CZ2005777A3 - Enhanced formulation of compositions for cobalt alloy matrices - Google Patents

Abstract

A method for producing a cobalt-based one-component matrix alloy composition for granular media formulated as Co.sub..fce.1.n.- (M.sub.unOsub.vn) .sub..fce.2.n. a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn) ), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf) ), tantalum (Ta) and tungsten (W), wherein u represents the number of atoms of parent metal M and v number of oxygen atoms (O), both in the oxide pattern, wherein. a .fce..sub.2.n. are molar fractions expressed by the equation .fce..sub.1.n. + (u + v) .fce..sub.2.n. = 1. The method comprises the steps of mixing the Co-M master alloy powder and the Co.sub.O.sub. to the corresponding formula formula (Co.sub.anMsub.1-an) .sub..fce.1 '.n.- (Co.sub.u´.nOsub.v´). fce.2´.n. and compacting the mixed powders.

Description

FIELD OF THE INVENTION The present invention relates generally to the manufacture of cobalt alloys, and more particularly to formulating compositions for cobalt alloy matrices that exhibit improved spray properties and improved distribution of significant alloy elements in order to improve the spraying process and produce better performance properties of the resulting thin film. .

BACKGROUND OF THE INVENTION In order to form very thin coatings on a substrate having a precisely controlled thickness and a low tolerance in atomic composition, the DC magnetron sputtering process is widely used in various fields of technology. It is used, for example, to coat semiconductors and / or to form thin layers on the surface of magnetic data recording media. In one commonly used embodiment, an electromagnetic field with an oval distribution is applied to the sputter target by placing magnets on the back surface of the target. Electrons are trapped near the sputter target, resulting in improved production of argon ions and an increase in sputtering rate. The ions inside this plasma collide with the surface of the sputter target, which results in the sputter target emitting atoms from its surface. Voltage difference between the cathode sputter target and the anodic substrate to be 9,999,999 9,999 · »·· · ·« · <

9 ··········· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

During prior art manufacturing / magnetic recording media, thin film layers are successively sputtered onto the substrate by a plurality of sputter targets, each sputter target being a different material, resulting in the deposition of a thin film layer. . Figure 1 shows one such thin film layer of the type known in the prior art for magnetic recording media. The substrate for the layer is a non-magnetic substrate 101, which is typically aluminum or glass. The seed layer 102, i. the first deposited layer imparts shape and orientation to the grain structure of the higher layers and is normally comprised of NiP or NiAl. Further, a weak magnetic undercoat (SUL) 104, which is often comprised of alloys such as FeCoB, CoNbZr, CoTaZr or CoTaNb, is applied and provides a double-sided path for a read / write magnetic field. The SUL 104 layer is amorphous, which prevents the formation of magnetic domains that could potentially cause a reduction in the signal-to-noise ratio (SNR).

Above the weak magnetic backing layer SUL 104, a seed crystal layer 105 is formed to promote oriented growth of the higher layers. The seed crystal layer 105 is often made up of ruthenium (Ru) because ruthenium (Ru) has a closely arranged lattice of a hexagonal system that is similar to a cobalt (Co) lattice. In applications requiring a high data recording density, a magnetic storage layer 106 is deposited on the seed crystal layer 105, the storage layer 106 being a metal matrix composite material consisting of a ferromagnetic alloy matrix and a metal oxide. The ferromagnetic alloy matrix is a conventional binary matrix alloy, such as CoPt,

A ternary matrix alloy such as CoCrPt or a quartz alloy! a matrix such as CoCrPtX, wherein X is an alloy of boron (B), tantalum (Ta), niobium (Nb), zirconium (Zr), copper (Cu), silver (Ag) or gold (Au). Although many different oxides can be used, the most common metal oxide is either SiO ₂ or TiO ₂ due to the high affinity of silicon (Si) and titanium (Ti) parent metals for oxygen and the favorable ability to store the data these oxides exhibit. As a last layer, a carbon lubricant layer 108 is formed on the magnetic data storage layer 106.

The amount of data per unit area that can be stored in the magnetic recording medium is inversely proportional to the grain size of the data storage magnetic layer 106. Thus, it is dependent on the material of the composition from which the data storage layer is sputtered, the 'grain' corresponding to a single, approximately 10-inch, thin film alloy crystal. Segregation of grain boundaries, which is a measure of physical grain separation, also contributes to increasing the storage capacity, and grain size and grain boundary segregation are directly influenced by the microstructure properties of the sputter target from which the storage layer has been sputtered and the degree of fineness of the seed layer structure. kcystalů.

To meet the ever-increasing demand for storage capacity required in the field of magnetic data storage, the technique known as perpendicular magnetic recording (PMR), as opposed to conventional longitudinal magnetic recording (LMR), seems to be the most promising and efficient technology. ) due to higher recording efficiency when using a single-pole recording head, in combination with a weak magnetic backing layer. Using PMR, the bits are recorded perpendicular to the magnetic recording medium surface, allowing for a smaller bit size and greater coercivity. In the future, PMR is expected to increase disk coercivity and amplify disk signal amplitude, resulting in improved data archiving capability.

Oxygen (O) containing composite PMR media can exhibit favorable grain boundary segregation by forming oxygen rich grain boundary regions. Early research on granular media has noted a significant effect of oxygen (O) on suppressing the degradation of the anisotropic constant (K _o ) resulting from thermal instability whenever the device was subjected to local overheating during operation. Oxygen (O) containing media also exhibit low noise and high thermal stability and are useful for high density PMRs. Therefore, oxygen (O) containing grain boundary regions in magnetic alloys act as a grain refining agent and as a grain growth inhibitor, resulting in effective physical grain separation. This physical separation, on the other hand, reduces the grain magnetic interconnection and increases the signal-to-noise ratio (SNR) and the thermal stability of the magnetization.

In prior art magnetic recording media, a magnetic data storage layer 106 is deposited on top of a ruthenium (Ru) -based seed crystal layer 105, the purpose of the seed crystal layer 105 being to produce shaped growth in the media layer. High recording density, up to 200 Gbit / in ² , is commonly achieved through nucleation of grain sizes of the order of nanometers and efficient grain isolation, resulting in a strong resistance to thermal agitation of magnetization within the grain. It is common for this type of grain structure to exhibit a magnetocrystalline anisotropy of grain K _u for a composite alloy such as (Co ₉₀ Crio) 8oPt ₂ o-10SiO ₂ (mole%) of the order of 7 x 10 ⁶ erg.cm ^-3 , this medium represents high thermal stability.

«· · * * * * * * * *

5 • · · · · · · • · · · · ······· · • · · ··· ·· ······ · »· ·· Z the above, that is desirable to create composition for alloy matrices on base cobalt with lower ferromagnetic mass fraction phase, and with reasonable objemovým a fraction of the oxide component , for to improve

a spray effect when the granular medium is sprayed. In particular, it is desirable to develop a method of producing oxygen-containing compositions having a reduced amount of total ferromagnetic phase in order to minimize the amount of ferromagnetic phase in the sputter target. This object, as well as others, is achieved according to the invention by replacing the oxide or oxides of the most reactive element that would be formed by sputtering with some oxide of the parent matrix alloy as the oxygen source and introducing some reactive elements directly into the matrix to achieve an even greater degree diluting the parent metal of the matrix.

