NZ200007A - Cemented bonded composite carbide bodies having a to b type porosity and a peripheral binder-enriched layer - Google Patents

Description

200007 Priority Date(s): . ?• '• & ■ • .Icmptete Specification Filed: r , - or; C ?2C 2. fj/<po . C 22.fi, ..

..Hm/t/.QC. -.hi cation Date: 11 0 SEP 1986 -.0 Journal, No: Patents Form No.5.

Patents Act 1953 COMPLETE SPECIFICATION "Preferentially Binder Enriched Cemented Carbide Bodies and Method of Manufacture" WE, KENNAMETAL INC., a Corporation of the Commonwealth of Pennsylvania, of One Lloyd Avenue, Latrobe, Pennsylvania 15650, United States of America, hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement ^°0007 Jmackground of the invention The present invention pertains to the fields of cemented carbide parts, having cobalt, nickel, iron or their alloys as a binder material, and the manufacture of these parts. More particularly, the present invention pertains to cemented carbide metal cutting inserts having a hard refractory oxide, nitride, boride, or carbide coating on their surface.

In the past, various hard refractory coatings have been applied to the surfaces of cemented carbide cutting inserts to improve the wear resistance of the cutting edge and thereby increase the cutting lifetime of the insert. See, for example, United States Patent Nos. 4,035,541 (assigned to applicant corporation); 3,564,683; 3,616,506; 3,882,581; 3,914,473; 3,736,107; 3,967,035; 3,955,038; 3,836,392; and Reissue 29,420. These refractory coatings, unfortunately, can reduce the toughness of cemented carbide inserts to varying degrees. The degree of degradation depends at least in part on the structure and composition of the coating and the process used for its deposition. Therefore, while refractory coatings have improved the wear resistance of metal cutting inserts, they have not reduced the susceptibility of the cutting edge to failure by chipping or breakage, especially in interrupted cutting applications.

Previous efforts to improve toughness or edge strength in coated cutting inserts revolved around the production of a cobalt enriched layer extending inwardly from the substrate/ coating interface. It was found that cobalt enrichment of the 200007" surface layers in certain C porosity substrates could be achieved during vacuum sintering cycles. These cobalt enriched zones were characterized by A porosity while most of the bulk of the substrate had C porosity. Solid solution carbide depletion was usually present to varying depths and degrees in the areas of cobalt enrichment. Cobalt enrichment is desirable in that it is well known that increasing cobalt content will increase the toughness or impact resistance of cemented carbides. Unfortunately, the level of enrichment produced is difficult to ) control in C porosity substrates. Typically, a coating of cobalt and carbon was formed on the surface of the substrate.

This coating of cobalt and carbon was removed prior to deposition of the refractory material on the substrate, in order to obtain adherent bonding between the coating and substrate. At times, the level of cobalt enrichment in the layers beneath the surface of the substrate was so high that it had an adverse effect on flank wear. As a result, sometimes the layer of cobalt enrichment on the flank faces of the substrate were ground away leaving cobalt enrichment only on the rake faces and 0 the possibility of C porosity material on the flank face. In comparison with A or B type porosity substrates, C porosity substrates are not as chemically homogeneous. This can result in less control over the formation of eta phase at the coating substrate interface (a hard and brittle phase affecting toughness), a reduction in coating adherency and an increase in nonuniform coating growth.

By way of definition, the porosity observed in cemented carbides may be classified into one of three categories recommended by the ASTM (American Society for Testing and Materials) as follows: Type A for pore sizes less than 10 microns in diameter.

Type B for pore sizes between 10 microns and 40 microns in diameter.

Type C for irregular pores caused by the presence of carbon inclusions. These inclusions are pulled out of the sample during metallographic preparation leaving the aforementioned irregular pores.

In addition to the above classifications, the porosity observed can be assigned a number ranging from 1 through 6 to indicate the degree or frequency of porosity observed. Theme thod of making these classifications can be found in Cemented Carbides by Dr. P. Schwarzkopf and Dr. R. Kieffer, published by the MacMillan Co., New York (1960) at Pages 116 to 120.

Cemented carbides may also be classified according to their binder carbon and tungsten contents. Tungsten carbide-cobalt alloys having excess carbon are characterized by C porosity which, as already mentioned, are actual free carbon inclusions. Tungsten carbide-cobalt alloys low in carbon and in which the cobalt is saturated with tungsten are characterized by the presence of eta phase, a or ^6^ carkide, where M represents cobalt and tungsten. In between the extremes of C porosity and eta phase, there is a region of intermediate binder alloy compositions which contain tungsten and carbon in solution to ».varying levels, but such that no free carbon or eta phase are present. The tungsten level present in tungsten carbide cobalt alloys can also be characterized by the magnetic saturation of the binder alloy, since the magnetic saturation of the cobalt alloy is a function of its composition. Carbon saturated cobalt is reported to have a magnetic saturation of 158 gauss-cm / gm cobalt and is indicative of C type porosity, while a magnetic 3 saturation of 125 gauss-cm /gm cobalt and below indicates the P.! .. B. & A. , presence of eta phase. f'wMs 4 &H J jIt is, therefore, an object of the present invention to provide a readily controllable and economic process for producing a binder enriched layer near the surface of a cemented carbide body.

It is a further object of this invention to provide a cemented carbide body having a binder enriched layer near its surface with substantially all porosity throughout the body being of the A or B types.

Preferably, this invention provides cemented • carbide bodies having carbon levels ranging from C porosity to 20 eta phase with a binder enriched layer near their peripheral surface.

It is an additional object of this invention to combine the aforementioned cemented carbide bodies according to the present invention with a refractory coating so as to provide coated cutting inserts having a combination of high wear resistance and high toughness. ■5- jh- patent "2 JUL 19S6 These and other objects of the present invention will become apparent upon review of the following description of the invention.

Wit, "in.

P- L. B. ®H®present invention provides a cemented carbide body comprising a first Per^?!ea-3?bide; a metallic binder alloy; a solid solution of said first carbide \ n/sc . with a second carbide whose free energy of formation is more negative than that of said first carbide at a temperature above the binder alloy melting point; the amount of said first carbide being greater than the amount of said p , o ^second carbide; a layer of binder enrichment near a peripheral surface of r . k-. l>. ^ _.r$lWsaid body; said body having substantially A to B type porosity throughout, p*r 'ay I !~1 I JmL 'Paid body.

According to the present invention, it has been found that a binder enriched layer can be formed near a peripheral surface of a cemented carbide body p . ^through the use of the following process: milling and blending a first I . L. o. pi a D0 J^fllcarbide powder, a binder powder, and a chemical agent powder selected from * ' 'the group of metals, alloys, hydrides, nitrides and carbonitrides of transition elements whose carbides have a free energy of formation more negative than that of the fi^st carbide near the binder melting point; and then, sintering or subsequently heat treating a compact of the blended material so as to at least partially transform the chemical agent to its carbide.

In accordance with the present invention, this process may be used to produce a layer of binder enrichment near a peripheral surface of a cemented carbide body, preferably, having substantially only A to B type porosity throughout said body. Enrichment can also be achieved in cemented carbide bodies having carbon levels ranging from eta phase to C porosity.

Cemented carbide bodies in accordance with the present invention have also been found to have a layer beneath said binder enriched layer which is partially binder depleted.

P. L. B. StP/sr.eferably, the first carbide is tungsten carbide. Preferably, p&K(A!/~.th.e .binder alloy may be cobalt, nickel, iron or their alloys, Ml ^ but is, most preferably, cobalt.

W.2. PATENT QFFtfev -2 JUL 1986 received ,o ^ L ('? ri W Preferably, the chemical agent is selected from the hydrides, nitrides, and carbonitrides of the Group IVB and VB elements and is, preferably, added in a small but effective amount, most preferably, 0.5 to 2 weight percent of the powder charge. Most preferably, the chemical agent is titanium nitride or titanium carbonitride.

Cemented carbide bodies in accordance with the present ^ invention have also been found to have a layer, at least partially depleted in solid solution carbide, near a peripheral 10 surface of the body. Cemented carbide bodies in accordance with the present invention have also been found to have a layer beneath said depleted solid solution layer which is enriched in solid solution carbides.

