US3214251A - Preparation of laminate metal stock by use of organic anti-welding materials - Google Patents

Preparation of laminate metal stock by use of organic anti-welding materials Download PDF

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US3214251A
US3214251A US44148A US4414860A US3214251A US 3214251 A US3214251 A US 3214251A US 44148 A US44148 A US 44148A US 4414860 A US4414860 A US 4414860A US 3214251 A US3214251 A US 3214251A
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resist
rolling
billet
hot
degrees
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Robert M Brick
Robert B Mesrobian
Hansson Ants
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Continental Can Co Inc
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Continental Can Co Inc
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Priority to GB42611/60A priority patent/GB969211A/en
Priority to CH39761A priority patent/CH400972A/fr
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
    • B21C37/14—Making tubes from double flat material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D51/00—Making hollow objects
    • B21D51/16—Making hollow objects characterised by the use of the objects
    • B21D51/26—Making hollow objects characterised by the use of the objects cans or tins; Closing same in a permanent manner
    • B21D51/2669—Transforming the shape of formed can bodies; Forming can bodies from flattened tubular blanks; Flattening can bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D51/00—Making hollow objects
    • B21D51/16—Making hollow objects characterised by the use of the objects
    • B21D51/26—Making hollow objects characterised by the use of the objects cans or tins; Closing same in a permanent manner
    • B21D51/2676—Cans or tins having longitudinal or helical seams
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4935—Heat exchanger or boiler making
    • Y10T29/49366—Sheet joined to sheet
    • Y10T29/49369—Utilizing bond inhibiting material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4998—Combined manufacture including applying or shaping of fluent material
    • Y10T29/49982—Coating
    • Y10T29/49984—Coating and casting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12292—Workpiece with longitudinal passageway or stopweld material [e.g., for tubular stock, etc.]

Definitions

  • the billet could be an ingot having one or more longitudinal channels filled by such a resist, and produced by casting the metal around a coherent core of such resist material; or longitudinal hollow channels could be formed during casting, or subsequently by drilling, and later filled with the resist material.
  • the billet may be originally 8, 12 or more inches in thickness, and the internal discontinuity may be /2 inch or more thick; noting that when the refractory resist powder is later introduced, the permissible minimum thickness depends upon the ability to produce an essentially uniform deposit of the powder therein: and that when a preformed core of coherent refractory powder is used, a similar minimum must be observed to avoid disruption during the casting.
  • the purpose of the resist or antiwelding compound is to prevent the welding or sticking together of the laminations, and for this a microscopically thin film is as effective as a thicker one: noting that the metal provides the laminations which produce the final product. It is desirtble to keep the resist dimension as thin as possible in the ingot but thicknesses of less than a half-inch, in an ingot which is 6 to 14 feet long, are not easily filled to uniform packing density with a dry refractory powder.
  • liquefiable materials as set out hereinafter may be introduced into billet channels, with the billet being heated and then subjected to a schedule of hot and cold rolling, without loss of the ability of the organic compound to function as an antiwelding material during the hot and cold rolling operations by which a billet 12 inches thick may be reduced to a total thickness of, say, 0.016 inch with two metal laminations each 0.008 inch thick being separated by a microscopically thin residual layer of the resist material.
  • the function of preventing welding is then not dependent upon the particle size of the resist residue, and therewith the original channel in the billet, for receiving the resist, may be made much thinner than with powder resists, e.g., organic resists in channel A; inch or less thick are found as effective in an ingot as a powder resist thickness of /z inch or more, and therewith calipering of the final thickness of the rolled laminate strip can directly determine the thickness of each lamination without need of allowance for the resist residue.
  • powder resists e.g., organic resists in channel A; inch or less thick are found as effective in an ingot as a powder resist thickness of /z inch or more, and therewith calipering of the final thickness of the rolled laminate strip can directly determine the thickness of each lamination without need of allowance for the resist residue.
  • Hot rolling refers to a temperature condition at which the metal does not exhibit strain-hardening: and cold-rolling of the metal to a temperature at which strain-hardening occurs.
  • hot-rolling of aluminum alloys ceases as the material cools to about 650 degrees F., and the subsequent rolling at lower temperatures effects strain-hardening.
  • organic compounds can be chosen, in accordance with this invention, which do not require removal, but which bond directly with later-applied organic enamels and lacquers and in effect become a part thereof.
  • the word liquid is herein used to define that state of the selected anti-welding substance in which the molecules are able to change their positions plastically with respect to one another at the temperature and under the local pressure effects of hot-reduction of the metal which surrounds and encloses the substance and in which the said substance spreads to occupy the cross-section of the channel during the hot-reduction: with the relative movement being restricted by inter-molecular forces so that an essentially fixed volume is maintained. Therewith the substance does not fracture under the heat and pressure of hot reduction, but retains continuity and in part moves along the channel as the metal and the anti-welding substance are being reduced in thickness and extended in length.
  • the word solid is herein used to define that state at a lower temperature of an organic compound, which is liquid at a higher temperature, at which the molecules are so strongly coupled that the compound does not flow under the action of gravity, and in which it exerts a stiff resistance to molecular change of relative position but has capability of being extended and of maintaining a continuous layer between the surfaces of the channel during cold-reduction, without exhibiting brittleness or breaking into fragments which separate from one another during the course of the cold reduction and permit the movement of the metal forming such surfaces into welding contact with one another.
  • melting and liquefaction are used herein to define the change of such anti-welding substances, upon heating to the hot reduction or treating temperature, so that its viscosity is lowered and its ability to flow is increased whereby it spreads and produces within the billet being rolled a continuous body of weld-preventing material.