SUMMARY OF THE INVENTION The present invention relates generally to the manufacture of a cobalt alloy, and more particularly to formulating matrix compositions containing cobalt alloys that exhibit improved spray properties and improved distribution of significant alloy elements to improve the spray process and provide better performance properties of the resulting thin film . It is an object of the present invention to provide a process, including developing a strategy and materials or compositions made therewith, thereby providing a convenient alternative process for producing sputter targets with improved sputtering properties and improved distribution of significant alloy elements.

Granular media alloys are composite materials in which a cobalt matrix or cobalt alloy is combined with one or more oxide particles, including oxide particles selected from oxides of: magnesium (Mg), titanium (Ti), vanadium (V). ), chromium (Cr), manganese (Mn), iron (Fe), nickel • 9 9

9 9

9 9 9 9 9 999

9

98 9 9 9 9 9

99 • 9

999 • 9 9

9 9

99 (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and / or tungsten (W). The resulting powder raw materials described herein can be used to produce a wide range of cobalt-based alloys for granular media.

According to a first embodiment, the present invention provides a method for producing a cobalt-based alloy composition with a one-component matrix for granular media formulated as Co / χ- (M _U O _V ) S 2> wherein M represents a parent metal selected from the group consisting of magnesium (Mg) , titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si) , yttria (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), india (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W) where u represents the number of atoms of the parent metal M and v the number of oxygen atoms (O), both in the oxide formula, af _x and f ₂ are molar fractions expressed by the equation / + (m + v) / ₂ = 1. The method comprises the steps of "mixing powder-M master alloy Co powder and Co _u O _V 'corresponding to the composition formula _(Co Mi- _a) / i> - (Co _u O _v') / 2 ', and densifying the blended powders. According to this embodiment, f ₂ is expressed by equation (1), is expressed by equation (2), and and is expressed by equation (3):

in (2)

In l- (u + v) f ₂ l- ~ (u '+ v') f ₂ -u · f ₂ a = -ϊ- ₌ —v- _: - ( ₃ ) i-4 ( _M '+ v' ) / ₂ ι-4 (Μλ vv) In this first embodiment, it is assumed that any composite a material with a binary matrix based on Co _u <0 _V 'is chemically equivalent to a composite material with a one-component oxide matrix M _u 0 _v if —— = -.

^{A, V 'in the} [0015] method further includes the step of grinding the mixed powder in a ball mill. In addition, the method comprises the steps of encapsulating the mixed powders in a container, evacuating gases from the container, and subjecting the container to high temperature and pressure.

[0016] According to a second embodiment of the present invention is a method of producing alloy compositions based on binary matrix cobalt granular media formulated as _(Co Pti_ _a) / χ- (M _{U V} O) 2R wherein M representing a base metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and t is the number of atoms of the parent metal M 'and v the number of oxygen atoms (O), both in the oxide formula, and represents the atomic fraction, /, and f ₂ represent the molar fractions expressed by the equation + (u + v) / ₂ ⁼ 1 · the method includes the steps of blending a Coa ^^ Pt master alloy and ^ '- *' and Co powder _at O _V 'corresponding to the composition formula _{(Co' and} Mb'Pti- '-b') / i'- (Co _u O _v ') f2', mixing and compacting ch powders. According to this embodiment, f ₂ is expressed by equation (1), and // is expressed by equation (2) (both see above), wherein a 'is expressed by equation (4) below and b' by equation (5):

/ io '= - at (4) In this second embodiment, it is assumed that any composite material with ternary a matrix based on oxides of Co _u O _W 'is chemically equivalent to the composite material with a matrix based on a binary oxide of M _U O _V, if applicable in

According to a third embodiment, the present invention provides a method for producing a cobalt-based alloy composition with a ternary matrix for granular media formulated as (Co _and CrbPti- _and -b) _fl - (M _U O _V ) _{ί 2} , wherein M. represents a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of atoms of the parent metal M and v the number of oxygen atoms (O), both in the oxide formula, a and b represent atomic fractions, j \ af ₂ represent the molar fractions expressed by /, + (m + v) f ₂ = 1. The method comprises the steps of mixing the precoat powder Co _and -Cr _b -Pt _C 'M _d - and the Co _u O _V powder into a corresponding composition with the formula Co _and 'Crb'Pt _C 'Cop' / r (Co _U '0 _V ') densification of the blended powders. According to this embodiment, f ₂ is expressed by equation (1), fj is expressed by equation (2), and 'is expressed by the above equation (4), and b', c 'and d' are expressed by equations (6) to (8) below. ):

fjb (5)

4

4

4 * 4

• · ·· 4 4

44 * 4 * 4

4 * 4 *

4 * 44 (7) (8) In this third embodiment, it is assumed that any composite material with a quaternary matrix based on Co _x O _v > is chemically equivalent to a ternary composite material

[0020] According to a fourth embodiment of the present invention is a method of producing alloy compositions based ternary matrix cobalt granular media formulated as _(Co CrtPtj- _and -t) (O M _{U V) I2>} M representing a base metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si ), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), india (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W) ), where u represents the number of atoms of the parent metal M and v number of oxygen atoms (O), both in the oxide formula, a and b represent atomic fractions, and f ₂ represent the molar fractions expressed by the equation /, + (w + v) / ₂ -1. The method includes the steps of blending a master alloy of Co _and CrbPt _C Md and a powder of Cr "O into _a corresponding composition having the formula _(Co CrbPt _C MDJ fi ~ (Cr _u 'O _v -), and densifying the blended powders. According to this embodiment, the conditions expressed by by equation (9) below:

Italy (9)

V • · ····

9 9 »9 9 '♦ · I

9 9 9 9 9 9 99 99

In addition, according to a fourth embodiment of the present invention / ₂ , it is represented by equation (10), it is expressed by equation (11), aa ", b", c "and d" are represented by equations (12) to (15) below. ):

v / ι = ι-4 (" ⁺ "'') λ v

fi-a (10) (11) (12) a ”= b” = -vi-X ( _M ” _{+ V} ”) / ₂ in

c ”= _ir_! _r (“ ” _{+ V} ”) _Á v

fi -M

1-Λ (“” _{+ ν} ”) _Λ i /”: i3:

(η:

(15) [0022] In this fourth embodiment, it is assumed · that any composite material based quaternary matrix Cr oxide _at O _V 'is chemically equivalent to the composite material with FTY "for ternary matrix oxide M _U O _V, if applicable According to a fifth embodiment, the present invention provides a method for producing a cobalt-based alloy composition with a quaternary matrix for granular media formulated as (Co _and CrhPt _c M ' _d ) _f (M _U O _V ) f 2, wherein M' represents an element selected from group consisting of boron (B), tantalum (Ta), niobium (Nb), zirconium (Zr), copper (Cu), silver (Ag), gold (Au) and ruthenium (Ru), M ··

9 9

9 999

9 9 9

9 9 9

99 represents a parent metal other than M 'and selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of atoms of the parent metal M and v the number of oxygen atoms (0), both in the oxide formula, a and b are atomic fractions, fa / ₂ are molar fractions + (w + v) / ₂ = 1, ad is expressed by the equation d = lab — c. The method comprises the steps of combining Co alloy &quot; Cr _b 'Pt _C ' M 'A' and Co _u powder> 0 _V 'into the corresponding composition of formula (COa'Cr _b -Pt _c -M'ďMe') f> - ( what _u O _V ') / 2' and densifying the blended powders. According to this embodiment, f ' ₂ is expressed by equation (1), is expressed by equation (2), and aj b' and c 'are expressed by the above equations (4), (6) and (7), and d and e' are expressed below by equations (16) and (17):

ï ·· f-d (16) e ’=

U- ^for i-4 ( _M ' _{+ V} ') / ₂ v

(17) In this fifth embodiment, it is assumed that any 5-element Co _U 'O _V ' matrix composite material is chemically equivalent to the M _U O _V quaternary matrix composite material, if applicable

According to a sixth embodiment, the present invention provides a process for the production of a cobalt-based alloy composition with a quaternary matrix for granular media formulated as (Co _and CrhPt _c M'd).