The cemented carbide bodies according to the present invention, preferably, have a cutting edge at the juncture of a rake face and a flank face with a hard dense refractory coating ^«4herently bonded to these faces. The binder enriched layer may be ground off the flank face prior to coating.

The refractory coating is preferably composed of one or more layers of a metal oxide, carbide, nitride, boride or carbonitride.

BRIEF DESCRIPTION OF THE DRAWINGS The exact nature of the present invention will become clearly apparent upon reference to the following detailed specification, reviewed in conjunction with the accompanying drawings, in which: 20000!? Figure 1 is a schematic, cross section through an * ^fenbodiment of a coated metal cutting insert according to the present invention^ Figure 2 is a graphical representation of the typical. levels of cobalt enrichment produced in a cemented carbide body according to the present invention as a function of depth P. L. B. & A. (below its rake surfaces;, p ®r.1\j2Ly i SC. Figure 3 is a graphical representation of the variation in binder and solid solution carbides relative concentrations as a function of depth below the rake surface in an Example 12 sample« . . . - . . ^ rreferred oy %ETAILED DESCRIPTION OF . THE INVENTION p *r<Ojd * 1 /~7 / «@o The aforementioned objects of the invention are achieved through the heat treatment of a cemented carbide compact containing an element having a carbide with a more negative free energy of formation than that of tungsten carbide at an elevated temperature close to or above the binder melting point. For cutting insert applications, this element or chemical agent can be selected from Group IVB and VB transition metals, their 20 alloys, nitrides, carbonitrides and hydrides. It has been found that the layer of material adjacent to the periphery of a cemented tungsten carbide body can be consistently binder enriched and, usually, at least partially solid solution carbide depleted during sintering or reheating at a temperature above the melting point of the binder alloy by incorporating Group IVB and VB nitride, hydride and/or carbonitride additions to the powder charge. -2 JUL 1986 200007 During sintering, these Group IVB and VB additions react with carbon to form a carbide or carbonitride. These carbides or carbonitrides may be present partially or wholly in a solid solution with tungsten carbide and any other carbides present. The level of nitrogen present in the final sintered carbide is typically reduced from the level of nitrogen added as a nitride or carbonitride since these additions are unstable at elevated o! B A (tjf''1" /temperatures above and below the binder alloy melting point and pel \ l~~) /t^will lead to at least partial volatization of nitrogen from the 10 sample if the sintering atmosphere contains a concentration of nitrogen less than its equilibrium vapor pressure. If the chemical agent is added as a metal, alloy or hydride, it will also be transformed to a cubic carbide, typically in solid solution with the tungsten carbide and any other carbides present. The hydrogen in any hydride added is volatilized during sintering.

The metals, hydrides, nitrides and carbonitrides of tantalum, titanium, niobium, hafnium can be used alone or in combination to promote consistent cobalt enrichment via sinter- ing or subsequent heat treating of tungsten carbide-cobalt base alloys having a wide range of carbon. Additions totaling up to approximately 15 weight percent have been found to be .useful. It is believed that the metals, nitrides, carbonitrides and hydrides of zirconium and vanadium are also suitable for this purpose. In A and B porosity alloys and carbon deficient P.L.B.&A. ^ e-DsW/.?v all°ys containin8 phase, cobalt enrichment occurs without \ f-v I ' ' ' peripheral cobalt or carbon capping, thus eliminating the need OFFIcs 20000? remove excess cobalt and carbon from the cemented carbide surfaces prior to refractory coating.

P. I-. B. A Additions of nn,a 11 .I.iii 11 i 1/ 0.5 to 2 weight percent, 11 } especially of titanium in the form of titanium nitride or titanium carbonitride, to tungsten carbide-cobalt base alloys are preferred. Since titanium nitride is not completely stable during vacuum sintering, causing at least partial volatization / of the nitrogen, it is preferable to add one-half mole of carbon per mole of starting nitrogen to maintain the carbon level necessary for a tungsten lean cobalt binder alloy. It has been found that cobalt enrichment via heat treating of tungsten carbide-cobalt base alloys occurs more readily when p. l.B.St A. q. btndtr- voKi eJ- Uttb. par^ih! t'ie all°y contains a tungsten lean cobalt binder. The tungsten ( I 1 3 lean cobalt binder preferably should have a 145 to 157 gauss-cm / gm cobalt magnetic saturation. Titanium nitride additions along P-L B. & A.with the necessary carbon additions to tungsten carbide-cobalt psrfak) * J- \jl l&hase Powc*er mi-xes promote the formation of a 145 to 15j^magnetic saturation cobalt binder alloy which is ordinarily difficult to achieve. Although a cobalt binder alloy having 145 to 157 gauss-cm /gm cobalt magnetic saturation is preferred, alloys containing tungsten saturated cobalt binder alloys (less than O 125 gauss-cm /gm cobalt) can also be enriched.

It has been found that a layer of cobalt enrichment thicker than six microns results in a significant improvement in the edge strength of refractory coated cemented carbide inserts.

While cobalt enrichment as deep as 125 microns has been achieved, a cobalt enriched layer having a thickness of 12 to 50 microns 200007 is preferred for coated cutting insert applications. It is also preferable that the cobalt content of the cobalt enriched layer on a refrac.tory coated insert be between 150 to 300 per cent of the mean cobalt content as measured on the surface by energy dispersive x-ray analysis.

The depth of cobalt enrichment is directly proportional to the soak time of the compact at the sintering hold temperature. For example, the composition of Example 3, when held at a temperature of 2650 degrees Fahrenheit for 30 minutes, will produce a cobalt enriched layer having a thickness of ten microns. The same composition, when held at 2650 degrees Fahrenheit for 60 minutes, will produce a cobalt enriched layer of 20 microns. However, a greater soak time will not produce proportionally greater depths of cobalt enrichment since the relationship become non-linear. Further, when the depth of cobalt enrichment exceeds 50 microns, one could possibly expect deformation to occur in the enriched zone, and this would, of course, be -u- 200007 Itfis^bli lie ve d that binder enrichment should occur~in~all tungsten carbide-binder-cubic carbide (i.e., tantalum, niobium, ^ titanium, vanadium, hafnium, zirconium) alloys which do not sinter to a continuous carbide skeleton. These alloys containing 10 binder from 3 weight percent and above should enrich utilizing the disclosed process. However, for cutting insert applications, it is preferred that the binder content be between 5 and 10 P L 8 & a percent cobalt and that the total cubic carbide content (li.aH lta«h ~70u>t>jkt pv cpaV" etxs-biJ^. i's , periSS?^,,. be 20 weight percent or less. While cobalt is the preferred (I -7/SC ^ binder, nickel, iron and their alloys with one another, as well p L. as with cobalt, may be substituted for cobalt. Other binder alloys * per —T, *llovG containing nickel or cobalt or iron should also be suitable.

! ! The sintering and heat treating temperatures used to obtain binder enrichment are the typical liquid phase sintering temperatures. For cobalt base alloys, these temperatures are 1285 to 1540 degrees Centigrade. Sintering cycles should be at least 15 minutes at temperature. Results can be further optimized by the use of controlled cooling rates from the heat treating temperatures down to a temperature below the binder alloy melting point. These cool down rates should be between to 85 degrees Centigrade/hour, preferably 40 to 70 degrees P. L ... o>. A. fceafcx^t- Centigrade/hour. Most preferably, the heat trsat cycle for 9\ i n /&<* -13L- iJ^ATENT OFFICE" "2 JUL J986 JfECElV^r) 20Q00J cutting insert substrates having a cobalt binder is 1370 to ^500 degrees Centigrade for 30 to 150 minutes, followed by a 40 to 70 degrees Centigrade/hour cool down to 1200 degrees Centigrade. Pressure levels during heat treating can vary from _3 torr up to and including those elevated pressures typically used in hot isostatic pressing. The preferred pressure level is .1 to .15 torr. If nitride or carbonitride additions are ^ being utilized, the vapor pressure of the nitrogen in the sintering atmosphere is preferably below its equilibrium 10 pressure, so as to allow volatilization of nitrogen from the substrate.

