U.S. patent number 3,871,840 [Application Number 05/219,973] was granted by the patent office on 1975-03-18 for abrasive particles encapsulated with a metal envelope of allotriomorphic dentrites.
This patent grant is currently assigned to Christensen Diamond Products Company. Invention is credited to Harold C. Bridwell, Arthur G. Wilder.
United States Patent |
3,871,840 |
Wilder , et al. |
March 18, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
ABRASIVE PARTICLES ENCAPSULATED WITH A METAL ENVELOPE OF
ALLOTRIOMORPHIC DENTRITES
Abstract
Abrasive particles are improved in function by encapsulating
them with a metallic envelope; preferably the envelope is made of a
pure metal in dendritic crystalline form. Desirably the abrasive
substrate is placed in contraction by the envelope which is heat
shrunk onto the abrasive substrate. The preferred method is to
deposit the metal on the substrate at an elevated temperature by
contacting a vapor of the metallic compound with the substrate
particle under reducing conditions. The preferred primary abrasive
is a diamond, and it is preferably etched before coating. Superior
formed abraders may be formed by metal bonding such encapsulated
abrasives with a metal matrix which forms a continuous phase in
which the abrasive particles may be positioned. The encapsulated
abrasive particle may form the primary abrasive together with a
secondary abrasive which is not as hard as the primary abrasive and
which may or may not be encapsulated with a metal. The primary and
secondary abrasive may in one form of the abrader be distributed in
the continuous phase metal binder forming the matrix.
Inventors: |
Wilder; Arthur G. (Salt Lake
City, UT), Bridwell; Harold C. (Salt Lake City, UT) |
Assignee: |
Christensen Diamond Products
Company (Salt Lake City, UT)
|
Family
ID: |
22821507 |
Appl.
No.: |
05/219,973 |
Filed: |
January 24, 1972 |
Current U.S.
Class: |
51/295; 51/298;
51/309; 427/215; 427/250 |
Current CPC
Class: |
C09K
3/1445 (20130101); B24D 7/00 (20130101) |
Current International
Class: |
B24D
7/00 (20060101); C09K 3/14 (20060101); B24d
003/06 (); B24d 003/34 () |
Field of
Search: |
;51/295,298,309
;117/1R,1B,1S |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
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|
|
|
|
|
306,271 |
|
Feb 1969 |
|
SW |
|
312,098 |
|
Oct 1969 |
|
SW |
|
Other References
Cutting Tool Eng. Vol. 15, p. 27, June 1963, Report on Process of
Molecular-Metallic-Coated Diamonds, Fred M. Ross..
|
Primary Examiner: Arnold; Donald J.
Attorney, Agent or Firm: Kriegel; Bernard
Claims
1. An article of manufacture consisting of abrasive particles
having a hardness of above about 2000 kg/mm.sup.2 encapsulated with
a metal envelope formed of allotriomorphic dendrites.
2. In the article of claim 1 in which the abrasive particles are
chosen from the group consisting of diamonds, tungsten carbide,
alumina and silicon carbide.
3. In the article of claim 2 in which the encapsulated metal is
chosen from the group consisting of tungsten, tantalum, columbium
(niobium) and molybdenum.
4. In the article of claim 1 in which the abrasive is diamond and
the encapsulating metal is tungsten.
5. In the article of claim 1 in which the abrasive is tungsten
carbide and the encapsulating metal is tungsten.
6. In the article of claim 1 in which the abrasive is alumina and
the metal is tungsten carbide.
7. In the article of claim 1 in which the abrasive has a
coefficient of linear expansion in the range of about 1 .times.
10.sup..sup.-6 inches per inch per degree Fahrenheit to about 5
.times. 10.sup..sup.-6 inches per inch per degree Fahrenheit and
said metal has a linear coefficient of expansion in the range of
from about 2 .times. 10.sup..sup.-6 to about 10.sup..sup.-5 inches
per inch per degree Fahrenheit and in which the linear coefficient
of expansion of said metal is in the range of from about 1.05 to
about 7 times the linear coefficient of expansion of said
unencapsulated particle.
8. In the article of claim 7 in which the abrasive particles are
chosen from the group consisting of diamonds, tungsten carbide,
alumina and silicon carbide.
9. In the article of claim 8 in which the encapsulated metal is
chosen from the group consisting of tungsten, tantalum, columbium
(niobium) and molybdenum.
10. In the article of claim 7 in which the abrasive is diamond and
the encapsulating metal is tungsten.
11. In the article of claim 7 in which the abrasive is tungsten
carbide and the encapsulating metal is tungsten.
12. In the article of claim 7 in which the abrasive is alumina and
the metal is tungsten carbide.
13. A shaped abrader structure comprising a continuous phase of
metal matrix and abrasive particles positioned in said matrix said
particles having a hardness in excess of about 2,000 kg/mm.sup.2
encapsulated with a metallic envelope formed of allotriomorphic
dendrites.
14. In the article of claim 12 in which the abrasive particles are
chosen from the group consisting of diamonds, tungsten carbide,
alumina and silicon carbide.
15. In the article of claim 14 in which the encapsulated metal is
chosen from the group consisting of tungsten, tantalum, columbium
(niobium) and molybdenum.
16. In the article of claim 13 in which the abrasive is diamond and
the encapsulating metal is tungsten.
17. In the article of claim 13 in which the abrasive is tungsten
carbide and the encapsulating metal is tungsten.