  • An object of this invention is the reparation of a metal billet containing a longitudinal internal channel, and the heating and rolling of the same for producing a laminate strip, with the employment in the: channel of an anti-welding or resist material which is stiffly resistant to flow at room temperature, which becomes liquid at the temperature and pressure scheduled for the hot-rolling of the billet, and which is later effective during cold-rolling to undergo deformation and extension or for maintaining its anti-welding action.
  • Another object of this invention is the preparation of a metal billet containing an organic resist, and the reduction of the same to a desired over-all thickness by a schedule including hot-rolling and heat treatment at temperatures appropriate to the metal.
  • Another object is the employment, as a resist, of a material of non-abrasive characteristics, and therewith having essentially no abrasive action upon the rolls, tools, and other equipment coming in contact therewith.
  • Another object is the employment, as a resist, of an organic compound compatible with an organic enamel or lacquer later applied thereover.
  • a further object is the employment, as a resist, of an organic compound which, during the course of a schedule of hot and cold rollings, remains effective to prevent welding of metal laminae separated thereby, and to maintain such behavior in extremely thin layers and therewith provide smooth adjacent surfaces on such laminae.
  • a further object is the preparation of laminate stock by forming an ingot with a small internal channel, filling the channel with a resist which is liquid at the beginning of hot-rolling, and final rolling of the same with passes which are at temperatures under which the resist is essentially an extensible solid.
  • FIGURE 1 is a perspective view of part of a billet having core channels or internal discontinuities with parallel plane sides and chisel-shaped edges;
  • FIGURE 2 is a perspective view of a part of a billet having core channels of rounded edge form
  • FIGURE 3 is a perspective view, showing the ingot end being closed by peening and welding;
  • FIGURE 4 is a perspective view of an ingot having longitudinal internal channels, being filled with an organic resist
  • FIGURE 5 shows in conventionalized block form a schedule of heating and rolling operations
  • FIGURE 6 is a conventionalized perspective view showing the placing of a resist in a billet channel immediately prior to hot rolling
  • FIGURE 7 shows, on a larger scale than FIGURES 1 to 6, a part of a multi-wide rolled strip
  • FIGURE 8 shows the opening or expansion of a section of the strip to form a tubular body
  • FIGURE 9 shows the application of an organic enamel to the interior surface of such a body.
  • a preliminary breakdown or conformance rolling may be accomplished to distribute the resist and reduce the channel section so that it is filled by the resist with expulsion of air, before the billet is heated to the temperature for the start of the hot rolling. The choice of specific procedure depends upon equipment available and economics, and upon the physical form of the resist at room temperature.
  • the melting and the escape of air from the pores may cause bubbling with passage of some of the liquid material into regions where closure welding is to be done: and in such cases, a low temperature heating for liquefaction is preferred, followed by the expulsion of air before the closure and heating to hot rolling temperatures.
  • a low temperature heating for liquefaction is preferred, followed by the expulsion of air before the closure and heating to hot rolling temperatures.
  • the available equipment permits the homogenizing heating of the empty billet, followed by a quick introduction of the resist, no sealing of the charged end of the channel is necessary, if this charging. is quickly followed by the initiation and completion of the hot rolling.
  • an epoxide resin (e.g., that sold commercially under the name Epon-1007), which appeared harder than aluminum, could be employed successfully by heating the billet and hot rolling until the epoxy resin resist film had a thickness of a few thousandths of an inch, during which the resist spread easily as a film: thereafter, a cold rolling proceeded with extension of the film by rupture into flakes which flattened and spread and prevented cold welding.
  • Epon-1007 epoxide resin
  • these organic resists work both when the rolling is hot with little work-hardening of the metal; and later when the rolling is cold with a relatively high workhardening of the metal.
  • a characteristic observed is that, because many of the resist materials appear to have greater adhesion to the metal than cohesion, the final strip produced permits the opening or expansion with both internal metal surfaces having parts of the residual resist layer clinging to them.
  • Example I An aluminum billet having a longitudinal internal channel was welded closed at one end. The billet was heated to 900 degrees F.; the open end raised, and a solid epoxide resin introduced as a resist into the chanel until the channel was substantially full. The resin melted as it entered and flowed downward to form the fill.
  • the epoxide resin was a bis-phenol epichlorohydrin condensate, and is illustrative of the epoxy resins which can be empolyed, being a solid at room temperature and becoming liquid at 300 degrees F., being obtainable as flakes or pellets which may be converted to a power: the resin commercially avilable under the trademark Epon- 1007 was satisfactory.
  • the billet was immediately hotrolled, with the open or charging end first presented to the rolls; and then cold-rolled, preferably after an anneal reheating to 900 degrees F., and a cooling before the coldrolling.
  • An original billet of 2 to 12 inch thickness can be hot-rolled to, say, 0.120 inch thickness, and then reduced to 0.016 inch by cold-rolling, to provide a laminate strip having two metal laminations connected integrally
  • a red brass billet (85 percent copper, 15 percent zinc) having an internal longitudinal channel with a metal wall thickness of Ms inch was heated to 950 degrees F., a slab or strip of the epoxide resin of Example 1 was introduced, and the hot rolling immediately started, bringing the billet to 0.060 inch gauge.
  • the strip was anealed at 1,100 degrees F., cooled and cold-rolled to a final gauge of 0.016 inch.
  • the metal laminations could readily be separated and bent apart to form a tubular body.
  • solvent extractions of the surface and infra red analyses indicated the presence of epoxide.
  • the internal surfaces were smooth and had a bright appearance.
  • Example 3 Like operations with billets of aluminum, zinc, magnesium and copper, and their alloys, can be performed with polyethylene as a resist, e.g., the so-called regular branched type sold under the trademark Dynk by Union Carbide Plastics Co., or the linear type sold under the trademark Marlex by Phillips Petroleum Company, or the commercial polyethylenes of other suppliers. These are obtainable in pellets which are solid at room temperature, rubbery at 300 degrees F., and melt easily when heated to 360 degrees F. or above. Such are charged into the heated billet, and the schedule of rolling from 900 degrees F. was accomplished. Upon opening the hot and cold rolled strip, the interior was found in good condition.
