JPH01500445A - Method for mechanically carbaniding metal materials and carbanid articles - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Resistant to corrosion, peeling and cracking between the plating metal particles and the material surface metal grains on a metal material by applying sufficient mechanical force to cause adhesion It is known to plate children. The machinery required to produce such adhesion forces such as plating metal particles, solid impact media (e.g. glass beads), etc. Substances and metal materials that promote plating are processed in a rotating ball mill or tumbler. mbl, ing barrel). this In this method, kinetic energy is transferred to the impact medium by the rotation of a ball mill or tumbler. The kinetic energy is transferred to the plating metal particles, and these particles It is applied as a coating to the surface of the material.

All the early research in this field of mechanical plating was done by Clayton (Clayton). U.S. Pat. No. 2,640.001, 2.64 Cl, 002 to on) et al. No. 23,861, Reissue Patent No. 2.689.808 and No. 2,723, It was disclosed in each specification of No. 204. Typically, these mechanical plating methods produce unsaturated In the presence of a liquid containing fatty acids, skin simulating substances and accelerators such as surfactants. It was conducted. U.S. Patent No. 3,460.977 to Golben The '999 patent discloses other promoters for mechanical plating. Simon U.S. Pat. No. 3,328,197 to teaches the use of accelerators in solid bulk or rod form containing combinations of There is. As the mechanical plating cycle progresses, the bars or chunks are mechanically plated. It dissolves at a rate that provides the optimum amount of accelerator for the process.

U.S. Pat. No. 3,268,356 to Simon (' No. 356 patent) connects accelerators and/or plating metal particles to a plating barrel. Plating metal coatings that can be added incrementally over the entire material surface in a continuous manner. The invention discloses optimizing the density and uniformity of the material.

Thin mechanically plated coating, i.e. 25III! (,975 mil)- ! Nie and Meyer (U, Meyer) to prevent corrosion of coatings in Author: [Mechanical Blasting Dee] Mechanical Plating Diegntwickl ung des Verfahrens) J Galvanotechnik (Galvan otecbnik), Volume 73, No. 9 (1982). A sandwich coating on the material (e.g. tin on zinc) It was proposed to apply a zinc coating on top of the

U.S. Patent No. 3,531,315 to G○1.ben ( '315 patent specification) discloses performing mechanical plating in the presence of strong acids. Ru. Prior to the '615 patent, plating metals, impact media, and The material was stirred in the presence of a weak organic acid such as citric acid. This includes Rinse the contents of the plating barrel with water and start the plating method using 9 tons of citric acid. All strong acids used to clean or copper plate parts prior to It is necessary to ensure that it does not contain. By the method of the '615 patent, Mechanical plating can be performed without the need for an intermediate water washing process. The method was made extremely economical.

Mechanical plating coats that are very thick (e.g. 71 mils to 1.0 mils thick) from about 1.0 mil to 5.3 mil) and heavier (e.g. Mechanically applied metal coat (approximately 7 ounces to 2.5 ounces per foot) The use of tings has become increasingly desirable. Thicker, heavier coating The above method of applying is called mechanical galvanizing method. It has become known. During the advancement of such mechanical galpanizing methods, A mechanically applied rubberizing coating is created by stacking thin layers of plated metal. It has been found that enhanced adhesion of adhesives can be achieved. According to the '656 patent specification As taught in This is achieved by the incremental addition of metal powder. As a result, the '656 patent specification The commonly used citric acid-based accelerators, such as those described above, Mechanically, it could be used for Lupine/G. About 3.0~ in this accelerator A pH of 3.5 is not very erosive to the metal powder and the accelerator is introduced in rod-like form. (see, e.g., U.S. Pat. No. 3,328,197), and the rod The accelerator slowly disintegrates during the operation and gradually disintegrates as galpanizing progresses. Release accelerator. However, organic acids and their salts are expensive and can be expensive. It tends to complex metal ions, and these complexed heavy metal ions are not effective waste disposal agents. Interferes with liquid processing.

optimizing mechanical galvanizing according to the teachings of the '615 patent; The same benefits achieved by mechanical plating in strong acids (e.g. It is also desirable to ensure that there is no need for cleaning. However, '615 Accelerators used with the patented method make incremental addition of metal powder difficult . This is because the operating pH of 0.5 to 1.5 in this method is excessive for the metal powder. This is because it is also erosive. Additionally, the accelerator typically used is galvanic During Hfm of the nizing operation, it is not necessary to make an intervening addition to the powder form. will be introduced. This accelerator can be used in conjunction with incremental additions of plating metal powders to Uncontrolled metal coating, resulting in an unsuitable chemical environment during the later stages of production. This will cause a certain amount of precipitation. Therefore, it is necessary to apply successive layers of well-fixed adhesive particles. It was not possible to maintain the necessary conditions uniformly.

