|Publication number||US3914507 A|
|Publication date||Oct 21, 1975|
|Filing date||Nov 20, 1973|
|Priority date||Mar 20, 1970|
|Publication number||US 3914507 A, US 3914507A, US-A-3914507, US3914507 A, US3914507A|
|Inventors||Fustukian David A W|
|Original Assignee||Sherritt Gordon Mines Ltd|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (16), Referenced by (54), Classifications (14)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States 1, I 3,914,507
Fustukian Oct. 21, 1975  METHOD OF PREP/111mg METAL ALLOY 2,853,398 9/1958 Mackiw et a1. 117/100 COATED COMPOSITE POWDERS 2,853,401 9/1958 Mackiw et a1. 117/100 2,853,403 9/1958 Mackiw et al. 117/100 I Inventor: David Fustukian, Edmonton, 3,062,680 11/1962 Mcddings 117/100 Canada 3,102,044 8/1963 Joseph 117/22 3,218,192 11/1965 Meddin SCI al. 117/100 [731 Shem M'nes 3,241,949 3/1966 Kunda... 117/100 Toronto Canada 3,386,814 6/1968 Alexander et a1... 117/100 3,415,639 12/1968 Daendliker et al. 75/0.5
 1973 3,468,699 9/1969 Kremith 117/100  Appl. No.: 417,689 3,535,103 /1970 Whitfield.. 117/100 3,591,362 7 1971 Benjamin 75/0.5
Related Applicafion Data FOREIGN PATENTS OR PPL CATION  Continuation-impart of Ser. No. 122,098, March 8, A I S 1971, abandoned, 821,728 10/195 United Kingdom 1l7/100 824.091 1l/l959 United Kingdom 117/100  Foreign Application Priority Data Primary Examiner-M1chael Sofocleous Mar. 20, 1975 I Canada 077934 Attorney g or Firm Frank p Ame I Fors  us. c1. 428/404; 29/192 CP; 75/05 1;
75/0.5 BB; 75/o.5 BC; 427/217; 106/1  ABSTRAQ [51 1m.c1. 11221 1/02 complslte mated Pamdes are Produced by  Field of Search 117/22, 31, 100, 71 R, blending finely divided metal coated composite P W131, 71 M, 160 R; 75/05 BA, 05 BB, cles, such as nickel coated graphite or cobalt coated 05 BC; 29/l92 CF tungsten carbide, with finely divided particles of at 1 least one alloying metal, such as chromium or alumi-  References Cited 7 num.hThe powder blend is heatfed in a prottefctive atmos ere at a tem erature and or a time su 1cient to UNITED STATES PATENTS cause the alloying inetal to alloy with the metal coatl,226,925 5/1917 Thowless 75/05 n of the composite powder Particles without extem 2,823,988 2/1958 Grant et al. 2,848,313 8/1958 Takahashi ct aim s1ve sintenng of the powder partlcles.
2,852,367 9/1958 Goetzel et a1 117/100 18 Claims, 2 Drawing Figures Ni DIOTOMACEOUS EARTH Cr PERCENT Cr IN SOLID SOLUTION AFTER 2 VARIOUS HEAT TREATING TIMES O 3 1500F 0 6- Z q b 4- & O
n )X --x --x 0 w r I 1 1 1 1 1 1 1 1 1 1 5 IO 2O 3O 4O 5O TIME- HR 1 0 NO DILUTING POWDER I u 10% BY wr M x 25%BY WT MgO US. Patent 0a. 21, 1975 Ni DIOTOMACEOUS EARTH Cr ZOFD Om 030m 2 U LEGEND o NO DILUTING POWDER v 10% BY WT M90 x 25lBY WT MgO TIME- HR.
20:38 030w z .6 a.
This application is a continuation-in-part of application Ser. No. 122,098 filed Mar. 8, 1971 and now abandoned.
This invention relates to a process for preparing c ompgsite powders haying a mgtallicprsnon-metallicpen; tralgore ar d a metallic .alloy .layer.coatingsthmcore. The invention also relates to the product of such process.
Composite powder particles comprising a central core coated with a mono-component metal layer are known and in commercial use in for example the flame and plasma spraying fields, nickle-coated graphite and nickel-coated diatomaceous earth particles are flame sprayed to make abradable seals for turbine engines. As another example, cobolt-coated tungsten carbide is plasma sprayed on carving knife blades to provide a hard cutting edge which is resistant to wear.
A variety of these powders is commercially available.
They can be made using hydrometallurgical techniques such as are described in US. Pat. Nos. 2,853,398; 2,853,401; 2,853,403; 3,062,680; 3,218,192; and 3,241,949. However, these methods describe production only of composite powders with a monocomponent coating and there is a need for composite powder particles having metal alloy coatings on the core material because such particles, owing to their heterogeneous nature, are capable of being formed from an unusual combination of materials. By appropriate choice of materials it is possible to tailor the properties of the composite particles closely to meet the requirements of their end use. By contrast, much less variation in properties is possible in composite particles having a mono-component coating.
It is therefore an object of this invention to provide a practical method for producing composite powder particles which have a metal alloy coating on a metallic or non-metallic core.
It is another object to provide composite powder particles which have central core and a metal alloy coating on the core, the constituents of the alloy coating being substantially uniformly distributed in one another.
It is another object to alter the properties of the mono-component metal coating of prior art composite powders by alloying such coating with one or more other constituents.
The method of the invention comprises: providing composite powder particles of a size within the range of l850 microns each such composite particles having a central core coated with a layer of metal; forming a powder mixture which. lacks a diluting or parting agent and which comprises the oomposite particles and finely divided particles of alloyingiinetal chosen from the group confpFi sing: chromium, and aluminum, said alloying metal being capable of alloying with the metal coating of the composite particles when the mixture of composite particles and alloying metal particles is heated; and heating the mixture under non-oxidizing condition at a temperature of from about 1650F. to about 2300F where said alloying metal is chromium and from about ll00F. to about l220F. where said alloying metal is aluminum, and continuing said heating alloys with the metal coating of the composite particles without gross sintering taking place.