^ While initial enrichment will occur upon sintering, subsequent grinding steps in the metal cutting insert fabrication process may remove the enriched zones. In these situations, a subsequent heat treatment in accordance with the above parameters can be utilized to develop a new enriched layer beneath the peripheral surfaces.

Binder enriched substrates to be used in coated cutting inserts can have binder enrichment on both the rake and flank 20 faces. However, depending on insert style, the binder enrich-^ ment on the flank face may sometimes be removed, but this is not necessary to achieve optimum performance in all cases.

The binder enriched substrates can be coated using the ^ refractory coating techniques well known to those skilled in the art. While the refractory coating applied can have one or more layers comprising materials selected from the Group IVB and VB carbides, nitrides, borides, and carbonitrides, and the 20000^ oxide or the oxynitride of aluminum, it has been found that a ^ combination of good cutting edge strength and flank wear can be achieved by combining a substrate having a binder enriched layer P. L. B. & A. according to the present invention with a coating of: aitaaaman I oxjLde over an inner layer of titanium carbide; or an inner layer of titanium carbide bonded to an intermediate layer of titanium carbonitride, which is bonded to an outer layer of titanium nitride, or titanium nitride bonded to an inner layer of titanium carbide. A cemented carbide body having a binder enriched layer according to the present invention in combination P- L 3, a A . . with a titanium carbide/alumimm oxide coating is most r n iz< /^- preferred. In this case, the coating should have a total coating thickness of 5 to 8 microns.

Referring now to Figure 1, an embodiment of a coated metal-cutting insert 2 according to the present invention is schematically shown. The insert 2 is comprised of a substrate or cemented carbide body 12 having a binder enriched layer 14, and a binder depleted layer 16 over the bulk 18 of the substrate 12 which has a chemistry substantially equal to the chemistry of 20 the original powder blend.

A binder enriched layer 14 is present on the rake faces 4 of the cemented carbide body and has been ground off the flank faces 6 of the body. Located inwardly of the binder enriched layer 14 may be a binder depleted zone 16. This binder depleted zone 16 has been found to develop along with the binder enriched layer when cemented carbide bodies are fabricated according to the disclosed process. •v- ' --—5pC£/V«n 20000Y The binder depleted zone 16 is partially depleted in ^binder material while being enriched in solid solution carbides. The enriched layer 14 is partially depleted in solid solution carbides. Inwardly of the binder depleted zone 16 Is bulk substrate material 18.

At the junction of the rake faces and flank faces 6, a cutting edge 8 is formed. While the cutting edge 8 shown here is honed, honing of the cutting edge is not necessary for all applications of the present invention. It can be seen in Figure 1 that the binder enriched layer 14 extends into this cutting edge area and is, preferably, adjacent to most, if not all, of the honed edge 8. The binder depleted zone 16 extends to the flank surface 6 just below the cutting edges 8. A refractory coating 10 has been adherently bonded to the peripheral surface of the cemented carbide body 12.

These and other features of the invention will become more apparent upon reviewing the following examples.

EXAMPLE NO. 1 A mix containing 7000 grams of powders was milled and blended for 16 hours with a paraffin, a surfactant, a solvent and cobalt bonded tungsten carbide cycloids, in the amounts and proportions shown below: .3 5.85 0.2 8.5 1.5 2 2.5 14 w/o* w/o* w/o* w/o w/o* w/o liter gram Ta (C) Ti(C) Nb (C) Co Ti(N) - 7000 gm 102.6 grams WC + C to produce a 2 w/o W - 98 w/o Co binder alloy paraffin (Sunoco 3420)(Sun Oil Co.) solvent (perchloroethylene) surfactant (Ethomeen S-15) (Armour Industrial Chemical Co.) ^weight percent of metal added.

^ Square insert blanks having dimensions of 15.1 mm x 15.1 mm x 5.8 to 6.1 mm and a weight of 11.6 grams were pill pressed using a force of 8200 kilograms. These inserts were vacuum sintered at 1496 degrees Centigrade for 30 minutes, and then cooled under ambient furnace conditions. After sintering, the inserts weighed 11.25 grams and were 13.26 mm x 13.26 mm x 4.95 mm in size. These inserts were then processed to SNG433 ground dimensions as follows: (this identification number is based on the insert identification system developed by the American Standards Association and which has been generally adopted by the cutting tool industry. The International designation is: SNGN 12 04 12) 1. Tops and bottoms (rake faces) of the inserts were ground to a thickness of 4.75 mm. 2. The inserts were heat treated at 1427 degrees Centigrade for 60 minutes under a 100 micron vacuum, then cooled at a rate of 56 degrees Centigrade/hour to 1204 degrees Centigrade, followed by cooling under ambient furnace conditions 3. The periphery (flank faces) was ground to produce a 12.70 mm square and the cutting edges honed to a 0.064 mm radius A titanium carbide/titanium carbonitride/titanium nitride coating was then applied to the ground inserts using the following chemical vapor deposition (CVD) techniques in the following order of application: -/ b.

M-Z. PATENT nggioe -2 JUL 1986 20000f TABLE I Coating Coating Reactions Type Temperature Pressure H 1. TiC 982-1025°C —1 atm. TiCl.+CH, y4 TiC, ,+4HCl 4 4 (s) 2. TiCN 982-1025°C —1 atm. TiCl4-t€H4+l/2N2 ^ TiCN^^HCl 3. TiN 982-1050°C ~1 atm. TiCl4+2H2+l/2N2 —» TiN^+4HCl Processed along with the above inserts were inserts made from the same powder blend but without the TIN and its attendent carbon addition. Microstructural data obtained from the coated inserts are shown below: Porosity EXAMPLE 1 without TiN Al None Cobalt Enriched Zone Thickness Solid Solution Depleted Zone None Thickness TiC/Substrate Interface Eta 4.6 microns Phase Thickness Coating Thickness TiC 5.6 microns TiCN 2.3 microns TIN 1.0 microns EXAMPLE 1 with TiN Al, B2 (non-enriched, bulk) Al (enriched) '—22.9 microns (rake face only) -—22.9 microns (rake face only) 3.3 microns .0 microns 3.9 microns 1.0 microns EXAMPLE NO. 2 • Green pill pressed inserts were fabricated according to Example 1 utilizing the Example 1 blends with and without the TiN and its attendent carbon additions. These inserts were sintered at 1496 degrees Centigrade for 30 minutes under a 25 micron vacutun and then cooled under ambient furnace conditions. They were then honed (0.064 mm radius), and subsequently TiC/TiCN/TiN CVD coated according to the techniques shown in -n- 200007 Table I. In this example, it should be noted the cobalt i enriched layer was present on both flank and rake faces.

The coated inserts were substantially evaluated and the following results were obtained: Porosity Cobalt Enriched Zone Thickness Solid Solution Depleted Zone None Thickness EXAMPLE 2 .without TiN A-l edges A-3 center None TiC/Substrate Interface Eta Phase Thickness Coating Thickness TiC TiCN TiN Average Rockwell "A" Hardness (Bulk Material) Coercive Force, He up to 5.9 microns 2.0 microns 1.7 microns 8.8 microns 91.2 EXAMPLE 2 with TiN A-2 enriched zone A-4 bulk up to 22.9 microns partial and intermittent up to 21 microns 3.3 microns 1.3 microns 1.0 microns 7.9 microns 91.4 134 oersteds 138 oersteds EXAMPLE NO. 3 A mix comprising the following materials was charged into a cylindrical mill, with a surfactant, fugitive binder, solvent and 114 kilograms of cycloids: fwc (2-2.5 micron particle size) 85.15 w/o -s (WC (4-5 micron particle size) .98 w/o TaC 2.6 w/o TiN 6.04 w/o Co 0.23 w/o C (Ravin 410-a product of Industrial Carbon Corp.) , 000 grams 27, 575 grams 2, 990 grams 1, 300 grams 3, 020 grams 115 grams 50, 000 grams The powder charge was balanced to produce 6.25 weight percent total carbon in the charge. The mix was blended and milled for 90,261 revolutions to obtain an average particle size of 0.90 microns. The blend was then wet screened, dried and 200007 hammer milled. Compacts were pressed and then sintered at 1454 degrees Centigrade for 30 minutes followed by cooling under ambient furnace conditions.