18. In the article of claim 13 in which the abrasive is alumina and
the metal is tungsten carbide.
19. As an article of manufacture an etched diamond particle
encapsulated in a metal envelope in which the metal is composed of
allotriomorphic dendrites.
20. In the article of claim 19 in which the metal is tungsten.
21. A method of producing an abrasive particle having a hardness of
above about about 1,700 kg/mm.sup.2 encapsulated with a metal
envelope formed of allotriomorphic dendrites which comprises
contacting said particle with a vaprous metal compound and with
hydrogen at an elevated temperature in the range of about
1000.degree. to about 1200.degree. F. and depositing metal as an
envelope on said particle and separating the said particles from
vapors and gases in contact therewith.
22. In the process of claim 19 in which the abrasive particles are
chosen from the group consisting of diamonds, tungsten carbide,
alumina and silicon carbide.
23. In the process of claim 19 in which the encapsulated metal
compound is chosen from the group consisting of tungsten, tantalum,
columbium (niobium) and molybdenum.
24. The process of claim 19 in which the abrasive particles are
diamonds etched by contact with a molten alkali metal nitrate or an
alkali earth nitrate at temperatures below the decomposition
temperature of the nitrate in an inert atmosphere.
25. The process of claim 24 in which the encapsulating metal is
tungsten.
Description
Abrasive, grinding, cutting and earthboring tools, hereinafter
referred to as abraders, have bound abrasive particles into an
abrader structure, using a binder such as a resin and, in some
cases, metal, which acts as the matrix to hold the abrasive
particles in the abrader structure.
The abrasive action places the abrasive particle in tension and
resultant excessive fragmentation of the abrasive particles may
thereby result in loss of the particle from the matrix.
We have solved the problems referred to above by producing a novel
metal encapsulated abrasive particle and novel abrader structures
by first encapsulating abrasive particle with a metallic
envelope.
When metal is used as a matrix to bind the abrasive particles in
the abrader structure, encapsulation of the abrasive particles
increases the grip of the metal matrix on the abrasive
particle.
The encapsulated particle is more easily wetted by the molten metal
than the non-metallic substrate. The improved interfacial tension
between the metal envelope and the metal matrix used to bond the
particles increases the grip of the metal matrix on the
encapsulated particle and thus helps to prevent the loss of the
particle in case excessive fragmentation of the particle does
occur.
In selecting the metal for the envelope when the encapsulated
particle is to be used with the metal matrix acting as a bonding
agent, it is desirable that the metal in the envelope have a
suitably higher melting point than the metal matrix.
The third advantage of the encapsulated abrasive particle of our
invention when used together with a metal matrix resides in the
increased rate of heat transfer from the abrasive particle
resulting from the more intimate contact surface between the
envelope and the substrate particle and the envelope and the metal
matrix. Heat generated at the abrading surfaces, if not readily
transmitted to and absorbed in the metal matrix, acting as a heat
mass, will cause a local rise in temperature which may have a
deleterious effect upon the life of the abrasive particle.
In order to obtain the increased bond between the abrasive
particles and the metal matrix any convenient method for deposit of
the metal envelope on the particle substrate may be employed. Thus
electrochemical or electrolytic methods which have been previously
employed in coating abrasive particles for use in abrader structure
will, when used together with a metal bonding agent in our novel
abrader structure, result in an improved bond between the metal
matrix and the coated particle due to the improved wetting by the
molten metal. In this respect, the use of the coated particle in a
composite structure employing a metal matrix is an improvement over
the use of an abrasive particle coated by an electrochemical or
electrolytic process when used with a resin binder. It is similarly
an improvement over the use of uncoated abrasive particles with
resin or metal binders acting as a matrix for the abrasive
particles.
Abrasive particles coated by such procedures result in deposits
which are contaminated by intergranular inclusions of impurities
from their aqueous environment. Furthermore, the deposits
particularily in the case of electrolytic deposits have
intergranular planes of weakness and the coating has a relatively
low tensile and bending strength. They do not improve, in any
substantial degree, the physical properties of the coated particle
as compared with the uncoated particle.
The metallic envelopes which constitute the abrasive particles of
our invention employed in the novel abrader structure of our
invention differ from the foregoing coatings in composition and
crystalline nature.
In contrast to these deposits, the deposits of our invention are
substantially pure metal envelopes, substantially free of
intergranular inclusions.
The metallic envelope of the abrasive in the abrader structure of
our invention is composed of crystal grains which are dendrites
starting at and extending from the substrate surface, creating a
super position of grain growth interrupted by other grain skeleton
deposit on top thereof. The grains thus deposited form a
mechanically interlocked grain structure giving to the metal sheath
high tensile strength. Such deposits are termed
"allotriomorphic."See FIG. 13.
We prefer to produce the aforesaid encapsulated abrasive of our
invention by a process of chemical vapor deposition, by subjecting
the abrasive particles to contact with a volatile metal compound at
an elevated temperature sufficient to maintain the metal compound
in vapor form and contact the vapor with a solid substrate under
metal deposition conditions.
We have also found it useful, where the chemical nature of the
abrasive particle substrate permits, to choose metallic envelopes
which form a surface chemical bond with the substrate by reason of
a limited chemical reaction between the metal and the substrate
surface, thus producing an encapsulated particle in the form of a
cermet.
The formation of the intersurface bond between the envelope and the
substrate is facilitated by the elevated temperature employed in
our preferred method of metal deposition.