4 4 4

4 4

4 4 4

4444 44 • · 4 4 ·

• 4 «

4

4 (M _U O _V ) _S 2, where M 'represents an element selected from the group consisting of boron (B), tantalum (Ta), niobium (Nb), zirconium (Zr), copper (Cu), silver (Ag), gold (Au) and ruthenium (Ru), M represents a parent metal other than M 'and selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), india (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of atoms of the parent metal M and v number of oxygen atoms (O), both in the oxide formula, and b represent atomic fractions , af ₂ represent the molar fractions expressed by the equation /, + (μ + v) / ₂ = 1, and d is represented by the equation d = 1 - a - bc. The method comprises the steps of mixing the master alloy powder Co _and Cr _b Pt _C M'dM _e and Cr _U O _v »powder into a corresponding composition of the formula (Co _and CrbPtcM'dM _e ) f - (Cr _U O _V ) f ₂ . the conditions expressed in equation (9) above apply.

In addition, in a sixth embodiment of the present invention it is assumed that / ₂ is expressed by equation (10), is expressed by equation (11), and a ", b" and c "are expressed by the above equations (12) to (14), d ”and e” are represented by equations (18) and (19) below:

</ ”= · Fi-d

Λ · «(19) (19)

1-2 (η ”+» ”) Λ h

[0027] In this sixth embodiment, it is assumed that any composite material based quaternary matrix _with chromium oxide »O _V is chemically equivalent to the composite material ternary ♦ • · ··"

99 99

9

9

9

9

9999 98 99

9 999

9

9

99 99 matrix oxide M _u 0 _Vf [0028] In other embodiments of the present invention, i.e. embodiments seventh to twelfth, also assumes the use of an alloy composition to a cobalt-based granular media, with a single-element matrix, binary matrix, ternary matrix or with a quaternary matrix, which are produced using the methods described above in embodiments one to six.

In the following description of the preferred embodiment, reference is made to the accompanying drawings which form part of the description of an exemplary embodiment and in which an exemplary specific embodiment of the invention is illustrated. It is to be understood that other embodiments may be used and changes may be made without departing from the scope of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS The invention is further described with reference to the drawings wherein the same reference numerals are used throughout the figures for the corresponding parts:

Figure 1 illustrates a 'thin film' layer of prior art embodiments;

Figures 2 and 2A illustrate a method of making a cobalt (Co) based alloy composition for granular media with a one-component matrix, a binary matrix, a ternary matrix, or a quaternary matrix according to an embodiment of the present invention;

Figure 3 illustrates a thin film layer for improved magnetic recording media, wherein the magnetic data storage layer is a cobalt-based alloy composition for a granular media according to a second embodiment of the present invention;

9 · 9 · 9 9 9 9 9 9 9 9 9 9 9 9 9 9

Figure 4 illustrates a typical microstructure of a reinforced composite material (Co ₈₉ Tin) ₈₂ (CoO) _X8 ;

[0035] Figure 5 illustrates a typical microstructure of a reinforced composite material (Co _{7X 9 28} Nb _{x) 8 7} (CoO) _4Xř3;

Figure 6 illustrates a typical microstructure of a reinforced granular alloy (Co ₇₄ Cr _xo Pt _x6 ) ₉₂ - (SiO ₂ ) ₈ , using SiO ₂ and Figure 7 illustrates a typical microstructure of a reinforced granular alloy (Co _{7 4} Cr _X0 Pt _{X6) 92} - (SiO ₂ ) ₈ reinforced granular alloys, using (CoSi ₂ ) and CoO.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention describes a method of preparation, including formulations, and materials or compositions made therewith, thus creating a preferred alternative process for producing sputter target with improved sputtering properties and advantageous distribution of significant alloy elements.

Granular media alloys are composite materials comprising a combination of a cobalt or cobalt alloy matrix and particles of one or more oxides, these oxides being selected from magnesium (Mg), titanium (Ti), vanadium (V), chromium ( Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (AI), silicon (Si), yttrium (Y), zirconium (Zr), niobium ( Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and / or tungsten (W). Based on an alternative approach to the formulations, the resulting powdered raw materials described herein can be used to produce a wide range of cobalt-based alloys for granular media. Specific groups of alloys intended for use in the present invention are described below:

SINGLE COMPONENT MATRIX: Co-M _u O _v , wherein the parent metal M for the oxide is magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese To «1 1 1 1 1 1 1 1 β β β β β β β β β β β β β β toto toto toto toto (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) or tungsten (W).

[0041] BINARY MATRIX: Co-Pt-M _u O _v, where the base metal M for the oxide is magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe ), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru) ), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) or tungsten (W).

[0042] Ternary MATRIX: Co-Cr-Pt-M _u O _v, where the base metal M for the oxide is magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) or tungsten (W).

QUARTER MATRIX: Co-Cr-Pt-M'-M _U O _V , where M 'is boron (B), tantalum (Ta), niobium (Nb), zirconium (Zr), copper (Cu), silver (Ag), gold (Au) or ruthenium (Ru), the parent metal M is magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper ( Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum ( La), hafnium (Hf), tantalum (Ta) and / or tungsten (W), and where Μ'ψ M.

Although the present invention is described, both above and below, using examples of one to four-component matrices, alternative embodiments of the invention are not limited to these explicitly described examples. The principles described herein can also be applied to cobalt (Co) matrix composite materials that are more than four-component.

«4 4 4 4 4 4 4 4 4 4 4 4 4 • 4 4

4

4 «

4 444

4 · 4

4 4 4

The most suitable compositions comprising cobalt (Co) alloys include Co-Pt-SiO ₂ (or-TiO ₂ ), Co-Cr-Pt-SiO ₂ (or TiO ₂ ) and, in some cases, combinations of the two oxides or other oxides in the range of predetermined molar fractions. While one method for producing these alloys for granular media used powders of pure elements, due to cost and practicality, cobalt (Co) has always been bound in the form of a Co-Cr or Co-Cr-B master alloy powder to control chemical homogeneity and PTF. . The oxide component is admixed as a pure powder because there is no possibility of producing a master alloy of the powdered composite oxide-based material. Platinum (Pt) is also admixed as a pure powder in order to better control its feed rate since it is a very expensive raw material.

Many possible alloy formulations can be used for a given granular media material. In a simple example of a Co-M grain alloy _at 0 _v , two different formulation formulations can be used. In one case, two powder components are mixed, i) powder, cobalt (Co), and ii) a powder of _U M O _In order to achieve the composition of the electrode corresponding to a Co / ι- (M _{U V} O) ₂ j, where /, f ₂ (a. / af ₂ ) are the molar fractions expressed by the equation f _x + (u + v) f ₂ = 1. In the latter case, the same composition is produced by mixing powdered matrix based master alloy Co-M oxide powder Co _u O _V 'into a corresponding composition having the formula _(Co Mi_ _a) y> - (Co _u O _v') f ₂ 'where f _x and f ₂ are represented by equations (1) and (2). For any raw material containing Co oxide _with O _V 'is selected as a source of oxygen (O) calculate the matrix composition based master alloy Co-M and the respective relative mole fractions, as described in detail below.