U.S. Pat. No. 4,389.431 to Erisman ('431 Patent Specification) for incremental metal powder addition of mechanical galpanizing. The method of the '615 patent was adapted. This is achieved by a two-accelerator system. It was. The first accelerator is used in the plating process prior to adding the plating metal to the system. A thin adhesive flash coating of a metal that is more noble than the metal it is used for. flash accelerator (fl sh coating) to coat the material. ash promoter). Then a second continuous accelerator (con, tin uing promoter) produces some of the finely pulverized mechanical plating metal. or added incrementally with all incremental additions so that the layer of metal is built up. Mechanical galpanizing is performed.

Despite this improvement, mechanical plating coatings do not have a mechanism that is not encountered. There continues to be a problem with mechanical rubberizing. Thicker mechanical gas One of the above problems encountered with rubberizing coatings is chipping ( chipping), III (flaking) and cracking ), which becomes more of a problem as the thickness of these coatings increases. It is. This results in large This is a particularly big problem regarding parts. For small parts such as nails, Coating adhesion (Ad, hesion of MetallicCoati) ngs) The standard test method for J is ASTM test ASTM B571. The entire coating may peel off or be scraped off when bent.

Development Mechanical plating used to create thick mechanical galvanizing coatings Incorporating a layer of a buffer metal different from the plating metal between the thin layers of the plated metal Chipping, which is unique to mechanical galvanizing coatings, It has been found that delamination and cracking can be avoided. In a preferred embodiment of the invention The buffer metal layer is more malleable than the plating metal layer, while the plating layer is more malleable than the plating metal layer. The layer of metal is more ductile than the layer of buffer metal. Ductility and malleability are tensile or is an object that deforms plastically without breaking under each compression. It is a descriptive term for quality competencies. Dee, Nis, Clark (D, S, C1a rk) and W, Earl, Varney (w, Ft,, Varney) , “Physical Metal Radio Engineers (Physical 1.4) etallurgy For F, ngineers) J 1952.

An example of a plating metal/buffer metal system having these characteristics is sub-metal as a plating metal. using lead and either tin, lead or a mixture thereof as a buffer metal; It is something that

Mechanically galvanized by building up a thin layer of mechanically plated metal The method of can be easily adapted. '315 Patent Specification and '431 Patent Specification A rotatable plating bag containing a glass beads impact medium as taught in Put the material to be galvanized into the rail. water, and strong acid surface compounds such as sulfuric acid. Conditioner is also added to the barrel and then dispersed by rotation of the plating barrel. let For example, as shown in the examples of the '461 patent specification, the '515 patent specification The method involves pre-cleaning and adding water and a strong acid surface conditioner. A water wash can optionally be included. This kind of pre-cleaning is done using an alkaline cleaning agent. Degreasing with an acidic detergent, descaling with an acidic detergent, or both degreasing and descaling. Depending on the I can do it. After pre-cleaning, the material is washed with water. According to the '615 patent specification, the surface coating Subsequent draining or water after addition of conditioner Do not wash. on the material between washing and the addition of water and a strong acid surface conditioner. However, if the sulfuric acid surface conditioner is turned on, Such scale is removed during its dispersion in the plating barrel.

Surface conditioning with sulfuric acid in a rotating plating barrel containing materials and impact media. draining the acid from the plating barrel after dispersion of the colorant and water, or A pot plating agent (e.g. copper sulfate pentahydrate) can be used without washing the material. ) f: Added to plating barrel. This causes copper to be deposited on the surface of the material, and then in which it acts as a basis for the adhesion of subsequent coatings to the material. .

Accelerators are then added to the plating barrel to provide a suitable environment for opportunistic plating. I can do it. In addition, the accelerator helps clean the plating metal powder that is added afterwards. It also helps to control the size of metal agglomerates for plating. Suitable accelerators are strong Acids or acid-forming salts and subsequently added plating metals are even more responsible. Contains salts of the genus. Optionally, the accelerator is added to the plating metal. Dispersants and/or corrosion inhibitors may also be included. than plating metals, Soluble salts of the more noble metals include cadmium, lead, and preferably tin (5 1J includes stannous chloride, stannous sulfate). Strong acids or acid-forming salts are examples. 5A acid, potassium or ammonium bisulfate, sulfamino acid, or It can be sodium bisulfate.

