f Compound or Knoop Ha.rdness 560 565 795 1052 1050 1048 - -- - ~~mpounds R UC" " 52 53 65.5 Ofr Scal ------ Knoop Hardness 792 760 592 487 .371 Eutectic R "C" II 65 6.3 54 46 36 Titanium. Knoop Hardness 850 841- 692 or R "ell II 70 69 60 Ti solid solution 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 0 100 ------4.50 * See Graph o. 1, page 29. * Handbook of Chemistry and Physics, 30th d., Chemical Rubber Publishing Co., 1947, p. 306, p. 287 50 Figure 12 l00x Titanium-Copper alloy, 28 wt. %Ti, as cast, NH~OH: etched in H20: H202; FeC13• Widmanstatten Structure. Dark portions of eutectic. White matrix which appears to be compound. 51 Figure 13 '1001 Titanimn-Copper alloy, 28 wt. %Ti, as annealed at 850°C for 48 hra. 5 sec. etch in 4% HF. Coarse Eutectic Structure. Black areas are polishing pits. Figure 14 500x Titanimn-Copper alloy, 28 wt. %Ti, as annealed at 850°C for 48 hrs. 5 sec. etch in 4% HF. Coarse Eutectic Structure. 52 Figure 15 lOOX Titanium-Copper alloy, 30 wt.% Ti, as cast, FeCl~. etched in NH40H: H20: H202; White area of compound and eutectic. Bla~k areas are polishing pits. F;1.gure 16 SOOX Titanium-Copper alloy, 30 wt. %Ti, as cast, etched in NH40H:H20:H202; FeC1 • White areas of compound and eutectic. 3 53 'Figure 17 lOOX Titanium-Copper alloy, 30 wt. %Ti, as annealed at 850°C for 48 hra. Etched in NHl&.0H:H20 ~02; FeC13• White areas of Compound and eutectic. Figure 18 500X Titanium-Copper alloy, 30 wt. %Ti, as annealed NH~OH:H20:H202; at 850°C for 48 hra. Etched in Fee13• White areas of compound and eutect~c. 54 Figure 19 1100X Titanium-Copp1er alloy, 40 wt.% Ti, as cast, etched in NH 0H:H20:H202; FeC13• White areas of compound 4and eutectic. ,Figure 20 500X Titanium-Copper alloy, 40 wt. %Ti, as cast, etched in NH40H:H20:H202; FeC1 " White areas of compound 8..1'1d eutectic. 3 55 'Figure 21 lOOX Titanium-Copper alloy, 40 wt. %Ti, as annealed at 850°C for 48 hrs. 10 sec. etch in 4% HF. Shaded areas of eutectic. Matrix of compound. Dark areas are polishing pits• . -:r Figure 22 500X Titanium-Copper alloy, 40 wt. %Ti, as annealed at 850°C for 48 hrs. 10 sec. etch in 4% HF. Shaded areas of eutectic in a matrix of compound. 56 !Figure 23 lOOX Titanium-Copper alloy, 50 wt. %Ti, as cast, etched in NH40H:H20:H202} FeCl~. Islands and stringers of eutectic in a mat~ix of compound. 57 Figure 24 Titanium-Copper alloy, 50 wt. %Ti, as annealed at 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 annealed at 9000C for 48 hrs. 10 s c etch in 5% HF. Dark portions of eutectic in a matrix of compound. 58 .Figure 26 lOOX Titanium-Copper alloy, 60 wt.. %Ti, a8 cast, et.ched in NHl&.0H: H20: H202; FeCl). Dark areas of eut.ectic in a matrix of compound. 59 .Figure 27 lOOX Titanium-Copper alloy, 60 wt. %Ti, as annealed at 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 .,OOX Titanium-Copper alloy, 60 wt. %Ti, as annealed at 950°C for 48 hra. 15 sec. etch in 5% HF. Shaded portions of eutectic in a matrix of compound. 60 ~igure 29 lOOX Titanium-Copper alloy, 70 wt. %Ti, as cast, etched in NH 0H:H20:H202; FeC1J • White portions of compound 4and eutectic• .Figure 30 ,500x Titanium-Copper alloy, 70 wt. %Ti, as east, etched in NH40H:H20:H202; Feel " White portions of compound and eutectic. J 61 Figure 31 100x Titanium-Copper alloy, 70 wt. %Ti, as annealed at 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 annealed at 1oo00 C for 48 hra. 15 sec. etch in 5% HF. Shaded 'areas of eutectic. White areas of compound. 62 Figure 33 lOOX Titanium-Copper alloy, 80 wt. %Ti, a s annealed at ll000 C for 48 bra. 15 Sec. etch in 5% HF. White dendrites of titanium in a matrix of what appears to be eutectic. Figure 34 500x Titanium-Copper alloy, 80 wt. %Ti, as annealed at llOOoC for 48 hre. 15 sec. etch in 5% HF. White dendrites of titanium in a matrix of what appears to be eutectic. 63 ~ .,..'\"'''r~..,..,'. _',,1.,· ,.•. ~ '. ; ~Qc~" . ".;':'~ ...~ '~. 0.'''. , 'j' , .. ~ "","0' "l '!J " • I .,.'~,,~~':""it', ~ ,",,"~.',i',,:, • '" I ,', 'l,''. >... ~,,', 1':, ",• ", " I ''''L'", '~,' '-:, T' '.,i/: ... .; "': ,/ l '. .,.- 'IIiJI' ," ;• ~t:. .: '" :"~ ,:: ',"I'l.... ':':.' : '" '":,-:' :. :,. ,l' ..'\. ~~ '.' ~ .. ,/,'.. 0 • , 0 - to ....·~t..,~~x...... I;~"O: , ,1,. .. iii'"I •.\ ',,":' ", . ~ .'.. '"... . 0".,:,." .--. ~ ""'\', "'. ,., " ' " ,.. .. ,,", ....,..'-' •,",;. ~"'''''",'i -" ,', '", .,/, ,'~, >; • ,'" 1 ''',' ;." ", 1 '''1. ••.••, '.','.: _.>' « ~~"t;'.$~.,,:. ,~, ' .. '."~ .¢!..; "-!Iv, .::-. ....'Y:, .. •"-~..•....I J .., ....~ lJ t- • '."\.~ " ',' '.." , t .. . , .>f)''..•."J . .1.....-1: -:--'~"~ ...\' I .\. -'\1." \ ~ Figure 35 100X Titanium-Copper alloy, 90 wt. %Ti, as annealed at 12000 C for 48 bra. 15 sec. etch in 5% HF. White dendrites of titanium in a matrix of '\toIhat a.ppears to be eutectic. n~re36 ~~ Titanium-Copper alloy, 90 wt. %Ti, as annealed at 12000C tor 48 br • 15 sec. etch in 5% HF. White dendrites ot titanium and a matrix that appears to be eutectic. 64 --- Figure 37 lOOX Titanium-Copper alloy, 95 wt. %Ti, as annealed at 12500 C for 48 hra. 15 sec. etch in 5% 1iF. White areas of titanium in a matrix of what appears to be eutectic. Figure 38 500X Titanium-Copper alloy, 95 wt. %Ti, as annealed at 12500C tor J.J3 hrs. 15 sec. etch in 51> HF. White areas of Titanium in a matrix of what appears to 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 on Metallurgical Research, 1940. 2. Wartmann, F. S., U. S. Bureau of Mines Conference on etallurgical 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 Series No.1, 1947, pp. 110 - 113. 10. Dean, R. S., and Silkes, B., I.C. 7381, U. S. Bureau of 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.