Where the metal envelope has a coefficient thermal expansion
substantially greater than that of the abrasive particle, by
depositing the metal envelope on the substrate particle, at a high
temperature the resultant particle on cooling is placed under
compression by the metallic envelope. Thus, the tensile force
necessary to rupture the abrasive particle must then be greater
than in the case of the unencapsulated particle.
This property has an advantage irrespective of the bonding agent
employed and may advantageously be used whether resin or metal acts
as the bonding agent.
Where the abrader structure is to be used as a cutter or abrader,
for example, in oil well drill bits or other boring and shaping
tools suitable for example in sawing concrete, masonry, rocks,
ceramics, bricks, etc., we prefer to use abrasive materials
preferably those having hardness of about 2000 kg/mm.sup.2 (Knoop
or Vickers) or more, for example, those shown in Table 1. An
additional useful criteria is that the abrasive material should
have a melting or softening point in excess of the highest
temperature reached in the process by which the abrader structure
is formed, such as is described hereinbelow.
We prefer to employ, because of their physical properties, such as
hardness, melting point, chemical stability, and other physical
properties, one of the following abrasive materials preferring
among them diamonds, either natural or synthetic. In addition to
diamonds, we may use any one of the following abrasive particles
shown in Table 1. The values reported in the table are taken from
the available literature.
TABLE 1
__________________________________________________________________________
M.P. .degree.C. Sp.G. Percent Hardness Linear Coeff. kg/mm.sup.2 of
Expansion Knoop* .times. 10.sup.4 Vickers** 0-1000.degree. F.
__________________________________________________________________________
Diamonds (Synthetic or Natural) 3.5 1.5 8000* Aluminum Oxide
(Al.sub.2 O.sub.3) 2060 3.5-4 4.4 3000* Cast Eutectic Tungsten
Carbide 4800 15 Tungsten Mono Carbide (WC) 4800 15.8 2.7 Ditungsten
Carbide (W.sub.2 C) 4800 17.3 1950-2400 Boron Nitride (Cubic)
>1700 3.48 .about.20 4700* Tetrachromium Carbide (Cr.sub.4 C)
1500 6.99 3 Trichromium Dicarbide (Cr.sub.3 C.sub.2) 1910 6.68 2.4
2650 Titanium Diboride (TiB.sub.2) 2870 4.52 4.2 3000-3500* Hafnium
Diboride (HfB.sub.2) 3250 11.20 4.2 3800* Zirconium Diboride 10
(ZrB.sub.2) 3100 6.09 4.6 2000* Calcium Hexaboride (CaB.sub.6) 4050
2.46 3.6 2740.+-. 220* Barium Hexaboride (BaB.sub.6) 4100 4.32 3.8
3000.+-. 290** Tantalum Carbide (TaC) 3.7 Silicon Carbide
>1000.degree. 3.21 2.4 2200-2900*
__________________________________________________________________________
In order to obtain a compressive force on the substrate, we select
a metal for the envelope having a substantially greater coefficient
expansion than the substrate. In such case, when the metal is
deposited on the substrate at an elevated deposition temperature,
on cooling, the metal sheath will contract more than the substrate,
putting the substrate under compression. Since the linear
coefficient of thermal expansion of suitable abrasives are in the
range of about 1 to about 5 .times. 10.sup..sup.-6 inches per inch
per degree Fahrenheit, we select metal sheaths having a higher
coefficient of expansion than the substrate. For example, we select
metals having linear coefficients of expansion of about 2 .times.
10.sup..sup.-6 to about 10.sup..sup.-5 inches per inch per degree
Fahrenheit. By matching the coefficients of expansion, as described
above, a useful encapsulation may be obtained. It is useful to
remember that the coefficients of cubic expansion may, for the
above purposes, be taken as about three times the linear
coefficient of expansion. In such a combination the disruptive
force sufficient to fragment the substrate particle must be greater
than that which would fracture the unencapsulated particle, since
it must overcome initially the compressive force which places the
underlying substrate in compression.
The following Table 2 lists metals having coefficients of expansion
above the lower limit of the coefficients of the abrasives listed
in Table 1. As in Table 1 the values are taken from available
literature.
TABLE 2
__________________________________________________________________________
Metal Specific Melting Percent Young's Gravity Point Thermal Modu-
.degree.C Coefficient lus of Linear .times.10.sup.6 Expansion
.times. 10.sup.4 /.degree.F 0-1000.degree. F
__________________________________________________________________________
Tungsten (W) 19.3 3380 4 50 Tantalum (Ta) 16.6 2966 3.9 27
Molybdenum (Mo) 10.2 2610 2.2 50 Niobium (Nb) i.e. Columbium (Cb)
8.5 2500 4 26 Vanadium (V) 5.89 1890 3.2 41 Zirconium (Zr) 6.4 1852
3 11 Titanium (Ti) 4.54 1675 4.7 16.8 Iron (Fe) 7.86 1535 6.5 28.5
Cobalt (Co) 8.9 1492 6.85 30 Nickel (Ni) 8.9 1453 7.2 30 Copper
(Cu) 8.9 1083 9.22 16
__________________________________________________________________________
Thus, for example, if diamond be the substrate, we may use for the
purpose any one of the metals listed in Table 2 to form the
encapsulating envelope. In each of these cases, the coefficient of
linear expansion of the metal is substantially greater than that of
diamond, and their use would also have the advantage of adding a
compressive force upon the diamonds to help in overcoming the
tensile forces which would tend to fracture the diamond when used
in an abrader structure as the abrasive particle.
