Corrosion resistant aluminum composite
United States Patent [191 Anthony et all.  
 [ 1 Apr. 22, 1975 1 1 CORROSION RESISTANT ALUMINUM COMPOSITE [73] Assignee: Saliss Aluminium Ltd., Chippis,  
 Switzerland [22] Filed: Nov. 12, 1973 [21] Appl. No.: 414,862  
 [52] U.S. Cl. 138/140; 29/191; 29/1916; 29/195; 29/1975; 75/141; 75/146; 75/148 [51] Int. Cl 1332b 15/00; C22c 21/02 [58] Field of Search 29/183, 183.5, 191, 191.6, 29/195, 197, 197.5; 75/141, 142, 143, 147, 148, 146; 138/140 [56] References Cited UNITED STATES PATENTS 3.312.535 4/1967 Anderson ct a1. 29/l83.5  
 3,496,620 2/1970 Wolfe 29/1975 Primary Examiner-R. Dean Attorney, Agent, or FirmR0bert l-l. Bachman [57] ABSTRACT A corrosion resistant aluminum composite material is disclosed which comprises a core containing from 0.2 to 0.8% manganese and from 0.05 to 0.5% silicon with the balance being essentially aluminum, and a layer of cladding material metallurgically bonded to at least one surface of the core with the cladding material consisting of from 0.8 to 1.2% manganese, and from 0.1 to 0.4% zinc, with the balance being essentially aluminum. The core material is particularly resistant to pitting corrosion. The composite material possesses a unique combination of corrosion resistance and good mechanical properties and is highly suited for the fabrication of objects for use in aqueous environments.  
 15 Claims, No Drawings BACKGROUND OF THE INVENTION A great deal of effort has been made to use aluminum and aluminum base alloys in situations where the alloys 1 contact flow streams of impure water. Specific attempts have been made to use aluminum alloys in heat exchangers wherein at least one of the fluids in the heat exchanger is impure water. In general, these efforts have not been successful and a great deal of difficulty has been encountered with the corrosion of alloys heretofore used.  
  The primary difficulty encountered with the use of aluminum alloys in aqueous situations is localized corrosion or pitting. Once small pits start to form, corrosion activity is largely limited to these pits and perforations and failure of the alloy occurs much more rapidly then it would if the corrosion were more general instead of being highly localized.  
  The preceding problem has been largely overcome by the novel composite material of the present invention. The composite material of the present invention possesses an extremely low general corrosion rate and has the property that pit depth is largely limited to the thickness of the cladding layer. Furthermore, the core possesses exceptional pitting resistance even when not protected by the cladding.  
 SUMMARY OF THE INVENTION The composite material of the present invention consists of an aluminum alloy core containing from 0.2 to 0.8% manganese and from 0.05 to 0.5% silicon, balance essentially aluminum. Metallurgically bonded to this core is an aluminum alloy cladding which contains from 0.8 to 1.2% manganese and from 0.1 to 0.4% zinc, balance essentially aluminum.  
  The core alloy possesses a unique resistance to pitting corrosion. The cladding alloy is anodic with re spect to the core material and provides sufficient galvanic currerirfor corrosion protection. The general corrosion rate of the cladding material is low relative to other commonly used aluminum cladding alloys. Thus, a relatively thin layer of cladding material can provide long term corrosion protection to the core material.  
  The composite material of the present invention may easily be fabricated using conventional commercial practice to join the two components by pressure welding. Additional advantages and benefits of the present invention will be made more apparent through reference to the following Description of the Preferred Embodiments in combination with the Drawings and the Claims.  
 DESCRIPTION OF THE PREFERRED EMBODIMENTS The composition of the components of the present invention is given in weight percentages in the following description unless otherwise specified.  
  The broad and preferred composition limits for the core material of the present invention are given in Table I below:  
 TABLE I Broad Preferred Magnesium 0 .3 0 .l Manganese .2 .8 .3 .6 Chromium 0 .1 0 .05 Silicon .05 .5 .15 .25 Copper 0 .l 0 .05 Zinc 0 .1 0 .05 Titanium 0 .2 .005 .15 Iron 0 .2 0 .08  
  The essential components of the core are manganese and silicon. The other elements listed in Table I have not been found to significantly effect the properties of the core alloy when they are present within the limits shown in the Table. Titanium may be present as a purposeful addition since it has been found to provide beneficial grain refining effect, thereby improving the mechanical properties of the core material. Naturally, any of the foregoing, non-essential impurity elements may be present in levels as low as 0.001%.  
