JPH01201436A - Hard alloy - Google Patents

Abstract

PURPOSE: To produce a sintered hard alloy having excellent wear resistance and toughness by forming a thickened layer of a binder on a front layer part at the time of mixing hard WC, powder of carbide of specific metals and Co, etc., as the binder at the time of sintering and sintering the mixture.

CONSTITUTION: An insert 2 is formed by mixing 70 to 90.5wt.% WC in a powder form, 5 to 20wt.% hard carbide of the transition metals selected from Ti, Hf, Ta and Nb of group IVB, group VB of periodic table and Fe group elements, such as Co, Ni and Fe and more particularly Co as the binder at the time of sintering the hard powders at a ratio of 5 to 10wt.%, mixing suitable ratios of paraffin, surfactant, etc., as lubricants with the mixture and molding the mixture. This insert is sintered at, for example, 1496°C. The WC and the carbide of the transition metals form a solid soln. carbide. The sintered hard alloy material as the machining insert having the thickened layer 14 of the binder at the peripheral edges and the decreased layer 16 of the binder thereunder and having the coating layer combined with both characteristics of the wear resistance and the toughness is developed.

COPYRIGHT: (C)1989,JPO

Description

[Detailed description of the invention]

The present invention relates to the technical field of sintered carbide alloy parts using cobalt, nickel, iron or alloys thereof as binder materials, and to the production of these parts. More specifically, the present invention has a hard refractory oxide on the surface,
The present invention relates to metal cutting inserts of sintered carbide alloys with nitride, boride or carbide coatings. In the past, various hard refractory coatings have been applied to the surface of sintered carbide cutting inserts to improve their cutting edge resistance and increase their cutting life. No. 4,035,541 (assigned to the applicant), No. 3,564,683.
No. 3,616,506, No. 3,882゜581, No. 3,914,473, No. 3,736,107,
m No. 3,967.035, $3,955,038, No. 3.836,392 and Reissue No. 29,420
Please refer to the issue. However, these refractory coatings can reduce the toughness of the cemented carbide insert to varying degrees. The extent of this degradation depends, at least in part, on the structure and composition of the coating and the method used for its application. Therefore, although refractory coatings improved the wear resistance of bullion cutting inserts, they did not reduce the susceptibility of the cutting edge to failure due to chipping or breakage, especially in intermittent cutting operations. Previous efforts to improve toughness or cutting edge strength in coated cutting inserts have focused on creating a cobalt enriched layer extending inwardly from the substrate-coating interface. It has been found that cobalt enrichment of the surface layer of the C-chamber length and porosity substrate is achieved during the full sintering cycle. These cobalt-enriched N-enriched zones were characterized by Ag porosity, and the bulk of the substrate had C-type porosity; It existed to some extent. Cobalt enrichment increases in part because it is well known that increasing cobalt content increases the toughness or impact resistance of cemented carbide alloys. however,
The level of III thickening that is produced is difficult to achieve in a C2 slotted substrate. Typically a cobalt and carbon coating was formed on the surface of the substrate. This cobalt and carbon coating was removed prior to applying a refractory material onto the substrate to obtain an adhesive bond between the coating substrates. in some cases,
The level of cobalt enrichment in the subsurface layer of the substrate was so high that flank JSl wear was adversely affected. As a result, sometimes the cobalt@thickened layer on the flank surface of the substrate is ground away, and the cobalt enrichment only on the rake surface.
lleL and oTl of C-type porous material on the flank surface.
l! I left my sexuality behind. Compared to Type A or B porous substrates, Type C porous substrates are less chemically homogeneous than Type I porous substrates. As a result, the formation of an ether phase (a hard and brittle phase that affects toughness) at the interface between the coating and the substrate becomes difficult, reducing the coating's 15M properties and creating a non-uniform coating. Growth increases. As a definition, in a flash-setting carbide alloy, tl! The observed porosity is ASTλ1 (American 5ociety f
or 'l'est+ngMate r i a l
a) Classified into one of the following three recommended categories. Type A for pore sizes smaller than 10 microns. Type B for pore sizes between 10 and 40 microns. ! Type C for irregular pores caused by the presence of A-core inclusions These inclusions are pulled out of the sample during metallographic investigation, leaving behind mI irregular pores. In addition to the above parameters, a number from 1 to 61 can be applied to the observed porosity to indicate the degree or degree of porosity observed. The method for making these classifications is
New York. Published by MacMillan (1960
), Dr. D. Schwarzkopf & Dr. R0kje
Cemented Carbides by Cemented Carbides, 1
Heading on pages 16-120. Flash-setting carbide alloys have a component strength of 1 depending on their binder carbon and tungsten content. The tungsten carbide-cobalt alloy that splits the supercharcoal wood is C8! It is characterized by an i-porosity, which, as mentioned above, is a real carbon inclusion. t & 3Pt
* Tungsten carbide-cobalt alloys, where the fit is low and the cobalt is saturated with tungsten, are characterized by the presence of eta, M, IC or M, C (M stands for cobalt and tungsten).cH porosity At the intersection of both tungsten and etherification, there is a region of intermediate binder alloy compositions that contain significant levels of dissolved tungsten and carbon, but where free carbon tubes or etaification are absent. - The tungsten level present in a cobalt alloy can also be characterized by the magnetic saturation of the binder alloy. Thus, the magnetic saturation of a cobalt alloy is a function of its composition. Carbon-saturated cobalt has a magnetic saturation of 158 gauss - o1/hn has been reported to have a magnetic saturation of cobalt, while 125 gau
Mountain air saturation below S 3-ct11/ p rrh cobalt indicates the presence of etaification. Accordingly, one object of the invention is to provide an easily controllable and inexpensive method for producing a binder-enriched layer near the surface of a sintered carbide alloy body. Another object of the present invention is to provide a carbide alloy body with a binder thickening 111 near its surface and essentially all pores throughout the body being of type A or type B. It is. A further object of the invention is to provide a sintered carbide alloy body having carbon levels ranging from C-type porosity to etherification, with an M mixture daughter thickening layer near its porosity. Still another object of the present invention is to combine the above-mentioned sintered carbide alloy body according to the present invention with a flame-retardant ink to provide a combination of pot wear resistance and high potability. It is an object of the present invention to provide a cutting insert having a coating that provides a cutting insert with a coating that
It will become clearer if you read more. It has been found that a binder-H layer is formed near the JhJ plane of a sintered carbide alloy body by using the method described in C.F. according to the present invention. a first carbide powder, a binder powder, and a metal region, suture, hydride of a transition element, the carbide of which has a more negative free energy of formation than the first carbide near the binder melting point; selected from the group of nitrides and carbonaceous compounds (
With Hiji drug powder? : Grinding and dispersing; then sintering or subsequently heat treating the compact of the compounded material to convert the chemical mulberry agent at least partially into its carbide. In accordance with the present invention, this method is preferably used to produce a binder-enriched layer near the surface of a sintered carbide alloy body that exhibits only a mucus or B-type porosity throughout. Concentration also occurs from Eta formation to C chamber long hole K.