In selecting the encapsulating metal with the view of obtaining the
advantage of the differential contraction, metals may be selected,
depending on the stress desired to be imparted.
For example, for the metals listed in Table 2 and the abrasives of
Table 1, metals having a coefficient greater than the substrate
coefficient by about 5 to 10 percent or more of the value of the
coefficient of the substrate. That is, the coefficient of the metal
should be about 1.05 or more, for example, up to about 7 times the
coefficient of the substrate.
In selecting the metal encapsulating materials, when employing
diamonds as a substrate, when we employ carbide-forming metals, we
prefer to employ those which have only a limited reaction rate at
the temperatures of deposition, as hereinafter described. For
example, we may use molybdenum, tungsten, tantalum, titanium, and
niobium, all of which are carbide formers but are unlike iron which
under the conditions of deposition or the production of the abrader
may result in excessive attack on the diamond forming carbides or
graphite.
For all of the foregoing reasons, we prefer to use in combination
with the abrasive particles tabulated in Table 1 above, and
selected according to their properties as described above,
tungsten, tantalum, niobium (columbium) and molybdenum, and, among
the primary abrasive particles, we prefer to employ diamonds,
either the natural or synthetic forms, and prefer to employ
tungsten as the encapsulating material, deposited under conditions
to produce pure tungsten of the crystal form as described
herein.
Where we employ the metal encapsulated abrasive in abrader
structures formed by metal bonding the encapsulated abrasive in a
metal continuous phase matrix, we prefer to employ as a bonding
agent a metal having a significantly lower melting point than the
metal sheath of the abrasive substrate. When employing diamonds as
the encapsulated abrasive particle, we prefer to limit the melting
point of the metal matrix to a temperature below about
2,800.degree. F. in order not to expose the diamonds to excessive
temperature which may impair the mechanical strength of the
diamonds.
Another important consideration is the coefficient of thermal
expansion of the metal matrix used as bonding agent. Since, in
general, the low melting metals and materials have high thermal
expansion, in the absence of an encapsulating metal which is wetted
by the molten metal, the mass of matrix on cooling would tend to
pull away from the abrasive material, thus impairing the bond. It
is one advantage of the encapsulating metal that the thermal
expansion of the metal sheath matches more closely the thermal
expansion of the metal matrix and that the interfacial tensions
will tend to prevent the pulling away of the metal matrix from the
metal sheath. Such metals having melting points so as to be fluid
in the formation of the abrader structure, for example at
temperatures below about 2,800.degree. F. when employing diamonds
are suitable.
However, we prefer to employ such metals which also have the
preferred properties as hereinafter described. The metal chosen
should be fluid at the temperature at which it is desired to employ
the molten metal in forming the composite abrader structure and
desirably should have, when solid, ductility as measured in the
terms of microhardness of below about 400 kg/mm.sup.2. Desirably,
also, it should have a compressive strength above about 90,000
p.s.i. and an impact strength above about 5 foot pounds.
For this purpose we may use copper-based alloys such as brass and
bronze alloys and copper-based alloys containing various amounts of
nickel, cobalt, tin, zinc, manganese, iron and silver.
Since when using encapsulated diamonds the diamond is protected
from attack by the metal, we may use cobalt-based, nickel-based,
and iron-based alloys of suitable properties. These alloys are
excluded from use as metal matrixes when using unencapsulated
diamonds because under molten conditions they attack the diamond
excessively. Thus we may with the encapsulated diamond, for
example, employ the nickel-copper-aluminum-silicon alloy having a
melting point below 2,000.degree. F.; cast iron, cobalt, chromium,
and tungsten alloys having melting points below about 2,800.degree.
F. may be used.
Where the abrasive particle is a tungsten carbide or diamond
particle which is attacked by nickel, cobalt or iron or alloys of
these metals, the encapsulation of the tungsten carbide by a metal
envelope of substantially higher melting point according to our
invention will prevent the attack which the unencapsulated particle
would otherwise suffer under the conditions of fabrication of the
abrader structure.
As described above, when using a molten metal to form the matrix,
unencapsulated cast tungsten carbide is attacked by iron-based or
nickel-based alloys. The W.sub.2 C tungsten carbide is attacked or
dissolved in the binder, and on freezing precipitates a new phase
called eta. This phase is M.sub.6 C type carbide, and in the case
of nickel binders will have the composition Ni.sub.3 W.sub.3 C. Eta
phase is more brittle than the original particle. The particle is
said to be "haloed." The "haloed" portion of particle will have a
hardness only of about 1,500 kilograms per square millimeter,
compared for example to 1,950 to 2,100 kilograms per square
millimeter (Knoop) for the core of the particle. By employing a
tungsten-coated tungsten carbide of the above characterization, the
"haloing" effect of these metals is avoided and they then may be
used as a binder metal.
In one form of the above abrader structures, a plurality of
different abrasive particles are employed. In addition to particles
of high hardness values, for example, diamonds which act on the
primary abrasives, there is distributed in the continuous phase of
the metal matrix binder a secondary abrasive of lower hardness
value, for example, those shown in Table 1.
The purpose of this secondary abrasive particle is to wear away
preferentially thus exposing new abrasive faces of the primary
abrasive particle.