  • polyethylene as a resist
  • Example 4 Billets of aluminum, zinc, magnesium, and copper, and their alloys, with an end of each sealed, were heated to 350 degrees F., and charged with pellets of commercial polypropylene (e.g., that available commercially under the trademark Profax), which was solid at room temperature and became rubbery at 300 degrees F. The pellets melted and the resist filled the channel without porosity. The open ends were welded shut without incident. The charged and sealed billets were heated to 900 degrees F. and rolled. After the schedule of hot and cold rolling, the laminations of the strip can be easily separated, and the interior surfaces and residual resist were found in good condition, without welds.
  • commercial polypropylene e.g., that available commercially under the trademark Profax
  • Example 5 Billets as in Example 4 were prepared, heated to 360 degrees F., and charged with the polyethylene pellets. The open ends were welded shut, and the billets heated to 900 degrees F. and rolled. There was minor leakage at welds, with darkening of the exudate: but the interiors were in good condition after opening.
  • Example 6 A silicone resin (e.g., that sold under the Dow-Corning trademark Z-6018) can be used as the resist during a heating and hot rolling schedule.
  • a heat-hardening cyclic tetramer resin was used, of the approximate formula where R is a phenyl and R is an isopropyl group. This is effective up to temperatures of 900 degrees F. in billets of aluminum and its alloys. Upon filling into the channel with the billet at 300 degrees, the hard solid became liquid with some foaming. The end was welded shut, and the billet heated to 900 degrees F. in its schedule.
  • the exudate When there was leakage by imperfect welding, the exudate showed polymerization: the internal resin, after cooling, was found to be a porous hard resin which swelled in acetone but was not totally soluble and exhibited no damage under infra red examination.
  • the practices with the resists of Examples 1 to 3 can be performed by charging the resist into the channel or channels of a cold ingot, sealing as by welding, and then heating to hot rolling temperature and effecting the schedule of rolling operations: and the resists of Examples 4 to 6 can be employed by pre-heating the ingot to hotrolling temperature, quickly charging with the resist and immediately conducting at least the breakdown or conformance passes of hot-rolling.
  • the channel thicknesses of the ingots or billets are determined by the necessities of making such channels, rather than by the need of having a large quantity of the resist originally present.
  • the channels may be open at the ends or become opened by internal liquid pressure during the rolling, so that half or more of the resist escapes without provoking welding, during the course of the hotrolling.
  • the internal layer of resist may be of the order of one or two thousandths of an inch: and this billet can be further reduced to a strip of 0.250 inch or less thickness without welding, with most of the resists set out.
  • Example 1 In general, it has been found that the behavior of the resist during a hot-rolling schedule of up to 15 minutes can be predicted by noting the behavior of the resist when heated for a like time in a sealed autoclave of the metal.
  • Example 1 a parallel test by welding the billet at one end, heating to 300 degrees F., charging essentially fully with the epoxy resin pellets and permitting foam to subside, sealing the other end by welding, and then heating to 900 degrees F. for an hour, resulted in some leakage apparently by weld imperfection with the efiluent charring, whereas after cooling and opening, the internal protected resist had not charred and infra red examination did not indicate damage.
  • Example 7 An aluminum block having an internal channel was filled at room temperature with a polycarbonate resin
  • n represents as usual the number of the stated units in the polymer.
  • Lexan of the formula where n represents as usual the number of the stated units in the polymer.
  • the open end is easily welded shut, and no leakage develops during the heating to 900 degrees F. After heating, the resist is found in good condition, as a hard tough resin which is insoluble in acetone, and shows no damage under infra red examination.
  • the hot billet was then subjected to thirteen hot rolling passes, reducing it from 4 inches to 0.15 inch: it was annealed and rolled to 0.090 inch, followed by a further annealing. It was reduced to 0.024 inch in two passes, again annealed, and rolled to 0.016 inch. Each intermediate annealing was for one hour at 800 degrees F. The rolled strip was completely openable.
  • Example 8 A linear polyamide resin (e.g., one of those polycaprolactams known commercially by the tradenames nylon-6 or Zytel) having the following structure is employed by introducing the pellets into an aluminum billet while the latter was heated to 440 degrees F., at which temperature the resin is rubbery and can be packed. The closure welding is efi'ected. When, because of imperfect welding, there was minor leakage, there was charring of the exudate during heating for one hour at 900 degrees F. After the heating at 900 degrees F, the internal residual resin material is a light straw-colored cheesy solid, insoluble in methyl alcohol, and showing no damage under infra red examination.
  • a linear polyamide resin e.g., one of those polycaprolactams known commercially by the tradenames nylon-6 or Zytel
  • Example 9 A hollow aluminum billet with the channel closed at one end was heated to 300 degrees E, and commercial iron stearate introduced and the channel welded shut. This was a mixture of ferric tristearate and (St) Fe-O-Fe (St) where St denotes -O-CO- (CH2)17H. It was a dry powder at room temperature and liquid at 300 degrees F. When there was leakage, due to imperfect welding, during heating to 900 degrees F., the exudate charred but the internal material was found not to have changed visually, being insoluble in acetone, and showing no damage under infra red examination.
  • Example 10 The procedure of Example 9 was followed, with aluminum stearate, which is a dry powder at room temperature and is rubbery at 300 degrees F.
  • the billet was heated to 380 degrees F. for the loading; and the billet channel welded shut before heating to 900 degrees F. Again, when, because of imperfect welding, there was leakage, there was charring of the exudate. The internal material yellowed but was otherwise visually unchanged; it was insoluble in acetone and showed minor damage upon infra red examination.