It can also be achieved in sintered carbide alloy bodies with carbon levels ranging up to 1. It has been found that the sintered carbide alloy body according to the invention has a partially binder-depleted layer below the binder-flotation layer. Preferably, the first carbide is tungsten carbide. Preferably the binder alloy is cobalt, nickel, iron or alloys thereof, most preferably cobalt. Preferably, the chemical agent is selected from hydrides, nitrides and carbon nitrides of Group IVB and VB elements, preferably in an effective small amount, most preferably 0.5 of the powder charge.
An amount of ~21% by weight is added. Most preferably, the chemical agent is titanium nitride or titanium carbonitride. The sintered carbide alloy body according to the present invention also has its R4tI!
It has been found that near the Li the solid solution carbides shoulder an at least partially depleted layer. The sintered carbide alloy body according to the present invention also reduces the solid solution!
It has been found that 'FK solid solution carbides give a blue color to the enriched layer. The sintered carbide alloy body according to the present invention preferably has a cutting edge at the junction between the ray Φ surface and the flank surface and a hard, compact, refractory coating that is closely bonded to these surfaces. The binder thickening layer is removed from the flank surface during application of the coating. The refractory coating preferably consists of one or more layers of metal oxides, carbides, nitrides, borides or carbon nitrides. The merits of the invention will become more apparent upon reference to the above detailed description in conjunction with the accompanying drawings. The object of the present invention is to produce a sintered carbide alloy compact containing an element having a good odor temperature close to or higher than the melting point of the binder. Achieved by heat treatment. When applied to cutting inserts, this elemental or chemical agent may be selected from group IVB and VB transition metals, their alloys, nitrides, carbon nitrides and hydrides. By adding sintered tungsten/carbon or carbon nitride to the powder charge, the binder is consistently thickened throughout the heat treatment at temperatures above the melting point of the binder alloy, and Usually I! It has been found that the i1 solution carbide is at least partially reduced. During sintering, these Group IVB and VHg fillers react with carbon to form carbides or carbon nitrides. These carbides or R-compounds exist partially or wholly as a find solution with tungsten carbide and other carbides present. The level of th1 elements present in the final sintered carbide is typically reduced from the level of th1 elements added as nitrides or carbonitrides. However, these additives are unstable at high temperatures above the melting point of the binder alloy, and if the sintering atmosphere contains nitrogen at a concentration lower than its vapor pressure. , causing at least partial evaporation of nitrogen from the sample. If the chemical is added as a monomer, alloy, or hydride, it is also converted to a cubic carbide, typically in solid solution with tungsten carbide and other carbides present. The hydrogen in the added hydride is evaporated during sintering. Tantalum, titanium, niobium, hafnium metals, hydrides and carbon nitrides used alone or in combination;
Cobalt enrichment can be promoted through sintering or custom heat treatment of tungsten carbide-cobalt based alloys with a wide range of carbons. Sokei Shiehabo 15o ILX
It has been found that the shu kimono that becomes 1 is used. Zirconium and vanadium metals, nitrides, IR hydrides and hydrides are also believed to be suitable for this purpose. In A and B chamber long hole alloys and in carbon-deficient alloys containing eta phases, cobalt enrichment occurs without peripheral cobalt or carbon capping, thus; Removal of cobalt and carbon weekly from carbide alloy surfaces Mtq Tungsten carbide ~ approximately 0.5-2% of titanium in cobalt-based alloys especially titanium nitride or titanium carbon nitride Additives are preferred. The titanium compound is not completely stable during annealing and causes at least partial 7A firing of the kettle, adding half a mole of carbon for every mole of nitrogen in the tungsten diluted cobalt. It is preferred to maintain the required carbon levels in the binder alloy. Cobalt enrichment via heat treatment of tungsten carbide-cobalt based alloys is easier when the alloy has a tungsten dilute cobalt binder. It has been found that by adding titanium nitride to the tungsten carbide-cobalt jh powder mixture with the necessary carbon, a saturation of 145 to 1571 + B, which is difficult to achieve in the past, can be achieved. Formation of Baltic mixture alloy is promoted.145-
A cobalt binder alloy with 157gauss--re'h cobalt pores is preferred, but a tungsten-saturated cobalt binder alloy (125galJls-c1L/
9n%:1 part) may also be enriched. A cobalt enriched layer thicker than 6 microns will cause refractory failure fj
It has been found that this results in a significant improvement in the cutting edge fineness of the sintered carbide alloy insert. Although deep cobalt enrichments as low as 125 microns have been achieved, cobalt enrichments as low as 12 to 50 microns are preferred for coated cut AIJ inserts. Cobalt content without cobalt enrichment in refractory M5 inserts is 150-300% of the average cobalt content as measured on the surface by energy dispersive Cedar X edge analysis
It is also preferred that Binder enrichment can be applied to all tungsten carbide-binder-cubic carbides (i.e., tantalum, niobium, titanium, vanadium,
It is believed that this should occur in octunium, zirconium) alloys. Those alloys containing 3JJL % or more of binder should be enriched using the method of the present invention. However, when applied to cutting inserts, the binder content is between 5 and tOX% cobalt and the total cubic carbide content is 20! It is preferable that the amount is less than or equal to %. Cobalt is a preferred binder, but nickel, iron, and alloys between each other and with cobalt may be substituted for cobalt. Other binders containing nickel or iron should also be used. 2. Thicken the binder! The sintering and heat treatment temperatures used to achieve the desired results are typical liquid phase sintering temperatures. For cobalt-based alloys, these temperatures range from 1285 to 1540°C.
