FIELD OF THE INVENTION
[0001] This invention relates to the preparation of high precision alloy, and in particular,
high-strength nickel-based amorphous compositions for fabrication of glass-coated
microwires.
BACKGROUND OF THE INVENTION
[0002] It has been the tendency in modem technologies to demand new materials and processes
for their production from material engineering. Strengthening of the structural materials
by reinforcing them with high strength fibers or wires is one of the problems of the
material engineering in the production of elements and structures operating under
harsh environment and exploitation conditions.
[0003] The modem methods for strengthening of metals and alloys employ various treatments,
e.g., strain hardening, thermal and thermal-mechanical treatment, precipitation hardening,
martensite reinforcement, etc. Such treatments allow to obtain, for example, steels
and alloys having tensile strength in the range of 1000 - 3000 MPa. In particular,
the forming in the metal matrix such strengthening phases as δ-phase (Ni-Mo), σ-phase
and ρ-phase (Cr
18Mo
42Ni
40) has a great potential for obtaining high strength materials.
[0004] Known techniques for casting microwires in glass insulation enable to form an amorphous
homogeneous structure and the strengthening phases in the material, and thereby increase
the strength characteristic up to 3000 - 4500 MPa. The high strength is,
inter alia, attained by providing a high degree of the melt oversaturation by applying reinforcing
components and "freezing" the alloy in this condition at quenching the material from
the liquid phase with the cooling rate of up to 3 x 10
6 K/s.
[0005] According to the microwire casting techniques, a glass tubing containing the desired
metal batch is heated to a temperature sufficient to melt the metal and soften the
glass. In general, the heating is obtained via electromagnetic induction for melting
the metal which, in turn, softens the glass. The outer glass shell is then drawn out
as fine as desired. As a result, two coaxial flows arise: one of the melted metal
in the center and another of softened glass around the metal one. After leaving the
heating zone, both flows pass through a water stream, for cooling and solidifying.
The result is a continuous microwire with the metal being continuously cast as a core
covered with a glass coating.
[0006] U.S. Pat. No. 6,325,868 discloses a nickel-based amorphous alloy having a superior
amorphous phase-forming ability. This alloy contains nickel, zirconium and titanium
as main constituent elements along with additional elements, such as Si or P. Also,
at least one kind of element selected from the group consisting of V, Cr, Mn, Cu,
Co, W, Sn, Mo, Y, C, B, P, Al can be added to the alloy composition in the range of
content of 2 to 15 atomic %.
[0007] One of the drawbacks of this alloy is that it contains a rather large amount of such
elements as Ti and Zr, i.e., from 40 to 60%, which are easy oxidizable metals. In
this case the alloy drop can turn into oxide during the microwire casting process
and prevent microwire manufacture.
[0008] US Patent No 4,668,310 discloses amorphous alloys having high strength and hardness.
The general composition formula of these alloys is T
aX
bZ
cM
d, where
T is at least one of Fe, Co and Ni;
X is at least one of Zr, Ti, Hf and Y;
Z is at least one of B, C, Si, Al, Ge, Bi, S, P;
M is at least one of Mo, Cr, W, V, Nb, Ta, Cu, Mn, Zn, Sb, Sn, Be, Mg, Pd, Pt, Ru,
Os, Rh, Ir, Ce, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy; and
a is 70-98 atomic %,
b is from 5 to 30 atomic %,
c is from 0 to 0.5 atomic %, and
d is not more than 20 atomic %,
and sum of a, b, c, and d is 100 atomic %.
[0009] One of the disadvantages of this alloy is in the fact that it is not suitable for
microwire casting, owing to the deficiency of such elements as B and Si (less than
0.5%). For such contents of B and Si, the wetting ability of silica-boride glasses
by the metal melt is not sufficient for providing a mass microwire manufacturing process.
Moreover, the content of such elements as Cr and Mo does not exceed 20%, that prevents
from forming the high strength ρ-phase.
[0010] USSR inventor's certificate No. 428,028 discloses an alloy for casting of the microwire.
This alloy was developed by taking into account the specific conditions of physical
and chemical interaction between the metal melt and glass during microwire casting
process. Alloy has the following content, by weight %:
Cr: 10.0 - 20.0%,
Mo: 25.0 - 40.0%,
Si : 0.2 - 3.0%,
B: 0.1 - 1.2%,
Ni : the base.