Figures 2 and 2A illustrate a method of producing a cobalt (Co) based alloy composition for granular media with a one-component matrix, with a binary matrix, with a ternary matrix, · · · · ··· · · · · · ····················································· matrix, according to a first embodiment of the invention. Briefly, it is a method of making a cobalt-based alloy composition for granular media, and comprises the steps of mixing a cobalt-based (Co) alloy masterbatch powder with a cobalt (Co) or chromium (Cr) -based oxide into a composition with the corresponding specific formula, and compacting. of mixed powders.

Specifically, the process begins with step S201 and further mixes cobalt powder (Co) or cobalt-based master alloy (Co) with cobalt oxide (Co) or chromium (Cr) powder (step S202).

One particular embodiment relates to the manufacture of a cobalt-based alloy composition with a one-component matrix for granular media formulated as Co / γ- (M _at 0v) / 2, wherein M represents a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), -molybdenum (Mo), ruthenium (Ru), india (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of atoms of the parent metal M and v the number of oxygen atoms (O), both in the oxide formula, and /, and f ₂ are the molar fractions expressed by the equation /, + (+ + v) / ₂ = 1. In this particular embodiment, at step S202, the Co-M master alloy powder and Co _u O _V 'powder are mixed into a corresponding composition of the formula (Co _a Mi- _a ) / i-- (Co _u O _V ') si ', where f ₂ is expressed by equation (1), // is expressed by equation (2) and and is expressed by equation (3):

(1) • 9

9

9 9 v

- (μ + v) / ₂ - Μ '· 4 · Λ 1 - 4 (m' + v ') / ₂ - · Λ z, - _______ Τ _____— ν

(2)

It should be noted that in all the formulas herein, the basic atomic fraction has been adjusted to a value equal to 1 for each alloy formula to accommodate the derivation of the atomic and molar fractions for the improved alloy formulations. For example, in the alloy formula (Coo, 71Cr_Q,and₃Pto, i610, 92 (Nb2O5) 0 (08, which shows a total molar fraction equal to 1.48, this molar fraction value could be reduced in the product to a value equivalent to the formula (Coo, 7Cr0, i3Pt0, x6) by, 622 (Nb2O5) o, an axis whose resulting total molar fraction is equal to 1.

In addition, in this first embodiment, it is assumed that any Co binary matrix composite material _u O _V 'is chemically equivalent to a one component oxide matrix composite material M _u 0 _v if u

Another embodiment relates to the production of a cobalt-based alloy composition with a binary matrix for granular media formulated as (Co _and Pti _-a ) f - (M _at 0 _v ) _{f 2t} wherein M represents a parent metal selected from the group consisting of magnesium (Mg) , titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (AI), silicon (Si) , yttria (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), india (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W) wherein u represents the number of parent metal atoms M and v represents the number of oxygen atoms (O) both in the formula

99 9 9

I 9 9 9 9 of the oxide, and represents the atomic fraction, f _x and f ₂ represent the molar fractions expressed by the equation f _x + (+ + v) / ₂ = 1. According to this particular embodiment, the master alloy powder is mixed with Co _and the M _b>? Ti- _a> - _b r Co powder _at O _V 'corresponding to the composition formula _(b -M Co _and Pt i ~ _a' - _b ') _fl > - (Co _u 0 '') f2 'in step S202, where f ₂ is

expressed by the equation (1) and f 'j® expressed by equation (2) (both see above), and where and 'a b ’ are expressed below equations (4) and (5): z- ^v (4) i-If + dA in y = -4 " (5)

l - (w '+ v') / ₂ v

[0053] According to this embodiment, it is assumed that any composite material with a matrix based ternary oxide Co _u O _W 'is chemically equivalent to the composite material a binary matrix f -b' u oxide M _U O _V, if applicable -ή- = -.

Λ · ^{ν 'in the} [0054] Another embodiment relates to a method of producing alloy compositions based ternary matrix cobalt granular media formulated as (Co _a Cr _b Ptx- _a - _b) / χ- (O M _{U V) I2,} where M represents a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the sum of the atoms of the parent metal M and v the number of oxygen atoms (O), both in the oxide formula, a and b represent atomic fractions, / af ₂ represent

9

9 mole fractions expressed by the equation /, + (w + v) / ₂ = 1 According to this particular embodiment, the alloy of Co _S 'Cr _b ' Pt _C 'Copper and Co _u O _V ' powder are mixed into a corresponding composition of formula (Co _a rCr _b > Pt _c > M _d >) _fl , - (Co _u <O _v <) _{/ 2} 'in step S202, where f ₂ is expressed by equation (1), f (is expressed by equation (2) and a' is expressed the above equation (4), and wherein b ', c' and dd are represented by equations (6) to (8) below:

(i) ´ = -—- (6) ι-4 (+) λ v

c '= - E- (7)

V '= -PZL- ₍₈ )

In [0055] According to this embodiment, it is assumed that any composite material based quaternary matrix of Co _u O _W 'is chemically equivalent to the composite material a ternary matrix oxide M _U O _V, if applicable fl · *' v '[ 0056] Another embodiment of the present invention relates to alloy compositions based ternary matrix cobalt granular media formulated as (Co _a Cr _b Pti- _and -i) / i (M _{U V} O) / 2 wherein M is a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al ), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta ) and tungsten (W), where u represents the number of atoms of the parent metal M and v the number of oxygen atoms (O), both in the formula, aab p represent atomic fractions, /, and f ₂ represent molar fractions expressed by the equation f _x + (u + v) f ₂ = I. According to this particular embodiment, the mixed powder ligatures _Co »Cr _b Pt _c, M _d and powder Cru» O into _a corresponding composition having the formula _{(Co, and} Cr / Pt _C W _d) (C _U O _V) / 2 in step S202 , applying the conditions expressed in Equation (9) below:

(9) According to this particular embodiment, f _{2 is} represented by equation (10), f _x is represented by equation (11), aa ", b", c "and d" are represented by equations (12) to (15) below. :

ii y / 2 ⁼ “'Λ in z' = i-é (“ ” ⁺ v”) rv

and - = - Uf-4 ("·. _{+ ν} ··) _Λ (10) (11) (12)"". _Λ * · = —ťv f \ ' ^c (13) (14) </ ”= l-4 (» ”+ in”) / ₂ in

Λ "(15) [0058] According to this embodiment, it is assumed that any composite material based quaternary matrix Cr oxide _U O _V is chemically equivalent to the composite material ternary ·

• 999

9 • · · · · · · ·

oxide matrix M _U O _V, if applicable [0059] Yet another aspect relates to an alloy composition based on cobalt with quaternary a matrix for granular media formulated as (Co _and Cr _h Pt _CJ M ' _d ) (M _U O _V ) / 2, wherein M' represents an element selected from the group consisting of boron (B), tantalum (Ta), niobium (Nb) , zirconium (Zr), copper (Cu), silver (Ag), gold (Au) and ruthenium (Ru), M represents a parent metal other than M 'and selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of base metal atoms M and v the number of oxygen atoms (0), both in the oxide formula, a and b represent atomic fractions, j 1 and / ₂ represent molar fractions expressed by the equation / 1 + (w + v) / ₂ = 1, and d is expressed by the equation cb = labc. According to this particular embodiment, the master alloy powder Co _a 'Crb'Pt _c >M' _d 'M _e ' and the powder Co _U 'CV are mixed into a corresponding composition of the formula (Co _a 'Crb'Pt _C 'M' _d 'M _e ' ) fi '- (what _a' 0 _V ') f2' in step S202. In this embodiment, f _{2 is} represented by equation (1), is represented by equation (2), and a ', b' and c 'are represented by the above equations (4), (6) and (7), and d', ae 'are represented by Equations (16) and (17) below:

(16) According to this embodiment, it is assumed that any

(17)

IN

9999 9 · »9 99 99 • · · ·

9 9 · 999 999 999 9 4

9 9 9 9 4 »9 99 99 composite material with 5 element matrix based on Co _u > O _v > is chemically equivalent to a quaternary composite material

Z · ¹ ^ 5 M oxide-based matrices _at 0 _v if A A = -.