The abrader structures thus formed are deemed self-sharpening. That
is, the matrix including the secondary abrasive should wear away
preferentially and uniformally exposing new primary abrasive
cutting surfaces. This tends to reduce the area of the interfacial
surfaces between the bonding metal of the matrix and the primary
and secondary abrasive particles. Where the bond is weak, the
particles are torn out of the metal matrix, causing excessive
wear.
The intermetallic bond between the metal matrix and the
encapsulated primary or secondary abrasive increases the retention
of the abrasive particle until its cutting life is ended by wearing
away of the particle or breaking away of fragments thereof from the
portion of the abrasive particle which has become free of the
encapsulation at the abrading surface during the abrading
action.
In selecting the secondary abrasive, we may, in order to add mass
to the abrader select from the abrasive particles having suitable
hardness and other desirable physical properties those having a
specific gravity to give mass to the abrader; i.e., those with
specific gravities substantially in excess of the abrasive
substrate.
For example, when employing unencapsulated diamonds as a primary
abrasive in an abrader we may use as the secondary abrasive
tungsten carbide or hafnium diboride or those of somewhat lower
specific gravity, i.e. 6 or more as set forth in Table 1.
However, as described above, we may employ the secondary abrasive
having a lower specific gravity by encapsulating the secondary
abrasive by metal having sufficiently high specific gravity to
produce a particle of substantially higher apparent density.
Thus we may use encapsulated secondary abrasive of suitable
hardness chosen for example from the list of Table 1 and
encapsulate the secondary abrasive with a metal of suitable
specific gravity to increase the apparent density of the particle.
This will permit the fabrication of an abrader having the required
volume percent of secondary abrasive but impart a greater weight to
the abrader structure as compared with one of like composition and
volume but employing the unencapsulated secondary abrasive
particle.
Thus for example as described above where unencapsulated tungsten
carbide has been used we may employ in its place alumina
encapsulated with tungsten to give a particle of substantially
higher specific gravity than the alumina. Reference to Table 2 will
permit the selection of suitable encapsulating metals for the
purpose.
The advantages obtained by using an envelope of higher specific
gravity than the substrate, in order to impart mass to a given
volume of the abrader structure become more evident as the
difference between the specific gravity of the substrate and of the
envelope becomes the greater.
We prefer to employ for the encapsulation of the abrasive particles
the reduction of a vapor of the metal compound.
For such purpose we prefer to select among the metals chosen
according to the aforesaid principles of our invention those which
form a compound which may be placed in the vapor state in contact
with the substrate under conditions to deposit the metal on the
substrate surface.
We prefer to employ a compound which may be vaporized at a
convenient temperature either because of its relatively low boiling
point or by reduction of its partial pressure and be introduced
into the contact zone with the abrasive particle for conversion to
the metal state deposited on the substrate.
The procedure we prefer, because it produces the superior envelope
when applied to produce our novel encapsulated abrasive particle,
is the conversion of a volatile compound of the metal into the
metal deposited on the substrate and a gaseous or vaporous reaction
product which may be removed from contact with the encapsulated
metal. This leaves an envelope substantially free of included
impurities.
For this purpose we prefer to use the halides or the carbonyls of
the metals. Preferably for convenience of operation, we prefer to
employ those compounds having a boiling point at atmospheric
pressure below the reaction temperature.
While compounds which may be placed in the liquid state and which
may be distilled by vacuum distillation or by reduction of their
partial pressure by means of a carrier gas are possible, the
compounds listed in Table 3, having reasonable boiling points, so
that their volatilization may be conveniently allowed, are
preferred by us.
TABLE 3 ______________________________________ B.P. .degree.C. at
760 m.m. * ______________________________________ Iron Carbonyl
[Fe(CO).sub.6 ] 102.8+ Molybdenum Pentachloride [MoCl.sub.5 ] 268
Molybdenum Hexafluoride [MoF.sub.6 ] 35 Molybdenum Carbonyl
[Mo(CO).sub.6 ] 156.4 Tungsten Pentabromide [WBr.sub.5 ] 333
Tungsten Hexabromide [WBr.sub.6 ] 17.5 Tungsten Pentachloride
[WCl.sub.5 ] 275.6 Tungsten Hexachloride [WCl.sub.6 ] 346.7
Tungsten Carbonyl [W(CO).sub.6 ] 175 at 766 m.m. Tantalum
Pentachloride [TaCl.sub.5 ] 242 Tantalum Pentafluoride [TaF.sub.5 ]
229.5 Titanium Tetraboride [TiB.sub.4 ] 230 Titanium Hexafluoride
[TiF.sub.6 ] 35.5 Titanium Tetrafluoride [TiCl.sub.4 ] 136.4
Columbium Pentabromide [CbBr.sub.5 ] 361.6 Columbium Pentafluoride
[CbF.sub.5 ] 236 Columbium Pentachloride [CbCl.sub.5 ] 236 Nickel
Hexafluoride [NiF.sub.6 ] 4 at 25 m.m. Vanadium Tetrafluoride
[VaCl.sub.4 ] 148+ Vanadium Pentafluoride [VaCl.sub.5 ] 111+
______________________________________ * Unless otherwise
indicated
In view of the above consideration, we prefer to employ tungsten as
an encapsulating metal because of its high density and high melting
point. It gives under the conditions of fabrication according to
our invention a coating of exceptional high strength. It is readily
wetted by the molten metal matrixes described above and forms a
strong metallurgical bond with the metal matrixes employed in our
invention. It is particularly useful where the substrate is diamond
or other substrates which will react with the tungsten such as
those which form cermets with tungsten.
