CA1036841A - Aluminum-coated nickel or cobalt core flame spray materials - Google Patents
Aluminum-coated nickel or cobalt core flame spray materialsInfo
- Publication number
- CA1036841A CA1036841A CA198,685A CA198685A CA1036841A CA 1036841 A CA1036841 A CA 1036841A CA 198685 A CA198685 A CA 198685A CA 1036841 A CA1036841 A CA 1036841A
- Authority
- CA
- Canada
- Prior art keywords
- component
- weight
- composite
- nickel
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 42
- 239000007921 spray Substances 0.000 title claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 title claims description 28
- 239000000843 powder Substances 0.000 claims abstract description 55
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims description 21
- 239000011733 molybdenum Substances 0.000 claims description 21
- 239000002966 varnish Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 230000006872 improvement Effects 0.000 claims description 4
- 238000000576 coating method Methods 0.000 abstract description 40
- 239000011248 coating agent Substances 0.000 abstract description 29
- 150000002739 metals Chemical class 0.000 abstract description 6
- UNQHSZOIUSRWHT-UHFFFAOYSA-N aluminum molybdenum Chemical compound [Al].[Mo] UNQHSZOIUSRWHT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- 239000000306 component Substances 0.000 description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 7
- 229910000765 intermetallic Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008358 core component Substances 0.000 description 3
- 238000010285 flame spraying Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 229910000951 Aluminide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- 241000518994 Conta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- 229910000713 I alloy Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical class [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- ZXTFQUMXDQLMBY-UHFFFAOYSA-N alumane;molybdenum Chemical compound [AlH3].[Mo] ZXTFQUMXDQLMBY-UHFFFAOYSA-N 0.000 description 1
- YYCNOHYMCOXPPJ-UHFFFAOYSA-N alumane;nickel Chemical class [AlH3].[Ni] YYCNOHYMCOXPPJ-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 239000010442 halite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
- Powder Metallurgy (AREA)
Abstract
Abstract of the Disclosure A flame spray material in the form of a composite comprising (1) as a first component an alloy containing at least about 40% of its weight of at least one of nickel and cobalt, and about 1 to 6% by weight of boron, and (2) aluminum powder as a second component, the first component being present in about 66 to 99% by weight of the composite. The material, desirably blended with about 10% of an aluminum-molybdenum-coated nickel fore powder, produces self-bonded wear resistant coating which can be ground without cracking. The flame spray material can be used to line metal surfaces with other metals of different mechanically superior properties to obtain the best properties of both metals.
Description
The invention relates to an alumlnum-clad nlckel-cobalt-boron based flame spray materlal which i8 characterlzed by excellent bondlng and workablllty of coated surfaces.
It is common to line metal surfaces with other metals of tifferent mechanically superior properties to obtain the beat properties of both metals, e.g. cylinders in aluminum engine blocks have been lined with iron sheets to give the bene-fits of the light weight of aluminum and the wear properties of iron. An improvement thereon involved flame spraying the wear surface onto the receiving surface. To ensure a secure bond between substrate and sprayed metal it was customary to - q~
db/~r _ I _ .. .... . . . .
/' "' ~ ~ , ,";........................................ I
,~` ., ,. I
; prepare the substrate by mechanical roughening. U. S. Patent
It is common to line metal surfaces with other metals of tifferent mechanically superior properties to obtain the beat properties of both metals, e.g. cylinders in aluminum engine blocks have been lined with iron sheets to give the bene-fits of the light weight of aluminum and the wear properties of iron. An improvement thereon involved flame spraying the wear surface onto the receiving surface. To ensure a secure bond between substrate and sprayed metal it was customary to - q~
db/~r _ I _ .. .... . . . .
/' "' ~ ~ , ,";........................................ I
,~` ., ,. I
; prepare the substrate by mechanical roughening. U. S. Patent
2 Nos. 2,588,421 and 2,588,422 made a furhter improvement thereon 'I
in that molybdenum was first flame sprayed onto the substrate ~ ¦
4 without need for special preparation of the substrate. There-after a hard wear surface such as high carbon steel could be ;
6 sprayed and the laminate would be securely held together.
7 In U. S. Patent No. 2,875,043 there were disclosed 8 spray-weld alloys, also known as self-fluxing alloys, 9 comprising nickel bases which could be sprayed and which, because of a content of boron and/or silicon, act as a fluxer 11 of the alloy and of the surface to be alloyed during subsequene 12 fusing of a sprayed coating. Other metallic components such ;~
13 as chromium, iron, carbon, copper and molybdenum could also 14 be present. In U. S. Patent No. 2,936,229 it was taught that such self-fluxing alloys might also contain about 0.2 to 5~L
16 of aluminum and that the nickel could be replaced in whole 17 or in part by cobalt. These modifications minimized the 18 formation of any small pores in the coating. Other elements could also be present in mi-nor amounts.
For certain purposes it was desired th~t the flame 21 sprayed surface constitute an intermetallic compound. In 22 U. S. Patent 3,305,326 there was disclosed a powder mixture 2~ as described in U. S. Patent Nos. 2,875,043 and 2,936,229 along J, 24 with coated powder particles comprising a metal nucleus and a metal coating reactable therewith at flame spray temperatures - 26 to form an intermetallic compound. The coated powder material ; rendered the blend self fusing, i.e. it automatically formed 28 a fused coating upon spraying without a separate fusing operatic n.
` L
. , .. . .. , . . . ~. .
~ l ~ 1C~3~i841 l In U. S. Patent No. 3,322,515 there were described modified flame spray composite materials whose components exothermically
in that molybdenum was first flame sprayed onto the substrate ~ ¦
4 without need for special preparation of the substrate. There-after a hard wear surface such as high carbon steel could be ;
6 sprayed and the laminate would be securely held together.
7 In U. S. Patent No. 2,875,043 there were disclosed 8 spray-weld alloys, also known as self-fluxing alloys, 9 comprising nickel bases which could be sprayed and which, because of a content of boron and/or silicon, act as a fluxer 11 of the alloy and of the surface to be alloyed during subsequene 12 fusing of a sprayed coating. Other metallic components such ;~
13 as chromium, iron, carbon, copper and molybdenum could also 14 be present. In U. S. Patent No. 2,936,229 it was taught that such self-fluxing alloys might also contain about 0.2 to 5~L
16 of aluminum and that the nickel could be replaced in whole 17 or in part by cobalt. These modifications minimized the 18 formation of any small pores in the coating. Other elements could also be present in mi-nor amounts.
For certain purposes it was desired th~t the flame 21 sprayed surface constitute an intermetallic compound. In 22 U. S. Patent 3,305,326 there was disclosed a powder mixture 2~ as described in U. S. Patent Nos. 2,875,043 and 2,936,229 along J, 24 with coated powder particles comprising a metal nucleus and a metal coating reactable therewith at flame spray temperatures - 26 to form an intermetallic compound. The coated powder material ; rendered the blend self fusing, i.e. it automatically formed 28 a fused coating upon spraying without a separate fusing operatic n.
` L
. , .. . .. , . . . ~. .
~ l ~ 1C~3~i841 l In U. S. Patent No. 3,322,515 there were described modified flame spray composite materials whose components exothermically
3 interacted with one another when melted so as to form such
4 intermetallic compound which was deposited upon the substrate.
The heat generated by the exothermic reaction aided in the 6 bonding, and these materials were an improvement over Ij 7 molybdenum for bonding other flame spray materials to the ! substrate. The composite could comprise separate strands of 9 the two components, e.g. a strand of nickel and a strand of I lO aluminum, the strands being simultaneously fed to a flame i ll spray gun. In accordance with a preferred technique one 12 of the components could be coated onto the other, e.g.