It is. The sintering cycle should be less than 15 minutes in the Rr isothermal run. The results can be further optimized by using a limited cooling rate from the heat treatment temperature to below the binder coalescence point. Yes, these cold thorns are δ-W℃/h
, preferably 40-b. Most preferably, the heat treatment cycle for the cutting insert substrate shouldering the cobalt binder is 1370-1500°C for 30-150 minutes, followed by cooling to 1200°C at a rate of 40-70'c/h. Got 2 goals. The pressure level during heat treatment is m”LO-”tor
r to the high pressures typically used in hot equalization pressing. The preferred pressure level is 0.1-0.15
It is torr. If a silica or nitride addition is utilized, the vapor pressure of the nitrogen in the fired MW atmosphere is preferably greater than or equal to its normal pressure, thereby reducing the nitrogen from the substrate in °C. allow evaporation. Although the initial thickening occurs during sintering, the grinding step in the metal cutting insert production process may remove the thickening zone. In this case, the binding heat treatment f! according to the above parameters.
Using this method, a new 1-thickened zone can be developed on the 74th surface. A binder-enriched substrate to be used in a coated cutting insert can have a binder-enriched layer on both the rake face and the flank face. However, depending on the type of insert, the binder enriched layer on the flank surface is sometimes removed, although this is not necessary in order to obtain optimum performance '1 in all cases. The binder-thickened substrate can be coated using refractory coating techniques well known to those skilled in the art. The fire-resistant coating applied is of Group IVB and '
/ one or more 1- consisting of a material selected from carbides, nitrides, boride layers and carbon compounds of element B, and oxides and FR nitrides of aluminum;
However, the combination of good cutting edge strength and flank wear resistance is achieved by combining a substrate with a binder-enriched layer according to the invention and a coating of aluminum oxide or titanium nitride on an inner layer of titanium carbide. It is bonded to the outer layer. achieved by combining a coating of aluminum oxide on an inner layer of titanium carbide bonded to an intermediate layer of titanium carbon nitride or a coating of aluminum oxide on a titanium oxide bonded to an inner layer of titanium carbide. The scales are dying. A sintered carbide alloy body with a binder enriched layer according to the invention in combination with a titanium carbide/aluminum oxide coating is most preferred. In this case, the coating should have a total rupture thickness of 5 to 8 microns. Referring now to Figure 81!1, an embodiment of a coated metal cutting insert 2 according to the invention is schematically illustrated. The insert 2 is composed of a substrate or a sintered carbide alloy body 12. The substrate I2 is composed of a binder enriched layer 1.
4 and the bulk of the substrate 12 having a chemical composition centrally equal to that of the powder formulation.
and a binder cryolayer 16 on I8. A binder enrichment layer 14 is present on the rake face 4 of the sintered carbide alloy body and has been ground away from the flank face 6. An inner VC binder reducing seam 716 of the binder enriched layer 14 is disposed.

[There is. This binder depletion zone 16 has been found to develop with a binder enriched layer when a sintered carbide alloy body is fabricated according to the method of the present invention. The binder-reduced zone 16 is partially depleted of binder but enriched with solute carbides. The binder thickening 1414 partially reduces solute carbides.
In the circular direction of the 0 amount mixture reduction zone,
There are 8. A cutting edge 8 is formed at the joint between the rake surface 4 and the flank surface 6.
ing. Although the illustrated cutting edge 8 is honed, the honing of the cutting edge is not necessarily necessary for the application of the cutting edge of the present invention. As seen in FIG. 1, the binder thickening J-14 extends into this cutting edge area and preferably the honing finish is applied to most, if not all, of the cutting edge 8. are in contact with each other. A binder reduction seam 716 extends at the flank surface 61 directly below the cutting edge 8 . A refractory coating 10 is thermally bonded to the circumferential surface of the sintered carbide alloy body 120. These and other features of the present invention are described in the following embodiments. :'4 It will become even clearer if you look at it.夷1 lafti1 At the following locations and proportions, a mixture containing 7000 grams of powder is mixed with paraffin, surfactant, solvent and cobalt-bonded tungsten carbide cyclolide.
The mixture was milled and blended for 6 hours. 2 ”10 Parafuy (5unoco 3
420) (Sun Oil Co,) 2.5
T? lJ (perchlorethylene 14k
Surfactant (Ethomeen 5-15)
(Armour 1nduslreal Chemical
al Co, ) + 1 - correct amount of added metal % 15.11 + 1X 15.1 ff1ffiX 5.8
Cubic insert blanks with dimensions of ~6.1121 and weight of 11.6 were pill-pressed using a force of 8200 kjl. These inserts were sintered at 1496 °C for (1) min. The inserts were then cooled under ambient furnace conditions.