Our preferred primary abrasive is diamond. Where encapsulated with
a metal under the preferred conditions as described herein, it will
produce a superior abrader structure of longer life. Where
encapsulated with tungsten or other suitable metals as described
above, it will after the exposed metal sheath in contact with the
work has been worn away be exposed to the work but will otherwise
be gripped by the encapsulating envelope which is in turn gripped
by the metal matrix.
In place of or in addition to the encapsulated diamond, we may use
the other abrasives as described above, preferring among them
encapsulated alumina but may also use the other abrasives described
above, particularly encapsulated tungsten carbide or silicon
carbide as is more fully described below.
The invention will be further described by reference to the
following figures:
FIG. 1 is a diagrammatic flow sheet of our preferred process of
encapsulation.
FIG. 2 is a section through a mold for use in the infiltrant
technique of forming abraders according to one form of our
invention.
FIG. 3 is a schematic showing of a mold for use in a hot press
technique employed in forming an abrader element.
FIG. 4 is a section on line 4--4 of FIG. 3.
FIG. 5 is a section taken on 5--5 of FIG. 2.
FIG. 6 is a schematic view of a saw on which the formed abrader is
mounted.
FIG. 7 is a section through a mold for the core bit shown in FIG.
8.
FIGS. 9-14 are photomicrographs of etched sections of metal
abrasive particles contained in a metal matrix according to our
invention.
FIG. 1 illustrated a flow sheet of our preferred process for
producing the novel encapsulated abrasive of our invention. The
particles to be coated are placed in the reactor 1, whose cap 2 has
been removed. The reactor has a perforated bottom to support the
particles of selected mesh size. With cap 2 replaced and the valves
3, 4, 5, and 13 closed, and with valve 7 open, the vacuum pump is
started to de-aerate the system. Valve 7 is closed and the system
filled with hydrogen from hydrogen storage 11, valve 5 being
open.
The reactor is heated by the furnace 9 to the reaction temperature,
for example, from about 1,000.degree. to about 1,200.degree. F.
while purging slowly with hydrogen. The hydrogen flow rate is
increased until a fluidized bed is established. Hydrogen prior to
introduction into the reactor passes through a conventional
palladium catalyst to remove any impurities, such as oxygen in the
hydrogen. Vaporized metallic compound is discharged from the
vaporizing chamber 10, which may if necessary be heated by furnace
14, together with an inert gas, for example, argon from argon
storage 6 into the reaction chamber.
Preferably we desire to employ the volatile metal halides referred
to above, although, in some cases, we may use the carbonyls listed
in Table 3. Where the halide is employed, the reaction forms
hydrogen halide, which is passed through the bubble traps and is
absorbed in the absorber. Where the volatile compound employed is a
fluoride, the product formed is a hydrogen fluoride, and we may use
sodium fluoride for that absorption. We prefer to employ hydrogen
in stoichiometric excess.
The reaction deposits metal on the substrate and the effluent
material, being in the vapor state is discharged, leaving no
contaminants on or in the metal. The metal is formed in its pure
state.
The rate of metal deposition depends on the temperature, and flow
rate of the reactants, being the greater the higher the temperature
and the greater the flow rate of the hydrogen and volatile metals
compound.
After the deposit is formed, the valves 4 and 5 are closed and
argon is continued to pass into the reactor and the metal
encapsulated abrasive is allowed to cool to room temperature in the
non-oxidizing condition of the argon environment.
The conditions in the reactor, both because of the mesh size and
particle size distribution of the particles and because of the
velocity of the vapors and gases fluidizes the particles. As will
be recognized by those skilled in the art, a dense phase is
established in the lower part of the reactor in which the particles
are more or less uniformally distributed in violent agitation in
the dense phase. This results in a substantially uniform deposit
per unit of surface of the particles.
The reaction products and the carrier gases and excess hydrogen
enter the upper space termed the disengaging space where they are
separated from any entrained particles.
Where the diamond particle is smooth as for example in the case of
synthetic diamonds, we may improve the bond of the metal envelope
to the substrate diamond surface produced in the process described
above by first surface etching of the diamond. The etching of the
diamonds will also have an advantage where the metal envelope is
produced by other processes such as electrochemical or electrolytic
deposition methods. However, for the reasons previously described,
the product produced by the process of vapor deposition described
above is superior and is preferred by us.
EXAMPLE 1
To etch the diamonds, we immerse them in a molten bath of an alkali
metal nitrate or alkaline earth nitrate at a temperature below the
decomposition temperature; thus in using potassium nitrate,
temperature would range from 630.degree.+ F. and under 750.degree.
F.; sodium nitrate, about 580.degree. F. and under about
700.degree. F.; barium nitrate, at or above 1,100.degree. F. and
below its decomposition temperature. We prefer to employ potassium
nitrate at about 630.degree. F. for about an hour. The bath is
contained in a nitrogen or other inert gas atmosphere.
At the completion of the heating process, the molten bath is cooled
and the cooled bath is then leached with water to dissolve the
salt, leaving the etched diamonds which may then be separated and
dried.
The degree of etching depends upon the immersion time and a
suitable time will be about an hour under which conditions the
particles will lose from about 1/2 to 1 percent of their weight.