This treatment produced a sintered blank having an overall (i.e., measurement included bulk and binder enriched O material) magnetic saturation of 117 to 121 gauss-cm /gm cobalt. Microstruetural evaluation of the sintered blank showed: eta phase to be present throughout the blank; porosity to be A-2 to B-3; the cobalt enriched zone thickness to be approximately 26.9 microns; and the solid solution depleted zone thickness to be approximately 31.4 microns.

EXAMPLE NO. 4 The following materials were added to a 190 mm inside diameter by 194 mm long mill jar lined with a tungsten carbide cobalt alloy. In addition, 17.3 kilograms of 3.2 mm tungsten carbide-cobalt cycloids were added to the jar. These materials were milled and blended together by rotating the mill jar about its cylindrical axis at 85 revolutions per minute for 72 hours (i.e., 367,200 revolutions).

CHARGE COMPOSITION 283 grams ( 4.1 wt. %) TaC 205 grams ( 3.0 wt. %) NbC 105 grams ( 1.5 wt. %) TiN 7.91 grams ( 0.1 wt. 7c) C 381 grams ( 5.5 wt. 7») Co 5946 grams (85.8 wt. 7o) WC 105 grams Sunoco 3420 14 grams Ethomeen S-15 2500 milliliters Perchloroethylene SOOOOf This mix was balanced to produce a 2 w/o W - 98 w/oCo ^binder alloy. After milling and blending, the slurry was wet screened to remove oversized particles and contaminants, dried at 93 degrees Centigrade under a nitrogen atmosphere and then hammer milled to break up agglomerates in a Fitzpatrick Co. J-2 Fitzmill.

Using this powder, compacts were pressed and then sintered ^ at 1454 degrees Centigrade for 30 minutes and cooled under ambient conditions.

The top and bottom (i.e., the rake faces) of the insert ^ were then ground to final thickness. This was followed by a heat treatment at 1427 degrees Centigrade under an 100 micron vacuum. After 60 minutes at temperature, the inserts were cooled at a rate of 56 degrees Centigrade/hour to 1204 degrees Centigrade and then furnace cooled under ambient conditions. The peripheral (or flank) surfaces were then ground to a 12.70 mm square and the insert cutting edges honed to a 0.064 mm radius. These treatments resulted in an insert substrate in which only the rake faces had a cobalt enriched and solid 20 solution depleted zone, these zones having been ground off the flank faces. J i The inserts were then loaded into a coating reactor and coated with a thin layer of titanium carbide using the follow-^ ing chemical vapor deposition technique. The hot zone containing the inserts was first heated from room temperature to 900 degrees Centigrade. During this heating period, hydrogen gas was allowed to flow through the reactor at a rate of 11.55 -2 JUL 198 j 2000&f liters per minute. The pressure within the reactor was main-► tained at slightly less than one atmosphere. The hot zone was then heated from 900 degrees Centigrade to 982 degrees Centigrade. During this second heat up stage, the reactor pressure was maintained at 180 torr. and a mixture of titanium tetrachloride and hydrogen, and pure hydrogen gas entered the reactor at flow rates of 15 liters per minute and 33 liters per minute, respectively. The mixtures of titanium tetrachloride and hydrogen gas was achieved by passing the hydrogen gas through a vaporizer holding the titanivim tetrachloride at a temperature of 47 degrees Centigrade. Upon attaining 982 degrees Centigrade, methane was then allowed to also enter the reactor at a rate of 2.5 liters per minute. The pressure within the reactor was reduced to 140 torr. Under these conditions, the titanium tetrachloride reacts with the methane in the presence of hydrogen to produce titanium carbide on the hot insert surface. These conditions were maintained for 75 minutes, after which the flow of titanium tetrachloride, hydrogen and methane was terminated. The reactor was then allowed to cool while Argon was being passed through the reactor at a flow rate of 1.53 liters per minute under slightly less than one atmosphere pressure.

Examination of the microstrueture in the final insert revealed a cobalt enriched zone extending inwardly up to 22.9 microns and a cubic carbide solid solution depletion zone extending inwardly up to 19.7 microns from the substrate rake surfaces. The porosity in the enriched zone and the remainder of the substrate was estimated to be between A-l and A-2. ~3.\- ^j^NTOFFIg, '2JULS986 20OOtff EXAMPLE NO. 5 ® The material in this example was blended and milled using a two stage milling process with the following material charges: Stage 1 (489,600 revolutions) 141.6 grams ( 2.0 wt.

%) TaH 136.4 grams ( 1.9 wt.

%) Titf 220.9 grams ( 3.1 wt.

%) NbC 134.3 grams ( 1.9 wt.

%) TaC 422.6 grams ( 5.9 wt.

%) Co 31.2 grams ( 0.4 wt.

%) C 14 grams Ethomeen S-15 1500 milliliters Perchloroethylene Stage II (81,600 revolutions) 6098 grams (84.9 wt. %) WC 140 grams Sunoco 3420 1000 milliliters Perchloroethylene This was balanced to produce a 2 w/o W - 98 w/o Co binder alloy. CfKs iher«^\.j' v#Jo 1 1 p-tr ^ The test inserts were then fabricated and TiC coated in accordance and along with the test blanks described in Example No. 4.

Microstructural evaluation of the coated inserts revealed the porosity in the cobalt enriched as well as the bulk material to be A-l. The cobalt enriched zone and the solid solution depleted zone extended inward from the rake surface to depths of approximately 32.1 microns and 36 microns, respectively.

EXAMPLE NO. 6 The following materials were charged into a 190 mm inside diameter mill jar: SOOOOf 283 grams ( 4.1 w/o) TaC 205 grams ( 3.0 w/o) NbC 105 grams ( 1.5 w/o) TiN 7.91 grams ( 0.1 w/o) C 381 grams ( 5.5 w/o) Co 5946 grams (85.8 w/o) WC 140 grams Sunoco 3420 14 grams Ethomeen S-15 2500 milliliters Perchloroethylene This mix was balanced to produce a 2 w/o W - 98 w/o Co binder alloy.

In addition, cycloids were added to the mill. The mixture was then milled for four days. The mix was dried in a sigma blender at 121 degrees Centigrade under a partial vacuum, after which it was Fitzmilled through a 40 mesh sieve.

SNG433 inserts were then fabricated using the techniques described in Example 4. The inserts in this Example, however, were CVD coated with a TiC/TiN coating. The coating procedure used was as follows: 1. TiC coating--The samples in the coating reactor were held at approximately 1026 to 1036 degrees Centigrade under a 125 torr vacuum. Hydrogen carrier gas flowed into a TiCl^ vaporizer at a rate of 44.73 liters/minute. The vaporizer was held at 33 to 35 degrees Centigrade under vacuum. TiCl^ vapor was entrained in the K carrier gas and carried into the coating reactor. Free hydrogen and free Methane flowed into the coating reactor at 19.88 and 3.98 liters/minute, respectively. These conditions were maintained for 100 minutes and produced a dense TiC coating adherently bonded to the substrate. .2. TiN coating--Methane flow into the reactor was discontinued and N2 was allowed into the reactor at a rate of vVV-l ~2 JUL /93$ 300OOf 2.98 liters/minute. These conditions were maintained for 30 ^linutes and produced a dense TiN coating adherently bonded to the TiC coating.