[0011] The tensile strength of a microwire obtained from this alloy is between 3000 and
4500 MPa.
[0012] One of the disadvantages of utilization of this alloy is that it is not suitable
for preparing long continuous microwire lines (more than 100 m) during the microwire
casting process. Moreover, the obtained microwire has a large dispersal of diameter
along its length (up to +/-20%). These drawbacks are associated,
inter alia, with insufficient purification of the alloy mainly from entrapped gas and other non-metallic
inclusions. These disadvantages limit and sometime even restrict practical utilization
of the microwires obtained from this alloy, especially when the strengthening of structure
is achieved as a result of the winding of the reinforced microwire. Likewise, due
to the lack of an amorphizer in the alloy composition, an amorphous structure of the
alloy cannot be achieved, that prevents from obtaining an amorphous homogeneous alloy.
[0013] USSR inventor's certificate No. 662611 discloses an alloy having the following composition,
by weight %:
Cr: 18 - 40%,
Mo: 30 - 40%,
Si: 0.2 - 3.0%,
B: 0.1 - 1.2%,
Zr: 0.3 - 1.0%,
Ni: the base.
[0014] The main disadvantage of this alloy, as well as in the above case, is the impossibility
of fabrication of the microwire having long continuous length and small dispersal
of the wire's diameter along its length. Notwithstanding the alloy composition includes
such effective amorphizer as Zr, it is still difficult to provide the amorphous structure,
because the amorphization for such alloy can be only achieved when the content of
Zr is not less than 1.2%.
SUMMARY OF THE INVENTION
[0015] Thus, despite the extensive prior art in the area of glass-covered microwires, there
is still a need for further improvements of the alloy's content. It is desirable that
the microwire obtained by a microwire casting production process would have very high
tensile strength and stable physical and mechanical properties along its length. It
is also desirable to produce long continuous microwires having the length of 1000m
and more. Such microwires with reproductive properties can be used for reinforcing
structural materials.
[0016] The present invention satisfies the aforementioned need by providing a novel Ni-based
amorphous alloy, which can contain Cr, Mo, Si, B and Zr along with Y and at least
one additional rare-earth element selected from Ce and La.
[0017] According to one embodiment of the invention, the amorphous Ni-based alloy has the
following composition, by weight %:
10.0 to 40.0% of Cr;
25.0 to 42.0% of Mo;
0.6 to 6.0% of Si;
0.3 to 3.0% of B;
1.2 to 5.0% of Zr;
0.1 - 1.8% of at least one element selected from the rare-earth group including Ce
and La;
0.1- 1.5% of Y, and
Ni is the balance.
[0018] For providing a stable casting process, preferably, Si and B must be in ratio of
about Si:B= 2:1.
[0019] According to another embodiment of the invention, the Ni-based alloy further comprises
0.1 - 1.8 weight % of at least one element selected from Nd and Pr.
[0020] According to an embodiment of the invention, the Ni-based amorphous alloy is provided
for use in casting of microwires with glass insulation. Examples of the glass material
include, but are not limited to, borosilicate glasses, aluminum-borosilicate glasses
and Quartz glass. For instance, in the case of aluminum-borosilicate glass insulation,
the alloy additionally contains 0.6 - 5.0 weight % of Al.
[0021] There has thus been outlined, rather broadly, the more important features of the
invention in order that the detailed description thereof that follows hereinafter
may be better understood. Additional details and advantages of the invention will
be set forth in the detailed description, and in part will be appreciated from the
description, or may be learned by practice of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] In order to understand the invention and to see how it may be carried out in practice,
a preferred embodiment will now be described, by way of non-limiting example only,
with reference to the accompanying drawing, in which:
Fig. 1 is a schematic illustration of the system for mass manufacture of continuous lengths
of glass-coated microwire, according to one embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0023] The development of the optimal alloy composition is carried out on the base of Ni-Cr-Mo
system having the most strength structure corresponding to P-phase. A relationship
between the components of the Ni-Cr-Mo system, corresponding to the ρ-phase can for
example, be the following, by weight %:
Ni : the balance;
Cr: 10.0 - 18.0%; and
Mo: 25.0 - 28.0%.