  The broad and preferred ranges for the cladding material are given in Table II below: 11  
 TABLE II Broad Preferred Magnesium 0 .1 O .05 Manganese .8 1.2 .9 1.1 Chromium 0 .l .02 .05 Silicon 0 .05 0 .03 Copper 0 .05 0 .01 Zinc .1-.4 .l5-.25 Titanium 0 .l .005 .03 Iron 0 .l 0 .08  
 - rial along with a low general corrosion rate.  
  The composite of the present invention may be produced utilizing a wide variety of processes. Typical processes which may be utilized include processes which utilize cold deformation such as swaging or rolling and processes which utilize the deformation at elevated temperatures such as hot rolling. An exemplary process for the fabrication of the composite of the present invention is described in US. Pat. No. 3,381,366 issued to JosephWinter and assigned to the Assignee of the present application. Of course, other well known processes such as those used to produce Alclad sheet may be used.  
  The composite of the present invention has a wide variety of uses. Almost any metallic item intended for use in a corrosive aqueous environment at moderate temperatures may be fabricated from the composite of the present invention. The thickness of the cladding material generally between 2 and 20% of the total thickness of the composite. The thickness of the core may be established on the basis of mechanical properties which the finished item must possess. In general, the cladding thickness will range from 0.001 to 0.100 inches.  
  1f the composite is produced in the form of sheet, further objects such as tubing may readily be fabricated from the sheet. If tubing is fabricated from the composite of the present invention for heat exchange purposes, the tubing will preferably have a wall thickness of from 0.010 to 0.10 and a cladding thickness of from 0.001 to 0.020 inches. Tubing made of the material of the present invention may be fabricated into further objects such as fin on tube heat exchangers. Of course, pipe having a wall thickness as great as 1.0 inch may also be fabricated from the composite of the invention.  
  Normally, it is only necessary to place a cladding surface on that surface which is to be exposed to the corrosive aqueous environment. As for example, in a surface condensor used to condense waste steam using corrosive cooling water, the cladding would be present These alloys were case, homogenized for 16 hours at l,lF and were then reduced to 0.050 inch gauge H14 temper strip by conventional processing techniques. Samples of these alloys were exposed to a flowing stream of New Haven tap water at a velocity of 4 ft./sec. in a semi-circulating system. The water was partially replenished on a continuous basis at a rate of about per hour. The water was maintained at a constant temperature of C. The samples were exposed to this environment for 180 days and samples were removed at 60 day intervals prior to the 180 day final examination. Commercial alloys in generally similar conditions were exposed to the same environment for comparative purposes. Table 111 lists the composition of sample alloys along with various measured corrosion parameters at 60, 120 and 180 days. Table IV lists the approximate composition of the water to which the samples were exposed.  
 It is evident from these experimental results that alonly on the water side. However, in the fabrication of 20 loys containing controlled amounts of silicon and manthe tubing heat exchanger to exchange heat between two media, both of which are corrosive it would be necessary to fabricate the tubing from a composite material having cladding on both sides.  
 ganese in an aluminum base containing a limited amount of iron have about twice the resistance to pitting as the commercial alloys which were tested at the same time.  
 Table 111 Percentage Composition Weight Loss mg cm Mean Pit Depth Mils Maximum Pit Depth Mils Fe Si Mn Mg Cr Cu 60 days 120 days 180 days 60 days 120 days 180 days 60 days 120 days 180 days .05 .23 .31 15.1 25.1 35.1 8.4 8.7 12.6 17.8 12.4 21.0 .06 .23 .45 15.4 23.9 33.6 8.8 9.5 11.7 15.3 15.8 15.3 .06 .10 .61 1.04 .21 10.3 18.7 23.1 16.7 12.4 19.4 22.4 19.3 26.4 6061 T6 20.9 30.4 24.1 16.4 19.4 21.5 24.0 36.0 34.4 1100 H14 15.5 27.2 34.3 26.9 26.3 33.7 43.7 39.2 39.8 3003 H14 17.7 26.2 29.2 274* 274* 274* 3004 H14 15.2 26.7 29.2 13.5 33.6 38.0* 38.0 5050 H34 8.0 15.4 23.2 43.2* 43.2 432* 5052 H34 5.1 10.6 17.2 392* 392* 392* The symbols and mean that the sheet has been perforated from one side. The starred figure is the gauge of the sheet.  
