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3-4 E 9%-4 a 77OARWAY CORROSION-RESISTANT ALLOYS Filed June 18, 1959 2

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3-4 E 9%-4 a 77OARWAY CORROSION-RESISTANT ALLOYS Filed June 18, 1959 2 Nov. 13, 1962 M, STERN 3,063,835 CORROSION-RESISTANT ALLOYS Filed June l8, 1959 2 Sheets-Sheet OOOO O - 3%% HC O,OOO O - 5% HC - O2, HC 4,000 OOO O O% BOING, HC oo: \\ e E 400 s t 5%. BOLING HC H O s \\ He: 2 2 as - O aw O u? ov 2 2 OCa 2/ g U O 3%. BOLNG HC U O O. O O. O2 O.3 0.4 O.5 .O.6 O7 PER CENT PALLADIUM 36/f INVENTOR. MILTON STERN /3-4 e 9%-4 a 77OARWAY CORROSION-RESISTANT ALLOYS Filed June 18, 1959 2. Sheets-Sheet 2 40,000 O - 4% H2SO4. 40,000 O-5% H2SO4. OOO 0 - 40%H2SO4 IO 400 O2 BOILING H2SO4. s f s E O O O 100 rg a/ O 5% BOILING H2SO4. asa Ol d 2 2 O 9. o O 3 2 R O oa sa da OU y O c S. O % BOILNG H2SO4. O O. O O. O.2 O3 O.4 O.5 PER CENT PLATINUM 12 2d2 INVENTOR. MILTON STERN BY /2414-6A 77OAWAY 2-y 3,063,835 United States Patent Office Patented Nov. 13, 1962 2 3,063,835 It is also an object of this invention to provide a meth CORROSION-RESESTANT ALLCYS od for increasing the resistance to non-oxidizing corrosive Milton Stern, Tonawanda, N.Y., assignor to Union Car media of the metals titianum, chromium, and their alloys. bide Corporation, a corporation of New York Other aims and advantages of this invention will be Fied June 18, 1959, Ser. No. 82,134 apparent from the following description and the append 0 Claims. (C. 75-175.5) ed claims. o In accordance with these objects a corrosion resistant This invention relates to corrosion-resistant alloys and, alloy is provided consisting essentially of from 0.005 to 5 particularly, to corrosion resistant alloys in which ti percent by weight in the aggregate of at least one metal tanium or chromium is the predominant metal. 0 selected from the group consisting of ruthenium, rhodium, Titanium and many of its alloys, as well as chromium palladium, osmium, iridium, platinum, gold, rhenium, and many of its alloys are noted for excellent resistance and alloys thereof, and the balance a metal selected from to oxidizing corrosive media. In non-oxidizing corrosive the group consisting of titanium, chromium, and alloys media, such as hydrochloric and sulfuric acid solutions, thereof wherein said selected metal is present in predomi these metals and alloys exhibit little or no resistance. It 5 nant amounts. would be most desirable to have available alloys capable It is believed that the important factor in obtaining the of withstanding corrosive environments ranging from desired improvement, and the principle upon which the in strongly oxidizing to weakly oxidizing or non-oxidizing. vention operates, lies in the production of sufficient local An alloy of this type would have the widest utility. For action current to anodically polarize the alloy into the plantexample, equipment. such an alloy would be invaluable in chemical 20 passive region. High local action currents are created Hydrochloric and sulfuric acids are prime examples of by high potential differences between the electrodes of non-oxidizing corrosive media. These acids enter into the galvanic couple and by shallow polarization curve many important commercial processes. They require slopes. The current required to change the potential of storing and handling equipment which combine the de 25 either cathode or anode a given amount by polarization sirable properties cited above. If a titanium alloy, for is proportional to the cathode and anode areas which, in example, were to possess resistance to non-oxidizing acid turn,alloy. are determined by the noble metal content of the solutions, in addition to its natural endowments of light ness, strength, and resistance to oxidizing acid solutions, Specific embodiments of alloys of the invention have it would be extremely useful in such applications. 30 been prepared and tested. Dramatic improvements in There have been attempts to design titanium alloys corrosion rates were obtained and are set forth in the specifically to resist attack by a strong non-oxidizing acid. following table in comparison with pure titanium and Most typical among these are compositions of 30 to 40 various titanium alloys. In these tests, the samples were percent molybdenum, balance substantially all titanium. degreased, pickled, dried, and weighed. They were then The corrosion resistance is derived in great measure from 35 immersed in boiling acid of composition and concentra the molybdenum which is itself resistant to these acids, tion as set forth, for one period of 24 hours duration, but the effectiveness of the molybdenum does not become removed, washed, and weighed again. The corrosion especially