The specific composition of the composite powder particles used as the starting material of the process is not important. The core material of these particles may be any substance which can be coated with a monocomponent metal layer and which is stable at the temperature required for the alloying step of the process. The core material may be graphite, diatomaceous earth and refractory materials such as aluminum oxide, tung- 1 sten carbide, titanium carbide, tungsten-titanium carbide, chromium carbide and chromium oxide.
Where the finished particles are to be used as abradable seals the core material must be both abradable and erosion resistant. In addition corrosion resistance of the core material in the environment in which the seals are used is also required. For example where the seals are used in turbine engines to minimize the clearance between the compressor blades and the casing and between the stator vanes and the rotor, the seals must be resistant to corrosion by the turbine exhaust gases.
Because graphite oxidizes at low temperatures, its use as a core material in alloy-coated composite particles in engine seals is limited to engine temperatures up to about 1022F. For higher service temperatures, composite powders having more refractory abradable cores are required. Diatomaceous earth and calcium fluoride are preferred for this purpose.
The metal coatings on the composite particles may be nickel, cobolt, copper or molybdenum deposited on the core by the hydrometallurgical methods described in the above noted patents, or it may be another metal such as zirconium, zinc or aluminum bonded to the core surface using a technique such as ball milling.
The starting composite particles must be within the general size range of 10-850 microns with the precise particle size being chiefly governed by the use to which the alloy coated product particles are put. For example, flame-spraying processes generally require. that the. feed powder be about 50-200 microns in size; on the other hand, plasma-spraying applications usually require l0 50 microns size feed particles.
For most applications, the mono-component metal coating on the starting powder particles is very thin,
e.g. in the order of 10 microns or less. This is usually nickel-coated graphite particles specify a graphite content of 15%. Since graphite has a low density, its volume in comparison with the metal coating is large so the nickel coating is relatively thin. An 15% by weight nickel-graphite composite particle of 50 microns in size has a nickel coating thickness in the order of 10 microns. As another example, plasma sprayers use 20/80% by weight cobolt coated tungsten carbide particles having a size of about 10 microns. These particles have a cobalt coating about 1 micron thick.
The operability of the process of the invention is dependent on the previously unrecognized fact that when thinly coated composite particles are heated to a high alloying temperature in close contact with particles of chromium or aluminum, the latter metals will form an alloy with the coating metal. The finished product will not be sintered at all or will be only lightly sintered so that it can be ground or otherwise broken down to par ticles which are of a size closely resembling the initial unheat-treated powder size and which have a complete alloy coating. When a mixtuure of line particles of the coating metal and particles of chromium or aluminum are heated to the same temperature however, rather than forming an alloy the mixture will be grossly sintered. For purposes herein the product is grossly sintered where it cannot be broken down to a size closely resembling the initial unheat-treated powder size without causing fractures to form through the particles making up the product as opposed to between adjacent particles.
To illustrate the foregoing, if a mixture of 2 l nickel and chromium particles is heated at 1650F. for minutes, a solid mass is produced. This mass cannot be broken down short of grinding it. If a grinding precedure is followed, the nickel and chromium particles making up the mass are fractured so that the original character of the powder particles is destroyed. By contrast where a mixture of nickel-coated graphite composite particles and chromium are heated to the same temperature, the mass is only slightly sintered and can easily be broken down without fracturing the chromized composite particles.
Thus a mixture of chromium or aluminum and composite particles can be heated to a higher temperature without gross sintering taking place than can a mixture of chromium or aluminum and particles of the same metal as the metal which coats the composite particles. This fact gives rise to significant results. Since at higher temperatures, the rate of alloying is much more rapid than at lower temperatures, the coating metal or composite particles can be alloyed with chromium or aluminum much more quickly than can particles of the coating metal per se which must be heated at a lower temperature to avoid gross sintering. The marked effect which temperature has on the rate of alloying is shown in the drawing and is described in Example 12.
It is known that in the presence of a diluting or parting agent such as alumina or magnesia, particles of the alloying metal and particles of the coating metal per se can be heated without sintering to temperatures which, in the absence of the parting agent would result in gross sintering. A number of problems are however caused by partingagents. First the agents retard the rate at which alloying takes place and hence the time required for the operation (the drawing illustrates the retarding effect which magnesia has on the rate of alloying). Se-
condly, the agents by definition dilute the quantity of -the alloying metal into a substrate than from the same volume of mixture containing no parting agents. Thirdly, the agents must be separated from the finished alloyed particles prior to use. In many cases, complicated and costly procedures are required to remove the parting agents from the alloyed powder particles.-
In view of the foregoing it is undesirable to use a parting agent to prevent sintering. In the absence of a parting agent, as pointed out before, the coating metal of composite powder particles can be alloyed at a much faster rate than can single component particles of the coating metal. Furnaces required for prolonged heat treatment of single component particles are accord ingly not required where composite particles are being treated.
Binary or ternary alloy coated composite particles can be produced by the process of the invention. For example finely divided metal coated composite particles such as nickel-coated graphite particles, and particles of for example chromium, can be heated at alloying temperatures for a period of time to obtain uniform solid state diffusion or reaction alloying. Similarly, coated composite particles can be mixed with both chromium and aluminum and heated to yield ternary alloy coated composite particles. Gross sintering of the alloy coated particles does not occur. The product obtained is either a powder or a lightly sintered cake which can be easily broken up to provide composite alloy coated particles of substantially the same size and shape as the starting composite particles.
The rate of transfer of the alloying metal into the coating of the composite powder can be greatly increased by the addition of a small amount of halogenbearing compound activator such as chromium chloride, bromide or fluoride or ammonium chloride, bromide or iodide. The temperature at which alloying of the composite powder and alloying metal occurs is also somewhat lessened bythe presence of the activator. The compound is added to the mixture of composite powder and alloying metal prior to the heating operation. In general no more than 2% of the compound by weight based on the total weight of the mixture is required for this puurpose. To prevent contamination of the alloy coating, it is preferable that the cation of the halogen-bearing compound be the same as one of the metals making up the alloy coating. For example, chromium chloride is the preferred activator when the alloying metal is chromium. Alternatively the cation should volatilize upon decomposition of the halogenbearing compound e.g. NH.,.