  The preceeding discussion of the present invention TABLE [V will be better understood through consideration of the following illustrative examples: chlorides 120 ppm Hardness (CaCO 38.0 ppm Agalinity (CaCO ppm C ppm EXAMPLE I O2 2 12.0 ppm Calcium 14.2 ppm It has been found that p1t format1on generally starts PP 8 pp ron PP at a defect 1n the surface the alloy. It has further Magnesium 00 ppm been found that a1um1num-s1l1con solid solut1ons gener- Sodium 5 PP&#39;&#34;&#39; Sulfate .0 ppm ally res1st pitting better than h1gh pur ty aluminum al- Tom Solids 1000 ppm loys. A particular type of defect wh1ch 1s extremely pH PP troublesome with regard to pit formation are iron bearing particles or inclusions such as FeA1 The core alloy EXAMPLE 11 of the present invention has been designed to have silicon in solid solution and have a minimum of iron containing particles. Manganese has been added to surpress the formation of FeAl It has been found that particles containing manganese such as MnAl do not measurably effect the corrosion behavior of the alloy.  
  Three castings of different compositions were produced in order to verify the reasoning discussed above.  
  This Example illustrates the corrosion behavior of alloys containing about .2% zinc with varying amounts of silicon and manganese. These alloy compositions were selected on the basis of electro-chemical behavior to be galvanically protecting to the alloys of Example 1. The spectroscopic analysis of these alloys is shown in Table V.  
  These ingots were processed in the same manner as the ingots of Example I to produce 0.050 inch gauge material in the H14 temper. Galvanic couples of the two alloys shown in Table V and the first two alloys shown in Table III were fabricated and exposed to flowing New Haven tap water as described in Example I. The resultant current between an anode and cathode was measured as a function of time. The resultant data indicates that a cladding alloy containing about 1% manganese, 0.17% zinc, and 0.03% silicon provides an adequate protective current to a cathode containing 0.2% silicon, and 0.5% manganese. However, an anode consisting of 0.2% silicon, 0.5% manganese, and 0.17% zinc failed to protect a very similar cathode alloy con- TABLE VII 0.2% Offset Yield Strength 20.9 KS1 Ultimate Strength 27.] KS1 Elongation 1n 2 Inches 3.  
 TABLE VIII Corrosion Of Experimental Alloy And Controls In Flowing New Haven Tap Water At C EXAMPLE III A composite material was produced based on the information developed in previous experiments. The composition of the cladding and the core of this composite is listed below.  
 TABLE VI It is apparent from these results that the general corrosion rate of the present invention is considerably less than that of Alclad 3004 and the 3003 alloy. It is significant that both the mean and max. depths of the experimental composite are significantly less than pit depths measured in the control alloys. The mean pit depth in the experimental alloys is approximately equal to the cladding thickness while the mean pit depth in the Alclad 3004 is nearly three times the cladding thickness. This demonstrates the effectiveness of the cladding in preventing pitting of the core alloy of the present invention.  
 Percentage Spectroscopic Analysis Of Example 111 Clad and Core Alloy lngots Si Fe Cu Mn Mg Cr Zn Ti Ingot A Cladding .035 .070 .01 1.07 01 02 .168 0.0135 Ingot B Core .198 .075 .310 0.0088  
 The cladding and core material were initially produced EXAMPLE IV in the form of ingots having a thickness of 1.75 inches. Despite the good corrosion behavior of the prasem The homogemzed for 12 hours at 1,100 composite, demonstrated in the previous example, it T claddmg mgot hot timed to a a of 0125 would be highly desirable if corrosion damage could be mch a hot ronmg tem&#39;pe ature of 800 The Core further reduced or even eliminated. It has been found ingots were milled to a thickness of 1.25 inches. The that a film of aluminum hydroxide, in the form of surfaces to be bonded together were cleaned by wire Boehmite AlzOH, can afford further Significant Prushmg and Y P decreasmg&#39; The hot rolled claddlng provements in corrosion resistance. The maximum pro- &#34;8 was cut two Parts ndyvelded to the core tective effect is observed when the thickness of the got. Cladding and core combination was then hot rolled Boehmite is between 2,000 and 20,000 Angstroms For at 800}: to a gage of The mate&#39;nal was then example, two samples of the experimental clad alloy air cooled and given a final cold reduction to 0.060  
 inch gage, resulting in a cladding thickness of about 10% of the total thickness. The longitudinal tensile properties of the finished material were as follows:-  
 discussed in Example 111 were machined so as to have a series of 7 mil deep slots in the surface of the composite. Since the thickness of the cladding layer is less than this, the machining operation serves to expose the core of the composite. This exposure of the core composite was intended to simulate forming operations which might destroy the integrity of the cladding layer. In particular, the slots were intended to simulate the welded joint in a tube formed from strip by a welding and scarfing process.  