Evaluation of the coated inserts produced the following results: Porosity A-l, throughout Cobalt Enriched Zone Thick- 17.0 to 37.9 microns ness Solid Solution Depleted Zone up to 32.7 microns AO Thickness ^ TiC/Substrate Interface Eta up to 3.9 microns Phase Thickness Coating Thickness TiC 3.9 microns TiN 2.6 microns Average Rockwell "A" Hard- 91.0 ^ ness of Bulk Coercive Force, He 98 oersteds EXAMPLE NO. 7 f A blend of material was made using the following two stage milling cycle: In Stage I, the following materials were added to a 181 mm inside diameter by 194 mm long WC-Co lined mill jar with 17.3 kg of 4.8 mm WC-Co cycloids. The mill jar was rotated about its cylindrical axis at 85 revolutions per minute for 48 hours (244,800 revolutions). ^ 140.8 grams ( 2.0 wt. 7.) Ta 72.9 grams ( 1.0 wt. %) TiH 23.52 grams ( 0.3 wt. 7,) C 458.0 grams ( 6.5 wt. 7°) Co grams Ethomeen S-15 120 grams Sunoco 3420 ) 1000 milliliters Soltrol 130 (a solvent) In Stage II, 6314 grams (90.2 wt. %) WC and 1500 ml Soltrol 130 were added and the entire charge rotated an additional 16 hours (81,600) revolutions. This mix was balanced 20GQOf to produce a 5 w/o W- 95 w/o Co binder alloy. After milling, ^^the slurry was wet screened through 400 mesh, dried under nitrogen at 93 degrees Centigrade for 24 hours and Fitzmilled through a 40 mesh screen.

Test samples were uniaxially pressed at 16,400 kilograms total force to 15.11 mm x 15.11 mm x 5.28 mm (8.6 gram/cc specific gravity).

^ The above green test samples were sintered at 1468 degrees Centigrade for 150 minutes under a 1 micron vacuum. The inserts 10 were then cooled under ambient furnace conditions. Flake graphite was used as the parting agent between the test inserts i and the graphite sintering trays.

The as sintered inserts were honed to a 0.064 mm radius. The inserts were then coated with a TiC/TiCN/TiN coating according to the following procedure: 1. Inserts were located into the reactor and air purged out of the reactor by flowing hydrogen through it. 2. Inserts were heated to approximately 1038 degrees Centigrade while maintaining hydrogen flow through the reactor.

Coating reactor pressure was held at slightly greater than one ^ atmosphere. 3. TiC coating--For 25 minutes, a mixture of H2 + TiCl^ entered the reactor at a rate of approximately 92 liters/minute | and methane entered the reactor at a rate of 3.1 liters/minute. The TiCl^ vaporizer was maintained at approximately 6 psi and 30 degrees Centigrade. i!£l£ATEfyr ■2JUi off tee 2000QJ 4. TiCN coating--For 13 minutes, the flow of the + ^^iCl, mixture was substantially maintained; the flow of methane 4 reduced by one-half; and N2 was introduced into the reactor at a rate of 7.13 liters/minute.

. TiN coating—For 12 minutes, the methane flow was discontinued and the nitrogen flow rate doubled. Upon completion of TiN coating, both the flow of the H2 + TiCl^ mixture and the were discontinued, the reactor heating elements shut off and the reactor purged with free H2 until it cooled to approximately 250 degrees Centigrade. At 250 degrees Centigrade, the reactor was purged with nitrogen.

It was determined that the insert substrates had an A-1 to A-2 porosity in their nonenriched interior or bulk material. A cobalt enriched zone and solid solution depleted zone extended in from the surfaces approximately 25 microns and 23 microns, respectively. The nonenriched interior had an average hardness of 91.7 Rockwell "A". The coercive force, He, of the substrate was found to be 186 oersteds.

EXAMPLE NO. 8 A 260 kg blend of powder, having carbon balanced to C3/C4 porosity in the final substrate, was fabricated using the following two stage blending and milling procedure: STAGE I The following charge composition was milled for 96 hours: 20006f ,108 grams TaC ( 6.08 w/o Carbon) 7,321 grams NbC (11.28 w/o Carbon) 3,987 grams TiN 1,100 grams C (Molocco Black--a product of Industrial Carbon Corp.) 16,358 grams Co 500 grams Ethomeen S-15 364 kilograms 4.8 mm Co-WC cycloids Naphtha STAGE II The following was added to the above blend, and the ^ mixture milled for an additional 12 hours: 221.75 kilograms WC ( 6.06 w/o Carbon) .0 kilograms Sunoco 3420 Naphtha The final blend was then wet screened, dried, and Fitz-^ milled.

Insert blanks were then pressed and later sintered at 1454 degrees Centigrade for 30 minutes. This sintering procedure produced a cobalt enriched zone overlying bulk material having a C3/C4 porosity. The sintered blanks were then ground and 20 honed to SNG433 insert dimensions, resulting in removal of the cobalt enriched zone.

The sintered inserts were then packed with flake graphite inside of an open graphite canister. This assembly was then ^ hot isostatically pressed (HIPed) at 1371 to 1377 degrees Centigrade for one hour under a 8.76 x 10^ dynes/cm^ atmosphere of 25 v/o N^ and 75 v/o He. Microstructural examination of a HIPed sample revealed that a cobalt enriched zone of approxi-^ mately 19.7 microns in depth had been produced during HIPing.

About 4 microns of surface cobalt and 2jl\ surface of carbon 30 were also produced due to the C type porosity substrate utilized. -3.1- '2 jul me ■£iSEjV$D 200007 SXAMFLE MO. 9 A batch containing the following materials was ball milled: .0 w/o WC (1.97 micron average particle 750 kg size) 51.4 w/o WC (4.43 micron average particle 1286 kg w/o size) 6.0 Co 150 kg .0 w/o WC-TiC solid solution carbide 124.5 kS. 6.1 w/o TaWC solid solution carbide 152 kg 1.5 w/o w 37.5 kg ^ This mix was charged to 6.00 w/o total carbon. These materials were milled for 51,080 revolutions with 3409 kilograms of cycloids and 798 liters of naphtha. A final particle size of 0.82 microns was produced.

^ Five thousand grams of powder were split from the blended and milled batch and the following materials added to it: 1.9 w/o TiN (premilled to approximately 96.9 gm 1.4 to 1.7 microns) 0.2 w/o C (Ravin 410) 9.4 gm 20 1500 ml Perchloroethylene These materials were then milled in a 190 mm inside diameter tungsten carbide lined mill jar containing 50 volume percent cycloids (17.3 kg) for 16 hours. Upon completion of milling, the lot was wet screened through a 400 mesh screen, dried under ^ partial vacuum in a sigma blender at 121 degrees Centigrade, and then Fitzmilled through a 40 mesh sieve.

SNG433 blanks were pressed using a force of 3600 kilograms to produce a blank density of 8.24 gm/cc and a blank height of ^ 5.84 to 6.10 mm.

The blanks were sintered at 1454 degrees Centigrade for minutes on a NbC powder parting agent under a 10 to 25 micron vacuum and then allowed to furnace cool. The sintered samples nvX-.

—OS - SOOOOf ^ad sintered dimensions of 4.93 mm x 13.31 mm square, a density of 13.4 gm/cc and an overall magnetic saturation value of 146 3 to 150 gauss-cm /gm Co. Microstructural evaluation of the samples showed A porosity throughout and a cobalt enriched layer approximately 21 microns thick.

The top and bottom of the inserts were then ground to a total thickness of 4.75 mm. The inserts were then heat treated at 1427 degrees Centigrade for 60 minutes under a 100 micron vacuvim cooled to 1204 degrees Centigrade at a rate of 56 degrees Centigrade/hour and then furnace cooled.

The flank faces of each insert were ground to a 12.70 mm square and the edges honed to a 0.064 mm radius.

The inserts were subsequently CVD coated with titanium carbide/aluminum oxide using the following techniques.

The inserts were placed in a coating reactor and heated to approximately 1026 to 1030 degrees Centigrade and held under an 88 to 125 torr vacuum. Hydrogen gas at a rate of 44.73 liters/ minute was passed through a vaporizer containing TiCl^ at 35 to 38 degrees Centigrade under vacuvim. TiCl^ vapor was entrained in the hydrogen and directed into the coating reactor.

Simultaneously, hydrogen and methane were flowing into the reactor at rates of 19.88 and 2.98 1iters/minute. These conditions of vacuum, temperature, and flow rate were maintained for 180 minutes producing an adherent TiC coating on the inserts. Hydrogen flow to the vaporizer and methane flow into the reactor were then terminated. Hydrogen and chlorine were now allowed to flow to a generator containing aluminum particles at 380 to 200QG7 ^00 degrees Centigrade and 0.5 psi pressure. The hydrogen and chlorine flowed into the generator at rates of 19.88 liters/ minute and 0.8 to 1. liter/minute, respectively. The chlorine reacted with the aluminum to produce AlCl^ vapors which were then directed into the reactor. While the hydrogen and AlCl^ were flowing into the reactor, CO^ at a rate of 0.5 liters/ minute was also flowing into the reactor. These flow rates were maintained for 180 minutes during which time the inserts were held at 1026 to 1028 degrees Centigrade under a vacuum of approximately 88 torr. This procedure produced a dense coating of A.I2O3 adherently bonded to a TiC inner coating.