  • a billet as in Example 7 was first heated at 900 degrees F. for three hours, with one end welded. It was then placed vertically, and the aluminum stearate powder introduced, with melting. The billet was then immediately pushed horizontally into the rolls for the first pass, starting with the open end: and the same rolling and annealling schedule observed. The welded trailing end burst open at the first pass, and much liquid resist was discharged. The rolled strip was completely openable.
  • Example 11 A terephthalic-isophthalic polyester (e.g., that commercially available under the tradename Videne), which is commercially available in pellets which become rubbery at 300 degrees F., was employed. It had the general formula where R represents the paraor meta-phenyl nucleus singly or in mixture.
  • the hollow aluminum billet was heated to 350 degrees F., loaded, and welded closed. Minor leakage of a resinous material occurred during heating for a hour to 900 degrees F.
  • the internal resin was a yellow wax-like solid which exhibited the effects of some depolymerization: it was insoluble in acetone or toluene, and had suffered no damage, according to infra red examination. It may be noted that infra red examination can reveal change of intra-molecular structure, but is not a sure guide as to polymerization or partial depoly-merization.
  • Example 12 A novolac phenolic resin (e.g., that available under the tradename BR254, Union Carbide) has been employed under the stated heating to 900 degrees F., with aluminum.
  • the resin was a para-phenylphenol-formaldehyde resin of the formula being a hard solid at room temperature, and a liquid at 300 degrees F.
  • the resin commercially available under the trademark BR-254 was used. This was charged into the cold billet; the billet was welded shut and heated to 900 degrees F. After cooling and opening, the resin had a very dark color, was partially soluble in acetone, and exhibited no damage effect under infra red examination.
  • a billet was filled with the phenolic resin at room temperature to a packing density of percent, as described for Example 7, and rolled with like annealings. The rolled strip was completely openable.
  • a like billet was heated at 900 degrees F. for three hours, with one end welded shut. It was placed with the open end up, and the phenolic resin introduced to substantial filling; then lowered to horizontal, and a like rolling schedule performed. The welded end burst open during the first rolling pass and a large amount of the liquid resist was discharged. The rolled strip was completely openable.
  • Example 13 A polymethyl styrene resin was used, of the general formula CI-I Z 1 This is commercially available as pellets under the trademark Cynac-400 from the American Cyanamid Company; and is rubbery at 300 degrees F.
  • the billet was heated to 340 degrees F., loaded, and the ends welded shut. Upon heating to 900 degrees F., there was leakage of a resinous material.
  • the internal resin was an amber-colored, fused, hard, britle resin; soluble in toluene, but showing no damage under infra red examination.
  • Polystyrene resin was packed to 50 percent density into a billet at room temperature, as set out for Example 7: the billet was then welded closed, and subjected to the heating and rolling schedule as in Example 7. The rolled strip was completely openable.
  • Examples 11 to 14 can be employed as in Examples 1 to 6.
  • Example 15 A magnesium billet had its internal channel filled with epoxide resin, as in Example 2, and sealed. It was heated to 700 degrees F. and hot rolled. The internal surfaces were smooth and bright.
  • Example 1 6 An aluminum billet 2 inches thick, with a 0.100 inch thick channel, received a polyethylene strip about 0.005 inch thick and slightly narrower than the channel width, at room temperature. It was welded shut and heated to 600 degrees F., and warm-rolled to 0.016 inch in the range 600 to 300 degrees F. During the early passes, the liquid resist broke the weld at the trailing end of the billet and a part of the resist was squeezed out. Upon opening, the internal surface was exceptionally bright, indicating that the material was liquid or highly plastic during the rolling. Both internal surfaces had resist material adherent thereto, as shown by the lesser action of caustic solutions than at exterior surfaces or filecleaned surfaces.
  • the ingot B has internal longitudinal channels 11, illustratively located in the median plane M between the billet surfaces which are to be rolled.
  • the organic resist materials act. by preventing interpenetration of the metal laminate material through the resist film and welding is prevented, and the film is continuous. It is not necessary to provide originally a thick resist layer as with the use of refractory powder resist where the resist residue must be several granules thick at the end of cold rolling; and hence a channel 11 may be inch thick or less, even with a 12 inch ingot which is to be rolled to a final thickness of 0.016 inch, or an extension of 700 times.
  • Channels of other cross-sections can be employed in accordance with the invention.
  • the channels 11a are oblong, with rounded contours at the edges.
  • the upper and lower surfaces of such channels move toward one another, and the resist maintains its coating upon the internal surfaces; ultimately providing a film of essentially uniform thickness.
  • the channels at the end 12 of the ingot are shown as closed by peening and a welded seam 13, it being understood that this closure extends across and closes the entire end in the complete ingot.
  • the resist material may be introduced as a slab, sheet, or powder, e.g., through a guide or hopper 14.
  • FIGURE 4 As it moves downward, it melts thereagainst to provide a coating: when a strip A inch thick and 2 or 3 inches wide is thus fed, lateral movements during feeding and While within the channel assure the coating: like spreading occurs with powder particles.
  • This coating effect is assisted by foaming and bubbling of the resist, FIGURE 4; in practice, by the completion of the feeding, fumes are billowing out, displacing the air from the channel.
  • the resist melts, discharges its air of porosity and its volatiles, if any, and the upper end 15 can now be peened and welded shut so that the resist material is totally enclosed against entry of gases from the atmosphere and against escape of any resist material.
  • the billet can be quickly brought to horizontal position, without sealing its open end, and pushed into the rolls. If the ingot is cold, the resist can be introduced, with tamping and vibration to assure a tight filling, and then peened and welded shut.
  • the loaded and closed billet B is then subjected to its schedule of heating and rolling. With aluminum and its alloys, this is usually a heating 30, FIGURE 5, to 900 degrees F., with a succession of hot-rolling passes 31 to reduce the material to about four to eight times the desired final thickness.