[0024] This ratio of the elements corresponds to the equilibrium composition for the alloy.
When the alloy is at the non-equilibrium state, there is an oversaturation, thus the
concentration ratio for the ρ-phase enlarges, accordingly. The enlarged ratio of the
components in the ρ-phase corresponds to the oversaturation that can be obtained under
quenching at the rate of about 10
6 K/s. An example of the enlarged ratio of the components that can be used for casting
microwires is:
Cr: 10.0 - 40.0%,
Mo: 25.0 - 42.0%,
Ni: as the balance.
[0025] The microwires fabricated from this alloy have the tensile strength of about 4600
- 4800 MPa. However, because of the low wetting between the glass and melt, being
at the ρ-phase state, a production of the microwire with length more than 1 m cannot
be attained. When the amount of Cr is less than 10% and Mo is less than 25% or amount
of Cr more than 40% and Mo more than 42%, the ρ-phase is not formed, thus the tensile
strength of this alloy is decreased up to 300 - 700 MPa.
[0026] According to an embodiment of the invention, in order to enhance the wetting of the
borosilicate glasses by the melt of the alloy, such elements as Si and B in the amounts
of 0.6-6.0 weight % and 0.3 - 3.0 weight %, respectively, are introduced into the
Ni-Cr-Mo system. It was found that the best result of the wetting, and therefore a
significant increase of length of the continuous microwires is attained when the ratio
between Si and B is about Si:B=2. The effect of the wetting enhancement is obtained
when the content of Si and B is 0.6% and 0.3%, respectively, or higher. However, when
the content of Si and B is higher than 6.0% and 3.0%, respectively, X-ray and mechanics
tests show the brittleness of the microwire is increased, due to the destruction of
the ρ-phase.
[0027] At the optimal content of Si and B, that corresponds to 0.6-6.0 weight % of Si and
0.3-3.0 weight % of B the microwire of length of higher than 100m can be obtained.
[0028] According to a still further embodiment of the invention, an additional element such
as Zr can be also introduced in the content of the alloy. Zr is an effective amorphizer.
The applicants have found that for preparation of an amorphous alloy on the base of
a transitional metal, for example a Ni-based alloy, it is beneficial to introduce
some amorphizers. The applicants found that in the presence amorpizers such as Si
and B in alloys containing Ni and Cr, the additional introduction of Zr provides an
effective result. In particular, at an optimal content of Zr that corresponds to about
1.2- 5.0 weight % an effective amorphization index may be established at a required
level, i.e. more than 70%.
[0029] When the content of Zr is less than 1.2%, it is still difficult to provide the amorphous
structure. On the other hand, when the content of Zr is higher than 5 % this element
exudes into isolated phases, and brittleness of the microwire is increased. It should
be noted that when introducing Zr, Zr is introduced into the melt after Si and B.
[0030] According to a yet further embodiment of the invention, the further improvement of
the technology for the microwire manufacture providing the increase of the continuous
length of the microwire having high tensile strength (more than 4500 MPa) may be attained
by means of intensive purification of the Ni-based alloy and elimination of the gas
and other nonmetallic inclusions, e.g., oxygen, hydrogen and nitrogen or their compounds.
The purification is especially important, because the obtained microwires have a rather
small diameter, ranging from 10 microns up to 150 microns.
[0031] For the purpose of the purification the introduction of small amounts of elements
having the best affinity to these gases can be used. Special care should be taken
in order to preserve the ρ-phase and maintain the complex of the obtained physical-chemical
properties and technological advantages.
[0032] Examples of the element that has the best affinity to oxygen, hydrogen, and nitrogen
include, but are not limited to, Ce (Cerium) for oxygen, at least one of the rare-earth
elements selected from La (Lanthanum), Nd (Neodymium), Ce, Pr (Praseodymium) for oxygen
and nitrogen, and Y (Yttrium) for hydrogen. It should be noted, these examples of
the elements were chosen for reasons of non-toxicity, chemical activity and technological
ability.
[0033] According to one example, for optimization of the Ni-based alloy composition the
complex introduction of elements is realized, in which the elements are added to the
alloy in the following content, by weight %:
at least one Rare Earth element selected from Ce and La: 0.1 - 1.8%, and Y: 0.1-1.5%.