3.26 @IX 13.26111X 4.95 s
It has a dimension of n. These inserts are then 5NQ433 as shown in t.
Processed to grind dimensions. (This identification #i is Ameri
can 8 standards as5 association
It is based on the insert identification system developed by Fukagawa and commonly used in the cutting tool industry. The international title is 5NGN 120412. )1,
The Ia part and bottom (rake surface) of the insert were ground to a thickness of 4.751mm! I was U-ed. The inserts were heat treated at 1427° C. in a 100 micron vacuum, cooled at a rate of 56° C./h cr) to 1204° C., and then cooled under ambient furnace conditions. 3. The periphery (flank surface) was ground to produce a radius of 12.70 mm, and the cutting edge was honed to a radius of curvature of 0.064111 m. A titanium carbide/titanium carbon nitride/titanium goldide coating was then applied to the grinding insert using the CVD technique described above in the application sequence described above. Table 1 3, TIN 9821025'C-1atm T
icA4+2H, +i, -+TIN+4HC/. Inserts without TIN and its associated carbon additives were made from the same powder formulation along with the inserts described above. The ξ-crostructure deme obtained from the coated insert is as follows. ~ Example 1 Example 1 Al (enriched) -22,9 microns Cobalt enriched zone thickness None (V-
-22.9 microns Solid solution reduction zone thickness None (V-
) UnoTie/substrate interface eta phase thickness 4.
6 microns 3.3 microns Coach Eve thickness Tic 5.6 microns
5.0 micron 'l'jcN
2.3 micron 3.9 micron TiN
1.0 microns 1.0 microns Example 2 Utilizing the formulation of Example 1, bill press inserts were made with and without °C TiN and its associated carbon additives according to Example 1. These inserts were sintered at 6 micron vacuum F 1496° C. for minutes and then cooled under ambient furnace conditions. These inserts were then honed (0,064 radius of curvature) and
Then, according to the technique shown in Table 1,
M-N CVD Co., Ltd. was m-an. It should be noted that in this example, the cobalt enriched layer was present on both the flank and rake surfaces. These coated inserts were evaluated practically and the following results were obtained. Example 2! jl! 9I12 No TIN TIN N Riporosity Person-1111 edge
In-2 enriched zone & -3 center In-4 mostly cobalt enriched zone thickness None -22,
9 micron solid solution reduction zone thickness None
Partial and intermittent - 21 microns T song/substrate interface eta phase thickness - 5,9 microns
3.3 micron coating thickness Tic 2.0 micron
1.3 micron TiC 81.7 micron 1.0 micron TiN 8.8 micron 7.9 micron Example 3 A mixture consisting of the following minerals was milled in a cylindrical mill with a surfactant, a fugitive binder, a solvent and a cycloid of 114k). It was charged to 5.98”10 TaC2,990jhs2.6
wloTiN 1,300a
n6.04w10co3,020k Corp product n 115 IhI&so,
ooo b This powder charge has 6.25 M It% during charging
Balanced to produce total carbon. The mixture was blended and ground by 90.261 revolutions to 0.90
A micron average grain IX was obtained. The blend was then wet screened, dried and ground in a non-marine kil. The compacts were pressed and sintered at 1454°C and then cooled under ambient furnace conditions. This treatment yields a magnetic saturation of 117=121 gausl-a4/h cobalt (ie, the measurement included mostly material and binder enriched material). A sintered blank was produced. Microstructural evaluation of the sintered blank shows that the eta phase is present throughout the blank and the porosity is A-
2 to B-3, the cobalt enriched zone thickness was approximately 26.9 microns, and the solid solution reduced zone thickness was approximately 31.4 microns. Performance 4 A 19011 m inside diameter, 194 inch long mill jar lined with tungsten carbide-cobalt alloy was added with the following materials. Furthermore, 17.3”1 of 3,
2 Ill tungsten carbide-cobalt cycloid was sewn into the jar. These @ families were milled and blended by rotating a mill jar about its cylindrical axis at rapid speeds of revolutions per minute (i.e., 367,200 revolutions) for 72 hours. Charge composition 283k (4,l ff1lX)
'l”ac205k (3,01% by weight)
NbClO3k (1, Sfl %)
TiN7.91 Jim (0,1 side 1g)
c381b (5.5mfa%)
・5946k (85,8m1
X) to V'::105 kn 5unoc
o 342014 pI%gthomeen 8-1
52500 艷Perchlorethylene This mixture was balanced to produce a 2M*% W-μs mass XQ) #i mixture alloy. After milling and compounding, the slurry was wet sieved to remove opener particles and contaminants, dried at 93°C under an IAX atmosphere, and then subjected to a
The agglomerates were milled in a 2 J% mass mill in a Fitxm111. Using this powder, compacts are pressed and then 14
It was sintered at 54° C. for minutes and then cooled under ambient conditions. The yA part and the seat part (the rake surface 2 of the insert were then ground to the final thickness of 'R'.