Dispersants and corrosion inhibitors are those disclosed in columns 6-4 of the '615 patent specification. It can be any one of the following. Accelerator: 100 square feet of plating surface fD, up to 400 grams of salt, which is even more important for plating metals. and about 10 to about 80 grams of soluble salt. Other effective amounts of dispersants and/or Corrosion inhibitors can be added as necessary for their intended purpose.

After charging the accelerator into the rotating barrel, the plating metal powder is added. metal for plating The addition of the accelerator metal causes flash coating from the liquid in the plating barrel onto the material. replaced as ting. Then the glass beads impact medium is released by rotating the barrel. The body hits the material, and the metal powder for plating is knocked into the material and becomes in close contact with the material.

or use the accelerator system disclosed by the '431 patent specification in place of the above. You can also. As indicated above, this system uses two types of accelerators: Using flash and continuing accelerators Ru. Flash accelerators contain the same ingredients in the same amounts as those used in the accelerators described above. have Continuous accelerator: about 20 to about 1 strong acid or acid-forming salt per bond of metal for plating 50 grams, about 1 to 20 grams of a soluble salt of the metal that is more important than the plating metal, and and optionally a dispersant capable of dispersing the plating metal ○ Effective amount and/or element Contains an effective amount of an inhibitor capable of inhibiting corrosion of materials and plating metals. Copper After plating is complete, but before adding the plating metal powder, the flash accelerator is added to the rotating barrel. Add to the bottle. With each incremental addition of plating metal powder added to the rotating barrel Add continuous accelerator. Insufficient amount of inhibitor in barrel before completion of mechanical plating or the dual accelerators disclosed in the '461 patent when a dispersant is present. systems are particularly useful. As above, as can be determined by the painter Continuous accelerators can be added if a shortage occurs. Continuous accelerator above Depending on the degree of corrosion and dispersion in the plating barrel, additions such as For each addition of plating metal, check whether it is necessary or not.

After one or more incremental additions of plating metal powder and optionally successive promoters Buffer metal powder can be added to the plating barrel. impact while the barrel is rotating. As a result of the impact medium hitting the material, the buffer metal powder is brought into close contact with the material. Ru. A buffer metal layer is formed by such close contact. After that, the buffer metal Further addition of the plating metal along with the interstitial layer More layers can be added to the .

Buffer metal is different from plating metal.

In a preferred embodiment of the present invention, the buffer metal can be used in many ways other than the metal for plating. It is flexible and ductile. These properties are particularly good. why If the material is similar, the wall of the plating barrel or other High resistance to chipping, cracking and delamination in case of impact with objects This is because it imparts to the coating. In the most preferred embodiment, plating The buffer metal is zinc, whereas the buffer metal is tin, lead, or any mixture thereof. It is.

The boundary between the plating metal layer and the buffer metal layer is unclear. Instead, each buffer The layers diffuse into each adjacent plated layer and vice versa. As a result of this diffusion , galpanized coatings have greater bendability. , 1ty) and chipping resistance.

Without wishing to be bound by theory, this diffusion boundary is Remaining plating metal powder in plating barrel when added and plating begins It is thought to be caused by continuous tightening at the end. There is residual buffer metal in the barrel. The same applies when plating metal powder is added to the barrel while it is in use and plating begins. Something is true.

The thickness of the plating metal and buffer metal layers is such that these materials are in powder form for plating. Variations will occur as a result of the volume added into the barrel. In adjacent layers of these substances Although a wide range of plating layer thickness to buffer layer thickness ratios can be employed, this It is desirable that the ratio be between about 2:1 and 10:1, preferably 5:1. Metsu The amount of plating metal powder and buffer metal powder added to the plating barrel is for each plating. The thickness of the metal may be between 5 and 6.0 mils, and the thickness of each buffer layer may be between 1 and 6.0 mils thick. The thickness should be limited to 4 mils. In addition, materials can be collected cumulatively. The total thickness of the alternating plating metal and buffer metal layers to be rubberized (i.e., The total thickness of the plating metal layer (in addition to the total thickness of the plating layer) is between 1.0 and 5.6 mils. thickness, preferably 1.5 to 4.5 mils. Metal layer and buffer layer for plating Since the thickness of , the respective one-to-one ratios to be adopted for these substances are preferably 2:1 and 10 to 1, preferably 5 to 1.