  • the hot-rolled strip is then annealed in step 32 at 900 degrees F. for 30 minutes, cooled, and subjected to a succession 33 of cold-rolling passes to bring it to final thickness as a strip S. More than one intermediate annealing can be employed, as set out above.
  • the billet may be brought to the desired condition and temperature for hot-working before the resist is introduced.
  • an aluminum alloy ingot B, FIGURE 6 can be heated to 900 to 1,000 degrees F., and a resist in liquid form can then be inserted into the channel at the end which is initially to be fed into the reduction rolls 16.
  • This can be done by an injecting pump cylinder 17 having a nozzle 18 which enters a channel or discontinuity 19 of the billet B, and deposits a quantity of the resist within the channel at the leading end, as shown by the dotted lines 20, continuing the deposit until the nozzle is fully withdrawn.
  • the billet has several channels, it is preferred to charge all channels at the same time, so that air-exposure of heated resist is kept to a minimum time.
  • the billet B is immediately introduced to the rolls I6 and a reduction made which closes the walls of the channels 19 upon the resist so that air access thereto is thereafter prevented, and the resist is spread and distributed between the internal wall surfaces, being pushed along the channel during the rolling and the excess squeezed out as the rolling pass is ended. Therewith, the resist provides a thin film which prevents welding of such internal surfaces.
  • Silicone greases or oils having the polysiloxane structure of a chain of silicon and oxygen atoms, with the silicon atoms having hydrocarbon groups connected thereto, for example of the formula Len. (H,
  • the pump delivering the resist at a room temperature of 70 degrees F., 'or a temperature of below 500 degrees F., e.g., 300 to 400 degrees F., at which there is essentially no degradation upon air contact during the time for injecting and the early rolling.
  • the resist is immediately heated from the hot billet, upon injection, but then it is protected against major contact with oxidizing substances such as air. Minor degradation can occur between the surface of the mass and the air present in the channel, but in practice, this has not been found harmful when the rolling is started quickly. There appears to be a time function for the degradation, so that when the hot-rolling at temperatures above, say, 600 degrees F.
  • the silicone is completed within five minutes, the silicone continues effective for the hot rolling, and during a subsequent cold rolling. has been cold-rolled to final gauge, and is heated for 30 minutes or more for annealing, the silicone decomposes, with the production of negligible amounts of gas and silica per unit area of the laminate stock, and no notable bulging of the laminations away from one another.
  • This pro-heating of the billet to hot-rolling temperature, and the immediate hot-rolling can be employed with the several resists and metals described above. It is applicable with other organic compound resists having the stated characteristics and even with resists which undergo polymerization at hot-rolling temperature, provided that the hot-holling is completed before polymerization has progressed to a stage at which the anti-welding effect is not maintained during the course of the rolling schedule.
  • the compound requires two minutes or more for the polymerization to a condition in which the product is no longer thermoplastic or extensible under rolling pressure, it can be used in a schedule of hot rolling and cooling to a temperature at which the progress of polymerization is slow; because it is feasible in practice to conduct the hot-rolling of selected billet sizes and the cooling within two minutes, with the resist then present in a form proper for cold rolling.
  • the invention can be employed with billets having a single channel and that, for some employments such as the making of heat exchange bodies, the internal channels may be connected within the billet body.
  • the billets need not be original hollow ingots, but can be prepared by other procedures known in the art of making laminate stock, with care taken to assure the closure of each channel or group of channels against atmosphere penetration or the escape of resist material into places where it can interfere with the regular course of reduction of the billet.
  • the channels may be provided by casting molten metal about cores which are later removed, by casting molten metal about hollow tubes which become integrated with ingot metal, or by boring or piercing.
  • the strip S (FIGURE 7) has a number of longitudinal internal resist residues 35 equal to the number of channe s 11 or 11a in the original billet; and these residues may be present in such thin layers that they are each represented by a single line in the drawing. These residues 35 separate the metal lalninations 36, 3'7, with the laminations connected at the lateral edges of the resist residues by the longitudinal metal portions 38.
  • the strip S can be called multi-wide because it can be parted into a number of single-wide strips by severance, as represented by the line 39, along upright surfaces which extend along the metal connections 38 between adjacent residues 35 so that each strip retains a part of such connection.
  • edges of the strip S may likewise be severed at surfaces represented by the line 40, so that each single-Wide strip has edge connections of essentially the same lateral dimensions from the corresponding edges of the resist residue.
  • Decoration such as the printing of pictures and Words can be done, before or after severance into blanks, and the laminate stock can be embossed with ribs and grooves for stiffening the walls after opening: wherewith the resist residue continues to act to prevent internal sticking or welding.
  • the strip S can likewise be severed transversely to provide container body blanks, which are opened or expanded as shown in FIGURE 8, wherewith the laminations 36, 37 provide the major portions of the tubular bodies T; and therewith the wall thicknesses of the bodies are determined by the final rolled gauge of the strip, being illustratively half this gauge because the resist layer 35 can be of insignificant thickness.
  • the parts of the integral connections 28 for the specific body T are present as externally projecting fins 4,1 which may be trimmed and conformed to the general body cross-section, FIGURE 9.
  • the residue is adherent to the internal walls of the body T, and is compatible with organic enamels and lacquers.
  • an enamel may be applied as by the conventionalized spray nozzle 45 during passage of the body along the same. The enamel can then be dried and baked.
  • Illustrative organic enamels or lacquers have solid components of oleo-resins, phenolic resins, epoxide resins, or vinyl resins along with pigments and fillers; and include resin solvents such as hydrocarbons, ketones and esters. Solvents which dissolve the resist residues merely form a modified organic coating, assuming the resist resin residue and the added resin are compatible. When the solvents do not act upon the resist residues, and are eliminated during drying, a fluxing together of the resist residues and the enamel resins can occur during baking.