FI-V 'V [0061] Still another embodiment of the present invention relates to alloy compositions based quaternary matrix cobalt-granular media formulated as (Co a Pt _and Cr _{H c} M'd) yj _(U M O _V) it, wherein M 'represents an element selected from the group consisting of boron (B), tantalum (Ta), niobium (Nb), zirconium (Zr), copper (Cu), silver (Ag), gold (Au) and ruthenium (Ru), M represents a parent metal other than M 'and selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta), and tungsten (W), u represents the number of atoms of base metal M and the number of oxygen atoms (O) per oxide formula, a and b representing atom fractions, j \ f ₂ representing mole fractions expressed by the equation /, + (m + v) / ₂ = 1, ad j e is expressed by the equation d = labc. According to this particular embodiment, the master alloy powder Co _and Cr _b Pt _C M'dMe and the powder Cr _U O _V are mixed into a corresponding composition of the formula (Co _a CrbPt _c -M'd »M _e ) / Cr - (Cr _U O _{V) 1/2} in step S202. According to this embodiment, the conditions expressed by the above equation (9) apply.

[0062] According to this embodiment, f ₂ expressed by Equation (10), fi ^e j expressed by equation (11), AA ', b' and c 'are represented by the formulas above (12) to (14). In addition, d ”and e” are expressed by equations (18) and (19) below:

··· (

í / ”= fd ι-4 ( ^μ ” + ^ ”) λ / ₂ · Μ

1_Λ (“” _{+ ν} ”) _Λ in” • · · 9

9 9

(18) (19) [0063] In this sixth embodiment, it is assumed that any composite material based quaternary matrix Cr oxide _at O _V 'is chemically equivalent to the composite material ternary f · e "of matrix oxide M _U O _V , if A- = -.

Λ - v v v The blended powders are ground in a ball mill (step S204).

Alternatively, the mixed powders may be milled using various techniques, or they may not be ground at all. Ball mill grinding is a technique well known to those skilled in the art of powder metallurgy. The mixed powders are compacted (step S205) and the process ends (step S206). As shown in more detail in Figure 2A, the compaction step (step S205) further comprises the steps of encapsulating the mixed powders in the container (step S205a), evacuating the gases from the container (step S205b), and subjecting the container to high temperature and pressure (step S205c). The powder compaction processes described in steps S205a to S205c are well known to those skilled in the art of powder metallurgy.

Let us now turn to a practical example of the improved production methods described above. Cogo- example, an alloy (SiO ₂₎ as well as granular media can be formulated as a composite material (Coo, 875Sio, I25) 80 (CoO) _{on the 20th} This formulation allows the introduction of Co-Si master alloy of the desired PTF.

cobalt (Co) through CoO and achieve atomizing Similarly granular alloy _(Co CrbPti_ _and _b) / _X ··· ♦ ♦ · · ··· · «· • • ···· ·· · 9 9 9 9,999 9 9 9 9 9

9 9 9 9 9

999999 99 9 9 9 9 9 (M O _{V U) i2} (Μ Ψ Co, Cr) may also be converted to cobalt oxide (Co) comprising composite material _(Co / Cr _b <M _c -pT _d ») _fl ~ (Co _u O _v ') f2' or chromium oxide (Cr) comprising a composite material _(as Co _{and Cr?} »M _c -pT _{d) fl"} - (C _U O _{v) f2} · Both these formulations are useful for achieving the desired sputtering properties and achieving the dual objective of improving the PTF electrode and reducing particle formation.

With respect to the electrode formulation, the nominal alloy composition for the granular media can be achieved using different approaches and using available raw materials. The present invention, through appropriate selection of raw materials, provides sufficient guidance for better distribution and composition of the resulting phases of the electrode microstructure. As a specific example, a composite spray material comprising a cobalt (Co) alloy matrix and an oxide designed to apply a granular medium with a segregation of grain boundaries of SiO ₂ or TiO ₂ . This material is formulated to reduce the resulting weight fraction of the ferromagnetic cobalt alloy matrix.

Also affected by this approach is the PTF electrode, which is a measure of the number of magnetic field lines that pass through the ferromagnetic electrode material of a given thickness, and which is inversely proportional to the permeability of the material. The permeability of the multi-component material is also directly proportional to the mass fraction of the ferromagnetic component. It follows that by minimizing the mass fraction of the ferromagnetic phase, the PTF electrodes and the sputtering effect are also improved.

In addition, for a given nominal composition and oxygen content of the granular media, the oxide is selected such that the resulting volume fraction is large enough to ensure an advantageous distribution of oxide particles throughout the electrode volume. Simultaneously ···································· •••• to ···· ········· · The choice of oxides of alloy elements other than silicon (Si) or titanium (Ti) allows the introduction of titanium directly into the ferromagnetic matrix, which is another way of increasing PTF through further dilution of the base cobalt (Co) matrix.

On the contrary, during sputtering, atoms and molecules of the electrode material dissociate and a plasma of free atoms is formed. The free atoms later merge again and deposit on disk to form a film of homogeneous grains of the base ferromagnetic material. The solubility of oxygen (O) in the solid state is very limited in the ferromagnetic material, with the result that most of the oxygen (O) is discharged to the grain boundaries, where this oxygen (O) forms the oxide or oxides of the most reactive media alloy elements in many cases, essentially SiO ₂ or TiO ₂ .

[0071] In the case of granular alloy (Co7iCri3Pti6) go ^- (SiO _2), also this solution is exemplified through two alternative formulations of the alloy which exhibit substantially the same nominal composition. In the first case, it is proposed to prepare a multi-component powder mixture of individual elements, such as cobalt (Co), chromium (Cr), platinum (Pt), and / or master alloys of these elements, to which SiO ₂ powder may be admixed. In the latter case, the oxygen source may be a cobalt oxide such as CoO, and silicon may be added directly or through the master alloy as a fourth element of an equivalent alloy of the formula (CO54,8gCri4 ₍ 62SIL2,50Pt18,00) 80 “(CoO) ₂ oxidu The volume fraction of oxide, which is a measure of the dispersion of the oxide phase, can in most cases be increased when the density of the alternative oxide is less than the density of SiO ₂ or TiO ₂ , or at least maintained at the same value. for microstructural composition are given in Table 1. Except • 4

4 · 4 • 4 ·· 4 44 • 4 * 4 44 * 4 * * 4 * 44 * 4 4 * * 4 4 * 4 * 4 ** 4 44 * 4 *

43 4 * * 4 ** 4

444444 4 * 4 44 * 4 additional dilution of cobalt (Co) to an atomic fraction equal to 0.5488 results from this alternative formulation reducing the mass fraction of the matrix while not significantly reducing the volume fraction of the oxide.