There are several methods of galpanizing metal materials depending on these thickness and weight ratios. Exists. Adding a buffer metal after each addition of plating metal to the plating barrel and vice versa. Alternatively, buffer metal powder can be used instead. Buffer layer or plating by adding powder and/or plating metal powder several times in succession Forming either or both of the layers is described in U.S. Patent No. 3,531.31. 6d according to the method described in Specification No. 5 and Specification No. 4,389,431. 1 kg of ordinary nails into a hexagonal plating barrel with a capacity of 0.25 cubic feet. It was cleaned, copper plated and then tin plated. Then 4 parts of zinc powder (8 grams each) were added to the barrel at 2 minute intervals.

Two minutes after the final addition, 10 grams of tin powder was added and the barrel was rotated for 3 minutes.

Then 8 grams of zinc powder was added to the plating barrel six times, the first, third and fifth In the second addition, mechanical galvanizing continuous accelerator C], together with 25 g Added. The barrel was rotated for an additional 5 minutes after the last zinc addition. Next is the barrel? A STM standard for removing nails, washing with water, and bonding metal coatings It was subjected to the test method ASTM symbol B571-72 (1974). the test showed no significant delamination of the mechanically galvanized coating.

Example 2 Example 1 was repeated using lead powder instead of tin powder. A-S T mentioned above The M test showed no modification of the mechanical galvanizing coating with only slight peeling. It showed improved adhesion.

Example 6 Example 1 was modified with the following changes. After tin-plating the parts, use a plating bath. Zinc powder was added to the barrel six times (8 grams each) at 2 minute intervals. 2 minutes after last addition Added 10 grams of tin and continued on rotation 7 for 3 minutes.

6 additions of zinc (8 grams each) Continuous accelerator in all 1st and 3rd additions (0,25F) at 2 minute intervals. Add tin powder (10 grams) , rotation continued for 6 minutes. Finally, three additions of 88 grams each, the second Additions of 2 min with continuous accelerator (0.25 g) were carried out at 2 minute intervals, and the final addition The barrel continued to rotate for 5 minutes after the lead addition. The parts were then taken out and washed with water.

ASTM test results show significant delamination of mechanically galvanized coatings Use lead powder instead of tin powder.Each addition is 5 grams L0.1 cubic foot. Example 3 was repeated on half scale in a separate container. A S T M The mechanical bending test showed no significant delamination of the lupanizing coating. .

Example 5 As a control test, Example 4 was repeated without adding lead powder. 10 of zinc addition with successive accelerator 0.19 in the 5th, 7th and 9th additions. I went to A S T M bending test is performed using mechanical galling/gunizing coating. showed no significant peeling.

Example 6 in a 20 cubic foot barrel according to U.S. Pat. No. 3,531,315. The cast iron clevis (U link) was thoroughly cleaned with 550 bond, copper plated, and then It was tin-plated. Addition of zinc and powder three times to the plating barrel (1 bottle each) d) for a total of 2 minute intervals, which results in a mechanically plated zinc core coating on the part. It was done. Next, tin powder 1? Add the compound to the barrel and plate for 3 minutes. I continued. Next, nine additions of material were made to the plating barrel at 1% minute intervals. Ta.

Each addition is 1 bond zinc powder, 1 ounce continuous accelerator, 5 grams aluminum powder, and 5 grams of Na2SiF6. After the last addition Rotation of the rail continued for 6 minutes. The parts were then removed, washed with water, and dried. finishing The coating (which has an average thickness of 6.6 mils) resists chips resulting from part-to-part collisions. It was very resistant to popping.

Example 7 Example 6 was repeated without adding the tin powder buffer metal. Finished parts available It had a significant amount of chipped coating.