  • Organic resists which have been found effective for the procedure have the common chemical and physical attributes that they have a molecular weight above 500; exhibit thermoplasticity, i.e., being liquid, upon heating under non-oxidizing conditions in the range of 500 to 1,000
  • Thermoplasticity herein has the usual meaning of capability of being deformable without rupture or significant decomposition when heated above room temperature. It has been found that the materials can be tested as to behavior during rolling, by filling a tube, made of the metal which is to form the laminate stock, substantially full with the material, sealing the ends as by welding, and heating to the proposed operating temperature, e.g., 900 degrees F. for one graph essentially the same as the untested material.
  • the properties of the useful organic resist materials include the ability to endure the temperatures of heating, with exclusion of oxygen, e.g., air, without loss of antiwelding properties, so that they continue effective for that purpose through the course of reduction, illustratively by a schedule of hot and cold rolling preferably with a maintained adhesion to the metal surface which is greater than the internal cohesion within the resist layer, and the ability to accept and establish adhesion to organic enamels later applied thereto.
  • the produced strip material is to be in contact with foodstuffs, e.g., when the tubular body T of FIGURE 6 is to be part of a food container, the resist material should not com-prise a toxic component or have a toxic or flavor-change effect.
  • the resist material should extend regularly and in proportion to the extension of length and reduction of thickness of the billet metal, so that smooth internal surfaces areproduced: that is, it should be extensible.
  • the satisfactory resist or anti-welding materials may be defined chemically as organic compounds (the term as usual including the silicone compounds having hydrocarbon groups in the molecular structure) which are waxy, rubbery, or resinous in behavior at room or slightly elevated temperatures, which endure exposure to temperatures around 900 degrees F. in the absence of oxygen, and which have a molecular weight above 500.
  • Resinous polymers of (CH -CR) structure where R can be hydrogen, alkyl hydrocarbon groups of 1 to 4 carbon atoms, phenyl, alkyl-substituted phenyl, and polyalkyl-substituted phenyl, and n denotes the presence of a plurality of such units in chain (inclusive of the resins known as polyethylene, polypropylene, polystyrene, polymethylstyrene, polyvinyl-toluene, polybutene, copolymer)s of polybutene with polyethylene and/ or polypropylene
  • Metal soaps of the structure R 'CH -CO -R where R is an aliphatic or olefinic hydrocarbon group of 10 to 16 carbon atoms, R is a metal ion, and p denotes a number of acid groups no greater than. the replacement valency of the metal whose ion is being used (inclusive of sodium and other mono
  • R represents a normal alkyl hydrocarbon group of 2 to 10 carbon atoms, meta-phenylene, para-phenylene,
  • R represents a normal alkyl group of 2 to 10 carbon atoms
  • q denotes the presence of multiple units in chain (inclusive of polycarbonates, polyamides such as the linear carboxylic acidzamine condensations including dibasic acid:diamine polymers and caprolactam polymers, and polyesters, e.g., of terephthalic, isophthalic, adipic and sebacic acids with ethylene glycol, propylene glycol and homologous glycols):
  • Thermoplastic resins having multiple phenyl nuclei in chain to wit: phenol-aldehyde or phenolic resins (inclusive of the novolacs such as para-phenyl-phenol:formaldehyde condensate resin), and epoxy resins with multiple phenyl nuclei (inclusive of the bis-phenol epichlorohydrin condensates):
  • the procedure comprises the exclusion of oxygen while the billet is at elevated temperature. This is preferably done by sealing the channel against entry of air: but under the invention the exclusion may be effected in other ways. For example, after first heatings and rollings, the ends may be clipped and the rolling continued. It has been found that with a silicone resist material in an aluminum billet, the ends could be peened without welding, so that part of the resist was extruded in the first rolling pass: the laminate stock after rolling to gauge was found to open easily and had a good internal appearance.
  • a billet having its channel partly filled with the resist may be initially rolled at a temperature below that at which the resist is degraded upon air contact; whereby to distribute the resist, expel air, and conform the billet to the resist without air-filled pockets or spaces.
  • a temperature can be a cold rolling condition for the metal, and one at which the resist extends easily under roll pressure effects upon and in the billet and is for example a stable fluid.
  • the degree of reduction can be small during this initial conformance rolling, e.g., with a billet 8 to 14 inches thick and the longitudinal channel inch thick, the over-all reduction of thickness may be less than 5 percent, and essentially no cracking develops. No internal pressure need develop, as the end or ends may be left open for escape of air and excess resist.
  • a suitable temperature for the described organic compound resists is 300 to 400 degrees F. It is difficult and often expensive to prepare billets with a channel less than around A; to inch in thickness; noting that a greater original thickness of resist is not required to maintain the anti- Welding action, since upon reduction of such channel to microscopic thinness, e.g., one ten-thousandth of an inch or less, the welding is still prevented.
  • the channel cavity can be filled part full of liquid resist or partly filled with a strip of resist material much thinner than the channel.
  • the billet is then rolled at a temperature, room or above, at which the resist is not damaged by air contact, by light passes until the resist is spread evenly over the channel surfaces, and therewith the billet has its channel thickness reduced to conform to the resist present and thus the residual channel space is full, with expulsion of air and some of the resist material.
  • the billet is then heated to the temperature at which the hot-rolling of the metal is to be started, e.g., 900 to 1,000 degrees F. for aluminum and its alloys, and the schedule of hot-rolling performed.
  • an advantage of the very thin resist residues is that intermediate annealing or reheating can be conducted during the couse of the hot-rolling without causing bulging or expansion, which may occur if a large thickness of resist having a gaseous product or an appreciable vapor tension at the heating temperature, is present.