13 a wire comprising a nickel core and an aluminum sheath.
14 These composites functioned in generally satisfactory fashion but had certain significant limitations. For example 16 the self-fusing mixture of U. S. Patent No. 3,305,326 did not 17 bond very well, and required either a special substrate 18 preparation such as roughening by grit blasting, or a lg preliminary layer of a bonding material such as molybdenum or exothermic composite described above 21 The surfaces, while of adequate bond strength for 22 most purposes, still imposed limitations upon the working Z3 to which the coated surfaces could be put.
24 It is accordingly an object of the present invention 2~ to provide flame sprayable compositions which are self-26 bonding and which produce coatings which may readily be worked without de-bonding.
_ 3 _ , . i A further object of the invention is to produce superior flame sprayed bearing surfaces.
These and other objects and advantages are realized in accordance with the present invention pursuant to which there is provided a flame spray material in the form of a composite comprising (1) as a first component an alloy con-taining at least about 40~ of its weight of at least one of nickel and cobalt, and about 1 to 6% by weight of boron and (2) aluminum powder as a second component, the first component being present in about 66 to 99% by weight of the composite.
The resulting coatings are characterized by excellent bonding and superior bearing and wearing surfaces. They can readily be worked, generally by grinding.
The first component, which preferably constitutes about 66 to 99% and most preferably about 85 to 95%
of the combined weights of the first and second components, may ~omprise any of the spray-weld, self-fluxing alloy compositions disclosed in above-mentioned U.S. Patent Nos. 2,875,043 and 2,936,229. Thus, the first component may further contain about 1 to 6% of its weight of silicon, preferably about 4 to 5~; up to about 20% of chromium; up to about 8~, and generally at least about 3% when present, of copper, preferably about 5 to 6~; up to about 10%, and generally at least about 3% when present, of ~molybdenum, preferably about 4.5 to 5.5%; and aluminum desirably in about 0.2 to 5% and preferably up to about 2%. Minor amounts of iron and carbon may also be present. While the nickel and/or cobalt should constitute cmj .. , 5. ,, ~ .. , .. ,~. ... . , .. . ,. , . ,, ~ ... . ... . . . .
st least about 40~ o~ the 1rst co~ponent as descrlbet, advan-tageously lt should constltute at least about 60%.
The secont component, a6 notet, comprises aluminu~ and preferably lt ls employed as a flne powter teposltet ln a blnder on partlcles of the first component.
The aluminum preferably ln as finely divitet form as possible, as for eYample a size of -325 mesh, is mixed in the requlret proportions with a binder or lacquer 80 as, in effect, to form a paint in which the aluminum particles correspond to the pigment. The paint is then used to coat the core particles and allowed to set or try.
The binder material may be any known or conventional binder material which may be uset for forming a coating or for bonding particles together or to a surface. The binder is pre-ferably a varnish containing a resin as the varnish solids, and may contain a resin which does not depend on solvent evaporation ln orter to form a dried or set film. The varnish may thus contain a catalyzed resin as the varnish solids. Examples of binders which may be uset include the conventional phenolic epoxy or alkyt varnishes, varnishes containing drying oils, such as tuna oil and linseed oil, rubber and latex binters and the like.
The coating of the high nickel-cobalt first or core com-ponent with the "paint" containing the aluminum may be effected in any known or desired manner, and it is simply necessary to mi~ the two materials together and allow the binder to set or dry which will result in a fairly free-flowing powder consisting of the nickel-cobalt core coatet with cladting of the aluminum.
The powders are sprayet in the conventional manner, using a powter type flame spray gun, though it is also possible to combine the same in the form of a wire or rod, using plastic or a similar binding, as for eYample polyethylene which decomposes tb~,~ 5 103~841 ln a heatlng zone of the gun. When formed a~ wire~, the sa~e may have conventional si~es and accuracy tolerances for flame spray wlres and thus, for example, may vary in slze between 1/4" and 20 gauge.
The spraying i9 in all respects effected in the conven-tional manner previously utilized for self-bonding flame spray material, and in particular nickel aluminum composites. Due to the self-bonding characteristics, special surface preparation other than a good cleanlng is not required though, of course, conventional surface preparation may be utilized if deslred.
The powder in accortance with the invention may be flame-~prayed as a bonding coat for subsequently applied flame spray material. The composites may furthermore be sprayet in con-~unction with. or in addition to, other flame spray materials conventionally used in the art.
When sprayed, the nickel and/or cobalt and aluminum are believed to react exothermically, forming a nickel and/or cobalt aluminide intermetallic. Complex aluminides and alloys with other metals, when present, may be formed.
The term "composite" as used herein is intended to designate a structurally integral unit and does not include a mere mixture of components which may be physically separated without any destruction of the structure. Thus, in the case of powder, the term "composite" does not include a simple mixture of individual granules of the separate components, but requires th~t each of the individual granules contain the separate com-ponents which will exothermically react, forming intermetallic compounds. In the case of wire, the individual components must be incorporated in a single wire. In the composite the com-ponents must be in intimate contact with each other.
In connection with powders, each grain may consist of an ~ggregate containing the components which wlll exothermically db/~ - 6 -rea^t, form~ng the lntermetallic compount, but preferably the lndivldual grains of the powter are in the form of a clad com-poslte consisting of a nucleus of one of the components ant at least one coatlng layer of the other components. Alternatively, the composite may consist of separate, concentric coating layers of at least two of the components ant a nucleus of two, three or even a fourth material.
In the case of wires, the composites may be in the form of a wire having a coating sheath of one material ant a core Of the others, alternate coating sheaths u4 two of the components and a core of the thirt or a fourth material, a wire formed by twi~ting o~ rolling separate wire strands of the components, a wlre consisting of a sheath of one component and a core con- .
tsining the other components in powder or compacted form, a ~lre consisting of a sheath of one component and a core containing a compacted powter mixture of this same component material and other components, a wire consisting of a plastic sheath and a core containing a compacted powder mixture of components, etc.
In order for the wires to be most satisfactory for spraying, it is preferable that the same must not cavitate at the tip when heatet, and should preferably be capable of forming a polnted or ~lightly tapered tip when being melted and sprayed.
Thus, if the wires have an outer layer or sheath of one component and an inner core of another component, the inner core should not have a lower melting point than the outer sheath, as other-~ise the inner core will initially melt, causing cavitation at the tip. For example, if the wire is in the form of a core with a coating sheath, the coating sheath should be aluminum, as otherwise during the spraying operation the wire will initially melt out, causing the cavitation which may interfere with a s-tisfactory spraying operation. The wire havlng the melting-point characterigtics so as to allow the ~elting off of the tip tb/~ 7 -wlthout thl~ cavitation i9 referred to herein and in the claims as "non-cavltating wire."
Whlle the components may be present ln the stolchio-metrlc proportions requlret for the formation of the lnter-metallic compound, it is, however, possible to also have an excess of one or the other provided the relative amounts are sufficient to release quantities of heat in the formation of the intermetallic compounds.
The clad powders, in accortance with the invention, may be formet in any known or desiret manner, including known chemical plating processes, in which coating material i8 deposited on a seed or nucleus of another material, or in which multiple lsyers of various materials are built up on the seet material, or in which various materials are co-tepositet in a single lsyer on the seed material.