Although the present invention has been described in detail for purposes of illustration, such details are merely relevant. However, changes may be made by those skilled in the art that would depart from the spirit and scope of the invention. It should be understood that this can be done without

Claims (1)

[Claims] 1. Adding particulate plating metal to a plating solution containing a metal material and an impact medium; agitating the plating solution so that the impact medium impacts the metal material; Adhering the plating metal to the metal material as a plating layer; adding a fine buffering metal different from the plating metal to the plating solution; agitating the plating solution so that the impact medium impacts the metal material; adhering the buffer metal to the metal material as a buffer layer on the plating layer; in It has improved chipping resistance and the metal material is cumulatively galvanized. The outer plating layer underlies the alternating buffer layer and plating layer that of said fine-grained plating metal and optionally said fine-grained buffer metal until provided on the material. repeating the addition and stirring; Mechanically galvanize metal materials with a chipping-resistant coating that includes How to Ising. 2. The buffer metal is less ductile than the plating metal, and 2. The method of claim 1, which is highly malleable. 3. the buffer metal is selected from the group consisting of tin, lead, and mixtures thereof; 3. The method according to claim 2, wherein said plating metal is zinc. 4. It has improved chipping resistance and cumulatively galvanizes the metal material. Alternating buffer and plating layers with a combined thickness of 1.5 to 4.5 mils. 4. The method according to claim 3, wherein: 5. 5. The method of claim 4, wherein each buffer layer is diffused into each adjacent plating layer. 6. 4. The method of claim 3, wherein each buffer layer is diffused into each adjacent plating layer. 7. 4. The method of claim 3, wherein said impact medium is a plurality of glass beads. 8. Chipping resistant and cumulatively galvanizing the metal material , the alternating buffer layers and plating layers have a combined thickness of 1.5 to 4.5 mils. A method according to claim 1. 9. 2. The method of claim 1, wherein each buffer layer is diffused into each adjacent plating layer. 10. 2. The method of claim 1, wherein said impacting medium is a plurality of glass beads. 11. The metal material is degreased, and then Prior to any addition of the fine plating metal or the fine buffer metal, Copper plating of degreased metal material, 2. The method of claim 1, further comprising: 12. Prior to the copper plating, the metal material is descaled after the degreasing. to do, 12. The method of claim 11, further comprising: 13. After the degreasing and prior to the copper plating, the metal material is washed with water, and then In Finally, add a strong acid surface conditioner solution to be used as the plating solution. 12. The method of claim 11, further comprising: 14. After the degreasing and prior to the water washing, the metal material is descaled. thing, 14. The method of claim 13, further comprising: 15. The method according to claim 13, wherein the strong acid surface conditioner is sulfuric acid. Law. 16. An accelerator is added to the plating solution to strengthen the adhesion of the fine plating metal. 2. The method of claim 1, further comprising adding. 17. A flash accelerator is added to the plating solution prior to the addition of the fine plating metal. and a continuous accelerator is added to the plating solution together with the fine plating metal. 17. The method according to claim 16. 18. Adding the fine plating metal powder to the plating solution 2. A process according to claim 1, which is carried out by several successive additions. 19. The addition of the fine buffer metal to the plating solution is controlled by the number of fine buffer metal particles. 2. A process as claimed in claim 1, which is carried out by adding three times in succession. 20. Mechanically gluing metal materials in an agitated pampering liquid containing an impact medium. In how to Rubanize: A fine plating metal is added to the agitated plating solution, thereby causing the impact A medium hits the metal material to plate the fine plating metal onto the metal material. Adhesion as a layer; A fine buffer metal different from the plating metal is added to the stirred plating solution. Then, the impact medium hits the metal material, causing the fine-particle buffer metal to adhering it to the metal material as a buffer layer on the plating layer; and A chipping-resistant and cumulatively galvanizing cross-section of the metal material is provided below. An outer plating layer is provided on the metal material, in which there are interleaved plating layers and buffer layers. The addition of the fine-grain plating metal and the addition of the fine-grain buffering metal are continued until The method comprises the step of repeating. 21. the buffer metal is less ductile than the plating metal, and 21. The method of claim 20, which is more malleable. 22. the buffer metal is selected from the group consisting of tin, lead, and mixtures thereof; 22. The method of claim 21, wherein said plating metal is zinc. 23. It is chipping resistant and does not cumulatively galvanize the metal material. The alternating buffer and plating layers must have a combined thickness of 1.5 to 4.5 mils. The method described in item 22 of the scope of the request. 24. 24. The method of claim 23, wherein each buffer layer is diffused into each adjacent plating layer. . 25. 23. The method of claim 22, wherein each buffer layer is diffused into each adjacent plating layer. . 