  • the billet and the resist afford mutual protection to each other: the billet encloses and protects the resist from decomposition or vapor formation, and the resist prevents oxidation of surfaces of the billet channel or channels.
  • the final laminate stock has bright and clean internal surfaces.
  • a silicone grease or oil such as that commercially known by the tradename DC-710
  • it can be employed at 70 degrees F., and the conformance rolling done at this temperature.
  • polyethylene a temperature of 300 degrees F. can be employed. Suitable temperatures for other compositions are indicated in the examples.
  • the procedure is effective with metals which can be rolled at temperatures of 1,100 degrees F. or below: inclusive of aluminum, zinc, copper, magnesium and other non-ferrous metals and their alloys: and is particularly of value with such materials which require hot-rolling or heat-treating temperatures of 500 to 1,100 degrees F.
  • the resist is preferably a liquid during initial rolling passes so that it conforms to the channel; and exhibits increased viscosity during later rolling passes at temperatures below 500 degrees F. and down to room temperature.
  • the procedure includes the employment of original resist channels of such original thickness that insignificant thicknesses of resist residues are present in the final step, e.g., below 0.001 or 0.0005 of an inch. This is particularly valuable when the adhesion of the resist residue to the metal is greater than the internal cohesion of the resist so that, upon opening or expansion, the inner surfaces of both metal laminations have films of the resist residue thereon, with the separation usually making the films of essentially the same and like thickness throughout.
  • the trailing end at one pass is made the entering end at the next pass, so that any effect of longitudinal movement of the resist, independently of the metal extension and with an effect of increasing the relative resist thickness at the trailing end compared to the entering end, is compensated by the reverse rolling.
  • the fluid ity of the resist expelled at the trailing end of the billet is not as destructive, e.g., by abrasion, as a resist of solid refractory particles would be when the trailing end is immediately fed to the rolls for the second or reverse pass.
  • the necessary residual thickness of resist material, in the final strip can be very small, that correspondingly a very thin channel can be effective in a thick ingot, that technical considerations restrict the minimum channel thicknesses which can be provided in ingots, and that in fact the quantity of original resist material can be less than that for filling the channel, as shown by the expulsion of a large part of the originally introduced resist at the end of the first and subsequent hot-rolling passes.
  • the action during the first hot pass is, on the one hand, to conform the ingot to the resist so that air is expelled and its re-entry prevented; and on the other hand to spread the resist so that it fills the reduced channel with coverage at all surfaces thereof.
  • the resist may be caused to travel along the channel at high velocity and without the amount of lateral spreading required to coat the entire internal surfaces. This is revealed during the hot rolling by proper coating of the inner surfaces for the first half of the billet, for example, and by the lack of full coating at the channel edges for the second half of the billet; so that local pressure welds occur at the channel edges, with decrease of the width of the resist residue at such pressure-Welded regions in the final strip whereby parts of the strip must be discarded if accuracy of width is demanded.
  • coating of the internal surfaces can be improved by a roughening of the 17 internal surfaces.
  • Such roughening need not be and preferably is not of major extent. For example, after an ingot has been cast with one or more internal channels, of say 0.120 inch thickness, and these are broached or burnished, a roughening not perceptible by touch will produce a retardation of the longitudinal flow of the liquid resist, during rolling, with development of a back pressure effect which causes lateral spreading and coating.
  • Such a roughening can be produced by etching: for example, with aluminum and aluminum alloys, a treatment with hot caustic alkali solution for a few minutes, following by rinsing produces a microscopically rough surface, of the order of to 50 micro inches between hills and valleys.
  • This etching and rinsing is preferably done before the ends are closed.
  • the roughened surfaces act to detain the resist at the metal: resist boundaries of the channels during the courses of the rolling passes.
  • the longitudinal extension of the billet to strip form gives internal surfaces, after opening, which have a somewhat matte appearance but without significant depths of the surface irregularities.
  • the invention permits the replenishment of resist.
  • the leading end of the strip can be opened, more liquid resist of the same or a dilferent type introduced, and the rolling continued, wherewith the added resist mass is caused to travel along the channel during the rolling and re-establish a desired film thickness for successive rolling passes. It is notable that this cannot be accomplished with resists which are granular, refractory solids, and do not have the flow properties for such replenishment.
  • the method of producing a laminate metal stock which comprises preparing a billet of a metal selected from the group consisting of aluminum, zinc, copper, magnesium and their alloys, and said metal requiring a hot-rolling temperature of 500 to 1100 degrees F., said billet having an internal cavity, introducing into the cavity an organic compound having a molecular weight above 500 and which at the temperature for hot rolling of the metal is a liquid and is extensible at cold rolling temperatures for the metal and heating the said organic compound to lower the viscosity of the same to a condi tion for easy spreading, reducing the billet at a temperature between 500 and 1,100 degrees F.
  • said heating and reduction including at least one step of bringing the billet to a temperature of 600 to 1,100 degrees F. with the said organic compound contacting the billet cavity walls at such temperature.
  • the said organic compound is a resin having units of the structure CH CHRl where R is selected from the class consisting of hydrogen, alkyl groups of 1 to 4 carbon atoms, phenyl, alkyl substituted phenyl and polyalkyl substituted phenyl, and n denotes the presence of a plurality of the units in chain.
  • said organic compound is a metal soap of the structure (R CH CO R where R is selected from the class consisting of aliphatic and olefinic hydrocarbon groups of 10 to 16 carbon atoms, R is a metal ion, and p is a number not greater than the replacement valency of the metal whose ion is selected.
  • R is selected from the class consisting of normal alkyl hydrocarbon groups of 2 to 10 carbon atoms, isopropylidene-bis- (para,p ara-phenoxy) :(normal C H -NH): O-R -O, NH-R -NH--; R is selected from the class consisting of normal alkyl groups of 2 to 10 carbon atoms, meta-phenylene, paraphenylene,
  • the said organic compound is a condensation polymer selected from the class consisting of thermoplastic resins derived from the reaction of phenols with aldehydes, and epoxy resins with multiple phenolic nuclei.