Heat treatment was also carried out at 1427° C. under micron vacuum. After holding at temperature for 0 minutes, the inserts were cooled on a 1204°C oven at 4°C per hour and then furnace cooled under ambient conditions. 8th side (or flank side) is followed by 12.7011
Ground to 1 square n and insert cutting edge is 0.064 u
Honed finish to radius of curvature. These treatments result in an insert substrate in which only the rake surface has a conobelt thickening zone and a solid solution depletion zone, these zones being ground away from the flank surface. The insert is then loaded into a coating reactor,
A thin layer of titanium carbide was coated using the chemical vapor deposition technique described below. The hot zone containing the inserts was initially warmed to 900°C from room temperature. The pressure inside the reactor is 1
The pressure was maintained slightly below atmospheric pressure. The hot zone was then heated from 900°C to 982°C. During this second heating stage, the pressure inside the reactor was maintained at 180 torr, and a mixture of titanium tetrachloride and hydrogen and pure hydrogen gas were introduced into the reactor at a rate of 15 liters per minute and 3317 torr per minute, respectively. It was done. A mixture of titanium tetrachloride and hydrogen scum was obtained by passing hydrogen gas through an evaporator that held titanium tetrachloride at a temperature of 47°C. 982
℃ and then methane gas was again allowed to enter the reactor at a flow rate of 2.5 liters per minute. The pressure inside the reactor was reduced to 140 torr. Under these conditions,
Titanium tetrachloride reacts with methane in the presence of hydrogen to form titanium carbide on the heating insert surface. These conditions were maintained for 75 minutes after which the flow of titanium tetrachloride, hydrogen and methane was stopped. The reactor was then allowed to cool while argon was passed through the reactor at a rate of 1.53 liters per minute at just less than 1 atmosphere. Inspection of the microstructure in the R-end insert was performed inwardly at 22.
It exhibited a cobalt enriched zone extending to 9 microns and a cubic carbide solid solution depletion zone retiring inwardly from the substrate rake surface to 19.7 microns. Kobal (substrate)
4 Thickening Zone and *i, Shinsai * Yosaku Kamokai Zento * Bell *
※※※It was evaluated that the porosity in the remaining part of the test was between A-1 and A-2. Example 5 The materials in this example were 2 with the following material charges:
The compound was milled using a stage milling professional. Stage 1 (489,600 rotations 141.65'm (2,0JliiX) Ta)
1136.4 hyh (1,9X amount N) TlN2
20.9 J's (3.1% by weight) NbCl54
．． 3k (1,9 storm suit X) TaC422,5
j'm (5.9 Emperor m%) C. 31.21m (0.4Mli%) C14kn
Ethomeen
S-151500 Perchlorethylene & IS! 'rll (81 is late 1 6098 h (84, 9-layer IN) WC140hyh
5unoco 34201000
The perchlorethylene was balanced to produce a 2% W-98/X Co binder alloy. A test insert was then fabricated and carried out 4/11.
TiC coating was applied according to Example 4 and with the test blank described in Example 4. Evaluation of the microstructure of the coated insert showed a porosity of A-1 in the cobalt enriched zone as well as in the bulk. The cobalt enriched zone and solid solution depleted zone are respectively i' from the rake surface.
i#! ! It extended inwardly to a depth of 32.1 microns and a micron. Implementation fl16 The following materials were charged in 19 (1 m inner diameter Mija). 283 Jim (4, I JS[tllX )
TaC205hn (3, OJi 澁%) tobe105
&(1.5% by weight) TiN7.91 b (0
, I Jl11%) C3811Prl&(5,5JI amount%) G. 5946 kn (85,8BLiiX) WC1
40hn 8unoco 242014
b Ethomeen 8-15 balanced. Furthermore, the cycloid is 27L1 in the mixture. This mixture was then ground for 4 days. This mixture was prepared under partial vacuum in a sigma blender at 121 °C.
1? : and then passed through a 40 mesh sieve and passed through a Fuinotsu mill (Fit 11). 8NG43 was then prepared using the technique described in Example 4.
3 inserts were printed. However, the inserts used in this example have a TiC/riN coating.
VD fi was overturned. The coatings and ridges used were as follows. 1. TiC coating...The sample is heated under 125 torr true nitrogen in the coating reactor.
The temperature was maintained at 1036°C. hydrogen carrier gas per minute
4.73 liters of TjCI flowed into the evaporator.
Ta. The evaporator is true! F33-35°C was maintained. TiC
The 1° vapor was entrained in a hydrogen carrier gas and conveyed into the coating reactor. Free hydrogen and free methane were flowed into the coding reactor at a rate of 70,19.88 and 3.98 liters/min. These conditions were maintained for 1 tlO to ensure the high T of the dense skin bonded to the substrate.
An iC coating was produced. The flow of methane into the λTiN:J-TiC coater was interrupted and nitrogen was allowed to flow into the reactor at a rate of 2.98 +7 tt/min. These conditions were met during the addition process to form a close bond to the TiC coating.
A high-density TIN coating was produced. Evaluation of the coated inserts produced the following results. A-1, the whole thing! Make your bath an illusion Small zone thickness Maximum 32.7 microns Coating thickness TiG 3.9 microns TiN
2.6 micron bulk average Rockwell A@! Coercivity: 91.0 Coercivity, He 98 Processed Example 7 A mixture of sieves was made using the two-step Millinck cycle described in Dell. In a stage l odor mill jar with WC-Go lining, 181 iu internal diameter and 19411 m length, the following cycloids were added along with a 4.8 haze WC-Co cycloid of 17.3 k). The mill jar was rotated about its cylindrical axis at a speed of 85 revolutions per minute for 48 hours (24
4,800Lg 1 turn). 140.8 Jh (2, OJ!11!%) Ta7
2.9 & (1,0 overlay%) TiH2352b
(0,B 4111%)C458,Okn (6,5f
f1ltX) C. 30 hEthomeen S-151209fn
Sunoco 3420 1000 fntSol trol 130 (solvent) In stage ■, 6314 kn L 90.2 yield%) of WC and 1500 m4 of 8o11rol 1
30°C was added and the entire charge was rotated for an additional 16 hours (81,600 revolutions). This mixture is 5! lid%
The W-95 was balanced to produce an XCo binder alloy. After milling, the slurry was wet screened through a 400 mesh screen, dried at 93°C under nitrogen for 24 hours, and then wet screened through a 40 mesh screen.