significant until amounts up to 20 percent are rate was calculated and reported as mils penetration per added. One disadvantage of this alloy is that the tend year. ency toward brittleness increases along with molybdenum 40 Table I indicates the results of noble metal additions content so that by the time 40 percent is reached, the to substantially pure titanium. Table II provides the alloy has become excessively brittle and difficult to fabri same information as to noble metal additions to binary cate. Moreover, as resistance to non-oxidizing acids is and tertiary titanium base alloys. The percentages given gained, the resistance to oxidizing acids is lost. in each case are percentages by weight of the total alloy. One widely used method for preventing corrosion is 45 to add passivating inhibitors to the environment which, it is believed, operate by producing local action current to TABLE I anodically polarize a metal into the passive potential Effect of Noble Metal Additions on Corrosion Rate of region. It is not always desirable, however, to alter the Titanium composition of a solution to prevent corrosion of the 50 equipment in which it is contained, particularly when the composition of the solution is critical or specific to Corrosion rate (mils/year) Some process. Such a means of preventing corrosion is Composition, percent noble limited to the particular case where the composition of metal Boiling T2SO4 Boiling HCl the contained solution is not critical. 55 According to scientific theory, corosion resistance can 1% 10% 3% 10% be achieved in non-oxidizing environments by artificially Ti----ss- 455.3 2,952.6 241.8 4,479.7 anodically polarizing the base metal by applying an ex Ti-0.0l Pt.-------------------------------------- 9.0 1, 41.8 Ti--0.37 Pt 1.3 39.0 1.0 71.2 ternal current (which might be termed anodic protection 60 Ti-2.00 Pt 1.0 86.0 -------------------- as opposed to cathodic protection). This method, for Ti5:00 Pt---------------------------- 46.6 ---------- 89.6 obvious reasons, would be extremely difficult to accom Ti-0.44Pd.---TiO.005Pd------------------------------------- ... 3 49.9 56.10.6 3,125.467.3 plish in chemical plant equipment. Ti--0.48 Au 3.2 206.4 8.7 145.5 Ti--0.60 Ir- Nil 44.8 2.6 87.6 It is, therefore, the primary object of this invention to Ti--(.48 Os 1.0 8.5 2.6 207.7 provide alloys of titanium and alloys of chromium which Ti--0.36 Re 8.7 ---------- 29.0 ---------- are resistant to the attack of oxidizing and non-oxidizing 65 Ti--0.5 Rh - - 2.6 48.0 ... 6 55. corrosive media. Tit).5Rul------------------- ... 6 48,0 2.3 12.7 3,063,835 4. 3 cent, no marked degree of improvement results. The TABLE noble metals may be present in the alloy either singly or Effect of Noble Metal Additions on Corrosion Rate of in any combination with each other. Titanium Base Alloys The titanium-base alloys shown in Table II also ex hibit improved corrosion resistance in non-oxidizing media Corrosion rate (mills|year) when alloyed with one of the noble metals listed. It is seen from Table II that alloys containing at least about Composition, percent additive BoilingH2SO4 Boiling HCl 80 percent by weight titanium are benefitted. Of especial significance is the titanium-molybdenum-noble metal al O loy shown in Table II. Some alloys of titanium and molybdenum are known 6 Al-H4 W--Ti--------- to possess resistance to corrosive non-oxidizing media : Al--4 W-Ti--0. P .5Al--15 V--Ti--------- because of the resistance to such media naturally possessed 2 5Al--15 V--Ti--0.1 Pd 8 Mn-Ti.--------------------- by molybdenum. The resistance to non-oxidizing media 8 Mn--Ti--0.1 Fd of a titanium-40 percent molybdenum alloy is much great 5 Mo-i-Ti------- 5 Mo-Ti--0.5 P. 500 er than the resistance of pure titanium in Such media. 0 Mo-Til----- However, the increased resistance to non-oxidizing media 10 Mo-Ti--0.2 Pd 15 Mo--C-Ti-------------. poossessed by this alloy is acquired at the expense of the 15 Mo--iC--ii--0.2 Pd resistance to oxidizing media normally possessed by ti 20 Mo-Ti----------------- 20 Mo-Ti-0.05Pd tanium. With amounts of less than 40 percent molyb 20 Mo-Ti--0. Pd denum in titanium, the resistance to non-oxidizing media 20 Mo-Ti--0.2 Pd is not as great. Below 15 percent molybdenum, a tit Corrosion rate anium molybdenum alloy shows little of this resistance (niiswear), to non-oxidizing media. However, by the addition to Composition, percent additive boiling titanium-molybdenum alloys of one of the noble metals H2SO4, 10% selected from the group ruthenium, rhodium, palladium, 4,990 0.5 C-Ti------------------------------ 177 osmium, iridium, platinium, gold and rhenium, a corrosion 0.5 C-Ti--0.5 Pt.
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