Evaluation of the coated inserts produced the following results: Porosity Cobalt Enriched Zone Thickness (rake surface) Solid Solution Depleted Zone Thickness (rake surface) Coating Thickness TiC ai2o3 Average Bulk Substrate Rockwell A Hardness Coercive Force, He EXAMPLE NO. 10 An additional 5000 grams of material were split from the initial batch of material produced in Example 9. Premilled TiCN in the amount of 95.4 grams (1.9 w/o) and 1.98 grams (.02 w/o) Ravin 410 carbon black were added to this material, mixed for 16 hours, screened, dried, and Fitzmilled, as per Example 9.

Al in enriched zone, Al with scattered B in the bulk material approximately 39.3 microns up to 43.2 microns .9 microns 2.0 microns 91.9 170 oersteds [ N.Z. PATENT Offr» "2 JUL 1936 <XDO? Test pieces were pill pressed, vacuum sintered at 1496 degrees Centigrade for 30 minutes, and then furnace cooled at the ambient furnace cooling rate. Evaluation of the sintered samples produced the following results: Porosity Cobalt Enriched Zone Thickness Solid Solution Depleted Zone Thickness Average Bulk Substrate Rockwell A Hardness Magnetic Saturation Coercive Force (He) EXAMPLE NO. 11 A-1 throughout approximately 14.8 microns up to 19.7 microns 92.4 130 gauss-cm^/gm Co 230 oersteds An additional 5000 grams of material were split from the initial batch made in Example 9. Premilled TiCN in the amount of 95.4 grams (1.9 w/o) was added, mixed for 16 hours, screened, dried and Fitzmilled as per Example 9. Test pieces were then pressed and sintered at 1496 degrees Centigrade with the Example 10 test pieces.

Evaluation of the sintered samples produced the following results: Porosity Cobalt Enriched Zone Thickness Solid Solution Depleted Zone Thickness Average Bulk Rockwell A Hardness Magnetic Saturation Coercive Force, He EXAMPLE NO. 12 Al, with heavy eta phase throughout approximately 12.5 microns up to 16.4 microns 92.7 O 120 gauss-cm /gm Co 260 oersteds The following mix was charged using the two stage milling cycle outlined below: •3>\- M-Z. PATENT OFF ire -2 JUL 1986 200007 Stage I ^ The following materials were added to a 181 mm inside diameter by 194 mm long WC-Co lined mill jar with 17.3 kg of 4.8 mm WC-Co cycloids. The mill jar was rotated about its cylindrical axis at 85 revolutions per minute for 48 hours (244,800 revolutions). 455 grams ( 6.5 wt. 7>) Ni 280 grams ( 4.0 wt. 7.) TaN A 112 grams ( 1.6 wt. 7.) TiN To 266 grams ( 3.8 wt. 7.) NbN 42.7 grams ( 0.6 wt. 7.) Carbon 14.0 grams Ethomeen S-15 1500 milliliters Perchloroethylene ^ Stage II The following were then added to the mill jar and rotated an additional 16 hours (81,600 revolutions): 5890 grams (83.6 wt. 7.) WC 105 grams Sunoco 3420 1000 milliliters Perchloroethylene This mix was balanced to produce a 10 w/o - 90 w/o Ni binder alloy. After discharging the mix slurry from the mill jar, it was wet screened through a 400 mesh sieve (Tyler), dried at 93 degrees Centigrade under a nitrogen atmosphere, and Fitz- milled through a 40 mesh sieve.

Test samples were pill pressed, sintered at~1450 degrees Centigrade for 30 minutes under a 6.9 x 10 dynes/cm nitrogen atmosphere, and then furnace cooled at the ambient furnace ^ cooling rate. Following sintering, the samples were HIPed at Q . 2 1370 degrees Centigrade for 60 minutes in a 1 x 10 dynes/cm 30 helium atmosphere. Optical metallographic evaluation of the HIPed samples showed the material to have A-3 porosity wg- patent '2 JUL 1986 RECCfycn 200007 throughout and a solid solution depletion zone thickness of approximately 25.8 microns.

Subsequently, the sample was reprepared and examined by energy dispersive x-ray line scan analysis (EDX) at various distances from the rake surface. Figure 3 shows a graphical representation of the variation of nickel, tungsten, titanium and tantalum relative concentrations as a function of distance ^ from the rake surface of the sample. It can be clearly seen that there is a layer near the surface in which the titanium 10 and tantalum, forming carbides which are in solid solution with ^ tungsten carbide, are at least partially depleted. This solid solution depleted zone extends inwardly approximately 70 microns. The discrepancy between this value and the value reported above are believed to be due to the fact that the sample was reprepared between evaluations so that different planes through the samples were examined in each evaluation.

Corresponding with the titanium and tantalum depletion is an enriched layer of nickel (see Figure 3>* The nickel concentration in the enriched layer decreases as the distance 20 from the rake surface decreases from 30 to 10 microns. This indicates that the nickel in this zone was partially volatilized during vacuum sintering.

The spike in titanium and tantalum concentration at 110 ^ microns is believed to be due to the scanning of a random large grain or grains having a high concentration of these elements. 20000f The two parallel horizontal lines show the typical scatter obtained in analysis of the bulk portion of the sample around the nominal blend chemistry.

EXAMPLE NO. 13 The following mix was charged using the two stage milling cycle outlined below: Stage I The following materials were milled per Stage I of Example 12: 455 grams ( 6 .4 w/o) Ni 280 grams ( 3 .9 w/o) TaH 112 grams ( 1 .6 w/o) TiN 266 grams ( 3 .7 w/o) NbN 61.6 grams ( o .9 w/o) C Ravin 410, 502 14 grams Ethomeen S-15 2500 milliliters Perchloroethylene Stage II The following were then added to the mill jar and rotated an additional 16 hours: 5980 grams (83.6 w/o) 140 grams WC Sunoco 3420 This mix was balanced to produce 10 w/o W - 90 w/o Ni binder alloy.

After discharging the mix, it was screened, dried and Fitzmilled per Example 12.

Pressed test samples were vacuum sintered at 1466 degrees Centigrade for 30 minutes under a 35 micron atmosphere. The sintered samples had an A-3 porosity throughout and a solid solution depletion zone up to 13.1 microns thick.

EXAMPLE NO. 14 A mix was charged using the following two stage milling cycle: -2.U- PATENT OFP^ -2 JUL 1986 20OOOf Stage I % The following materials were added to a 190 mm inside diameter by 194 mm long WC-Co lined mill jar with 17.3 kg of 4.8 mm WC-Co cycloids. The mill jar was rotated about its axis at 85 revolutions per minute for 48 hours (244,800 revolutions): 177 grams ( 2.5 w£. %) HfH„ ^ 182.3 ggrams ( 2.5 wt. 7„) TiH- w 55.3 grams ( 0.8 wt. °L) Carbon 459 grams ( 6.4 wt. X) Co 14 grams . Ethomeen S-15 2500 milliliters Perchloroethylene Stage II ^ The following was then added to the mill jar and rotated an additional 16 hours (81,600 revolutions): 6328 grams (87.9 wt. 7«) WC 140 grams Sunoco 3420 This mix was balanced to produce 10 w/o W - 90 w/o Co binder alloy.

After discharging the slurry from the mill jar, it was wet screened through 400 mesh, dried at 93 degrees Centigrade under a nitrogen atmosphere, and Fitzmilled through a 40 mesh ^ screen.

Insert blanks were pressed and then sintered at 1468 degrees Centigrade for 30 minutes under a 35 micron vacuum allowing volatization of a majority of the hydrogen in the ^ samples. During sintering, the samples were supported on a NbC powder parting agent.