The particles of alloying metal or metals which are mixed with the composite particles should be smaller in size than the composite particles and preferably should be less than microns. The smaller the alloying metal particles, the faster the alloying reaction rate, so it is desirable to utilize the smallest alloying metal particles that are available. The alloying metal particles must be formed of a metal which is capable of alloying quickly with the composite. particle coating metal when a mix ture of the particles is heated to alloying temperatures.
The selection of the composite powder and the alloying metal particles is a matter of choice, depending on the properties desired in the final alloy coated composite powder product. However, the process of the invention is particyla rlygffective for alloying chromium and aluminum with nickel, cobalt or copper cgatgsl 3939,51,; metallic coreparticles. R
The mixing step of the invention can be carried out by any of the known metal powder blending techniques, such as tumbling, which ensure substantially uniform blending of the powder constituents.
The powder mixture is heated to and maintained at I alloying temperature for a predetermined period of time selected to ensure that the required degree of alloying occurs without appreciable sintering. The precise heating time and temperature have to be deter mined for each case although 48 hours is usually about the maximum time thatcan be expended on the heating step in any case while still providing an economically desirable process. If the coating material of the composite particles and chromium are being alloyed, heating should be carried out at about l650F. to 2300F. Above 2300F. no significant increase in alloying rate is obtained with increases in temperature and sintering starts to become a problem.
While alloying of chromium with the coating metal will occur at temperatures as low as 1500F. it is desirable to heat the powder mixture to temperatures in excess of about 1650F. Where the powder mixture is heated at temperatures below 1650F., the rate of diffusion of chromium into the coating material increases rapidly in the initial stage of heating but then as time passes the rate decreases and eventually virtually ceases. Thus at these temperatures there is a maximum chromium level which can be reached and prolonging the heat treatment will not serve to increase this level. For many applications finished composite particles having such a low chromium level in the coating material are not suitable. By contrast, a much higher chromium level can be attained where heating is conducted at temperatures of above about 1650F. By appropriate control of heating time the level of chromium in the coating material can be adjusted within a very wide range to suit the application intended for the finished particles.
In the particular case of composite nickeldiatomaceous earth particles and chromium powder alloying should preferably be conducted at no higher than I900F. Since at higher temperatures the chemical constituents of the diatomaceous earth begin to react with the metals.
In the case where nickel coated composite particles and aluminum are being alloyed, the heating should be carried out between about ll00F. and about l220F. Below 1 100F. the alloying reaction is too slow. Above 1220F. the aluminum melts. From the foregoing, it is seen that each system of components has its own requirements. The specific temperature used in alloying has to be tailored for each system by carrying out routine experimentation.
The heating step is carried out in any suitable furnace which permits the provision of a protective atmosphere to avoid oxidation. Preferably, hydrogen, having a dewpoint below 40F. is flowed through the heating zone throughout the alloying operation.
Where ternary alloy coated particles are being produced, the chromium and aluminum particles may be mixed simultaneously with particles of the composite powder before the mixture is passed to the heating operation. Alternatively, the production of the particles may be carried out in two stages. In the first stage, the composite powder is mixed with one alloying metal and the mixture is heated to effect alloying of the coating of the powder with the alloying metal. In the second stage, finely divided particles from the first stage are mixed with the second alloying metal and heated as before. For example the starting composite particles may first be mixed with particles of chromium and heated to an alloying temperature of 1650F. to 2300F. After chromizing has occurred, the resulting particles may be heated in contact with aluminum particles to temperatures as high as 1400F.
The temperature within the furnace and the duration of the heating step will depend upon the constituents of the ternary alloy coated powder, and whether the composite powder starting material is blended simultaneously with both alloying metals or whether each alloying metal is blended separately with the composite In some cases, the product from the heating step is in the form of a powder. ln other cases, it is in the form of a lightly sintered mass which can be easily commi- EXAMPLE I This example illustrates preparation of nickelchromium coated diatomaceous earth composite powder. The starting material for this example was nickel coated diatomaceouseggthgggpgsitepgyvder containta nickel by weight. The powder which was prepared in accordance with US. Pat. No. 3,062,680 had the following physical characteristics.
TABLE 1 Standard Tyler screen analysis: Fraction Percent 48 I00 L6 I00 I50 5.6 l50 200 13.0 200 250 I00 -250 325 3 l .4 325 38.4
Apparent density: 0.83 grams/cubic centimetre Flow rate: 107.2 seconds/gram Fisher Number: 14
grams of the composite powder were blended with 16 grams of commercial grade, a micron size chro mium powder. The powders were blended by manually shaking them together in a bag and then mixing them in a highspeed blender for 2 minutes.
After blending, the powder mixture was placed in a nickel boat and positioned in the cooling zone of an electrically heated laboratory tube furnace. At this stage, the bed of powder was purged with hydrogen to remove entrapped oxygen. This was done by passing hydrogen, having a dew point of 40F. through a 2 inch diameter chamber of the furnace at 1% cubic feet per minute for 20 minutes. The hydrogen has been preheated by passing it through the hot zone of the furnace.
The boat was then moved to the hot zone of the furnace. This zone was maintained at 1900F. Hydrogen was passed through the zone at 1% cubic feet per min ute. Heating was continued for 4 hours.
The boat was then returned to the cooling zone and left there for a period of 1 hour. The boat was then removed from the furnace and the powder mixture, in the form of a sinter cake, was broken into pieces and placed in a high speed blender for 1 minute. It easily broke up in the blender to a powder product having a following physical characteristics:
TABLE ll-Continued Standard Tyler screen analysis: Fraction Percent Apparent density: 1.08 grams/cubic centimetre Fisher Number: 12.1.
The coating of the product powder was examined for alloying using electron microprobe analysis and relative ferro-magnetism testing. The coating was found to be comprised of a uniform alloy of nickel and chromium.
Conventional metallographic examination of a polished section of powder particles showed that the individual particles consisted of a core and a uniform metallic coating.
A qualitative microanalysis of the particles was carried out using an electron microprobe and revealed that the metallic coatings were comprised of a homogeneous mixture of chromium and nickel and the cores were comprised of a compound containing silicon and oxygen (diatomaceous earth).
Comparison of the ferromagnetic nature of the blend before heat treatment and after heat treatment indicated that the heat-treated powder was nonmagnetic. Therefore the intimate mixture of chromium and nickel in the coating was in fact a solid solution of chormium in nickel.