A mote of forming the clad powders lnvolves the déposi-ting of a metal from a solution by reduction on a seed or nucleus, such as by the hydrogen reduction of ammonical solutions of nlckel and/or cobalt aad ammonium sulfate on a seed powter catalyzet such as by the atdition of anthraquinone. It is also possible to form the coating by other processes, such as coating by vapor deposition, by the thermal decomposition of metal car-bonyls, by hydrogen reduction of metal halite vapors, by thermal deposition of halides, hydrides, carbonyls, organometals, or other volatile compounds, or by displacement gas plating and the like.
A preferred and greatly simplified mode of forming the clat powders in accordance with the invention is the depositing of one component as coating in the form of a paint on the other component. ThuR the component which is to form the coating or cladting may be dispersed in finely tividet form in a binder or lac~uer so as, in effect, to form a palnt in which this component db/~ - 8 -` 10368~1 corresponds to the pigment. The palnt i8 then used to coat core partlcles of the other component and the binder or lacquer allowed to set or dry. The blnder materlal 19 preferably a resin which does not depend on solvent evaporatlon ln order to form a dried or set film, and which film will decompose or break down in the heat of the spraying process. The binder, for example, may be a phenolic varnish or any other known or conventional varnish, preferably conta~ning a resin as the var-nish solids. The components which are initially mlxed with the blnder or varnish should preferably be as finely divided as possible, as for example -325 mesh. The other component which constitute6 the core should be approximately or only s~lightly below the particle size ultimately desired for the spray powder.
The coating of the core component with the "paint" may be effected in any known or desired manner, and it is slmply necessary to;
~ls the two materials together and allow the binder to dry or ~et, which will result in a fairly free-flowing powder consisting of the core component coated with a cladding of the other com-ponent bound in the binder.
The aggregates may be formet by any other known method, suc~ as by compacting or briquetting the various components into the lndividual granules, or into larger aggregates and then breaking these aggregates into the granules.
The wires may be formed in the known conventional man-ner for forming wires with various components as, for example, by shrinking a sheath on a core, by forming the core with powder, by twisting the component wires, followed by rolling, drawing, swagging, or the like if tesired.
In accordance with one mode of manufacture, one of the components may be formed into a tube or sheath and filled with a powder of the other component or a powder comprising a mixture of the two components, vr containing atditional components. The db¦~ ~ 9 ~
., .. ~. . . . , r 103684~
tube ends are then sealed and the wlre reduced to the desired w$re tlameter by swagging, rolllng or drawlng. Preferably the powder or powder mlxture is flr~t compressed into cylindrical briquettes before being placed in the sheath or core. The ~eallng of the tube ends after loading with the powder or pow-der mlxture can be effected, for lnstance, by insertion of a plug, for example of the metal of the sheath, by welding, twlsting, crimping, or the like.
Powders in accordance with the invention should have 10 the general over-all shape and size of conventional, flame spray powders, and thus for example should have a size between -60 mesh and +3 microns and preferably -140 mesh and +10 microns (U.S. Standard screen mesh size). Most preferably the powder should be as uniform as posslble in grain size, with the indivi-dual grains not varying by more than 250 microns and preferably 75 microns.
Dependlng on the partlcular flame spray process and the tesiret purpose, the composite powder may be sprayet per se or ln co~bination with other different composlte powders, or in 20 combination wlth other conventional flame spray powders or powder components.
- While the powders are preferably sprayet, as such, in a powder-type of flame spray gun, it i5 also possible to combine the same in the form of a wire or rod, using a plastic or simi-lar binder, which decomposes in the heating zone of the gun, or in certain cases the powders may be compacted and/or sintered together ln the form of a rod or wire. The wires must have the conventional sizes and accuracy tolerances for flame spray wires and thus for example may vary in size between 1/4" and 20 gauge, ~0 and are preferably of the following sizes: 3/16" + .0005" to -.0025", l/8" t .0005" to -.0025", ll gauge ~ .0005"
to -.0025", and 15 gauge + .OOOl" wlth a smooth clean finish tb/ ' ' - lO -........ ~ .. ~, .... . . . .
-"` ` 1036841.
free from surface marks, blemlshes, or defects. The wires are sprayet in the conventional manner uslng conventlonal ~lre-type flame spray guns.
In combining, in the exothermic reaction, forming the lntermetallic compound, the components generate heat ln situ in the actual material which is to form at least a part of the coating. This is to be distinguished from flame-spray processes ant materials in which heat is generated by a reaction, such as 8n oxitation reaction in whlch a oreign ant non-metallic element is introduced ant in which untesirable components may be pro-ducet. Asite from greatly contributing to the thermal efficiency of the process, the heat generated in situ in the formation of the intermetallic compount produces novel results, in many in-stances forming a tenser, more adhering coating, having charact-eristic~ ~ at least a partially fused coating. In many in-stances the coating has self-bonting characteristics, so that ~pecial surface preparation, other than a good cleaning, is not requiret. The spraying in all other respects is effected in the conventional, well-known manner, using conventional flame spray equipment, ant the conventional surface preparation may be utilizet, if tesired. The composites in accordance with the invention may be sprayet in con~unction with or in addition to other flame spray materials db~
.
conventionally used in the art, or may be sprayed in combination or conjunction with the others.
The use of the nickel- and/or cobalt- aluminum composites will generally improve the bond of the total sprayed material, and thus of the other component or components, to the substrate, sometimes making the mixture self-bonding. The particle bond will be improved and the coating will be denser, 80 that its porosity may be decreased. In general, as little as about 5% by weight of the composites in accordance with the invention will be sufficient to substantially improve the bonding characteristics and decrease the porosity of other flame spray materials, such as conventional flame spray metals, alloys or ceramics. There is, of course, no upper limit on the amount as the composite may be sprayed per se.
An especially suitable blend comprises the novel composite and up to about 20% of its weight, preferably about 5 to 15% of its weight, of another composit~. The other composite may simply be aluminum-clad nickel although preferably it is aluminum- and molybdenum-clad nickel as described more fully in Canadian Application Serial No. 198,563 filed April 30, 1974. In such other composite based on the weight of nickel, aluminum and molybdenum the nickel is present :n about 66 to 97.5%, the aluminum in about 2 to 18% and the molybdenum in about 0.5 to 16%; preferably the nickel is present in about 73 to 89%, the aluminum in about 5 to 15% and cm/ 1 2 ..~
10;16841 l the molybdenum in about 6 to 12%. Such other compo8ite which 2 is preferably a clad core is generally produced in the same 3 manner as described hereinabove for the composite forming 4 I the basix of this in~ention. Such blends produce coatings which will not crack upon working even when extremely thick, 6 e.g. more than about 0.050 inch and even more than about ¦ 0.100 inch.
8 Materials with which the novel composites may be 9 admixed before flame spraying include carbides as described l I 10 in U. S. Patent No. 3,305,326. ~hen blended with a refractory i ¦ ll carbide, such as tungsten carbide, titanium carbide, zirconium l ¦ 12 carbide, tantalum carbide, columbium carbide, hafnium carbide, , 13 chromium carbide or the like, extremely high quality coatings 14 are produced, which are superior in various respects to the conventional carbide coatings. li 16 The carbides used in accordance witl this embodiment 17 should have a particle size between about -140 mesh U. S.
18 Standard screen size and 8 microns, and preferably between l9 about -270 mesh and ~15 microns, with the amount of carbide being between about 5-95% and preferably 25-85% and most prefer 21 I ably 45-55% by weight, based on the total powder mixture.