The surface of the diamonds is roughened and pitted and forms a
desirable and improved substrate base.
For purposes of illustration, not as limitations of our invention,
the following examples are illustrative of the process of
depositing a metal sheath upon a substrate.
EXAMPLE 2
Diamonds, either synthetic or natural, preferably etched as above,
of mesh size suitable for fluidizing are introduced into the
reactor 1. The actual mesh size employed depends upon the service
to which the abrader is to be placed. For use in oil well tools,
cutters, saws, and grinders, we may use particles of size (Tyler
mesh) through a 16 and on a 400 mesh (-16 + 400). Preferably we
employ 40 to 100 mesh material, for example -40 + 50 mesh. In
depositing tungsten, we may and prefer to employ tungsten
hexafluoride, which is contained and vaporized in 10. It is
volatile at atmospheric temperatures and need not be heated. In the
reactor employed after the system has been deaerated and back
filled, hydrogen flow is established at a low flow rate of about
100 ml/min and as described above, the temperatures in the reactor
1 having been adjusted to 1,150.degree. F., as measured by the
thermocouples, the hydrogen flow is increased to about 1,250-1,350
ml/min, and the flow of the tungsten fluoride vapor to about 150
ml/min and the argon gas is adjusted to about 285 ml/min, all as
measured by the flow meters as indicated in FIG. 1, the hydrogen
being in stoichiometric excess over the tungsten hexafluoride.
The thickness of the coat of the tungsten on the diamond depends on
the duration of the treatment and suitably for the 40 to 50 mesh
diamonds described above, the coat will be 1 mil. thick in about 1
hour. Suitable thickness deposit will run from about 0.1 to about
1.5 mils thick.
EXAMPLE 3
Instead of diamonds, we may use alumina. The mesh size,
temperature, and procedure as described in Example 2 may be
followed to produce a tungsten coat of the thickness previously
described.
EXAMPLE 4
Similarly, a tungsten carbide may be coated with tungsten,
following the procedure described in Example 1.
In the above example, the substrate surface is completely coated,
indicating that the process of vacuum chemical vapor deposition has
great throwing power. The outer surface of the coated particles is
topographically congruent to the outer surface of the underlying
substrate and reproduces it. The interlocked structure produces a
coating of high tensile and bending strength.
Since the coating is produced at high temperature, on cooling the
contraction of some 1,100.degree. F. will be substantially in
excess of the contraction of the substrate as described and the
resultant eventual contraction will produce a compress of the
underlying abrasive particle. (See FIGS. 9 through 14).
EXAMPLE 5
The process of Example 2 was employed in coating silicon carbide
particles of -80 + 100 mesh.
EXAMPLE 6
The metal coated particles may be employed in producing improved
abrader structures by any of the techniques previously used with
unencapsulated abrasive particles. These include what have become
known as surface set, infiltration, hot pressing, and flame
metalizing procedures.
For example, a surface set oil well drill (see FIGS. 7 and 8) (such
as described in the Austin Pat. No. 2,838,284) may be formed in a
graphite mold which is formed with sockets positioned in the
interior surface of the mold adjacent to the boring surface of the
drill to be formed in the mold. A steel shank is positioned in the
mold spaced from the interior surfaces of the mold. Between the
space in the mold between the shank and the diamonds is contained a
matrix composed of a mixture of sized particles of cast tungsten
carbide as the secondary abrasive and a powdered metal such as
nickel or tungsten. This mixture extends in the mold above the
surface on which the diamonds are deposited. The grain size of the
tungsten carbide is chosen to give the proper compaction and void
volume; for example, in the range of 35 to 75 percent of the total
volume, e.g., -30 + 60 mesh such as described above. The mold is
vibrated to compact the tungsten carbide particles.
Superimposed on the layer of tungsten carbide particles is a layer
of powdered binder metal such as is described above. The mold is
introduced into a furnace and heated to a temperature sufficient to
melt the infiltrant metal, for example, the range of 2,000.degree.
to 2,500.degree. F., employing, for example, a copper-nickel-zinc
alloy. The metal melts and percolates through the interstices, thus
producing a continuous phase metal matrix bonding the tungsten
carbide particles and binding the portions of the diamond particles
protruding from the mold surface.
In this procedure we prefer to employ the tungsten coated diamonds
prepared according to the process previously described, having a
coating, for example, of about half a mil or more, e.g. 1 to 1.5
mils. Instead of tungsten carbide, we may employ as the secondary
abrasive any of the other abrasives other than diamonds listed in
Table 1, or the aforesaid second abrasive particles encapsulated in
a metal capsule, as described above, for example, alumina coated
with tungsten according to the above procedure.
As previously described, in carrying out this procedure we wish to
select a temperature of formation which will be below about
2,800.degree. F., in order not to expose the diamonds to an
excessive temperature. Because of the metallic coating which is
placed upon the diamond and, if desired, on the secondary abrasive
particles, the binder metal will wet the surfaces of the
encapsulated particles, thus producing a tight bond to the matrix.
The encapsulation of the primary and secondary abrasive materials
reduced the attack by the infiltrant metal upon these products,
whereas the uncoated abrasives might be readily attacked by
infiltrant metals as described above.