Ferro-magnetism tests were carried out by first balancing the sample weight, then determining the force of attraction to a fixed magnetic field. Pure iron powder was used as the standard (100%). The nickelcoated diatomaceous earth blended with chromium had relative ferro-magnetism of 19% relative to pure iron.
The effects of time, when treating at 1900F. on the magnetic properties of the nickel-coated diatomaceous earth and chromium blend were studied in detail. The results shown in Tale III indicate that alloying was taking place. The virtual elimination of ferro-magnetisrn was an indication of the completeness of the alloying reaction.
TABLE III Ferromagnetism of the blend Time (Minutes) relative to iron,
EXAMPLE 2 TABLE lV Standard Tyler screen analysis: Fraction Percent Apparent density: 2.13 grams/cubic centimctre Qualitative microana lysis and ferro-magnetic comparison in accordance with Example 1 showed that the desired complete alloying of the aluminum and nickel was achieved.
EXAMPLE 3 This Example illustrates preparation of nickelchromium alloy coated raphite composite powder.
Nickel coated graphite composite pbVid'TEb'fifining 25% core material by weight was provided. The powder had the following physical characteristics:
TABLE V Standard Tyler screen analysis: Fraction Percent Apparent density: 1.95 grams/cubic centimetre Flow rate: 91.0 seconds/gram.
100 grams of the composite powder were blended with 18.75 grams of the chromium powder of Example 1. The blend of powders was treated in accordance with the procedure of Example 1 with the exception that the furnace was operated at 2200F. and the blend was heated for 16 hours.
No screen analysis was carried out on the powder product. However, qualitative microanalysis and ferromagnetic comparison in accordance with Example 1 showed that the desired alloying of chromium and nickel was achieved.
EXAMPLE 4 This Example illustrates preparation of nickelchromium alloy coated boronwnit-ride composite pgyv;
Hydrometallurgically produced, nickel-coated boron nitride composite powder containing 48% by weight of the core material was provided. The powder had the Apparent density: 1.17 grams/cubic centimetre EXAMPLE This Example illustrates preparation of cobaltchromium alloy coated tungsten carbide powder.
Hydrometallurgically fifb ducedmated tungsten carbide composite powder containing 80% core material by weight was provided. The powder had the following physical characteristics:
TABLE VII Buckbee Mears screen analysis (in microns):
Fraction Percent Apparent density: 4.54 grams/cubic centimetre Fisher Number 12.7.
100 grams of the composite powder were blended with 5 grams of commercial grade, 8 micron 'size chromium powder using the procedure described in Example l. h
After blending, the powder was treated in accordance with the procedure of Example I with the exception that the heating was continued for 21.5 hours at I900F. The coating of the product powder was examined using electron microprobe analysis and relative ferro-magnetism. Comparison of the ferro-magnetic nature of the blend before heat treatment and after heat treatment indicated that the heat treated powder was substantially less magnetic indicating that the intimate mixture of chromium and cobalt in the coating was in fact a solid solution of chromium in cobalt.
EXAMPLE 6 This Example illustrates preparation of nickelchromium coated calcium fluoride composite powder. The starting material for this example was nickel calcium fluoride composite powder containing 75% by weight nickel. The powder was prepared in accordance with US. Pat. No. 3,062,680 and had the following physical characteristics.
TABLE VIII Standard Tyler screen analysis: Fraction Percent Apparent density: 1.20 grams/cubic centimetre.
100 grams of the composite powder were blended with 19 grams of commercial grade, 8 micron size chromium powder. The powders were blended by manually shaking them together in a bottle.
After blending, the powder mixture was heat treated as in Example 1 except that heating was continued in the hot zone of the furnace for 16 hours.
The powder was removed from the furnace and was observed to be in the form of a sinter cake. The cake was easily broken into pieces and was pulverized in a high speed blender to yield a finely divided powder substantially 100 mesh in size.
The coating of the product powder was examined for alloying and relative ferro-magnetism and was found to be comprised of a uniform alloy of nickel and chromium.
Conventional metallographic examination of a polished section of powder particles showed that the individual particles consisted of a core and a uniform metallic coating.
Comparison of the ferro-magnetic nature of the blend before and after heat treatmentindicated that the heat-treated powder was non-magnetic. Thus the intimate mixture of chromium and nickel in the coating was in fact a solid solution of chromium in nickel.
EXAMPLE 7 This Example illustrates the preparation of a composite powder composed of a diatomaceous earth core with a ternary alloy. The elements making up the ternary alloy are nickel, chromium and aluminum.
A composite powder having a diatomaceous earth core encased in a nickel-aluminum coating was used as the starting material. The composite powder was prepared in accordance with the procedure described in Example 2 except that the temperature within the furnace was 1200F. and the heat treatment was continued for 1% hours. Following the heat treatment, the nickel-aluminum coated diatomaceous earth particles were removed from the furnace and placed in a high speed blender to break the particles down into a finely divided powder. 100 grams of the powder was blended with 16 grams of commercial grade 8 micron size chromium powder and heat treated in the manner described in Example I except that the temperature within the furnace was maintained at 1800F. and the heat treat TABLE IX Ferromagnetism Material (Iron 100%) Pure Nickel reference 31.5 k
Blend of Nickel coated Diatomaceous earth plus aluminum:
Before heat treatment 2 After heat treatment Blend of Diatomaceous earth core coated with nickel aluminum alloy plus chromium:
Before heat treatment After heat treatment The negligible ferro magnetism of the heat treated blend of chromium and the composite powder composed of a diatomaceous earth core and a nickel alumi- EXAMPLE 8 4500 grams of composite powder (N1 20.9%, TiC 79.1%) were blended with 225 grams of chromium powder having an average size of 8 microns and 11 grams of chromium chloride.,
The powder mixture was placed in a nickel boat and Thls Example illustrates the improvement in the rate positioned in the cooling zone of an electrically-heated of transfer of the alloylng metal into the coating of the laboratory tube furna e, The owde was ed ith compos te powder caused by the addltlon of a vaporizhydrogen for 30 minutes to remove entrapped oxygen. able halide prior to heat treatment. 1n the first test, hy- The hydrogen had been preheated by passing it through drated chromlum chloride was blended with a mixture h h zone of h furnace, of 'f and COmPQSiIe p In eaCh Case, the The boat was then moved to the hot zone of the furf g f C(mtamed approximately 81-53% y nace. This zone was maintained at 1900F. Hydrogen weght composltfi Powder, 162% y Welght chromlllm was passed through the-zone at 1% cubic feet per minand WClght hydrated chromium chloride. The u[e Heating was continued for 4 hours mixtures were heat treated at various temperatures and 15 The boat was then returned to the cooling zone and for varying lengths of tlme m purified y r g The left there for a period of 1 hour following which the degree of y g as as the relative boat was removed from the furnace. It was found that magnetism re determin a o ing to h p the powder was present in the form of a sinter cake. q p E p The results are Summa- The screen analysis of the product after light grinding the following table in a mechanical blender was as follows:
TABLE X 82 NickellDiato- Powder 75 Nickel/Graphite maceous earth 8 Coarse Cr Medium Cr Coarse Cr Chromicrons) (8 microns) (40 microns) mlum Additive GrCl Nil CrCl Nil CrCl Nil Temperature Time Cr/rel- 7k Cr/ 7: Cr/ 7: Cr/ Z Cr/ '7? Cr/ "F hr ative Ferrorel. rel. rel. rel. rel. magnetism fer. fer. fer. fer. fer.