22 If the refractory carbide powder is in a form so that 23 the refractory carbide is bound in a matrix, as for example 24 a cobalt or nickel matrix containing S-20% by weight of either cobalt or nickel, unusually hard and wear-resistant 26 coatings will be produced which do not contain the individual 27 carbide particles imbedded in a fused matrix, but instead -` 103684~, contain alloy phase~ who~e micro-hardnes~ i9 actually sub-stanelally hlgher than that ordlnarlly obtalned from a bonded carbide.
When the powder, ln accordance wlth the inventlon, con-tainlng this matrix-bonded refractory carbide is plasma-sprayed, the same is self-bonding, so that the conventlonal surface pre-paration for flame spraying, as for example a deep surface roughening, is not requiret.
The carbide coatings formet in accortance with the above are extremely hart and wear-resistant, and may be useful as bearing surfaces, abrasive surfaces, and for any other purpose wherein a working surface requires extremely wear-resistant coating.
The refractory carbide, need not be matrix-bound, but should be a pure crystalline carbide, also having the particle size and u~ed in the amounts lndicated above. The crystalline carbite-containing coatings formed in accordance with the in-vention will have extremely high wear-resistance due to the carbide particles, which are tispersed ant tightly bound in the fused coating. Coatings may be uset for the same type of ap-plications as mentioned in connection with the coatings formed with the matrix-bound carbide.
The following examples, wherein all parts are by weight unless otherwise expressed, are given by way of illustration and not limitation.
1~ .
.
tb/-~
1 I ~xAMpLE 10;UiE~
¦ Finely divided aluminum powder (-325 mesh) was 3 ¦ admixed with a conventional phenolic varnish having 4 approximately 10% solid contents so as to form a mixture having the consistency of heavy syrup and containing about 60% by weight of the metal particles. 100 grams of the 7 ¦ varnish powder mixture was then added to about 900 grams 8 of a self-fluxing alloy powder comprising -200 +325 mesh partic es 9 of the composition O~15~/o carbon, 2.5% silicon, 2.5% boron, 2.5% iron, 10% chromium, balance nickel. The two were ll thoroughly mixed, with the mixing continued until the 12 varnish dried, leaving a fairly free-flowing powder in 13 which all of the core particles were clad with a dry film 14 which contained the aluminum particles. The powder was then warmed to about 250F. to ensure complete drying. The 16 ¦ powder was then screened and hand-milled to reduce the same 17 ¦ to a -100 mesh powder. The powder was flame-sprayed on a 18 mild steel plate which had been surface cleaned by smooth 19 grinding. The spraying was effected under different conditions using three different flame spray guns sold by 21 I Metco, Inc., of Westbury, N.Y., as described in Table I.
22 The process conditions and the results are set forth in 23 Table II along with those Eor one oE the best grindable .
Z4 compositions heretofore available, which composition however is not self-bonding. The novel coatings are hard, grindable 26 ¦ and durab .
1036~141 Table I
2 ¦ Spray Parameters for a Self-Bondin~ Grindable Coatin~
l (1) (1) (2) 4 METC0 "5P" ThermoSpray METC0 "N" ThermoSPray METC0 "3MB"
Plasma Spray Gun Nozzle = P7G N7B Gas - N2 ~ 2 r Meter Valve - 12 15 Press (psi)-50/50 8 Clicks - 8 9 Flow - 100 ~ 0 9 2 Flow - 25 Press - 0213 Current - 500 AMPS
Acet. Flow - 40 Press Acet. 15 Voltage - 73 Volts 11 Carrier ' 2 2 Carrier = 37 12 Vibrator Vibrator Nozzle - G
13 Spray Dis~. = 10" 7" Port ~ 2 14 Spray Rate - 9 Lbs.~Hr. 6 ~r. "S" Wheel 20 15 ¦Deposit Efficiency = 75% 85% Spray Rate-10 Lbs. 'Hr 16 ¦Hardness - Rc 37 Rc 34 Spray Distance ~ 6 17 Hardness - Rc47-49 18 ¦(1) As described in U.S. Patent No. 2,961,335.
20 1(2' As desc ibed in U.S. Patent No. 3,145,287.
. _ _ . ~ r 1 _ ~ = ~ d ~ ~ ", ,` ,; ~ ; ;~
~ ~ 3 , ,, ~"
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; ~ ~ O h I I
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; h I 1~ 1 t:q rl u~ u~ ~i z æ ~ ~ ~ h 17 ~ -~ EXAMPLE 2 10 36 ~ ¦
2 ¦ When 90% of the composite aluminum clad self-fluxing 3 alloy in Example 1 was admixed (blended~ with 10% composite 4 powder of aluminum-molybdenum clad nickel core (Example 1 of S ¦ METC0 347), and sprayed per Example 1, a hard grindable coating 6 ¦ was produced which did not crack upon working even when 7 ¦ extremely thick. The coating also had a bond strength of 8 ¦ 5,260 psi (Table II).
9 . l 11 ¦ Uhen 50% of the 90/O composite aluminum self-fluxing 12 alloy with 10% composite aluminum-molybdenum-nickel powder 13 was admixed (blended) with 50% refractory molybdenum metal 14 ¦ powder, and sprayed per Example 1, a hard, grindable, wear resisting coating was produced. (See U.S. Patent 3,313,633, 16 Example 5 - 50% molybdenum). The coating hardness was Rc 35-40 17 and bond strength was 5,027 psi.
18 l i 20 I When 50% of the 90% composite aluminum self-fluxing 21 I alloy with 10% composite aluminum-molybdenum-nickel powder 22 ¦ is admixed (blended) with 50% of a refractory tungsten carbide 23 ¦ powder (See U.S. Patent 3,305,326 Example 3-crystalline 24 carbide~, a hard grindable coating was produced, with Rc hardnes of 53-S5, and a bond strength of 6,444 psi.
28 _ _ I
1 ~ EXAMPL1 1036841 Repeating Example 4 using 50% of the composite powder 3 of Example l (without the addition of the aluminum-molybdenum- .
4 nickel powder) produces similar results.
It will be appreciated that the instant specification 7 and examples are set forth by way of illustration and not 8 limitation, and that various modifications and changes may 9 be made without departing from the spirit and scope of the 11l02 ~ present ention.
3 .
The heat generated by the exothermic reaction aided in the 6 bonding, and these materials were an improvement over Ij 7 molybdenum for bonding other flame spray materials to the ! substrate. The composite could comprise separate strands of 9 the two components, e.g. a strand of nickel and a strand of I lO aluminum, the strands being simultaneously fed to a flame i ll spray gun. In accordance with a preferred technique one 12 of the components could be coated onto the other, e.g.
13 a wire comprising a nickel core and an aluminum sheath.
14 These composites functioned in generally satisfactory fashion but had certain significant limitations. For example 16 the self-fusing mixture of U. S. Patent No. 3,305,326 did not 17 bond very well, and required either a special substrate 18 preparation such as roughening by grit blasting, or a lg preliminary layer of a bonding material such as molybdenum or exothermic composite described above 21 The surfaces, while of adequate bond strength for 22 most purposes, still imposed limitations upon the working Z3 to which the coated surfaces could be put.
24 It is accordingly an object of the present invention 2~ to provide flame sprayable compositions which are self-26 bonding and which produce coatings which may readily be worked without de-bonding.
_ 3 _ , . i A further object of the invention is to produce superior flame sprayed bearing surfaces.