The sintered sample had A-2 porosity in the enriched zone 30 and A-4 porosity in the nonenriched bulk of the sample. The ~ ^ ~ 1 -jjg- pATEIVTOPP^T "2 JUL 1986 20000/ sample had an average Rockwell "A" hardness of 90.; a zone of solid solution depletion 9.8 microns thick; and a coercive force, He, of 150 oersteds.

EXAMPLE NO. 15 A batch of material having a composition equivalent to the Example 9 batch was blended, milled and pressed into insert blanks. The blanks were then sintered, ground, heat treated and ground (flank faces only) in substantial accordance with the procedures used in Example 9. However, a 69 degrees Centigrade/ 10 hour cooling rate was used in the final heat treatment.

An insert was analyzed by EDX line scan analysis at various distances from the insert rake surfaces. The results of this analysis is shown in the Figure 2 graph. It indicates the existence of a cobalt enriched layer extending inwardly from the rake surfaces to a depth of approximately 25 microns followed by a layer of material partially depleted in cobalt extending inwardly to approximately 90 microns from the rake surfaces. While not shown in the Figure 2 graph, partial solid solution depletion has been found in the cobalt enriched layer 20 and solid solution enrichment has been found in the partially depleted cobalt layer.

The two horizontal lines indicate the typical scatter in analysis of the bulk material around the nominal blend chemistry.

The preceding description and detailed examples have been provided to illustrate some of the possible alloys, products, processes and uses that are within the scope of this invention as defined by the following claims. -2JUL06 200007

Claims (2)

WHAT WE CLAIM IS:

1. A cemented carbide body comprising: a first carbide; a metallic binder; a solid solution of said first carbide with a second carbide whose free energy of formation is more negative than that of said first carbide at a temperature above the binder melting point; the amount of said first carbide being greater than the amount of said second carbide; and a layer of binder enrichment near a peripheral surface of said body; said body having substantially A to B type porosity throughout.

2. A cemented carbide'body comprising: a first carbide; a metallic binder; a transition metal present as a second carbide whose free energy of formation is more negative than that of said first carbide at a temperature above the binder melting point; wherein the amount of said first carbide is greater than that of said second carbide; said second carbide being in a solid solution with said first carbide; and a layer of binder-enrichment near a peripheral surface of said body; said body having substantially A to B type porosity throughout.

3. A cemented carbide body according to Claim 1 or Claim 2 further comprising: nitrogen present as a carbonitride in a solid solution Of said first and second carbide. k. A cemented carbide body comprising: tungsten carbide; a metallic binder; a solid solution carbonitride having tungsten and a metal selected from the group consisting of the Group IVB and VB transition metals; and a layer near a peripheral surface of said body being binder-enriched and at least partially depleted of said solid solution carbonitride.

5. A cemented carbide body according to Claim 4 wherein said solid solution carbonitride is a tungsten titanium carbonitride. 37 J4.Z, f'Af ; c r,'- ;■ 17 Julm .6 2OOO0J

6. A cemented carbide body comprising: at least 70 w/o tungsten carbide; a metallic binder; a metal carbide selected from the group consisting of the Group IVB and VB transition metal carbides; said metal carbide being present in an amount less than the amount of tungsten carbide; said metal carbide having a free energy of formation more negative than that of said tungsten carbide at a temperature above the binder melting point; said body having substantially A to B type porosity throughout said body; said metal carbide combined with said tungsten carbide forming a solid solution carbide; and a binder-enriched layer of at least partially solid solution carbide depleted material near a peripheral surface of said body.

7. A cemented carbide body according to any one of Claims 4, 5 or 6, wherein said binder is selected from the group consisting of cobalt, nickel, iron and their alloys.

8. A cemented carbide body comprising: at least 70 w/o tungsten carbide; a cobalt binder; a metal carbide selected from the group consisting of the Group IVB and VB transition metal carbides; said metal carbide having a free energy of formation more negative than that of tungsten carbide at a temperature above the binder melting point; said metal carbide combined with said tungsten carbide forming a solid solution carbide; a binder-enriched layer near a peripheral surface of said body; said layer being at least partially solid solution depleted; and wherein said cobalt binder has an overall magnetic saturation value of less than 158 gauss-cm3 /gm cobalt.

9. A cemented carbide body according to Claim 8 wherein said cobalt binder has an overall magnetic saturation value of 145 to 157 gauss-cm3/gm cobalt. I N^L PATENT Of " 38 " -2jul RECEIVE 200007

10. A cemented carbide body according to claim 8 wherein said cobalt binder has an overall magnetic saturation value of less than 125 gauss-cm3/gm cobalt.

11. A cemented carbide body comprising: at least 70 w/o tungsten carbide; cobalt; a second metal carbide selected from the group consisting of the Group IVB and VB transition metal carbides; said second metal carbide having a free energy of formation more negative than that of said tungsten carbide at a temperature above the binder melting point; and a layer of cobalt enrichment near a peripheral surface of said body; said body having substantially A to B type porosity throughout.

12. The cemented carbide body according to claim 11 wherein the level of said second metal carbide in said layer of cobalt enrichment is at least parially depleted.

13. A cemented carbide body according to Claim 11 or 12 wherein said second metal carbide is selected from the group consisting of titanuim, hafnium, tantalum and niobium.

14. A cemented carbide body according to Claim; 11 or 12 wherein said second metal carbide is present at the level of 0.5 - 2.0 weight percent.

15. A cemented carbide body according to Claim 13 wherein said second metal carbide is present at the level of 0.5 - 2.0 weight percent.

16. A cemented carbide body according to claim 11 or 12 wherein the cobalt-enriched layer has a cobalt content at said peripheral surface equal to 1.5 to 3 times the mean cobalt content of the body as measured by energy dispersive x-ray analysis. 39 200007

17. A cemented carbide body according to Claim 11 wherein the cobalt-enriched layer extends inwardly from said peripheral surface of said body to a minimum depth of 6 microns.

18. A cemented carbide body according to claim 16 wherein the cobalt-enriched layer extends inwardly from said peripheral surface of said body to a minimum depth of 6 microns.

19. A cemented carbide body according to claim 17 wherein the cobalt-enriched layer extends inwardly from said peripheral surface of said body to a depth of 12 to 50 microns.

20. A cemented carbide body according to claim 18 wherein the cobalt-enriched layer extends inwardly from said peripheral surface of said body to a depth of 12 to 50 microns.

21. A cemented carbide body according to any one of claims 1, 2, 11 or 19 wherein said peripheral surface of said body comprises a rake face; said rake face joined to a flank face; a cutting edge located at the juncture of said rake and flank faces; and wherein said enriched layer extends inwardly from said rake face.

22. A cemented carbide body according to claim 21 further comprising a hard dense refractory coating bonded to said peripheral surface of said body, and said coating having one or more layers.

23. The cemented carbide body according to claim 22 wherein the material comprising the or each layer of said coating is selected from the group consisting of the carbides, nitrides, borides and carbonitrides of titanium, zirconium, hafnium, 200007 niobium, tantalum and vanadium,and the oxide and oxynitride of aluminium.

24. The cemented carbide body according to claim 22 wherein I said coating comprises a layer of titanium carbide.

25. The cemented carbide body according to claim 22 wherein said coating comprises a layer of titanium carbonitride.

26. The cemented carbide body according to claim 22 wherein said coating comprises a layer of titanium carbide and a layer of titanium nitride.

27. The cemented carbide body according to claim 26 wherein said coating further comprises a layer of titanium carbonitride.

28. The cemented carbide body according to claim 22 wherein said coating comprises a layer of aluminium oxide.

29. The cemented carbide body according to claim 28 wherein said coating further comprises a layer of titanium carbide. any one of

30. A cemented carbide body according to/claims 1, 2, 4, 5 and 8, further comprising a hard dense refractory coating bonded to said peripheral surface of said body, and said coating having one or morp layers.

31. The product prepared by the process of forming a binder- enriched layer near a peripheral surface of a cemented carbide body, in which said process comprises: obtaining a compact having a substantially uniform distribution of: a first carbide, a metallic binder and a chemical agent selected from the group MX PA'i :q:r - 41 - 1 .'•m •or- consisting of the nitrides and carbonitrides of transition metals whose carbides have a free energy of formation more negative than that of said first carbide at a temperature above the binder melting point; densifying said compact; and transforming, at least partially, said chemical agent to a second carbide by a heat treatment, the amount of said first carbide being greater than the amount of said second carbide; said heat treatment increasing binder content towards said peripheral surface to form said enriched layer.