16 12.2/ 1.17 l.6/32.3 2 5 now 7 I 2.96 13.6/ 0.61 00/343 1.25 6.2/ 5.14 7 /4.70 0.5 5.4/ 8.13 1 /30.4 5.4/ 8.60 0.6/35.5 1300 64 24111.3 2.0/26.0 5.0/ 2.2 4 00/145 1.5/ 1.5 5.1 2 2.4/19.0 1.5/1 1.48 0.5 6.2/19.6 l2.8/l5.8 l2.2/10.0
0 0 n.d./34.7 n.d./35.0 n.d./35.0 n.d./36.3 n.d./38
It is apparent from the results tabulated above that in 45 TABLE XI every case the addition of chromium chloride dramatically increases the diffusion rate of chromium in the powder Size inMici-ons nickel coating of the composite powder. Substantial Fraclion Peta"! diffusion at temperatures as low as 1300F. occurs. +44 Further tests establish that the time required to achieve 44 +30 25.0 -30 +20 40.0 a glven amount of alloying in a sample contalnmg CrCl +10 '8 6 and heat treated at the same temperature is signifi- 71 cantly less than for a sample containing no CrC1 and heat treated at the Same temperature Apparent density: 1.86 grams/cubic centimetre The effect of the presence of ammonlum chlorlde on the diffusion rate of the alloying metal in the coating of composite powder was also treated. Deoxidized 75 Qualitative microanalysis and ferro-magnetlc comnickel/graphite 25 composite powder was blended with parison in accordance with Example 1 showed that the chromium powder and ammonium chloride. The blend desired complete alloying of chromlum and nickel had analyzed 82.5% by weight 75 Ni/C25, 16.3% by weight been achieved. Cr and 1.2% Nl-l Cl. The blend was heated for 30 minutes at 1800F. then analyzed. About 10% of the chromium was alloyed with the nickel coating and the rela- EXAMPLE 10 tive ferro-magnetism was 5.3%. This example illustrates the preparation of nickelchromium coated chromium carbide powder.
EXAMPLE 9 This example illustrates the preparation of nickel chromlum coated titanium carbide powder.
,4770 grams of powder (Ni 16%, Cr C 84%) were blended with 258 grams of chromium powder (average size 8 microns) and 50 grams of CrCl The blend of powders were treated in acccordance with the procedure of Example 9.
The screen analysis of the product after light grinding in a mechanical blender was as follows:
Apparent density: 2.78 grams/cubic centimetre Qualitative microanalysis and ferro-magneticlcom-.
parison in accordance with Example 1 showed that the T desired complete alloying of the aluminum 'and nickel had been achieved.
EXAMPLE 11 This example illustrates the preparation of nickelchromium and nickel-chromium-aluminum coated tungsten-titanium carbide powders.
800 grns of Ni/WTiC (15/85) were blended with 25 gms of fine chromium powder (average particle size about 8 microns) and 8 gms of CrCl powder. The blend was placed in a covered boat and purged in the cold zone of a muffle furnace. The blend was purged with dry hydrogen for 30 min. Following this the blend was heated for 2% hours at 1950F. in a dry hydrogen atmosphere and then cooled to room temperature.
The blend was found to have sintered lightly, but was easily broken up into powder. Most of the powder passed through a 250 mesh screen and was found to be satisfactory for plasma spraying. An experimental plasma spray coating was found to have D.P.l-l. microhardness of 1290.
A sample of the nickel-chromium coated tungstentitanium carbide powder was further treated to produce a more complex oxidation resistant composite powder.
400 gms of the NiCr/WTiC powder was blended with 5 gms of fine leafing-grade aluminum. The blend was treated in a similar manner as above with the exception that the heating temperature was 1400F. and the heating time was 1 hour.
The resultant powder was found to be satisfactory for plasma spraying. An experimental plasma spray coating of the NiCrAl/WTiC powder had D.P.H. microhardness of 950.
EXAMPLE 12 1 (Fisher No. 14) to a composition of 4 parts Ni, 1 part Cr. Part of the mixture was blended with a magnesia parting agent to produce first and second samples, the first containing MgO and the second containing MgO (by weight). Third sample contained no parting agent. l/2% by weight CrCl activator was combined with each sample.
The samples were subjected to various heat treatments and the amount of chromium in the nickel coating was determined at various times during the treatments by following the shift in the 220 line according to the standard XRD technique. The accuracy of this technique is about t 1%. The results are shown in FIGS. 1 and 2 of the drawing.
At l500F. in the sample containing no parting agent there is an initial fairly rapid increase,in chromium level of the nickel coating followed by a more gradual increase followed thereafter by negligible or no increase in the chromium level. In samples containing parting agent there is a much less rapid increase in the chromium level of the nickel coating to only 2% followed by no increase even after 64 hours of heat treatment. At 1830F. the rate of chromizing without a parting agent is much more rapid than at l500F. Furthermore the level of chromium in the nickel coating in the absence of a parting agent increases with heating time and does not reach a maximum at the same point in time as does the chromium level in the sample heated at l500F.