These and other objects and advantages are realized in accordance with the present invention pursuant to which there is provided a flame spray material in the form of a composite comprising (1) as a first component an alloy con-taining at least about 40~ of its weight of at least one of nickel and cobalt, and about 1 to 6% by weight of boron and (2) aluminum powder as a second component, the first component being present in about 66 to 99% by weight of the composite.
The resulting coatings are characterized by excellent bonding and superior bearing and wearing surfaces. They can readily be worked, generally by grinding.
The first component, which preferably constitutes about 66 to 99% and most preferably about 85 to 95%
of the combined weights of the first and second components, may ~omprise any of the spray-weld, self-fluxing alloy compositions disclosed in above-mentioned U.S. Patent Nos. 2,875,043 and 2,936,229. Thus, the first component may further contain about 1 to 6% of its weight of silicon, preferably about 4 to 5~; up to about 20% of chromium; up to about 8~, and generally at least about 3% when present, of copper, preferably about 5 to 6~; up to about 10%, and generally at least about 3% when present, of ~molybdenum, preferably about 4.5 to 5.5%; and aluminum desirably in about 0.2 to 5% and preferably up to about 2%. Minor amounts of iron and carbon may also be present. While the nickel and/or cobalt should constitute cmj .. , 5. ,, ~ .. , .. ,~. ... . , .. . ,. , . ,, ~ ... . ... . . . .
st least about 40~ o~ the 1rst co~ponent as descrlbet, advan-tageously lt should constltute at least about 60%.
The secont component, a6 notet, comprises aluminu~ and preferably lt ls employed as a flne powter teposltet ln a blnder on partlcles of the first component.
The aluminum preferably ln as finely divitet form as possible, as for eYample a size of -325 mesh, is mixed in the requlret proportions with a binder or lacquer 80 as, in effect, to form a paint in which the aluminum particles correspond to the pigment. The paint is then used to coat the core particles and allowed to set or try.
The binder material may be any known or conventional binder material which may be uset for forming a coating or for bonding particles together or to a surface. The binder is pre-ferably a varnish containing a resin as the varnish solids, and may contain a resin which does not depend on solvent evaporation ln orter to form a dried or set film. The varnish may thus contain a catalyzed resin as the varnish solids. Examples of binders which may be uset include the conventional phenolic epoxy or alkyt varnishes, varnishes containing drying oils, such as tuna oil and linseed oil, rubber and latex binters and the like.
The coating of the high nickel-cobalt first or core com-ponent with the "paint" containing the aluminum may be effected in any known or desired manner, and it is simply necessary to mi~ the two materials together and allow the binder to set or dry which will result in a fairly free-flowing powder consisting of the nickel-cobalt core coatet with cladting of the aluminum.
The powders are sprayet in the conventional manner, using a powter type flame spray gun, though it is also possible to combine the same in the form of a wire or rod, using plastic or a similar binding, as for eYample polyethylene which decomposes tb~,~ 5 103~841 ln a heatlng zone of the gun. When formed a~ wire~, the sa~e may have conventional si~es and accuracy tolerances for flame spray wlres and thus, for example, may vary in slze between 1/4" and 20 gauge.
The spraying i9 in all respects effected in the conven-tional manner previously utilized for self-bonding flame spray material, and in particular nickel aluminum composites. Due to the self-bonding characteristics, special surface preparation other than a good cleanlng is not required though, of course, conventional surface preparation may be utilized if deslred.
The powder in accortance with the invention may be flame-~prayed as a bonding coat for subsequently applied flame spray material. The composites may furthermore be sprayet in con-~unction with. or in addition to, other flame spray materials conventionally used in the art.
When sprayed, the nickel and/or cobalt and aluminum are believed to react exothermically, forming a nickel and/or cobalt aluminide intermetallic. Complex aluminides and alloys with other metals, when present, may be formed.
The term "composite" as used herein is intended to designate a structurally integral unit and does not include a mere mixture of components which may be physically separated without any destruction of the structure. Thus, in the case of powder, the term "composite" does not include a simple mixture of individual granules of the separate components, but requires th~t each of the individual granules contain the separate com-ponents which will exothermically react, forming intermetallic compounds. In the case of wire, the individual components must be incorporated in a single wire. In the composite the com-ponents must be in intimate contact with each other.
In connection with powders, each grain may consist of an ~ggregate containing the components which wlll exothermically db/~ - 6 -rea^t, form~ng the lntermetallic compount, but preferably the lndivldual grains of the powter are in the form of a clad com-poslte consisting of a nucleus of one of the components ant at least one coatlng layer of the other components. Alternatively, the composite may consist of separate, concentric coating layers of at least two of the components ant a nucleus of two, three or even a fourth material.
In the case of wires, the composites may be in the form of a wire having a coating sheath of one material ant a core Of the others, alternate coating sheaths u4 two of the components and a core of the thirt or a fourth material, a wire formed by twi~ting o~ rolling separate wire strands of the components, a wlre consisting of a sheath of one component and a core con- .
tsining the other components in powder or compacted form, a ~lre consisting of a sheath of one component and a core containing a compacted powter mixture of this same component material and other components, a wire consisting of a plastic sheath and a core containing a compacted powder mixture of components, etc.
In order for the wires to be most satisfactory for spraying, it is preferable that the same must not cavitate at the tip when heatet, and should preferably be capable of forming a polnted or ~lightly tapered tip when being melted and sprayed.
Thus, if the wires have an outer layer or sheath of one component and an inner core of another component, the inner core should not have a lower melting point than the outer sheath, as other-~ise the inner core will initially melt, causing cavitation at the tip. For example, if the wire is in the form of a core with a coating sheath, the coating sheath should be aluminum, as otherwise during the spraying operation the wire will initially melt out, causing the cavitation which may interfere with a s-tisfactory spraying operation. The wire havlng the melting-point characterigtics so as to allow the ~elting off of the tip tb/~ 7 -wlthout thl~ cavitation i9 referred to herein and in the claims as "non-cavltating wire."
Whlle the components may be present ln the stolchio-metrlc proportions requlret for the formation of the lnter-metallic compound, it is, however, possible to also have an excess of one or the other provided the relative amounts are sufficient to release quantities of heat in the formation of the intermetallic compounds.
The clad powders, in accortance with the invention, may be formet in any known or desiret manner, including known chemical plating processes, in which coating material i8 deposited on a seed or nucleus of another material, or in which multiple lsyers of various materials are built up on the seet material, or in which various materials are co-tepositet in a single lsyer on the seed material.
A mote of forming the clad powders lnvolves the déposi-ting of a metal from a solution by reduction on a seed or nucleus, such as by the hydrogen reduction of ammonical solutions of nlckel and/or cobalt aad ammonium sulfate on a seed powter catalyzet such as by the atdition of anthraquinone. It is also possible to form the coating by other processes, such as coating by vapor deposition, by the thermal decomposition of metal car-bonyls, by hydrogen reduction of metal halite vapors, by thermal deposition of halides, hydrides, carbonyls, organometals, or other volatile compounds, or by displacement gas plating and the like.
A preferred and greatly simplified mode of forming the clat powders in accordance with the invention is the depositing of one component as coating in the form of a paint on the other component. ThuR the component which is to form the coating or cladting may be dispersed in finely tividet form in a binder or lac~uer so as, in effect, to form a palnt in which this component db/~ - 8 -` 10368~1 corresponds to the pigment. The palnt i8 then used to coat core partlcles of the other component and the binder or lacquer allowed to set or dry. The blnder materlal 19 preferably a resin which does not depend on solvent evaporatlon ln order to form a dried or set film, and which film will decompose or break down in the heat of the spraying process. The binder, for example, may be a phenolic varnish or any other known or conventional varnish, preferably conta~ning a resin as the var-nish solids. The components which are initially mlxed with the blnder or varnish should preferably be as finely divided as possible, as for example -325 mesh. The other component which constitute6 the core should be approximately or only s~lightly below the particle size ultimately desired for the spray powder.