[0034] According to a yet embodiment of the invention, the Ni-based alloy further comprises
0.1 - 1.8 weight % of at least one element selected from Nd and Pr.
[0035] When the content of these rare-earth elements is less than that in the above example,
the purification effect is not obtained. On the other hand, when the content of these
elements is larger than in the above example, these ingredients exude into isolated
phases and, as a result, the brittleness of the microwire is increased.
[0036] According to a further embodiment of the invention, when the Ni-based alloy is used
for casting a microwire in aluminum-borosilicate glass insulation, an additional element
such as Al is further introduced in the content of the alloy Preferably, the content
of the Al is in the range of 0.6 - 5.0 weight %. Such amount provides a rather good
wetting of the glass by the metal.
[0037] It should be noted when more than 5.0 weight % of Al is in the alloy, a large amount
of oxides of the type of Al
2O
3 is formed at the microwire casting process. These oxides can lead to interruption
of the casting process, when they are in the capillary formed by the glass coating.
On the other hand, when less than 0.6 weight % of Al is in the alloy, the required
wetting of the glass by the metal is not achieved, that also results in the interruption
of the casting process and inability to manufacture long wires with stable properties.
[0038] Table 1A and 1B illustrate several examples of compositions of the alloy according to the above embodiments
of present invention and the properties of microwires made from this alloy, correspondingly.
Table 1A.
| Composition of the alloy, wt % |
| No. |
Ni |
Cr |
Mo |
Si |
B |
Zr |
Ce (La) |
Y |
| 1 |
balance |
10.0 |
25.0 |
0.6 |
0.3 |
1,2 |
0.1 |
0.1 |
| 2 |
balance |
40.0 |
32.0 |
2.8 |
1.8 |
2.4 |
0.9 |
0.8 |
| 3 |
balance |
34.0 |
42.0 |
6.0 |
3.0 |
5.0 |
1.8 |
1.5 |
| 4 |
balance |
9.9 |
24.9 |
0.5 |
0.2 |
1.1 |
0.09 |
0.09 |
| 5 |
balance |
40.1 |
42.1 |
6.1 |
6.1 |
5.1 |
1.9 |
1.6 |
Table 1B.
| Properties of the microwires made from the alloy of Table 1A |
| No. |
Tensile strength (σ), MPa |
Tensile strain (ε), % |
Length of wire, m |
| 1 |
4100 - 4500 |
2.5 - 3.2 |
1200 - 1800 |
| 2 |
4300 - 4500 |
2.5 - 3.2 |
1500 - 2000 |
| 3 |
4200 - 4500 |
2.5 - 3.2 |
1800 - 2100 |
| 4 |
700 - 900 |
2.5 - 3.2 |
1- 1.5 |
| 5 |
800 - 1000 |
2.5 - 3.2 |
80 - 100 |
[0039] As can be understood from these tables, alloys 1, 2 and 3 have optimal compositions
of the components, while alloys 4 and 5 have the compositions comprising the components
in the range of content smaller or higher than the optimal content.
[0040] According to the invention, the alloy is melted in alundum crucibles by the induction
furnace.
[0041] According to one embodiment of the invention, the ingredients are added in the following
order:
1. Nickel, chromium, molybdenum;
2. Silicon and boron are added in series after melting of the triple system;
3. Zirconium is introduced after silicon and boron;
4. At least one Rare-Earth Element selected from Ce and La, (along with Nd and Pr,
when required) and Y is introduced.
[0042] The alloy sample prepared thereby is identified as being substantially in amorphous
phase when tested by X-ray diffraction analysis techniques.
[0043] A glass-coated microwire with an amorphous metal core is produced by providing a
glass tube containing the desired metal and melting the metal in a high frequency
induction field. The heat of the metal melt softens the glass tube and a thin capillary
is drawn out from the softened glass tube. Thereafter, the metal-filled capillary
enters a cooling zone where it is rapidly cooled such that the desired amorphous microwire
is obtained. The optimal diameters of the obtained microwire is in the range of 10
to 150 µ. When the rate of the casting is decreased, microwires having a diameter
higher than 200 µ can also be obtained.