It was posted on itzmi11. Test h Jti family is 16,400 k) (1) W resultant force Te 15.11111X15.11111X5.2811
1C ratio 18.6h (cc) Single axis press n
Ta. The above test bottle is placed at 150℃ at 1468℃ under 1 micron vacuum.
Sintered for minutes. These test inserts #1 were honed to a cutting edge radius of 0.064 tsw. Insert is 1% Lie 111K following: TiC/7riCN/TiN:
L-ting! 11 were overturned. 1. The insert is placed in the reactor and passed through the reactor [
Hydrogen was removed from the jCC gas reactor by flowing through the reactor. 2. The insert was heated to approximately 1038° C. while maintaining hydrogen flow in the reactor. The pressure in the reactor was maintained at a pressure slightly higher than 1 atm. 3. A mixture of Tie coating and 100 liters of oil was poured into the reactor for 5 minutes at a pressure of approximately 92 t/min, and methane was heated at a flow rate of 3.1 liters/min for the same period of time. Ti1l, the evaporator was approximately 6ρ31 and (capital) ℃
was maintained. 4, T1CN kof ink-・=・)im+'
1 r C146Js compound Kn was maintained commercially for 13 minutes, n1 methane flow rate was low *R n and Nezuki was 7.1317 ttle/min rJ! Four people were placed in the reactor at Ll. 5. TjN coating--For 12 minutes, the methane flow was interrupted and the chamber temperature was doubled. Coating Ti coated with free hydrogen at 1, the mixture of C14 and N was interrupted, the heating element of the reactor was turned off, and the reactor was cooled to approximately 250 °C. At 250°C, the reactor was purged with a wire. The four bodies may have A-1 to A-2 pores in their non-thickened internal S or bulk material. determined n
Ta. The cobalt thickening zone and the solid bath thinning zone extended 5 and 1 microns from the surface, respectively. The non-thickness ratio inside was 91.70 Tsukwell A with an average of 4°H. The coercive force, He, of the substrate was found to be 186 oersted. EXAMPLE 8 A 260 kjl powder mixture with carbon balanced to C-3-0-4 porosity in the final substrate was made using the two-stage blending and grinding procedure described below. Step 1 The charge composition described in F was milled for % time. 10.108 ihn 'l'ac (6,08JI
@X Coal L) 7.321 Jh NbC (11,28J
illX carbon] 3.987 lm 16.358 kn C. 500 hyh Ethomeen S-15364
Nino 4. BIla Go-WC Cycloid Naphtha Stage ■ Materials listed in F were added to the above mixture and the mixture was further milled for 12 hours. 221.75 kjIWC (6,06% carbon by weight) 5,
□k) 5unoco 3420 Naphtha This final mixture was then wet screened, dried and subjected to a Fitzmill. The insert blank is then pressed and then 145
It was sintered during addition at 4°C. This sintering procedure is C-3~c-
A cobalt-enriched zone covering the majority of the 4-porosity zone was generated. - The sintered blank was then ground and honed to 8NG 433 insert size, so that the cobalt enriched zone was removed. The sintered inserts were then made into open island lead canisters.
ster) was packed with fish boat flakes inside. This assembly is then δvol%N. and 8.76 x 10" dyne/-pressure atmosphere of 75 vol. % He at 1371-1377°C for 1 hour hot equalization press name tN. Microstructural examination of this sample was n1
This indicates that one zone has been created. Approximately 4 microns of surface cobalt and 2 microns of surface carbon were also produced due to the C-type porosity substrate utilized. Example 9 A patch containing the following materials was ball milled. 30.0 imaginary IX WC (1-97 micron average grain skin) 750ky51.4F [iiX We
(4,43 micron average particle size) 1286 kps, o
a*x Co 1
50kp5.0J11X WC-TiC solid solution carbide 124.5kJF6.1 breathability X T
aWC solid solution carbide 152k11.5 11% W 37.
5 kp This mixture was charged to 6.00 point weight percent total carbon. These materials together with 3409ky cycloid and 798t naphtha
crushed during rotation. 0.82 micron! & final coarse grain size was produced. 50009Fm powder was divided from the blended milling batch;
To this, 1 ton of the following @ family was added. g, 211ii% C (Ravin410)
9.4j1m1500 艷 Perchlorethylene These materials are then cycloid (1
The mill jar was milled for 16 hours in a tungsten carbide-lined mill jar containing 7.3 kp) of 190 mm diameter and tungsten carbide lining. After 1% milling, the lot was wet screened through a 400 mesh screen, dried at 121°C under true nitrogen inside a Sidama blender, and then
It was passed through a Metsuyu sieve and put through a Huitutsu mill. An 8N0433 insert blank was pressed using a force of 3600 k) to produce a blank density of 8.24 kv'cc and a blank height of 5.84-6.1011. The blanks were bonded over LO~25 micron A nitrogen-under-NbC powder mold release agent at 1454°C for an additional period of time and then allowed to cool in the oven. The sintered sample has sintered dimensions of 4.93 square x 13.31+n square, g degree of 13.4 hV/cc and 146-1
l46-15O-L-! It had an overall magnetic saturation value of 4//Is Co. The overall microstructural evaluation of the sample was A.