The coating of the core component with the "paint" may be effected in any known or desired manner, and it is slmply necessary to;
~ls the two materials together and allow the binder to dry or ~et, which will result in a fairly free-flowing powder consisting of the core component coated with a cladding of the other com-ponent bound in the binder.
The aggregates may be formet by any other known method, suc~ as by compacting or briquetting the various components into the lndividual granules, or into larger aggregates and then breaking these aggregates into the granules.
The wires may be formed in the known conventional man-ner for forming wires with various components as, for example, by shrinking a sheath on a core, by forming the core with powder, by twisting the component wires, followed by rolling, drawing, swagging, or the like if tesired.
In accordance with one mode of manufacture, one of the components may be formed into a tube or sheath and filled with a powder of the other component or a powder comprising a mixture of the two components, vr containing atditional components. The db¦~ ~ 9 ~
., .. ~. . . . , r 103684~
tube ends are then sealed and the wlre reduced to the desired w$re tlameter by swagging, rolllng or drawlng. Preferably the powder or powder mlxture is flr~t compressed into cylindrical briquettes before being placed in the sheath or core. The ~eallng of the tube ends after loading with the powder or pow-der mlxture can be effected, for lnstance, by insertion of a plug, for example of the metal of the sheath, by welding, twlsting, crimping, or the like.
Powders in accordance with the invention should have 10 the general over-all shape and size of conventional, flame spray powders, and thus for example should have a size between -60 mesh and +3 microns and preferably -140 mesh and +10 microns (U.S. Standard screen mesh size). Most preferably the powder should be as uniform as posslble in grain size, with the indivi-dual grains not varying by more than 250 microns and preferably 75 microns.
Dependlng on the partlcular flame spray process and the tesiret purpose, the composite powder may be sprayet per se or ln co~bination with other different composlte powders, or in 20 combination wlth other conventional flame spray powders or powder components.
- While the powders are preferably sprayet, as such, in a powder-type of flame spray gun, it i5 also possible to combine the same in the form of a wire or rod, using a plastic or simi-lar binder, which decomposes in the heating zone of the gun, or in certain cases the powders may be compacted and/or sintered together ln the form of a rod or wire. The wires must have the conventional sizes and accuracy tolerances for flame spray wires and thus for example may vary in size between 1/4" and 20 gauge, ~0 and are preferably of the following sizes: 3/16" + .0005" to -.0025", l/8" t .0005" to -.0025", ll gauge ~ .0005"
to -.0025", and 15 gauge + .OOOl" wlth a smooth clean finish tb/ ' ' - lO -........ ~ .. ~, .... . . . .
-"` ` 1036841.
free from surface marks, blemlshes, or defects. The wires are sprayet in the conventional manner uslng conventlonal ~lre-type flame spray guns.
In combining, in the exothermic reaction, forming the lntermetallic compound, the components generate heat ln situ in the actual material which is to form at least a part of the coating. This is to be distinguished from flame-spray processes ant materials in which heat is generated by a reaction, such as 8n oxitation reaction in whlch a oreign ant non-metallic element is introduced ant in which untesirable components may be pro-ducet. Asite from greatly contributing to the thermal efficiency of the process, the heat generated in situ in the formation of the intermetallic compount produces novel results, in many in-stances forming a tenser, more adhering coating, having charact-eristic~ ~ at least a partially fused coating. In many in-stances the coating has self-bonting characteristics, so that ~pecial surface preparation, other than a good cleaning, is not requiret. The spraying in all other respects is effected in the conventional, well-known manner, using conventional flame spray equipment, ant the conventional surface preparation may be utilizet, if tesired. The composites in accordance with the invention may be sprayet in con~unction with or in addition to other flame spray materials db~
.
conventionally used in the art, or may be sprayed in combination or conjunction with the others.
The use of the nickel- and/or cobalt- aluminum composites will generally improve the bond of the total sprayed material, and thus of the other component or components, to the substrate, sometimes making the mixture self-bonding. The particle bond will be improved and the coating will be denser, 80 that its porosity may be decreased. In general, as little as about 5% by weight of the composites in accordance with the invention will be sufficient to substantially improve the bonding characteristics and decrease the porosity of other flame spray materials, such as conventional flame spray metals, alloys or ceramics. There is, of course, no upper limit on the amount as the composite may be sprayed per se.
An especially suitable blend comprises the novel composite and up to about 20% of its weight, preferably about 5 to 15% of its weight, of another composit~. The other composite may simply be aluminum-clad nickel although preferably it is aluminum- and molybdenum-clad nickel as described more fully in Canadian Application Serial No. 198,563 filed April 30, 1974. In such other composite based on the weight of nickel, aluminum and molybdenum the nickel is present :n about 66 to 97.5%, the aluminum in about 2 to 18% and the molybdenum in about 0.5 to 16%; preferably the nickel is present in about 73 to 89%, the aluminum in about 5 to 15% and cm/ 1 2 ..~
10;16841 l the molybdenum in about 6 to 12%. Such other compo8ite which 2 is preferably a clad core is generally produced in the same 3 manner as described hereinabove for the composite forming 4 I the basix of this in~ention. Such blends produce coatings which will not crack upon working even when extremely thick, 6 e.g. more than about 0.050 inch and even more than about ¦ 0.100 inch.
8 Materials with which the novel composites may be 9 admixed before flame spraying include carbides as described l I 10 in U. S. Patent No. 3,305,326. ~hen blended with a refractory i ¦ ll carbide, such as tungsten carbide, titanium carbide, zirconium l ¦ 12 carbide, tantalum carbide, columbium carbide, hafnium carbide, , 13 chromium carbide or the like, extremely high quality coatings 14 are produced, which are superior in various respects to the conventional carbide coatings. li 16 The carbides used in accordance witl this embodiment 17 should have a particle size between about -140 mesh U. S.
18 Standard screen size and 8 microns, and preferably between l9 about -270 mesh and ~15 microns, with the amount of carbide being between about 5-95% and preferably 25-85% and most prefer 21 I ably 45-55% by weight, based on the total powder mixture.
22 If the refractory carbide powder is in a form so that 23 the refractory carbide is bound in a matrix, as for example 24 a cobalt or nickel matrix containing S-20% by weight of either cobalt or nickel, unusually hard and wear-resistant 26 coatings will be produced which do not contain the individual 27 carbide particles imbedded in a fused matrix, but instead -` 103684~, contain alloy phase~ who~e micro-hardnes~ i9 actually sub-stanelally hlgher than that ordlnarlly obtalned from a bonded carbide.
When the powder, ln accordance wlth the inventlon, con-tainlng this matrix-bonded refractory carbide is plasma-sprayed, the same is self-bonding, so that the conventlonal surface pre-paration for flame spraying, as for example a deep surface roughening, is not requiret.
The carbide coatings formet in accortance with the above are extremely hart and wear-resistant, and may be useful as bearing surfaces, abrasive surfaces, and for any other purpose wherein a working surface requires extremely wear-resistant coating.