[0044] Referring to
Fig. 1, a system for a mass manufacture of continuous lengths of glass coated microwire
is shown in schematic form in order to illustrate the process according to an embodiment
of the invention. It is understood that this drawing is given for illustrative purposes
only and is not meant to be limiting. It should be noted that the blocks in
Fig. 1 are intended as functional entities only, such that the functional relationships
between the entities are shown, rather than any physical connections and/or physical
relationships. The system of
Fig. 1, generally identified by reference numeral
10, includes a suitable glass feeder mechanism diagrammatically represented by a circle
101 for providing a supply of a glass tubing
102. The system also includes a rod feeder mechanism diagrammatically represented by
a circle
103 for providing a supply of a rod, bar or wire
104 made of a core material. According to the present invention, the core material is
the Ni-based allow described above.
[0045] It should be appreciated that the mechanisms
101 and
103 can be both configured in one feeder device that may serve a multiple function for
providing a supply of glass and core materials. The glass feeder mechanism
101 is controllable by a glass feeder signal and includes a driving motor (not shown)
which acts on the glass tubing
102 for providing a supply of a glass material with a required speed. By the same token,
the rod feeder mechanism 103 is controllable by a rod feeder signal and includes a
driving motor (not shown) which acts on the rod
104 for providing a supply of a core material with a required speed. The glass and rod
feeder signals are generated by a controller
109 configured to control the system
10.
[0046] Examples of the glasses of the glass tubing
102 include, but are not limited to, glasses with a large amount of oxides of alkali
metals, borosilicate glasses, aluminosilicate glasses,
etc. It should be understood that various alternative glasses may be selected by one skilled
in the art for the particular desired application and environment in which the coated
wire composite is to be used.
[0047] A tip of the glass tubing
102 loaded with the rod
104 is introduced into a furnace
106 adapted for softening the glass material making up the tubing
102 and melting the rod
104 in the vicinity of the exit orifice
107, such that a drop
105 of the wire material in the molten state is formed.
[0048] According to one embodiment of the invention, the furnace
106 includes at least one high frequency induction coil, e.g. one wind coil. The operation
of the furnace
106 is
known per se, and will not be expounded in details below.
[0049] An exemplary furnace that has been shown to be suitable for the manufacturing process
of the present invention is the Model HFP 12, manufactured by EFD Induction Gmbh,
Germany
[0050] The temperature of the drop is measured by a temperature sensor pointing at the hottest
point of the drop and diagrammatically represented by a box 108. An example of the
temperature sensor includes, but is not limited to, the Model Omega OS 1553-A produced
by Omega Engineering Ltd.
[0051] The temperature sensor
108 is operable for producing a temperature sensor signal. The temperature sensor
108 is coupled to the controller
109 which is,
inter alia, responsive to the temperature sensor signal and capable of providing a control by
means of a PID loop for regulating the temperature of the drop
105 for stabilizing and maintaining it at a required magnitude. For example, the temperature
of the drop can be maintained in the range of 800 °C to 1500 °C.
[0052] It should be appreciated that one way of regulating the drop temperature is the regulation
of the temperature of the furnace
106 by changing the furnace's power consumption. For this purpose, controller
109 is capable of generating a furnace power signal, by means of a PID control loop,
to a power supply unit
113 of the furnace
106. For example, when the consumption power increases, the drop temperature should also
increase, provided by the condition that the position of the drop
105 does not change with respect to the furnace
106. However, since the furnace includes a high frequency induction coil, the increase
of the consumption power leads to the elevation of the drop, due to the levitation
effect. Hence, the temperature of the drop depends on many parameters and does not
always change in the desired direction when only the consumption power is regulated.
[0053] An example of the power supply unit
113 includes, but is not limited to the Mitsubishi AC inverter, Model FR-A540-1 I k-EC,
Mitsubishi, Japan.
[0054] According to one embodiment of the invention, the compensation of the levitation
effect is accomplished by the regulation of the gas pressure in the tubing
102. Thus, in order to avoid the droplet elevation due to the increase of the consumption
power, the negative gas pressure (with respect to the atmospheric pressure) is decreased
to a required value calculated by the controller
109.