Both at 1830F. and at l500F. the rate of chromizing is greatly influenced by the level of parting agent in the sample. Not only is the chromizing rate greatly retarded by magnesia but the magnesia appears to impose a maximum level of chromium in the nickel coating.
EXAMPLE 13 4 the same as Sample 3 except that 10% by weight MgO was added to the blend 5 a blend of nickel-coated diatomaceous earth composite particles, aluminum particles (67% Ni/De', 33% Al) and 1/2% CrCl The five samples were heated under the conditions specified below and the resulting products were examined for degrees of sintering. The extent of alloying was also checked in products which were not grossly sintered. The results are set out in the following table:
TABLE Xlll Condition of Sample Heating Conditions heated product 1. (Fe Cr) 1650F. for 20 minutes grossly sintered 2. (Ni Cr) 1650F. for 20 minutes grossly sintered 3. (Ni Al) 00F. for 1 hour grossly sintered in presence of H, 4. (Ni Al ll00F. for 1 hour no sintering; no
+MgO) in presence of H, alloying 5. (Ni/De IIOOF. for 1 hour no sintering; Al) in presence of H, extensive alloying The results show that when single component particles are mixed with chromium and aluminum particles and are heated to the lowest temperature recommended for chromizing and aluminizing according to the subject process. gross sintering occurs. Where a parting agent (MgO) is added to the mixture containing aluminum particles, gross sintering does not take place but, on the other hand, aluminizing also does not occur. By contrast where a mixture of composite particles and aluminum are heated under the same conditions alloying occurs. The results of Example l2 show that the same is also true of chromium containing mixtures.
What i claim as new and desire to protect by Letters Patent of the United States is:
l. A process for producing powder particles having a central core coated with an alloy which comprises the steps of: providing finely divided particles of an alloying metal and composite particles of a size within the range of 10 to 850 microns, said alloying metal being chosen from the group consisting of chromium and a mixture of chromium and aluminum, egh said composite pa riticlahaving a central gorge cga tje d with,a layer of material which is metallic. whichi is'differenLfrorn the material of the core and which is capable of alloy ing with said alloying metal when a mixture of said compositve particles andsaid alloying metal particles is heated; forming a powder mixture which consists of said composite particles and said alloying metal particles; and heating said powder mixture under nonoxidizing conditions at a temperature of from about 1650F toabout 2300F; and continuing said heating step for a period of time sufficient to ensure that a required quantity of said all gying n etal diffuses ipto and alloys with the metal coating otlthfigftpgsjte particles.
without gross sintering tal iing place.
2. The process defined in claim 1 including the additional step of mixing the alloy coated particle with a second alloying metal and heating the resulting mixture under non-oxidizing conditions at a temperature and for a period sufficient to ensure that said second alloying metal forms an alloy with the alloy coating of the composite particles without gross sintering taking lace. p 3. The process defined in claim 1 wherein the particles of alloying metal are less than 50 microns in size.
4. The process as defined in claim 1 wherein the.
product from the heating step is comminuted to powder form.
5. The process defined in claim 1 wherein the metal coated on said central core is chosen from the group consisting of nickel, cobalt and copper.
6. The process as claimed in claim 1 wherein the heating step is carried out at a temperature above about 1830F.
7. The process defined in claim 1 wherein the central core is chosen from the group consisting of graphite, calcium fluoride, diatomaceous earth, aluminum oxide, tungsten carbide, titanium carbide, tungsten-titanium carbide, chromium carbide and chromium oxide.
8. The process as defined in claim 7 wherein the metal coated on said central core is nickel.
9. The process defined in claim 8 wherein the core is diatomaceous earth and the heating step is carried out at a temperature between l650F. and 1900F.
10. A process for producing powder particles having a central core coated with an alloy which comprises the steps of: providing finely divided particles of an alloying metal consisting of aluminum and composite particles of a size within the range oflO to 850 microns,
each said composite particle having a central core coated with a layer of material which is metallic, which is different from the material of the core and which is capable of alloying with said alloying metal when a mixture of said composite particles and said alloying metal particles is heated; forming a powder mixture which consists of said composite particles and said alloying metal particles; and heating said powder mixture under non-oxidizing conditions at a temperature of from about llO0F to about l220F; and continuing said heating step for a period of time sufficient to ensure that a required quantity of said alloying metal diffuses into and alloys with the metal coating of the composite particles without gross sintering taking place.
11. The process defined in claim 10 including the ad ditional step of mixing the alloy coated particle with a second alloying metal and heating the resulting mixture under non-oxidizing conditions at a temperature and for a period sufficient to ensure that said second-alloying metal forms an alloy with the alloy coating of the composite particles without gross sintering taking place.
12. A process for producing powder particles having a central core coated with an alloy which comprises the steps of: providing finely divided particles of an alloying metal and composite particles of a size within the range of l0 to 850 microns, said alloying metal being chosen from the group consisting of chromium and a mixture of chromium and aluminum, each said composite particle having a central core coated with a layer of material which is metallic, which is different from the material of the core and which is capable of alloying with said alloying metal when a mixture of said composite particles and said alloying metal particles is heated; forming a powder mixture whichconsists of said composite particles, a halogen-bearing compound and said alloying metal particles; and heating said powder mixture under non-oxidizing conditions at a temperature of from about l650F to about'.2300F; and continuing said heating step for a period of time suffi' cient to ensure that a required quantity of said alloying metal diffuses into and alloys with the metal coating of the composite particles without g ross sintering taking place.
13. A process for producing powder particles having a central core coated with an alloy which comprises the steps of: providing finely divided particles of an alloying metal consisting of aluminum and composite powder particles of a size within the range of 10 to 850 microns, each said composite'iparticle having a central core coated with a layer, oft'naterial which is metallic, which is different from the material'of the core and which is capable of alloying with said alloying metal when a mixture of said composite particles and said alloying metal particles isheate d; forming a powder mixture which consists of said composite particles, a halo gen-bearing compound and said alloying metal particles; and heating said powder mixture under nonoxidizing conditions at a temperature of from about llO0F to about l220F; and continuing said heating step for a period of time sufficient to ensure that a required quantity of said alloying metal diffuses into and alloys with the metal coating of the composite particles without gross sintering taking place.