The refractory carbide, need not be matrix-bound, but should be a pure crystalline carbide, also having the particle size and u~ed in the amounts lndicated above. The crystalline carbite-containing coatings formed in accordance with the in-vention will have extremely high wear-resistance due to the carbide particles, which are tispersed ant tightly bound in the fused coating. Coatings may be uset for the same type of ap-plications as mentioned in connection with the coatings formed with the matrix-bound carbide.
The following examples, wherein all parts are by weight unless otherwise expressed, are given by way of illustration and not limitation.
1~ .
.
tb/-~
1 I ~xAMpLE 10;UiE~
¦ Finely divided aluminum powder (-325 mesh) was 3 ¦ admixed with a conventional phenolic varnish having 4 approximately 10% solid contents so as to form a mixture having the consistency of heavy syrup and containing about 60% by weight of the metal particles. 100 grams of the 7 ¦ varnish powder mixture was then added to about 900 grams 8 of a self-fluxing alloy powder comprising -200 +325 mesh partic es 9 of the composition O~15~/o carbon, 2.5% silicon, 2.5% boron, 2.5% iron, 10% chromium, balance nickel. The two were ll thoroughly mixed, with the mixing continued until the 12 varnish dried, leaving a fairly free-flowing powder in 13 which all of the core particles were clad with a dry film 14 which contained the aluminum particles. The powder was then warmed to about 250F. to ensure complete drying. The 16 ¦ powder was then screened and hand-milled to reduce the same 17 ¦ to a -100 mesh powder. The powder was flame-sprayed on a 18 mild steel plate which had been surface cleaned by smooth 19 grinding. The spraying was effected under different conditions using three different flame spray guns sold by 21 I Metco, Inc., of Westbury, N.Y., as described in Table I.
22 The process conditions and the results are set forth in 23 Table II along with those Eor one oE the best grindable .
Z4 compositions heretofore available, which composition however is not self-bonding. The novel coatings are hard, grindable 26 ¦ and durab .
1036~141 Table I
2 ¦ Spray Parameters for a Self-Bondin~ Grindable Coatin~
l (1) (1) (2) 4 METC0 "5P" ThermoSpray METC0 "N" ThermoSPray METC0 "3MB"
Plasma Spray Gun Nozzle = P7G N7B Gas - N2 ~ 2 r Meter Valve - 12 15 Press (psi)-50/50 8 Clicks - 8 9 Flow - 100 ~ 0 9 2 Flow - 25 Press - 0213 Current - 500 AMPS
Acet. Flow - 40 Press Acet. 15 Voltage - 73 Volts 11 Carrier ' 2 2 Carrier = 37 12 Vibrator Vibrator Nozzle - G
13 Spray Dis~. = 10" 7" Port ~ 2 14 Spray Rate - 9 Lbs.~Hr. 6 ~r. "S" Wheel 20 15 ¦Deposit Efficiency = 75% 85% Spray Rate-10 Lbs. 'Hr 16 ¦Hardness - Rc 37 Rc 34 Spray Distance ~ 6 17 Hardness - Rc47-49 18 ¦(1) As described in U.S. Patent No. 2,961,335.
20 1(2' As desc ibed in U.S. Patent No. 3,145,287.
. _ _ . ~ r 1 _ ~ = ~ d ~ ~ ", ,` ,; ~ ; ;~
~ ~ 3 , ,, ~"
`.. .~ ~, ~ ) 68~
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t) 3 ~1 ~
h ~~ O O ~ u~ U
. ~ . h ~;
V~ D ~ Oh ~0 ^ V~
. tn ,.1 aJ C~ s , ~ ~n O~
a) ~u, e e ~ i u_~ ~ u~ r~ ~ ~ ~ ~ 1 1. U~ ~ ~ JJ t . ~ l~ 0 , ~I ~ I h ~i . ~ ~ U
~ 0 1 .
)~ O~ `J ~ h ~ . ~ ~0 0 ~D ~ O ~ ^ e e ~
~ D ~ ~ ~ O
F ~r~ ¢ ~ s c~J ~ o C~
a~ , . ul ~ ~ oo c~ o~ ~r Ei !
~ n 0`~ ~ J o Z; o ~
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~-~1 I I JJ 1~ ~ 0 X~ > C~l FJ I~
~U 0 ~) Fi 0 0 ql O ~ C ~` C - - Ir) O F I 'O
0 o ~ D O
; ~ .~ ~ ~ o ~ h ~ ~ ~ O O X
U .~ ~ ~ ~ N O ON O o0 U~ al ,1 ,1 ' ~1 ~; ~ ~ ~ ~ N ~ ON P. O~1 ~1 U~
i ' ~ 0 ~ r-~
aJv~ ,1 ~ c~ ~ æ ~ æ c~o ~
. 0 ~ ~ O O O O ~ ~ Z ~ U O ;~ ' ; 0 ~ 0~ Z .n ~ 6 .~ .00 rl ~t ~ X ~ u~ 0 h ~ J~ ,~ m ~
I ~ a~ ,. _ ~; _ ~ ,~
, al ~ a~ O ~0 tn ~ X 0 0 ~
, O ~ v~ ~ h .. I . (~
¢ ,~ o ra ; ~ o o ~ .
_~ h 6~ ~ ~ ~ U
~1 . C~ O C~ 0 0 ~ E~ ~ t Q~
'. ~ ~0 ¢ ,1 h _ h h O 0 ~2:; ~;
.. r~ ~t ~ ~ O ~ V ~1 ~I t~ ¢ ~ t~ o ~ t~ O O ~ a .,1 ~ ,( ~ ~ ~ V~ ~i ~ ~
; ~ ~ O h I I
, .c ~ ~ ~ a) ~ t ^ h ~ ~ ~ _ I t~ rl ~ ~ C~ E E ~ aJ ~ O
~J h ~1 ~1 ~ Cl ~ Ul Ul ~ ~ J~ ~ ~ ¢ tO
E~ ~ ~ ~ X v, ~ ,, ,1 ~ ~--~ æ ~ P~ ~ O
I ~
I ~
; h I 1~ 1 t:q rl u~ u~ ~i z æ ~ ~ ~ h 17 ~ -~ EXAMPLE 2 10 36 ~ ¦
2 ¦ When 90% of the composite aluminum clad self-fluxing 3 alloy in Example 1 was admixed (blended~ with 10% composite 4 powder of aluminum-molybdenum clad nickel core (Example 1 of S ¦ METC0 347), and sprayed per Example 1, a hard grindable coating 6 ¦ was produced which did not crack upon working even when 7 ¦ extremely thick. The coating also had a bond strength of 8 ¦ 5,260 psi (Table II).
9 . l 11 ¦ Uhen 50% of the 90/O composite aluminum self-fluxing 12 alloy with 10% composite aluminum-molybdenum-nickel powder 13 was admixed (blended) with 50% refractory molybdenum metal 14 ¦ powder, and sprayed per Example 1, a hard, grindable, wear resisting coating was produced. (See U.S. Patent 3,313,633, 16 Example 5 - 50% molybdenum). The coating hardness was Rc 35-40 17 and bond strength was 5,027 psi.
18 l i 20 I When 50% of the 90% composite aluminum self-fluxing 21 I alloy with 10% composite aluminum-molybdenum-nickel powder 22 ¦ is admixed (blended) with 50% of a refractory tungsten carbide 23 ¦ powder (See U.S. Patent 3,305,326 Example 3-crystalline 24 carbide~, a hard grindable coating was produced, with Rc hardnes of 53-S5, and a bond strength of 6,444 psi.