The secondary abrasive used in the above construction may be
usefully a tungsten carbide ranging from WC having 6.12 wt. percent
of carbon to W.sub.2 C having a carbon content about 3.16 wt.
percent. A useful material is so-called sintered tungsten carbide
and consists of microsized WC crystals and cobalt metal bonded by
liquid phase sintering at high temperature. The cobalt content
varies from 3 wt. percent to over 25 wt. percent. This material has
a harness of about 1,250 to 1,350 kg/mm.sup.2 (Knoop). Another form
of eutectic alloy containing about 4 percent by weight of carbon
having a hardness in the range of 1900 to 2,000 kg/mm.sup.2 (Knoop)
may also be used.
Abrader elements may also be produced by an impregnation technique
by mixing the primary and secondary abrasive materials in powder
form, vibrating or packing the mixture in a suitable mold, and
infiltrating the mixture with a low-melting binder metal alloy as
described above.
EXAMPLE 7
FIGS. 2 and 5 show a suitable graphite mold for use in such
techniques for producing saw blade segments to be brazed to a saw
blade. The mold is composed of a base 101, the mold proper 102,
with an anchor 103, carrying a funnel 104, clamped by clamp bolt
105, and covered with a furnace cap 106. The mold proper consists
of circumferentially space mold cavities having substantially
smaller circumferential extension than their radial length. The
primary abrasive, for example, a mix of diamond particles 20 + 45
or - 45 + 60 mesh screen and powdered tungsten carbide is tamped
into the mold 102. The funnel contains a bronze-copper-tin-alloy
powder through a 200 mesh screen. The diamonds form about 25
percent by volume of the mixture of the metal-diamond finally
formed in the mold cavity 103. The mold is heated to about
2,000.degree.-2100.degree. F. to melt the alloy which percolates
through the interstices between the diamond particles in the mold
cavity, i.e., infiltrates the pores filling them to form the
continuous phase binding the coated diamond particles and the
tungsten carbide in the continuous metal matrix.
Example 8
The process of Example 7 and the product then produced may also be
carried out by replacing the tungsten carbide with a metal coated
tungsten carbide for example tungsten carbide coated with tungsten
metal or other tungsten coated secondary abrasive such as alumina
or silicon carbide.
For example, in forming a 12 inch saw blade on which about 19 of
the above sections are brazed at the periphery of the saw blade, we
may use sections of about 17/8 inches long, one-eighth inch wide,
and about five thirty-seconds inch thick may be formed suitably by
introducing about 3,500 stones of mesh size -45 + 60 grit or about
1.1 carats of diamonds grit. (See FIG. 6)
Instead of employing the infiltrant process, we may employ a hot
press procedure to formulate the abrader of our invention. In such
procedure, the mixture in the mold is a mixture of abrasive
particles and powdered metal which is to form the continuous metal
matrix to bind the abrasive particles.
Example 9
The mold employed is shown in FIGS. 4 and 3. The mold is similar to
that of FIG. 2 except that no funnel is employed and the nut 105 is
now a plug 107 and the funnel 104 is replaced by the cap 108 in
place of cap 106. The mold is formed for the insertion of the cap
as shown. The mold is placed in a press and heated for example in
an induction furnace.
To produce the saw blade element according to the hot press method
described above, a mixture of tungsten metal power, powdered
tungsten carbide -35 + 50 mesh diamond grit which has been coated
with a 10 micron tungsten metal envelope as described above is
mixed with a -200 mesh bronze-tin alloy and tamped into the mold of
FIG. 4. The concentration of diamonds in the mix may be suitably
about 25 percent. The mold is heated to about 1,600.degree. F. at
about 3,000 p.s.i. pressure to produce the saw blade element.
Instead of tungsten carbide, we may use tungsten coated tungsten
carbide or other metal coated secondary abrasive described above,
for example, tungsten coated alumina or silicon carbide.
Instead of using the low temperature melting bronze as an example,
we may use the higher melting metals as binder matrix such as iron,
cobalt, nickel or alloys of these metals and heat the hot press
mold to temperatures as high as above 1,535.degree. F. depending on
the melting point of the metal selected to form the binder.
In carrying out the procedures of Examples 3 through 9 where we
have referred to encapsulated abrasive, we prefer to employ the
process of encapsulation described in Example 2 and where diamonds
are referred to we prefer, where they are synthetic diamonds having
a smooth face, that this be etched, for example, by the procedure
of Example 1.
The superior product produced by the encapsulation method of
Example 1 and 2 when used in the production of the abraders by the
hot press or infiltrant method is illustrated in:
FIG. 9 which shows a 0.025 inch tungsten coat on an aluminum oxide
particle in the metal matrix at 140 .times. magnification and
having an apparent density of 9.3 grams per cubic centimeter.
FIG. 10 shows a similar tungsten coated alumina particle in a metal
matrix at 280 X magnification.
FIG. 11 shows a tungsten coated diamond particle hot pressed into a
metal matrix at 210 .times. magnification.
FIG. 12 shows a portion of the particle at 840 .times.
magnification.
FIG. 13 shows -80 + 100 mesh silicon carbide particle coated with
tungsten hot pressed into a metal matrix at 280 .times.
magnification.
FIG. 14 shows tungsten coated Al.sub.2 O.sub.3 hot pressed in a
metal matrix at 1700.degree. F., polished and etched at 560 .times.
magnification to show the allotriomorphic dendrite crystal
structure.
It will be seen the excellent throwing power of the process and the
intimate coating produced. The metal sheath is congruent to the
substrate surface coproducing it faithfully. The resultant intimate
bond produces the advantages of compression and hot transfer
referred to above. We claim :
* * * * *