26. 23. The method of claim 22, wherein the impact medium is a plurality of glass beads. . 27. It is chipping resistant and does not cumulatively galvanize the metal material. The alternating buffer and plating layers have a combined thickness of 1.5 to 4.5 mils. The method according to claim 20. 28. 21. The method of claim 20, wherein each buffer layer is diffused into each adjacent plating layer. 29. 21. The method of claim 20, wherein the impact medium is a plurality of glass beads. . 30. The metal material is degreased, and then Prior to any addition of the fine plating metal or the fine buffer metal, Copper plating of degreased metal materials, 21. The method of claim 20, further comprising: 31. Prior to the copper plating, the metal material is descaled after the degreasing. to do, 19. The method of claim 18, further comprising: 32. After the degreasing and prior to the copper plating, the metal material is washed with water, and then In Finally, add a strong acid surface conditioner solution to be used as the plating solution. That, 31. The method of claim 30, further comprising: 33. After the degreasing and prior to the water washing, the metal material is descaled. thing, 33. The method of claim 32, further comprising: 34. The method according to claim 32, wherein the strong acid surface conditioner is sulfuric acid. Law. 35. Adding an accelerator to the plating solution to enhance adhesion of the fine plating metal thing, 21. The method of claim 20, further comprising: 36. A flash accelerator is added to the plate prior to the addition of the particulate plating metal. In addition, a continuous accelerator is added to the plating solution together with the fine plating metal. 36. The method of claim 35. 37. The addition of the fine grain plating metal to the plating solution is added to the fine grain plating metal. 21. A method according to claim 20, which is carried out by several successive additions of the genus. 38. Adding the fine buffer metal to the plating solution 21. The method according to claim 20, which is carried out by several consecutive additions. 39(a) cleaning the surface of the metal material by contacting it with an acidic solution, and a step of descaling; (b) a step of washing the material with water; (c) applying a surface conditioner containing a strong acid to an impact medium and said material; Added to stirred matting barrel to clean and oxidize the surface of the material. The process of keeping it free of substances; (d) a thin copper coating on the cleaned and oxide-free surface of said material; The copper plating agent that forms the plating agent is added to the agitated plating barrel without intermediate washing with water. Step of adding (e) A metal salt that is more solid than the final plating metal and a small amount of fine plating metal. The above-mentioned is added to the above-mentioned stirred matting barrel without intermediate water washing. The copper-plated surface of the material is flash-coated with a layer of metal. (f) fine grain plating metal into the stirred plating barrel; without intermediate water washing, whereby the impact medium affects the plating metal. , the metal material is copper-plated and coated with a more translucent metal. (g) A step of adhering a metal as a plating layer to the surface of the plating metal; Grain buffering metal is added to the agitated mating barrel without intermediate water washing. As a result, the impact medium transfers the buffer metal to the plating metal material. adhesion as a buffer layer on the plating layer; and (h) An external plating metal layer with alternating buffer layers and plating layers below; step (f) and optionally step (g) with intermediate water washing until applied to the metal material. The process of adding without A thick mechanically applied coating of plating metal comprising a metal material How to govern. 40. metal materials and From layers of alternating plating metals and buffer metals different from the plating metals. a coating consisting of a metal plate, wherein said coating comprises a metal coating; an outermost layer, wherein said alternating layers of plating metal and buffer metal are said Galvanized objects that cumulatively galvanize metal materials Goods. 41. the buffer metal is less ductile than the plating metal, and 41. The galvanized article of claim 40 which is more malleable. 42. the buffer metal is selected from the group consisting of tin, lead, and mixtures thereof; Galvanidin according to claim 41, wherein the plating metal is zinc. Goods that have been 43. Alternating chipping resistant and cumulatively galvanizing the metal material Claims wherein the plating layer and buffer layer of the arrangement have a combined thickness of 1.5 to 4.5 mils. 43. A galvanized article according to paragraph 42. 44. 44. The gasket of claim 43, wherein each buffer layer is diffused into each adjacent plated layer. Rubanized goods. 45. 43. The glass of claim 42, wherein each buffer layer is diffused into each adjacent plated layer. Rubanized goods. 46. Claim further comprising a layer of copper between the metal material and the coating. 43. The galvanized article of claim 42. 47. Claim further comprising a layer of copper between the metal material and the coating. The galvanized article of claim 40. 48. The coating is pitting resistant and cumulatively coats the metal material. Includes alternating galvanizing plating layers and buffer layers, both layers totaling 1 ．． 41. The galvanized coating of claim 40 having a thickness of 5 to 4.5 mils. Goods. 49. Claim 4, wherein the buffer layer comprises a mixture of a plating metal and a buffer metal. Galvanized article according to item 0.