28 _ _ I
1 ~ EXAMPL1 1036841 Repeating Example 4 using 50% of the composite powder 3 of Example l (without the addition of the aluminum-molybdenum- .
4 nickel powder) produces similar results.
It will be appreciated that the instant specification 7 and examples are set forth by way of illustration and not 8 limitation, and that various modifications and changes may 9 be made without departing from the spirit and scope of the 11l02 ~ present ention.
3 .
5 1 8 .
19 ', 22o ..
24 l 9 251 ~
- 28 .
19 ', 22o ..
24 l 9 251 ~
- 28 .
Claims (20)
1. A flame spray material in the form of a composite comprising (1) as a first component an alloy containing at least about 40% of its weight of at least one of nickel and cobalt, and about 1 to 6% by weight of boron, and (2) aluminum powder as a second component, the first component being present in about 66 to 99% of the combined weight of the first and second components.
2. A flame spray material according to claim 1, wherein the first component comprises about 85 to 95% of the combined weights of the first and second components, said first component containing at least about 60% by weight of nickel and cobalt.
3. A flame spray material according to claim 2, said first component further comprising up to about 6% of silicon, up to about 20% of chromium, up to about 8% of copper, up to about 10% of molybdenum, and up to about 5 % of aluminum.
4. A flame spray material according to claim 1, wherein the second component is secured by a binder to the first component as a core.
5. A flame spray material according to claim 4, wherein said binder is a varnish.
6. A flame spray material according to claim 5, wherein the composite is a powder and the first component comprises about 85 to 95% of the combined weights of the first and second components, said first component containing at least about 60% by weight of nickel and cobalt.
7, A flame spray material according to claim 1, in the form of a blend with up to about 20% by weight of a second composite comprising nickel plus at least one of aluminum and molybdenum, the nickel comprising about 66 to 97.5% the weight of said second composite.
8. A flame spray material according to claim 3, in the form of a powder blend, the composite having the second component secured by a varnish to the first component as a core, the blend including about 5 to 15% of a second composite comprising about 2 to 18% by weight of aluminum, about 0.5 to 16% by weight of molybdenum and about 66 to 97.5% by weight of nickel, the nickel being present as a powder having the aluminum and molybdenum secured thereto by a varnish.
9. A flame spray material according to claim 6, in the form of a blend with up to about an equal weight of a metal carbide or molybdenum.
10. A powder blend according to claim 8 further blended with up to about an equal weight of a metal carbide or molybdenum.
11. In the flame spray coating of a substrate, the improvement which comprises employing a flame spray material according to claim 1.
12. The process of claim 11, wherein the first component comprises about 85 to 95% of the combined weights of the first and second components, said first component containing at least about 60% by weight of nickel and cobalt.
13. The process of claim 12, said first component further comprising up to about 6% of silicon, up to about 20% of chromium, up to about 8% of copper, up to about 10% of molybdenum, and up to about 5% of aluminum.
14. The process of claim 11, wherein the second component is secured by a binder to the first component as a core.
15. The process of claim 14, wherein said binder is a varnish.
16. The process of claim 15, wherein the composite is a powder and the first component comprises about 85 to 95%
of the combined weights of the first and second components, said first component containing at least about 60% by weight of nickel and cobalt.
of the combined weights of the first and second components, said first component containing at least about 60% by weight of nickel and cobalt.
17. The process of claim 11, wherein the composite is present as a blend with up to about 20% by weight of a second composite comprising nickel plus at least one of aluminum and molybdenum, the nickel comprising about 66 to 97.5% the weight of said second composite.
18. The process of claim 13, wherein the composite is present as a powder blend, the composite having the second component secured by a varnish to the first component as a core, the blend including about 5 to 15% of a second composite comprising about 2 to 18 by weight of aluminum, about 0.5 to 16% by weight of molybdenum and about 66 to 97.5%
by weight of nickel, the nickel being present as a powder having the aluminum and molybdenum secured thereto by a varnish.
by weight of nickel, the nickel being present as a powder having the aluminum and molybdenum secured thereto by a varnish.
19. The process of claim 16, wherein the composite is blended with up to about an equal weight of a metal carbide or molybdenum.
20. The process of claim 18, wherein the blend further contains a metal carbide or molybdenum in up to about an equal weight based on the combined weights of first and second composites.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US37715273A | 1973-07-06 | 1973-07-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1036841A true CA1036841A (en) | 1978-08-22 |
Family
ID=23487977
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA198,685A Expired CA1036841A (en) | 1973-07-06 | 1974-05-01 | Aluminum-coated nickel or cobalt core flame spray materials |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS5536066B2 (en) |
CA (1) | CA1036841A (en) |
DE (1) | DE2432061C2 (en) |
FR (1) | FR2236015B1 (en) |
GB (1) | GB1460086A (en) |
IT (1) | IT1013258B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51126944A (en) * | 1975-04-30 | 1976-11-05 | Mitsubishi Heavy Ind Ltd | Method of oneeside welding |
US4181525A (en) * | 1978-07-19 | 1980-01-01 | Metco, Inc. | Self-bonding flame spray powders for producing readily machinable coatings |
DE2841552C2 (en) * | 1978-09-23 | 1982-12-23 | Goetze Ag, 5093 Burscheid | Spray powder for the production of wear-resistant coatings on the running surfaces of machine parts exposed to sliding friction |
JPS5838506B2 (en) * | 1980-08-26 | 1983-08-23 | 川崎重工業株式会社 | Anti-adhesive thermal spray material for high temperature gas furnaces |
JPS59109114A (en) * | 1982-12-16 | 1984-06-23 | 松田 淳 | Edible mushroom culture medium and method |
US4578115A (en) * | 1984-04-05 | 1986-03-25 | Metco Inc. | Aluminum and cobalt coated thermal spray powder |
US4725508A (en) * | 1986-10-23 | 1988-02-16 | The Perkin-Elmer Corporation | Composite hard chromium compounds for thermal spraying |
JPH06235057A (en) * | 1992-12-07 | 1994-08-23 | Ford Motor Co | Combined metallizing line and method for use thereof |
DE19841619C2 (en) | 1998-09-11 | 2002-11-28 | Daimler Chrysler Ag | Material wire for producing wear-resistant coatings from hypereutectic Al / Si alloys by thermal spraying and its use |
DE10041974B4 (en) * | 2000-08-25 | 2008-02-14 | Daimler Ag | Coating process for cylinder heads and use |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2936229A (en) * | 1957-11-25 | 1960-05-10 | Metallizing Engineering Co Inc | Spray-weld alloys |
NL302658A (en) * | 1963-04-23 |
-
1974
- 1974-05-01 CA CA198,685A patent/CA1036841A/en not_active Expired
- 1974-05-16 FR FR7417122A patent/FR2236015B1/fr not_active Expired
- 1974-05-27 IT IT5123074A patent/IT1013258B/en active
- 1974-05-31 JP JP6174474A patent/JPS5536066B2/ja not_active Expired
- 1974-06-03 GB GB2443474A patent/GB1460086A/en not_active Expired
- 1974-07-04 DE DE19742432061 patent/DE2432061C2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
FR2236015B1 (en) | 1977-10-14 |
GB1460086A (en) | 1976-12-31 |
DE2432061C2 (en) | 1983-07-07 |
DE2432061A1 (en) | 1975-01-23 |
FR2236015A1 (en) | 1975-01-31 |
JPS5536066B2 (en) | 1980-09-18 |
IT1013258B (en) | 1977-03-30 |
JPS5021942A (en) | 1975-03-08 |
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