  • the method of producing a laminate metal stock which comprises preparing a billet of a metal selected from the group consisting of aluminum, zinc, copper, magnesium and their alloys, and said metal requiring a hot-rolling temperature of 500 to 1,100 degrees B, said billet having a longitudinal internal channel with an open end, introducing through said end and into the channel an organic compound which at a temperature for hot-rolling of the metal is a liquid and subject to decomposition in air and is extensible at cold-rolling temperatures for the metal, thereafter rolling the billet while at a temperature of 500 to 1,100 degrees F. for closing the channel surfaces upon thesaid organic compound and thereby expelling gases and a quantity of said organic compound from the channel, and continuing the rolling while the metal is at a hot-rolling temperature and with air excluded from contact with the organic compound by the metal undergoing reduction.
  • the method of making laminate strip stock which comprises introducing into a longitudinal internal channel of a billet of metal which requires a temperature of 600 to 1,100 degrees F. for hot-rolling an organic compound which at the hot-rolling temperature for the metal is subject to decomposition in air and is a liquid at a temperature above room temperature and below 500 degrees F. and is extensible at cold-rolling temperatures for the metal, and hot-rolling the billet by successive passes from a temperature of 900 to 1,100 degrees F. and thereafter cold-rolling the hot-rolled strip.
  • the method of producing a hollow metal body having an internal coating of a selected organic enamel composition which comprises introducing into an internal cavity of a billet of metal selected from the group consisting of aluminum, zinc, copper, magnesium and their alloys, and said metal requiring a hot-rolling temperature of 500 to 1,100 degrees R, an organic compound which is a liquid and subject to decomposition in air at a temperature for hot-rolling of the metal and is extensible at cold-rolling temperatures for the metal and is compatible with the selected enamel, heating the said organic compound to melt the same within the cavity, hot-reducing the billet at a temperature of 600 to 1,100 degrees F.
  • the method of producing a hollow tubular metal body which comprises introducing into a longitudinal internal channel of a billet of metal which requires a temperature of 600 to 1,100 degrees F. for hot-rolling a thermoplastic organic compound which at the hot-rolling temperature for the metal is a liquid and subject to decomposition in air and is extensible at cold-rolling temperatures for the metal, heating the said organic compound to melt the same within the channel, hot-rolling the billet at a temperature of 600 to 1,100 degrees F.
  • An article of manufacture comprising a cold and hot-rolling laminated metal strip having at least one longitudinal internal channel containing a continuous microscopic film of less than 0.001 of an inch thick; said film consisting of an organic resist compound capable of decomposing in air at temperatures above 600 F. and having been subjected to the hot-rolling temperatures of about 9001,l00 F. in the absence of air; and laminations being integrally connected by metal; along the longitudinal edges.
  • the article of claim 27 further characterized as a hollow metal body formed from the laminated metal strip; said hollow metal body having integral walls, the inner surfaces of which contain an enamel-coating composition which is compatible with said film of the organicresist compound.

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  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Metal Rolling (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Rigid Containers With Two Or More Constituent Elements (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
US44148A 1960-07-20 1960-07-20 Preparation of laminate metal stock by use of organic anti-welding materials Expired - Lifetime US3214251A (en)

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CH39761A CH400972A (fr) 1960-07-20 1961-01-13 Procédé de fabrication d'une matière métallique stratifiée, moyen pour la mise en oeuvre ainsi que produit obtenu selon ce procédé

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4312906A (en) * 1977-11-23 1982-01-26 The Boeing Company Stop-off composition for metals
US4434930A (en) 1981-10-15 1984-03-06 Texas Instruments Incorporated Process for producing reinforced structural articles
US4538756A (en) * 1981-10-15 1985-09-03 Texas Instruments Incorporated Process for producing reinforced structural members

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106493251B (zh) * 2016-11-30 2018-04-17 广东韩江轻工机械有限公司 覆膜铁方罐感应加热封口设备和感应加热封口方法

Citations (5)

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Publication number Priority date Publication date Assignee Title
GB774008A (en) * 1954-09-17 1957-05-01 Ici Ltd Method of making sheet metal elements with passages therein
GB814979A (en) * 1956-04-30 1959-06-17 Ici Ltd Metal sheet or strip with integrally formed inflatable passageways
US2986810A (en) * 1959-02-11 1961-06-06 Continental Can Co Production of composite metal stock having internal channels
US2990608A (en) * 1957-03-18 1961-07-04 Ici Ltd Method of making sheet metal elements with passages therein
US3029155A (en) * 1959-08-21 1962-04-10 Continental Can Co Enamel-powder resist systems

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB774008A (en) * 1954-09-17 1957-05-01 Ici Ltd Method of making sheet metal elements with passages therein
GB814979A (en) * 1956-04-30 1959-06-17 Ici Ltd Metal sheet or strip with integrally formed inflatable passageways
US2990608A (en) * 1957-03-18 1961-07-04 Ici Ltd Method of making sheet metal elements with passages therein
US2986810A (en) * 1959-02-11 1961-06-06 Continental Can Co Production of composite metal stock having internal channels
US3029155A (en) * 1959-08-21 1962-04-10 Continental Can Co Enamel-powder resist systems

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4312906A (en) * 1977-11-23 1982-01-26 The Boeing Company Stop-off composition for metals
US4434930A (en) 1981-10-15 1984-03-06 Texas Instruments Incorporated Process for producing reinforced structural articles
US4538756A (en) * 1981-10-15 1985-09-03 Texas Instruments Incorporated Process for producing reinforced structural members

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GB969211A (en) 1964-09-09

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