It exhibited a porosity of 11i and a cobalt enrichment of approximately 2 microns thick. in? The Y4 section and bottom of the top were then ground to a total thickness of 4.75 mm. The inserts were then heat treated at 1427°C for 0 minutes at a temperature of 56°C/h, cooled at 1204°C at a rate of 56°C/h, and then furnace cooled. The flank surface of the insert was ground to 12.701411 squares, and the cutting edge was honed to a radius of curvature of 0.064. The inserts were then CVD-broken from titanium carbide/aluminum oxide using the technique described below. The insert is placed in the coating reactor with 102
It was heated to 6-1030°C and held under a vacuum of 88-125 torr. Hydrogen gas at a flow rate of 44.731 J/min was passed through an evaporator containing TiC1 at a temperature of 44.731 J/min. l'iel, the steam was directed into the hydrogen. At the same time, hydrogen and methane were flowing into the reactor at a rate of 19.88 and 2.98 t/min. These conditions of vacuum, temperature and flow rate were maintained for 180 minutes to produce a solid TiC coating on the insert. The flow of hydrogen to the evaporator and methane flow into the reactor was terminated with a drop. Hydrogen and chlorine were then allowed to flow into the generator containing the aluminum particles at a temperature of 380-400° C. and a pressure of Q, 5 psi. Hydrogen and chlorine entered the generator in an amount of 70 liters and 0.8 to 1.0 tons. The chlorine reacts with aluminum to produce ILtC4a vapor, Then reaction! Directed to P3.Darkness where hydrogen and AICL s are entering the reactor, 0
．． A flow rate of 5M was also flowing into the reactor. These IITs were maintained for 180 minutes, during which time the inserts were approximately 1026 to 1028 m
It was kept at ℃. This hand implant has Ai 10. produced a thick coating with a density of . Evaluation of the coated inserts produced the following results. Coating thickness 1'] C5,9 micron All OB, 2.0 mij
o 7 average substrate Rockwell A hardness 91.9 coercive force, Hc
170 Millimeter Sted Example 1O 5000 k of material was divided from the initial batch of material produced in Example 9. 95.4 for this material
k (1,9JtiiX) (7) Pre-crushing T1CN
Oh! Hi1.98jis (0.02M*N)
-Yjn 41Q Carho 7 Black was added as in Example 9, mixed for 16 hours, screened, dried and filtered. The specimen was bill pressed and subjected to an additive test at 1496°C.
! ! sintered and then furnace cooled at ambient furnace cooling rates. Evaluation of the sintered samples produced the following results. Porous! ! t A-1, Total cobalt enriched zone thickness: 14.8 microns Solid solution reduced zone thickness: 19.4 microns at most Average substrate Rockwell A hardness: 92.4 Coercive force (Hc): 230 millimeters Sted Example 11: Further K 5000 #x of material was split from the initial patch made in Example 9. 95.4k (1,9!il
X) f) A quantity of pre-ground T1CN was added as in Example 9, mixed for 16 hours, screened, dried and filtered. The specimens were then pressed and tested at K 1496°C with the real mfiIto specimens.
#8 was tied. Evaluation of the sintered samples produced the following results. Cobalt enriched zone thickness ~12.5 microns Solid solution reduced zone thickness ~16.4 microns Average substrate Rockwell A hardness 92.7 Magnetic saturation 120 gauss-cII
vknC. Coercivity, Hc 260 Mills Stead 5A Example 12 The following mixture was charged using the i-stage milling cycle described below. Stage l The following materials were made into a we-
A 17.3mm 4.0mm diameter co-lined shoulder mill jar.
6 were added along with BwWC-Go psyroid. The mill jar rotates around its cylindrical axis at a speed of 48 revolutions per minute.
Time rotated (244β00 rotations). 455 ha (6,5 劃IX) Ni280 J
lm (4,0J1(ilX) TaN112
k* (1,6 intensity x) TiN266 kn
(3,8fillX) NbN42.7 Jl
m (0.6% by weight C14.0Pr1%
Ethomeen S-151500
Perchlorethylene stage■ The following materials are then added to the mill jar, and then 1
Rotate for 6 hours. (81,600 rotations) 5890
h(83,6ffiflX) Wc105 ha
5unoco 34201000m4
A mixture of perchlorethylene and methane was balanced to produce Cliff 11XW-90 Arashi t% Ni binder alloy. Upon discharging the mixture slurry from the mill jar, the slurry was wet sieved through a 400 mesh sieve (Tyler), dried at 93° C. under a nitrogen atmosphere, and then passed through a cut mesh sieve to a feed mill. The test sample was Bill Press graded, 6.9XlO'dyne/-
It was sintered at 1450° C. under a nitrogen atmosphere and then furnace cooled at an ambient furnace cooling rate. After sintering, the sample is lXl011
Hot equalization pressing was carried out for ω minutes at 1370°C in a dyne/-helium atmosphere. A weave evaluation of this sample showed that the material had an A-3 porosity throughout and a solid solution reduction zone thickness of approximately 25.8 microns. The sample was then subjected to Mffi and energy dispersive $X class line scan analysis (MDX) at shoulders at various distances from the rake plane.
inspected by. FIG. 3 is a graph depicting the change in relative concentrations of nickel, tungsten, titanium, and mental as a function of distance from the rake surface of the sample. As evident in this figure, near the rake surface there is an at least partially depleted grain of titanium and mental which forms a carbide in solid solution with the tungsten carbide. This solid solution depletion zone extends approximately 70 km inward. The discrepancy between this value and the above-mentioned values is believed to be due to the fact that the sample was readjusted at the planned volume, so that different cross-sections of the sample were examined for each evaluation. Corresponding to the reduction of titanium and tantalum there is a layer of enrichment of nickel (see Figure 3). The nickel concentration in the concentrated flotation l- decreases as the distance h1 from the rake surface decreases from 10 microns to 10 microns. This indicates that the nickel in this zone was partially evaporated during hair sintering. The titanium and tantalum peaks at 110 electrons are believed to be due to the scanning of random large particles with high concentrations of these elements. The two parallel horizontal lines indicate the specific distributions observed in the analysis of the bulk portion of the sample around the nominal mixture chemical composition. Example 13 The mixture described in F was charged using the two-stage IJ cycle described in F. Step I The following materials were ground according to Step 1 of Example 12. 455hnt6.4mMN) Ni280 Im
(3, t7;) TaH112 k (1,
6 Hawkbar%) TiN266 jhs (3,7 type temperature%n NbN61.6 hn (0.9J(@%n C, Ravin 410.50214 hrs
Ethomeen 8-15
25009nt Perchlorethylene Stage■ The following materials are then added to the mill jar and an additional 1
It was rotated for 6 hours. 5980 b (83,6311X) WC140
1m 5unoco 3420 This mixture was balanced to produce 10% Ni binder alloy. Following Example 12, the mixture was sieved, dried and run through a Fitzmill. The pressed test sample was 146 microns under Makabe atmosphere.