[0055] For this purpose, the system
10 is further provided with a vacuum device identified by reference numeral
120 for evacuating gas from the tubing
102. The vacuum device
120 is coupled to the tubing
102 via a suitable sealable coupling element (not shown) so as to apply negative gas
pressure to the inside volume of the tube
102 while allowing passage of the rod
104 therethrough.
[0056] The vacuum device
120 is controllable by a vacuum device signal generated by the controller
109 for providing variable negative pressure to the molten metal drop in the region of
contact with the glass. The pressure variation permits the manipulation and control
of the molten metal in the interface with the glass in a manner as may be suitable
to provide a desirable result.
[0057] The system
10 is further provided with a cooling device
110, arranged downstream of the furnace
106 and adapted for cooling a microwire filament
111 drawn out from the drop
105. The microwire filament
111 can be drawn at a speed in the range of 5 m/min to 1500 m/min through the cooling
device
110. The cooling device
110 is built in such a way that the filament
111 being formed passes though a cooling liquid where it supercools and solidifies, and
thereafter proceeds as a microwire
112 towards a receiver section
130 arranged downstream of the cooling device
110. The rate of cooling can be regulated, for example, in the range of 10
5 °C/sec to 10
6 °C/sec for amorphous core materials.
[0058] The receiver section
130 comprises a spooler
138 for collecting the finished microwire product. The spooler
138 includes at least one receiving spool
141, a spool diameter sensor
142, a drive motor assembly
143 and a guide pulley assembly
144. The spool diameter sensor is configured for measuring an effective core diameter
of the spool and generating a spool diameter sensor signal representative of the value
of the spool diameter.
[0059] The drive motor assembly
143 is controllable by a spool speed signal generated by the controller module
109 for rotating the spool with a required cyclic speed in response to the spool diameter
sensor signal. The cyclic speed is regulated in order to maintain the linear speed
of the microwire at the desired value.
[0060] An example of the spooler
138 includes, but is not limited to, the Model M/HOA-0/1-63S, produced by MAG, Austria.
[0061] The receiver section
130 can further include a tension unit
131 having a tension sensor
145 configured for generating a tension sensor signal. An example of the tension sensor
includes, but is not limited to, a tension meter produced by Tensometric Messtechnik,
Strohmann & Co GmbH.
[0062] The tension unit
131 includes a tension generator
146 controllable by a wire tension signal produced by the controller module
109 in response to the tension sensor signal. The tension generator
146 is arranged to create tension of the microwire.
[0063] The receiver section
130 can also include a wax applicator
136 for waxing the microwire. The system
10 can also include a micrometer
135 arranged downstream of the tension unit
131 and configured for measuring the microwire overall diameter, length and other parameters,
e.g., a microwire speed. The micrometer
135 is configured for producing,
inter alia, a wire diameter sensor signal representative of the microwire overall diameter. The
micrometer
135 is operatively coupled to the controller module
109 that is responsive to the diameter sensor signal and operable for generating a corresponding
signal for regulating,
inter alia, the drop temperature, for stabilizing the overall microwire diameter.
[0064] For instance, the micrometer
135 can be mounted in the receiver section
130. An example of the micrometer
135 includes, but is not limited to, a laser micrometer LDS 150, produced by CERSA, France.
[0065] The receiver section
130 also includes a required number of guide pulleys
132 arranged for providing a required direction to the microwire.
[0066] As such, those skilled in the art to which the present invention pertains, can appreciate
that while the present invention has been described in terms of preferred embodiments,
the concept upon which this disclosure is based may readily be utilized as a basis
for the designing of other structures, systems and processes for carrying out the
several purposes of the present invention.
[0067] It should be apparent that the alloy in accordance with the present invention may
be equally well-suited for use in the manufacture of a wide variety of coated wire
composites and is not necessarily limited to the manufacture of the particular examples
described herein.
[0068] Although the system for production of wire shaped materials have been described above,
it should also be understood that the alloy of the present invention can be used for
preparation of thin ribbons by using known fabrication apparatuses.
[0069] Also, it is to be understood that the phraseology and terminology employed herein
are for the purpose of description and should not be regarded as limiting.
[0070] It is important, therefore, that the scope of the invention is not construed as being
limited by the illustrative embodiments and examples set forth herein. Other variations
are possible within the scope of the present invention as defined in the appended
claims and their equivalents.