32. The product prepared by the process of forming a binder-enriched layer near a peripheral surface of a cemented carbide body, in which said process comprises: obtaining a compact having a substantially uniform distribution of: tungsten carbide, a metallic binder and a chemical agent in ah amount less than that of the tungsten carbide; the chemical agent being selected from the group consisting of the metals, alloys, hydrides, nitrides and carbonitrides of transition metals whose carbides have a free energy of formation more negative than that of tungsten carbide at a temperature above the binder melting point; densifying said compact; and transforming, at least partially, said chemical agent to a second carbide by a heat treatment; said heat treatment increasing the binder metal content toward said peripheral surface to form said enriched layer.

33. The product prepared by the process of forming a binder-enriched layer near a peripheral surface of a substantially A to B type porosity cemented carbide body, in which said process comprises; milling and blending a first carbide powder, a metallic binder powder and a chemical agent powder selected from the group consisting of metals, alloys, hydrides, nitrides and carbonitrides of Group IVB and VB transition metals whose carbides have a free energy of formation more negative than that i t-'ATENT OFFICE I - — " 42 " ' -2JUU986 £00007 said first carbide at a temperature above the binder melting point; pressing a compact utilising said powders, sintering said compact at a temperature above the binder melting temperature so as to transform, at least partially, the chemical agent to a second carbide in the layer to be binder enriched; the amount of said first carbide being greater than the amount of said second carbide; removing said binder enriched layer in selected areas of said product; and resintering said compact at a temperature above the binder melting temperature so as to transform, at least partially, the chemical agent to a carbide in the layer near the peripheral surface of the selected area of the product.

34. The product of claims 31 or 32 wherein said process further comprises the step of: removing said binder-enriched layer in selected areas of part of said product.

35. The product of claim 33 or 34 wherein said process further comprises the step of: depositing on said peripheral surface of the product an adherent hard wear resistant refractory coating having one or more layers.

36. The product of claim 35 wherein the material comprising each of said layers is selected from the group consisting of the carbides, nitrides and carbonitrides of titanium, zirconium, hafnium, niobium, tantalum and vanadium, and the oxide and oxynitride of aluminium.

37. The product of claim 33 wherein said first carbide powder comprises tungsten carbide.

38. The product of claim 32 wherein said chemical agent comprises a carbide selected from the group consisting of the Group IVB and VB transition metal carbides. ii.z. PATENT o; ^ ■2 JUL 1986 43 - RECSlVgp~~ | § 200007

39. The product according to claim 37 wherein said metallic binder is selected from the group consisting of cobalt, nickel, and iron and their alloys.

40. A process for forming a binder-enriched layer near a peripheral surface of a cemented carbide body, said process comprising the steps of: obtaining a compact having a substantially uniform distribution of a first carbide, a metallic binder and a chemical agent selected from the group consisting of the nitrides and carbonitrides of transition metals whose carbides have a free energy of formation more negative than said first carbide at a temperature above the binder melting point; P-L.Fi.aA. . , e densifying said compact; .transforming, at least partially, said T lC / 7,^84 chemical agent to a second carbide in solid solution with said first carbide by a heat treatment, so as to increase the binder content near said peripheral surface; the amount of said first carbide being greater than the amount of said second carbide.

41. A process for forming a cobalt binder-enriched layer near a peripheral surface of a substantially A type porosity cemented carbide body, said process comprising the steps of: milling and blending powders comprising tungsten carbide, cobalt and a metal compound selected from the group consisting of nitrides and carbonitrides of Group IVB and VB transition metals whose carbides have a free energy of formation more negative than than of said first carbide at a temperature above the binder melting point; pressing a compact utilizing said powders, and sintering said compact at a temperature above the melting temperature of said binder so as to transform, at least partially, the metal compound to a second metal carbide in the layer to be binder enriched; the amount of said first carbide being greater than the amount of said second carbide.

42. The process according to claims 40 or 41 further comprising | K.2.PATEWT OFFICE 44 !, ::; 2000&7 the step of: removing said binder enriched layer in selected areas of part of said peripheral surface.

43. The process according to claim 42 further including resintering the compact at a temperature above the melting temperature of the binder so as to transform, at least partially, the metal compound to a metal carbide in the layer to be binder-enriched near the peripheral surface of the selected area of the product.

44. The process according to claims 40 or 41 further comprising the step of: depositing on said peripheral surface an adherent hard wear resistant refractory coating having one or more layers wherein the material comprising each of said layers is selected from the group consisting of the carbides, nitrides, borides and carbonitrides of titanium, zirconium, hafnium, niobium, tantalum and vanadium, and the oxide and the oxynitride of aluminium.

45. The process according to claim 41 wherein said powders further comprise a second carbide powder selected from the group consisting of the Group IVB and VB metal carbides and their solid solutions.

46. The process according to claim 40 wherein said densified compact further comprises a substantially uniform distribution of a second carbide powder selected from the group consisting of the Group IVB and VB metal carbides and their solid solutions.

47. The process according to claim 41 further comprising the step of at least partially volatilizing an element selected from the group consisting of hydrogen and nitrogen during the sintering step. - 45 tr —LATENT OP I'- ax " 2 JUL iyo6 Receiver 200007

48. The process according to claim 41 further comprising the addition of free carbon during milling and blending in an amount sufficient to produce a tungsten lean cobalt binder in the sintered compact.

49. A cemented carbide body comprising: a first carbide; a metallic binder; a solid solution of said first carbide with a second carbide whose free energy of formation is more negative than that of said first carbide at a temperature above the binder melting point, the amount of said first carbide being greater than the amount of said second carbide; a layer of binder enrichment near the peripheral surface of said body; and a layer of partial binder-depletion beneath and separate from a peripheral surface of said body.

50. A cemented carbide body according to claim 49 wherein the binder content in the binder depleted layer is below the mean binder content for the body.

51. A cemented carbide body according to claim 49 wherein said first carbide comprises tungsten carbide; said metallic binder comprises cobalt; and said body further comprises a layer of partial cobalt depletion beneath said layer of cobalt enrichment.

52. A cemented carbide body according to claim 49 wherein said first carbide comprises tungsten carbide; said metallic binder comprises cobalt; said second carbide in said solution is selected from the group consisting of the carbides of the Group IVB and VB elements; and a binder-enriched layer at least partially depleted in said solid solution between said peripheral surface 2QQQ0f cobalt; a solid solution of tungsten carbide with a second carbide selected from the group consisting of the carbides of the Group IVB and VB elements, whose free energy of formation is more negative than that of said tungsten carbide at a temperature above the binder melting point; the amount of said second carbide being less than the amount of tungsten carbide; a first layer enriched in cobalt at least partially depleted of said solid solution; said layer being near a peripheral surface of said body; and a second layer partially depleted of cobalt and enriched in said solid solution, said second layer being beneath said first layer.

54. A cemented carbide body according to any one of claims 49-53, further comprising: a hard dense refractory coating bonded to said peripheral surface of said body; and said coating having one or more layers.

55. A cemented carbide body according to claim 54 wherein said coating comprises a layer of titanium carbide.

56. A cemented carbide body according to claim 54 wherein said coating comprises a layer of titanium carbonitride.

57. A cemented carbide body according to claim 54 wherein said coating comprises a layer of titanium nitride.

58. A cemented carbide body according to claim 54 wherein said coating comprises a layer of aluminium oxide.

59. A cemented carbide body as claimed in claim 1 and substantially as hereinbefore described with reference to any 20000"? one of Examples 1-15. *■;60. A process for forming a binder-enriched layer near a peripheral surface of a cemented carbide body as claimed in claim 40 and substantially as hereinbefore described with reference to any one of Examples 1-15.;KENNAMETAL INC;by their authorised agents;P.L. BERRY & ASSOCIATES;P K;».Z. PATENT ( •2JULm;-I't&ZIV* D - 48 -