Table 1. Phase composition and theoretical representation of microstructural phases

alloy pattern by weight of the matrix % by volume of the oxide (CO7lCri3Pti6) 90 ^- _(SiO2) 10 92.30 28.85 (CO54.88Cr 14.62Si 1 ₂ , 50P118.00) 80 ^- (CoO) 20 80.75 27.05

Figure 3 illustrates a thin film layer for improved magnetic recording media, wherein the magnetic data storage layer is a cobalt-based alloy composition for a granular media according to a second embodiment of the present invention. As mentioned above, the thin film layers are successively sputtered onto the substrate by a plurality of sputter target, the individual sputter target being comprised of different materials or compositions.

The base of the improved thin film layer is formed by a non-magnetic substrate 101, followed by a seed crystal layer 102, which confers shape and orientation to the grain structure of the higher layers. Further, a SUL 104 layer is provided that provides a bidirectional path for a read / write magnetic field, wherein the SUL 104 layer is amorphous to prevent the formation of magnetic domains and reduce the signal-to-noise ratio (SNR).

Above the SUL 104 layer, a seed crystal layer 105 is formed to promote oriented growth of the higher layers. A magnetic storage layer 306 is deposited on the seed crystal layer 105, which layer 94

9 9 4

9 9 ··· 9 9995

444 4,444 44 99 4

49 49 9 4494

4449 94 44

The data storage 306 is a metal matrix composite material consisting of a ferromagnetic alloy matrix and a metal oxide. In order to deposit the composition as a magnetic data storage layer, any of the production methods described above produces a cobalt-based alloy composition for granular media, is formed into a sputter target using conventional techniques, and sputtered onto a substrate. Finally, a carbon lubricant layer 108 is formed on the magnetic storage layer 306.

According to a seventh to twelfth embodiments, the present invention provides a cobalt-based alloy composition for granular media, which is produced by any of the above production methods. For the sake of brevity, further description of the alloy compositions or manufacturing methods used to manufacture these compositions is omitted.

We now focus on three practical examples of experimental compositions that have been produced using the above production methods under laboratory conditions. The Co9i (TiO2) g granular alloy was formulated into a cobalt oxide composite material of the formula (Co ₈₉ Tin) ₈₂ (CoO) ₁₈ . The powder blend consisted of a mixture of cobalt (Co) powder of 99.9% purity and CoO powder of 99.5% purity and Co-50 Ti powder (at.%). Table 2 shows the percent by weight of the composition.

Table 2: Cogi (TiO ₂ ) granular alloy composition g

powdered material sieve size (mesh) % by weight What -100 62.0175 CoO -325 22.1705 Co-50Ti -325 15.8120

The powder was subjected to ball milling for 16

• · · <

• · ···· · · · * f f f f f f

Hours to achieve optimal mixing of the components of the mixture and complete dispersion of the oxide particles. Prior to consolidation, the powder was encapsulated and evacuated at 450 ° C to a partial pressure of 10 ^-3 torr before dosing into the HIP container. The consolidation was completed at 1236 ° C for 3 hours and a container pressure of 29.5 kiloponds per square inch (ksi). A typical microstructure of a fully consolidated product is shown in Figure 4.

In the second example relating to the formulation and preparation of the Co ₉ i (Nb ₂ 0 ₅ ) ₉ granular alloy, a similar approach was followed as in the first case. The Co ₉₁ (Nb ₂ 0 ₃ ) ₉ granular alloy was prepared by mixing cobalt (Co) powders with a purity of 99.9% and CoO with a purity of 99.5% and Co-43.2 atomic%. The composition of the composition for the equivalent composite material (CO 7, ₉ Nb ₂ e, i) 58.7 (CoO) 41.3 is shown in Table 3 below.

Table 3: Composition of Co ₉ i (Nb ₂ 0 ₅ ) granular alloy ₉

powdered material mesh size % by weight What -100 16, '97 CoO -325 43, 48 Co-43.2Nb -325 39.55

The powder mixture was subjected to ball milling for 16 hours to achieve optimal mixing of the components of the mixture and complete dispersion of the oxide particles. Before hardening, the powder was encapsulated and evacuated at 450 ° C at a partial pressure of 10 ³ torr before loading into the HIP container. The consolidation was completed at 1236 ° C for 3 hours at a container pressure of 29.5 ksi. A typical microstructure of the fully consolidated product is shown in Figure 5.

Figure 6 illustrates a typical reinforced microstructure of rt ········

granular alloys (Co ₇₄ Crx ₀ Pti ₆ ) ₉₂ - (SiO ₂ ) g, using SiO ₂ , and Figure 7 illustrates a typical microstructure of a reinforced granular alloy (Co ₇ 4CrioPti ₆ ) ₉₂ - (SiO ₂ ) ₈ , using (CoSi ₂ ) and CoO. In the first case, which is illustrated in Figure 6, the alloy (CO7 ₄ CrioPti6) 92 ^_ (SiO ₂₎ 8 prepared by first calculates an equivalent nominal alloy, Co ₇ 6 o8Cr _{9 (2} OPTI ₄ 7 ₂ - (SiO ₂ ) g, expressed in atomic%, is used in a mixture of cobalt (Co) sieve with a mesh size of 100 mesh equal to 29.53 wt%, Co-24.22Cr powder with a mesh size of 100 mesh 27.73 wt.%, a SiO ₂ powder having a grain size <5 µm in an amount of 6.13 wt.% and a platinum (Pt) powder in an amount of 36.61 wt.%.

In the second, improved example illustrated in Figure 7, an alloy (Co ₇₄ Cr ₁₀ Ptx 6) g ₂ - (SiO ₂ ) g is produced by mixing 16.97 wt% cobalt powder (Co), 5.49 wt%. % CoSi ₂ powder, 14.52 wt% CoO powder, 26.4 wt% Co-24.22Cr powder, and 36.62 wt% Platinum (Pt) powder. As shown in Figure 7, this improvement achieves a much lower cobalt (Co) content.

In the second example relating to the formulation and preparation of the Co ₉₁ (Nb ₂ O ₅ ) ₉ granular alloy, a similar approach was followed as in the first example. The Co ₉ x (Nb ₂ 0 ₅ ) ₉ granular alloy was prepared by mixing cobalt (Co) powders with a purity of 99.9% and CoO with a purity of 99.5% and Co-43.2 atomic%. Compositions for the equivalent composite material (CO7x _{9 28} Nb x) _{58 7} (COO) ₄ and ₃ are shown below in Table 3.

The present invention also takes into account a situation where more than one oxide is required for alloys in which the desired oxygen (O) content is higher than the theoretical content achieved by a single oxide. For example, if an alloy having the composition X (Co-Pt-Cr) Y (Si) -3Y (O) is desired, the alloy cannot be made using SiO ₂ alone, since the necessary Si: O ratio of 1: 3. Using only SiO ₂ would achieve a ratio of 1: 2. In order to increase the oxygen content (0), an addition of cobalt oxide (Co) or overwhelming (Cr) is also used in this case.

The invention has been described by way of examples of specific embodiments. It is to be understood that the scope of the invention is not limited to the embodiments described therein, and that various changes and modifications may be made by one of ordinary skill in the art without departing from the spirit and scope of the invention.