  One of the samples was exposed to steam at 250F for 8 hours to provide a Boehmite film having a thickness of approximately 8750 Angstroms. The other sample was left untreated. The Boehmite treated specimen was then scratched on the opposite surface to the machines slots to simulate the effect of scouring of a condenser tube by solids carried through in the cooling water or by a cleaning operation. Both samples were then exposed to flowing New Haven tap water for a period of 60 days. After this 60 day exposure the samples were evaluated for corrosion damage. The results are summarized below in Table IX.  
 TABLE IX nium, 0.001 to 0.03% silicon, 0.001 to 0.01% copper, 0.15 to 0.25% zinc, and 0.001 to 0.08% iron, balance aluminum.  
  4. A composite as in claim 11 wherein the cladding has a thickness of 0.001 to 0.100 inches.  
 5. A corrosion resistant aluminum alloy composite comprising:  
 A. an aluminum alloy core consisting essentially of from 0.001 to 0.3% magnesium, 0.2 to 0.8% manganese, 0.001 to 0.1% chromium, 0.001 to 0.2% titanium, 0.05 to 0.5% silicon, 0.001 to 0.2% iron, 0.001 to 0.1% copper, and 0.001 to 0.1% zinc, balance aluminum;  
  an aluminum alloy cladding, metallurgically bonded to at least one surface of the core consisting essentially of from 0.001 to 0.1% magnesium, 0.8 to 1.2% manganese, 0.001 to 0.1% chromium, .001 to .l% titanium, 0.001 to 0.05%silicon, 0.001  
 General Corrosion Evaluation Of Example IV Test Samples *Crevice corrosion near point of support. Insufficient data to form an accurate mean value.  
 It is apparent that the Boehmite treatment has significantly reduced the corrosion tendency of the composite material over the time period investigated. In particular, the weight loss in milligrams per square centimeter was 0, to within the limits of the experimental apparatus used, and the only sign of pit formation was a form of crevice corrosion which occurred near the point where the samples were supported. This form of corrosion can easily be avoided by proper design. Even the destruction of the Boehmite film integrity by scratching does not lead to pit formation.  
 What is claimed is:  
  1. A corrosion resistant aluminum alloy composite comprising:  
 A. an aluminum alloy core consisting essentially of from 0.001 to 0.3% magnesium, 0.2 to 0.8% manganese, 0.001 to 0.1% chromium, 0.001 to 0.2% titanium, 0.05 to 0.5% silicon, 0.001 to 0.2% iron, 0.001 to 0.1% copper, and 0.001 to 0.1% zinc, balance aluminum; and  
  an aluminum alloy cladding, metallurgically bonded to at least one surface of the core, consisting essentially of from 0.001 to 0.1% magnesium, 0.8 to 1.2% manganese, 0.001 to .l% chromium, .001 to .l% titanium, 0.001 to 0.05% silicon, 0.001 to 0.05% copper, 0.1 to 0.4% zinc, and 0.001 to 0.1% iron, balance aluminum.  
  2. A composite as in claim 1 wherein the core contains from 0.001 to 0.1% magnesium, 0.3 to 0.6% manganese, 0.001 to 0.05% chromium, 0.005 to .15% titanium, 0.15 to 0.25% silicon, 0.001 to 0.08% iron, 0.001 to .05% copper, 0.001 to 0.05% zinc, balance aluminum.  