14. A powder composition comprising non-grossly sintered particles within the size range of 10-850 microns and each consisting essentially of single central core chosen from the group consisting of diatomaceous earth, graphite and calcium fluoride, a continuous coating firmly bonded to the core, said coating comprising an alloy in the form of a solid solution of at least two constituents, one constituent being chosen from the group consisting of chromium and aluminum.
15. The powder composition defined in claim 14 wherein said alloy is in the fonn of a solid solution of chromium, aluminum and another constituent.
16. The powder composition defined in claim 14 wherein said alloy is in the form of a solid solution composed of nickel, chromium and aluminum.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US1226925 *||Aug 9, 1915||May 22, 1917||Arthur J Thowless||Ductile filament.|
|US2823988 *||Sep 15, 1955||Feb 18, 1958||Sintercast Corp America||Composite matter|
|US2848313 *||Aug 23, 1955||Aug 19, 1958||Takahashi Rintaro||Method of chemically disintegrating and pulverizing solid material|
|US2852367 *||Aug 27, 1954||Sep 16, 1958||Sintercast Corp America||Method of manufacturing heat resistant sintered articles|
|US2853398 *||Apr 11, 1956||Sep 23, 1958||Sherritt Gordon Mines Ltd||Method of producing composite nonmetallic metal powders|
|US2853401 *||Apr 11, 1956||Sep 23, 1958||Sherritt Gordon Mines Ltd||Method of incorporating a metal binder or matrix phase in mixes of metals and/or metals and metal compounds|
|US2853403 *||Apr 11, 1956||Sep 23, 1958||Sherritt Gordon Mines Ltd||Method of producing composite metal powders|
|US3062680 *||Jun 20, 1960||Nov 6, 1962||Sherritt Gordon Mines Ltd||Hydrogenation catalysts for reducing reactions|
|US3102044 *||Sep 12, 1960||Aug 27, 1963||United Aircraft Corp||Applying protective coating from powdered material utilizing high temperature and low pressure|
|US3218192 *||Mar 8, 1962||Nov 16, 1965||Sherritt Gordon Mines Ltd||Process of coating phosphorus particles with nickel and/or cobalt|
|US3241949 *||Oct 21, 1963||Mar 22, 1966||Sherritt Gordon Mines Ltd||Method of producing molybdenum alloy compositions from ammoniacal solutions|
|US3386814 *||Oct 22, 1965||Jun 4, 1968||Fansteel Metallurgical Corp||Process for making chromium, cobalt and/or nickel containing powder having dispersed refractory metal oxide|
|US3415639 *||Apr 5, 1966||Dec 10, 1968||Ciba Ltd||Method for the manufacture of tantalum and/or niobium powder|
|US3468699 *||Oct 14, 1966||Sep 23, 1969||Giannini Scient Corp||Method of providing malleable metal coatings on particles of lubricants|
|US3535103 *||Apr 10, 1968||Oct 20, 1970||Atomic Energy Commission||Method of making metal alloy powders|
|US3591362 *||Mar 1, 1968||Jul 6, 1971||Int Nickel Co||Composite metal powder|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4086391 *||Sep 1, 1976||Apr 25, 1978||United Technologies Corporation||Alumina forming coatings containing hafnium for high temperature applications|
|US4189315 *||Dec 6, 1978||Feb 19, 1980||Ford Motor Company||Process for the desulphurization of molten cast iron and treating agent|
|US4229234 *||Dec 29, 1978||Oct 21, 1980||Exxon Research & Engineering Co.||Passivated, particulate high Curie temperature magnetic alloys|
|US4291089 *||Nov 6, 1979||Sep 22, 1981||Sherritt Gordon Mines Limited||Composite powders sprayable to form abradable seal coatings|
|US4374173 *||Dec 4, 1980||Feb 15, 1983||Sherritt Gordon Mines Limited||Composite powders sprayable to form abradable seal coatings|
|US4421799 *||Feb 16, 1982||Dec 20, 1983||Metco, Inc.||Aluminum clad refractory oxide flame spraying powder|
|US4447501 *||Aug 28, 1981||May 8, 1984||National Research Institute For Metals||Ceramic based composite material for flame spraying|
|US4519840 *||Oct 28, 1983||May 28, 1985||Union Carbide Corporation||High strength, wear and corrosion resistant coatings|
|US4588608 *||Mar 18, 1985||May 13, 1986||Union Carbide Corporation||High strength, wear and corrosion resistant coatings and method for producing the same|
|US4606948 *||May 20, 1985||Aug 19, 1986||Sherritt Gordon Mines Limited||Process for the production of nickel-chromium/chromium carbide coatings on substrates|
|US4626476 *||Feb 20, 1986||Dec 2, 1986||Union Carbide Corporation||Wear and corrosion resistant coatings applied at high deposition rates|
|US4626477 *||Feb 20, 1986||Dec 2, 1986||Union Carbide Corporation||Wear and corrosion resistant coatings and method for producing the same|
|US4741973 *||Dec 15, 1986||May 3, 1988||United Technologies Corporation||Silicon carbide abrasive particles having multilayered coating|
|US4919718 *||Jan 22, 1988||Apr 24, 1990||The Dow Chemical Company||Ductile Ni3 Al alloys as bonding agents for ceramic materials|
|US5015290 *||Oct 12, 1989||May 14, 1991||The Dow Chemical Company||Ductile Ni3 Al alloys as bonding agents for ceramic materials in cutting tools|
|US5312648 *||Sep 5, 1991||May 17, 1994||Technalum Research, Inc.||Method for coating particles using counter-rotating disks|
|US5318746 *||Dec 4, 1991||Jun 7, 1994||The United States Of America As Represented By The Secretary Of Commerce||Process for forming alloys in situ in absence of liquid-phase sintering|
|US5419976 *||Dec 8, 1993||May 30, 1995||Dulin; Bruce E.||Thermal spray powder of tungsten carbide and chromium carbide|