J minute sealing was carried out at 6°C. The sintered sample is ``C'' throughout
It had a -3 porosity and a 13.1 micron thick solid solution reduced zone. Example 14 The mixture was charged using the two-stage milling cycle shown below. Stage l F is a WC with an inner diameter of 1901mm and a length of 1941mm.
-Co-lined mill jar with 17.3k) of 4.8 ill WC-Go psiroids. The mill jar was rotated about its axis at a speed of 85 revolutions per minute (244,800 revolutions) for 48 hours. 177 b (2,5 button @%) ) if) i. 182.3 J's (2.5mm 549g) Ti)
i. 55.3 Jls (0.81%) C459k (
6.4 equipment%)C. 14 In Ethomeen S-
152,500 ml perchlorethylene stage [The following ingredients were then added to the mill jar and an additional 1
This mixture, which was rotated for 6 hours (81,600 revolutions), was balanced to produce a 101 weight percent CO binder alloy. After discharging the slurry from the mill jar, the slurry 400
Wet sieving δ through mesh screen, nitrogen ′
The material was dried under a temperature of 93° C. and then passed through a 40 mesh mill. The insert blank is graphed and then micron J
The sample was then heated at 1468° C. for an additional time of 4 J to evaporate most of the hydrogen in the sample. During sintering, the sample was supported on NbC powder m-type agent. The baked sample had A-2 porosity in the thickened zone and A-4 porosity in the unthickened bulk. The sample exhibited (a) an average Rockwell A hardness ff, a solid solution reduction zone of 9.8<Kron thickness and a coercive force, Hc, of 150 Oersteds. Example 15 A batch of material having a composition equal to the patch of Example 9 was compounded, milled and pressed into insert blanks. The blank was then sintered, ground, heat treated and ground (flank surface only) substantially according to the hand ridge used in Example 9. The cooling rate was used. The insert was cooled at one distance from its rake face.
Analyzed by line scan analysis. The results of this analysis are shown in the m21f type graph. As shown in the figure, a thickened layer of copal extends inward from the rake surface to a depth of approximately 6 microns, and a thickened layer of cobalt extends inward from the rake surface to a depth of approximately (a) microns. A layer of material that is reduced in size extends. Although not shown in the graph of FIG. 2, partial solid solution reduction was found in the cobalt coagulation layer and solid solution thickening was found in the partial cobalt reduction 1-. The two horizontal lines represent a typical distribution in bulk plumage analysis around the nominal formulation chemical composition. The above explanation and detailed actual m91j are %#! f are given to illustrate some of the possible alloys, products, processes and preparations that fall within the scope of this invention as defined in the claims.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view of one embodiment of a coated gold jA cutting insert according to the present invention. The second graph is a graph showing typical cobalt thickening levels produced in a sintered carbide alloy according to the present invention as a function of depth under the rake (3). FIG. 3 is a graph showing the relative a degree of binder and solid solution carbide in Example 12 as a function of depth below the rake surface. 2 ... insert 4 ... rake 6 ... flank surface 8 ... cutting edge 10 ... coating 12 ... sintered carbide alloy body 14 ... binder enriched layer 16 ... Binder reduction layer 18... Bulk

Claims (1)

Claims: 1. A cemented carbide formed by sintering a substantially homogeneous mixture of components, the alloy comprising: tungsten carbide 70;
-90.5% by weight; 5-10% by weight of a metal binder selected from the group consisting of cobalt, nickel, iron and alloys thereof; selected from the group consisting of carbides of transition metals of groups IVB and VB. 5 to 20% by weight of metal carbides; ANSI/AST B-276-
having substantially type A to type B porosity according to 79;
the metal carbide combines with tungsten carbide to form a solid solution carbide; a first layer enriched with metal binder and a corresponding reduction in solid solution carbide is present near the peripheral surface of the alloy; Cemented carbide as described above, characterized in that below the layer there is a second layer with reduced metal binder and a corresponding enrichment of solid solution carbide. 2. Claim 1, characterized in that the metal binder is a cobalt binder alloy, and the cobalt binder alloy has a magnetic saturation of less than 158 Gauss-cm^2/gm^C^o. Cemented carbide mentioned. 3. Cemented carbide according to claim 2, characterized in that the cobalt binder alloy has a magnetic saturation of a value of about 145 to 157 Gauss-cm^2/gm^C^o. 4 Cobalt binder alloy is 126 Gauss-cm^2/
Cemented carbide according to claim 2, characterized in that it has a magnetic saturation of a value smaller than gm^C^o. 5. The cemented carbide according to claim 5, wherein the metal of the transition metal carbide is selected from the group consisting of titanium, hafnium, tantalum, and niobium. 6. Cemented carbide according to claim 1, characterized in that the metal binder enriched layer has a cobalt content on the peripheral surface that is 1.5 to 3 times the average cobalt content of the cemented carbide. 7. The method of claim 1, wherein the metal binder enriched layer extends inwardly from the peripheral surface of the alloy to a depth of at least substantially 6 microns. Hard metal. 8. Cemented carbide according to claim 7, characterized in that the metal binder enriched layer extends inwardly from the peripheral surface of the alloy to a depth of 12 to 50 microns.