Claims (14)

PATENT CLAIMS 1-4 (m '+ v') / ₂ v compaction of mixed powders. 1 - / (»’ +> ”) /, h Z ' ^c 9 9 1-4 ('' + ν ·) / ₂ v • «♦ · ï = In the ^{case of} (a '+ v') /, compaction of the blended powders. 1 -! ("· +" ’) /, Compaction of mixed powders. 1 - («+ v ') / ₂ -«' · 4 · Λ ¹ - ~ ( ^m '+ ^v ') / 2 v. in compacting the blended powders. 1. A process for producing a cobalt-based alloy composition with a one-component matrix for granular media formulated as Co _f - (M _u O _v ) _{f 2} , wherein M represents a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V) , chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr) , niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of base metal atoms M and v the number of oxygen atoms (0), both in the oxide formula, and af ₂ are the molar fractions expressed by the equation /, + (μ + v) / ₂ = 1, the method comprising the steps of: blending a Co-M master alloy powder and a Co "O _V 'corresponding to the composition formula _(Co Mi- _a) it' - (Co _u '0 _V') / 2 'where f ₂ is expressed by the formula: is expressed by the formula where and is represented by the formula / 2/2> where is expressed by the formula / 2 ~ fi 'in where /, is expressed by the formula f \ = i- ~ («” + v ”) / ₂ , ^and where a”, b ”, c”, d ”and e” are represented by the formulas fyb ~ -u "-F ₂ b" = -vl-4 ( _M "+ in") / ₂ c "= · fl ' ^C d" = i-4 (# "+ in") A f'd ι-4 ("" ^{+ ν} ”) Λ compaction of mixed powders. The method of claim 1, further comprising the step of grinding the blended powder in a ball mill. 3. The method of claim 1, wherein the compacting step further comprises the steps of: · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · encapsulating the mixed powders in a container; evacuating the gases from the container; and subjecting the container to high temperature and pressure. 4 4 oxidu of oxide, a and b represent atomic fractions, /, and f ₂ represent molar fractions expressed by the equation γ + ((+ v) f ₂ = 1, wherein the composition is produced using the following steps: mixing the master alloy powder Co _a > Cr _b 'Pt _C ' M _d 'and powder Co _u O _v / into the corresponding composition with the formula (Co _a ' Cr _b 'Pt _C ' M _d ') fi' (CO _U '0 _V ' ) f2 ', where f ₂ is expressed by the formula: where is represented by the formula fi =! - 7 ( ^Μ ' ^{+ ν} ') Λ> ^and v where a ’, b’, c ’and ï are represented by the formula ï = -? e = —— I-4 (m '+ v') / ₂ v d = ^f ^ ^U ; and in compacting the blended powders. 4 4 * 4 4 4 4444 A method of making a cobalt-based binary matrix alloy composition for granular media formulated as (Co _and Pti _-a ) yi - (M _u Ov) S 2> wherein M represents a parent metal selected from the group consisting of magnesium (Mg), titanium ( Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium ( Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), wherein u represents the number of atoms of the parent metal M and v the number of oxygen atoms (0), both in the oxide formula, and represents the atomic fraction, and af ₂ is the molar fractions expressed by the equation /, + (m + v) / ₂ = 1. steps: mixing the powder of Co _a 'M _b ' Pti- _a '-b' and Co _u O _V 'powder into the corresponding composition with the formula (Co _a 'Mb'Pti- _a '-b') fi '~ (CO _U O _V) -) / 2 ', where f ₂ is represented by the formula: v wherein is represented by the formula = 1 - ^ (m '+ v') / ₂ , and wherein a 'and b' are represented by the formulas f _x -a-u '--- f ₂ a' = -Yv; a b - = - £ tl— A process for producing a ternary matrix cobalt-based alloy composition for granular media formulated as (CoaCrhPti-gi,)) ^- (M _at 0 _v ) _{ί 2} , wherein M represents a parent metal selected from the group consisting of magnesium (Mg), titanium ( Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium ( Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of base metal atoms M and v the number of oxygen atoms (0), both in the oxide formula, a and b represent atomic fractions, f _x and f ₂ represent molar fractions expressed by the equation f _x + («+ v) / ₂ = 1, the method comprising the steps of: mixing the master alloy Co _and .Cri, 'Pt _C ' M _d , and the powder Co _u O _V 'into the corresponding composition with the formula (Οο ^ Ο ^ ΡίοΉτ) f> ~ (Co _u ' 0 _v ') / 2'! where / ₂ is expressed by the formula: where is expressed by the formula // = 1-4 (m '+ v') / ₂ , and in where a ', b', c 'and ï are represented by the formula α' = -ι-4 (* Μ / ₂ v i_r ("> _{+ v} .) yv A process for producing a cobalt-based alloy composition with a ternary matrix for granular media formulated as (Co _a Cr _b Pti _-a - _b ) / i- (M _u 0 _v ) / 2; wherein M represents a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of parent metal atoms M and v the number of oxygen atoms (0), both in the oxide formula, a and b represent atomic fractions, f, and / ₂ are molar fractions expressed by /, + (w + v) / ₂ = 1, the method comprising the steps of: mixing the master alloy powder Co _a Cr _b Pt _C Md and the powder Cr _U 0 _V into the corresponding composition with the formula (Co _a Cr _b Pt _C Md) _f - (Cr _U 0 _V ) / 2 / where /, · ά - 2 · _Μ ”· / ₂ > 0, where / ₂ is expressed by the formula: f2 ⁼ “'f2> where is represented by the formula = 1 - ;; («” + v ”) / ₂ , and in where a”, b ”, c” and d ”are represented by formulas 4 «-·-----4 4 4 4 4 IN Ι · «ι-4 (” + ”·’) λ In compaction of mixed powders. 7) · = 1-4 ("" + ν ") Λ, and where a", b ", c" and d "are expressed by the formulas f ' ^and b" = -vl-4 (n "+ v") / ₂ V f ₂ - ^u v ”compaction of mixed powders. 7. A process for the production of a cobalt-based alloy composition with a quaternary matrix for granular media formulated as (Co _and CrhPt _c Ard) / 7- (M _at 0 _v ) / 2r wherein M 'represents an element selected from the group consisting of boron (B), tantalum (Ta), niobium (Nb), zirconium (Zr), copper (Cu), silver (Ag), gold (Au) and ruthenium (Ru), M represents a parent metal other than M 'and selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), wherein: u represents the number of atoms of the parent metal M and v number of oxygen atoms (0), both in the oxide formula, a and b represent atomic fractions, j \ af ₂ represent the molar fractions expressed by the equation f + (m + v) / ₂ = 1; by the equation d = 1- ab — c, the method comprising the steps of: mixing the powder of Co _a 'Cr _b ' Pt _C 'M' d M _e 'and Co _u powder <0 _V ' into the corresponding composition with the formula (Co _a 'Crb' Ph _C 'M'd'M _e ') fi '~ (Co _u > O _in >) / 2'r A process for producing a cobalt-based alloy composition with a quaternary matrix for granular media formulated as (Co _and Cri, Pt _c M ' _d ) _f - (M _at 0 _v )) ₂ , wherein M' represents an element selected from the group consisting of boron ( B), tantalum (Ta), niobium (Nb), zirconium (Zr), copper (Cu), silver (Ag), gold (Au) and ruthenium (Ru), M represents a base metal different from M 'and selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (AI), silicon (Si ), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), india (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W) ), where ú represents the number of atoms of the parent metal M and v the number of oxygen atoms (0), both in the oxide formula, and b represent atomic • 99 9 9 9 · · · · · 99 9 · «·· ι-4 (» + ν) IN 9 9 9 9 9 9 9 999 9 9 9 9 9 9 9 9 9999 99 99 99 99 9 9 9 9 9 9 9 9 9 999 9 9 9 9 9 9 99 99 99 9 9 9 9 9 999 «« 9 99 9 «9 9« represents the number of atoms of the parent metal M and v the number of oxygen atoms (O), both in the oxide formula, and represents the atomic fraction, faf ₂ represents the molar fractions expressed by /, + (w + v) / ₂ = 1, wherein the composition is produced using the following steps: mixing the powder of the master alloy COad ^ Pti-a '- *' and the powder Co _u O _V 'into the corresponding composition with the formula (Co _a ' M _b 'Pti- _a ' -t, ') si' ~ (CO _U '0 _V ' ) f2>, where f ₂ is expressed by the formula: where is expressed by the formula fi = 1-4 ( ^m ' ^{+ v} ') / 2 / ^and v where a 'and b' are represented by the formulas fa-u '--- f ₂ and' = - ^v -v; and < i-lk + d / j v compaction of mixed powders. 