|US5453293 *||Nov 14, 1994||Sep 26, 1995||Beane; Alan F.||Methods of manufacturing coated particles having desired values of intrinsic properties and methods of applying the coated particles to objects|
|US5601924 *||Jun 7, 1995||Feb 11, 1997||Materials Innovation Inc.||Manufacturing particles and articles having engineered properties|
|US5614320 *||Jun 7, 1995||Mar 25, 1997||Beane; Alan F.||Particles having engineered properties|
|US5711866 *||May 9, 1995||Jan 27, 1998||The United States Of America As Represented By The Secretary Of Commerce||Acid assisted cold welding and intermetallic formation and dental applications thereof|
|US5765624 *||Oct 23, 1995||Jun 16, 1998||Oshkosh Truck Corporation||Process for casting a light-weight iron-based material|
|US5820721 *||Jun 7, 1995||Oct 13, 1998||Beane; Alan F.||Manufacturing particles and articles having engineered properties|
|US5951892 *||Dec 10, 1996||Sep 14, 1999||Chromalloy Gas Turbine Corporation||Method of making an abradable seal by laser cutting|
|US5976695 *||Oct 2, 1996||Nov 2, 1999||Westaim Technologies, Inc.||Thermally sprayable powder materials having an alloyed metal phase and a solid lubricant ceramic phase and abradable seal assemblies manufactured therefrom|
|US5997248 *||Dec 3, 1998||Dec 7, 1999||Sulzer Metco (Us) Inc.||Silicon carbide composition for turbine blade tips|
|US6001289 *||Oct 4, 1994||Dec 14, 1999||Materials Innovation, Inc.||Acid assisted cold welding and intermetallic formation|
|US6042781 *||Dec 10, 1996||Mar 28, 2000||Materials Innovation, Inc.||Ambient temperature method for increasing the green strength of parts|
|US6162497 *||Jul 20, 1998||Dec 19, 2000||Materials Innovation, Inc.||Manufacturing particles and articles having engineered properties|
|US6203021 *||May 12, 1999||Mar 20, 2001||Chromalloy Gas Turbine Corporation||Abradable seal having a cut pattern|
|US6317913||May 8, 2000||Nov 20, 2001||Alcoa Inc.||Method of depositing flux or flux and metal onto a metal brazing substrate|
|US6344237 *||Mar 3, 2000||Feb 5, 2002||Alcoa Inc.||Method of depositing flux or flux and metal onto a metal brazing substrate|
|US6375894||May 9, 1995||Apr 23, 2002||The United States Of America As Represented By The Secretary Of Commerce||Acid assisted cold welding and intermetallic formation and dental applications thereof|
|US6434876 *||Sep 26, 2000||Aug 20, 2002||General Electric Company||Method of applying a particle-embedded coating to a substrate|
|US6560870 *||May 8, 2001||May 13, 2003||General Electric Company||Method for applying diffusion aluminide coating on a selective area of a turbine engine component|
|US6821615 *||Feb 11, 2003||Nov 23, 2004||Ensci Inc.||Metal non-oxide coated nano substrates|
|US6821621 *||Feb 11, 2003||Nov 23, 2004||Ensci Inc.||Metal non-oxide coated porous substrates|
|US6821622 *||Feb 11, 2003||Nov 23, 2004||Ensci Inc||Thin film metal non-oxide coated substrates|
|US7041370 *||Feb 11, 2003||May 9, 2006||Ensci Inc||Metal non-oxide coated substrates|
|US7052527 *||Apr 29, 2004||May 30, 2006||Sulzer Metco (Canada) Inc.||Thermal spray composition and method of deposition for abradable seals|
|US20040005452 *||Jan 14, 2003||Jan 8, 2004||Dorfman Mitchell R.||High temperature spray dried composite abradable powder for combustion spraying and abradable barrier coating produced using same|
|US20050049394 *||Aug 26, 2003||Mar 3, 2005||Jiawen Dong||Method of separating a polymer from a solvent|
|US20050287390 *||Apr 29, 2004||Dec 29, 2005||Karel Hajmrle||Thermal spray composition and method of deposition for abradable seals|
|US20070012900 *||Jun 27, 2006||Jan 18, 2007||Sulzer Metco (Canada) Inc.||Enhanced performance conductive filler and conductive polymers made therefrom|
|US20070098913 *||Oct 27, 2005||May 3, 2007||Honeywell International, Inc.||Method for coating turbine engine components with metal alloys using high velocity mixed elemental metals|
|US20110108775 *||May 12, 2011||Sulzer Metco (Canada) Inc.||Enhanced performance conductive filler and conductive polymers made therefrom|
|USRE40785 *||Jul 12, 2006||Jun 23, 2009||Sandvik Intellectual Property Aktiebolag||Method of making a submicron cemented carbide with increased toughness|
|CN103691938A *||Jan 1, 2014||Apr 2, 2014||北京矿冶研究总院||Metal-coated powder surface alloying method|
|CN103722170A *||Jan 1, 2014||Apr 16, 2014||北京矿冶研究总院||Agglomeration type copper aluminum nickel graphite sealing composite powder material and preparation method thereof|
|EP0028475A1 *||Oct 17, 1980||May 13, 1981||Sherritt Gordon Mines Limited||Thermal spray powder and method of forming abradable seals therewith|
|WO1993004807A1 *||Aug 31, 1992||Mar 18, 1993||Technalum Research, Inc.||Method of producing coated particles using a disintegrator apparatus|
|WO1993010927A1 *||Dec 4, 1992||Jun 10, 1993||THE UNITED STATES OF AMERICA, as represented by THE SECRETARY, UNITED STATES DEPARTMENT OF COMMERCE||Process for forming alloys in situ in absence of liquid-phase sintering|
|WO1995010379A1 *||Oct 5, 1994||Apr 20, 1995||The United States Of America, As Represented By The Secretary Of Commerce||Acid assisted cold welding and intermetallic formation and dental applications thereof|
|U.S. Classification||428/404, 427/217, 428/570, 75/255, 427/214, 106/1.5, 419/35|
|International Classification||C23C10/00, C23C10/34, B22F1/02|
|Cooperative Classification||C23C10/34, B22F1/025|
|European Classification||C23C10/34, B22F1/02B|