  3. A composite as in claim 1 wherein the cladding contains 0.001 to 0.05% magnesium, 0.9 to 1.1% manganese, 0.02 to 0.05% chromium, 0.005 to 0.03% titato 0.05% copper, 0.1 to 0.4% zinc, and 0.001 to 0.1% iron, balance aluminum; and  
 C. a layer of Boehmite, having a thickness of from 2,000 to 20,000 A, formed on the cladding.  
  6. A composite as in claim 5 wherein the core contains from 0.001 to 0.1% magnesium, 0.3 to 06% manganese, 0.001 to 0.05% chromium, 0.005 to .15% titanium, 0.15 to 0.25% silicon, 0.001 to 0.08% iron, 0.001 to 0.05% copper, 0.001 to 0.05% Zinc, balance aluminum.  
  7. A composite as in claim 5 wherein the cladding contains 0.001 to 0.05% magnesium, 0.9 to 1.1% manganese, 0.02 to 0.05% chromium, 0.005 to 0.03% titanium, 0.001 to 0.03% silicon, 0.001 to 0.01% copper, 0.15 to 0.25% zinc, and 0.001 to 0.08% iron, balance aluminum.  
 8. A composite tubing comprising:  
 A. an aluminum alloy core consisting essentially of from 0.001 to 0.3% magnesium, 0.2 to 0.8%. manganese, 0.001 to 0.1% chromium, 0.001 to .2% titanium, 0.05 to 0.5% silicon, 0.001 to 0.2% iron, 0.001 to 0.1% copper, and 0.001 to 0.1% zinc, balance aluminum; and  
 B. an aluminum alloy cladding, metallurgically bonded to at least one surface of the core, consisting essentially of from 0.001 to 0.1% magnesium, 0.8 to 1.2% manganese, 0.001 to 0.1% chromium, 0.001 to 0.1% titanium, 0.001 to 0.05% silicon, 0.001 to 0.05% copper, 0.1 to 0.4% zinc, and 0.001 to 0.1% iron, balance aluminum.  
  9. A composite tubing as in claim 8 wherein the core contains from 0.001 to 0.1% magnesium, 0.3 to 0.6% manganese, 0.001 to 0.05% chromium, 0.005 to 0.15% titanium, 0.15 to 0.25% silicon, 0.001 to 0.08% iron, 0.001 to 0.05% copper, 0.001 to 0.05% zinc, balance aluminum.  
  10. A composite as in claim 8 wherein the cladding contains 0.001 to 0.05% magnesium, 0.9 to 1.1% manganese, 0.02 to 0.05% chromium, 0.005 to 0.03% titanium, 0.001 to 0.03% silicon, 0.001 to 0.01% copper, 0.15 to 0.25% zinc, and 0.001 to 0.08% iron, balance aluminum.  
  11. A composite tubing as in claim 8 wherein the cladding has a thickness of 0.001 to 0.100 inches.  
 12. A composite tubing comprising:  
 A. an aluminum alloy core consisting essentially of from 0.001 to 0.3% magnesium, 0.2 to 0.8% manganese, 0.001 to 0.1% chromium, 0.001 to 0.2% titanium, 0.05 to 0.5% silicon, 0.001 to 0.2% iron, 0.001 to 0.1% copper, and 0.001 to 0.1% zinc, balance aluminum;  
 B. an aluminum alloy cladding, metallurgically bonded to at least one surface of the core, consisting essentially of from 0.001 to 0.1% magnesium, 0.8 to 1.2% manganese, 0.001 to 0.1% chromium, 0.001 to 0.1% titanium, 0.001 to 0.05% silicon,  
 0.001 to 0.05% copper, 0.1. to 0.4% zinc, and 0.001 to 0.1% iron, balance aluminum; and  
 C. a layer of Boehmite, having a thickness of from 2,000 to 20,000 A, formed on the cladding.  
  13. A composite tubing as in claim 12 wherein the core contains from 0.001 to 0.1% magnesium, 0.3 to 0.6% manganese, 0.001 to 0.05% chromium, 0.005 to 0.15% titanium, 0.15 to 0.25% silicon, 0.001 to 0.08% iron, 0.001 to 0.05% copper, and 0.001 to 0.05% zinc, balance aluminum.  
  14. A composite tubing as in claim 12 wherein the cladding contains 0.001 to 0.05% magnesium, 0.9 to 1.1% manganese, 0.02 to 0.05% chromium, 0.005 to 0.03% titanium, 0.001 to 0.03% silicon, 0.001 to 0.01% copper, 0.15 to 0.25% zinc, and 0.001 to 0.08% iron, balance aluminum.  
 15. A composite tubing as in claim 12 wherein the cladding has a thickness of 0.001 to 0.100 inches.