9 99 99 999999 99 9 99 99 represents a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper ( Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum ( La), hafnium (Hf), tantalum (Ta), and tungsten (W), u represents the number of atoms of base metal M and the number of oxygen atoms (0) per oxide formula, AFAF ₂ being mole fractions represented by the equation f _x + (+ + V) / ₂ = 1, wherein the composition is produced using the following steps: mixing the Co-M master alloy powder and the Co _u O _V 'powder into the corresponding composition with the formula (Co _and Mi _-a ) - (Co _u O _V ') f ₂ 'r where f ₂ is expressed by the formula: where is represented by the formula / = 1 - / - (m '+ v') / ₂ , and in which a is represented by the formula l- («+ v) / ₂ -« '· / - · / 2 1-4 ( ^w ' ^{+ v} ') / 2-w / ₂ and = -Y- =; and ι-4 (Μ / ₂ vv in compaction of mixed powders). A cobalt-based alloy composition with a one-component matrix for granular media formulated as Co / χ- (M _u 0 _v ) / 2, wherein M • • 9 99 99 9 99 99 9999 999 999 ··· 9999 999 999 99,999 9,999 99,999 9 9 9 9 9 4 4 • 44 • 4 9 4 4 < 44 fractions, / and / _2, represent the molar fractions expressed by the equation / + (m + v) / ₂ = 1, and d is expressed by the equation d = labc, the method comprising the steps of:. blending a master alloy Co _and Cr _b Pt _C M dM _e and Cr powder _U O _V to a corresponding composition having the formula _(Co CrbPt _C M'ď'M _e) fi "- (Cr _V O _U) / 2, where F - where / ₂ is expressed by the formula: 9 * 9 * where / 'is expressed by the formula = 1-4 ( ^m ' + ^v ') / 2 ^ and v where a ', b', c ', d' and e 'are represented by the formulas a' = -vV '· =. s < ^b ι-r ("·" ·) /, v β = -il_4 (". _{+ v} -) y." In f'- ^d ι-4 (»'+'') λ v e ’= -, and‘ - / • (“’ + νΟΛ In compaction of mixed powders. 9 * * * * * * 9 9 9 9 9 9 · « 9 9 9 • · · · · 99 9 · A binary matrix cobalt-based alloy composition for granular media formulated as (Co _and Pti _-a ) / 1- (M _U O _V ) f ₂ , wherein M represents a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), wherein: u 9 9 9 9 9 99 99 9 9 9 9 9999 9 9 9 9 A ternary matrix cobalt alloy composition for granular media formulated as (Co _and CrbPti- _and -b) (M _U O _V ) wherein M represents a parent metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of base metal atoms M and v the number of oxygen atoms (O), both in the formula 12th Alloy composition based ternary matrix cobalt granular media formulated as _(Co CrbPti- _a - _b) fi ~ (M _u 0 _{v) f2} of M representing a base metal selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum * * * * * * * * * * * * * * * * * * * * * * * 999999 99 9 9 9 9 9 (Ta), and tungsten (W), u represents the number of atoms of base metal M and the number of oxygen atoms (0) per oxide formula, a and b representing atom fractions, j \ f ₂ representing mole fractions represented by the equation + (u + v) f ₂ = 1, wherein the composition is produced using the following steps: mixing the master alloy powder Co _and CrbPt _C M _d and the powder Cr _U O _V into the corresponding composition with the formula (Co _and Cr ^ Pt _C M _d ) _f (Cr _u O _v ) j2 r where fb—- · μ ”· / ₂ > 0, v ”where f ₂ 'is expressed by the formula: A cobalt-based alloy composition with a quaternary matrix for granular media formulated as (Co _a Cr _b Pt _c M ' _d ) _{f 1} - (M _u 0 _v ) _{f 2r} wherein M' represents an element selected from 43 · < • · · * · • · • · 4 ·· • · · • · · • · · · «· · ·· • • · • · · · »·· · • groups consisting of boron (B), tantalum (Ta), niobium (Nb), zirconium (Zr) copper (Cu), silver (Ag), gold (Au) and ruthenia (RU), M represents base metal different from M 'and selected from groups consisting magnesium (Mg) , titanium (Ti), vanadium (V), of manganese (Mn) iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), of aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium And (Nb), molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and of tungsten (W), where u represents the number of atoms of the parent metal M and v the number of oxygen atoms (O), both in the oxide formula, a and b represent atomic fractions, /, and f ₂ represent molar fractions expressed by /, + (m + v) f ₂ = 1, and d is represented by the equation d = 1 — ab — c, wherein the composition is made using the following steps: blending the powder of Co _a >Crb'Pt _C 'M' _d > M _e 'and Co _U ' 0 _V 'powder into the corresponding composition of the formula (Co _a 'Crb'P ^ c'M'd'M _e ') fi '~ (Co _u O _v >} f2 <, where f ₂ is expressed by the formula: where is represented by the formula / 1 ' ^{= 1} - ^ (''+v') / ₂ , and in which a ', b', c ', ï and e' are represented by the formula b '= IN A-b 14. Alloy composition based on cobalt s quaternary matrix for grained media formulated as (Co _a Cr _b Pt _c M ' _d ) / j- (Co _u O _v ) / 2z wherein M' represents an element selected from the group consisting of boron (B), tantalum (Ta), niobium (Nb), zirconium (Zr) ), copper (Cu), silver (Ag), gold (Au) and ruthenium (Ru), M represents a parent metal other than M 'and selected from the group consisting of magnesium (Mg), titanium (Ti), vanadium (V) , manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), silicon (Si), yttrium (Y), zirconium (Zr), niobium (Nb) , molybdenum (Mo), ruthenium (Ru), indium (In), lanthanum (La), hafnium (Hf), tantalum (Ta) and tungsten (W), where u represents the number of parent metal atoms M and v the number of oxygen atoms ( O), both in the oxide formula, a and b represent atomic fractions, /, and f ₂ represent the molar fractions expressed by the equation /, + (m + v) / ₂ = 1, and d is expressed by the equation d = 1a 1 -c, using the following steps: blending a master alloy _of Co _and «CrbPtcM 'DME and powder of Cr _U O _V to a corresponding composition having the formula _(Co» CR _b »Pt _c ^' _d ^ _e U (C _U O _{V) i2",} where /, · Ζ? - ^ · μ ”· / ₂ > 0, h where f ₂ is expressed by the formula: Kde ⁼ ~ 'fi> where it is expressed by the formula to * · e e to to to to to to to to to to to to to to to to to to to to to to to to • «to to kde kde kde a where a”, b ”, ί = 1-4 (“ ”+ ν”) ) Λ, a In c ”, d” and e ”are represented by formulas fi and ι-4 (» ”+ ν”) Λ V b ”= f _be » .f ₂ in f ^{c c} -4 («” ++ ”) Λ </” = · fx-d L · «l-4 (“ ”+ +”) / 2 v compaction of mixed powders.