# Patent

## Title
Movable joint through insert

## Abstract

Provided in one embodiment is a method of forming a movable joint or connection between parts that move with respect to one another, wherein at least one part is at least partially enclosed by at least one second part. The method includes positioning an etchable material over an at least one first part, molding or forming an at least one second part over at least the etchable material, and removing the etchable material.

## Background
FIELD OF INVENTION
This invention relates to methods of joining bulk solidifying amorphous alloy parts to one another, and providing a movable joint therebetween. The connection between the respective parts enables them to move with respect to one another thus providing a molded article capable of movement.
BACKGROUND
Bulk-solidifying amorphous alloys have been made in a variety of metal systems. They are generally prepared by quenching from above the melting temperature to the ambient temperature. Generally, high cooling rates on the order of 105° C./sec, are needed to achieve an amorphous structure. The lowest rate by which a bulk solidifying alloy can be cooled to avoid crystallization, thereby achieving and maintaining the amorphous structure during cooling, is referred to as the “critical cooling rate” for the alloy. In order to achieve a cooling rate higher than the critical cooling rate, heat has to be extracted from the sample. Thus, the thickness of articles made from amorphous alloys often becomes a limiting dimension, which is generally referred to as the “critical (casting) thickness.” A critical casting thickness can be obtained by heat-flow calculations, taking into account the critical cooling rate.
Until the early nineties, the processability of amorphous alloys was quite limited, and amorphous alloys were readily available only in powder form or in very thin foils or strips with a critical casting thickness of less than 100 micrometers. A new class of amorphous alloys based mostly on Zr and Ti alloy systems was developed in the nineties, and since then more amorphous alloy systems based on different elements have been developed. These families of alloys have much lower critical cooling rates of less than 103° C./sec, and thus these articles have much larger critical casting thicknesses than their previous counterparts. The bulk-solidifying amorphous alloys are capable of being shaped into a variety of forms, thereby providing a unique advantage in preparing intricately designed parts.
The use of hard materials in the formation of intricately designed parts for a variety of uses significantly improves the life of the article, but also imposes difficulties in its manufacture and assembly. Many parts of articles, such as electronic devices, machine parts, engines, pump impellers, rotors, and the like, must be assembled and connected to one another. Other objects or articles sometimes require the connection to be a pivotal connection, enabling movement of the respective parts. Most of the conventional pivotal connections, which are common in many orthopedic applications, are made after the parts have been molded, machined, or otherwise fabricated. These pivotal connections, or movable joints, suffer insofar as they sometimes become dislodged from one another, which for orthopedic applications (such shoulders, hips, and knees), such dislocation may be extremely painful. In other applications, dislocation of the movable parts may cause the device to malfunction or be completely destroyed.
It would be desirable to provide a connection or joint between parts that can move with respect to one another, and that will not become dislodged during use. It also would be desirable to provide a connection between extremely hard parts that are difficult to precision machine after molding.
SUMMARY
A proposed solution according to embodiments herein is to provide a connection or joint between parts that move with respect to one another, wherein at least one first part is at least partially enclosed by at least one second part. The method includes forming at least one first part having at least one contact surface, depositing an etchable material on at least the one contact surface of the at least one first part, and forming at least one second part at least on the etchable material, wherein the at least one second part at least partially encloses the at least one first part. The method further includes etching away the etchable material to form a space between the at least one first part and the at least one second part such that the at least one first part and the at least one second part move with respect to one another.
In accordance with another embodiment, there is provided a method of forming a connection or joint between parts that move with respect to one another, wherein at least one part is at least partially enclosed by at least one second part. The method includes forming at least one first part having at least one contact surface, depositing an etchable material on at least the one contact surface of the at least one first part, and forming at least one second part at least on the etchable material, wherein the at least one second part at least partially encloses the at least one first part. The at least one first part and/or the at least one second part is formed of a bulk-solidifying amorphous alloy material. The method further includes etching away the etchable material to form a space between the at least one first part and the at least one second part such that the at least one first part and the at least one second part move with respect to one another.
Another embodiment includes a method of molding a movable joint made of bulk-solidifying amorphous alloy using a mold, the movable joint including a first mold part configured to move within a second mold part. The method includes providing a first mold part formed of a bulk-solidifying amorphous alloy material having at least one contact surface, and applying an etchable material on the at least one contact surface. The method further includes overmolding a second mold part formed of a bulk-solidifying amorphous alloy material over at least the etchable material on the at least one contact surface of the first mold part. The method also includes removing the etchable material such that at least a portion of the first mold part is configured to move freely within the second mold part.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 provides a temperature-viscosity diagram of an exemplary bulk solidifying amorphous alloy.
FIG. 2 provides a schematic of a time-temperature-transformation (TTT) diagram for an exemplary bulk solidifying amorphous alloy.
FIG. 3 provides a cross-sectional view of a first part having positioned on at least one surface an etchable material in accordance with an embodiment.
FIG. 4 provides a cross-sectional view of the arrangement of FIG. 3, with at least a second part molded over the first part and etchable material.
FIG. 5 provides a cross-section view of the arrangement of FIG. 4 in which the etchable material has been removed.
FIG. 6 provides a cross-sectional view of a first part having positioned on at least one surface an etchable material in accordance with another embodiment.
FIG. 7 provides a cross-sectional view of the arrangement of FIG. 6, with at least a second part molded over the first part and etchable material.
FIG. 8 provides a cross-section view of the arrangement of FIG. 7 in which the etchable material has been removed.
FIG. 9 provides a cross-sectional view of a first part having positioned on at least one surface an etchable material in accordance with another embodiment.
FIG. 10 provides a cross-sectional view of the arrangement of FIG. 9, with at least a second part molded over the first part and etchable material.
FIG. 11 provides a cross-section view of the arrangement of FIG. 10 in which the etchable material has been removed.



DETAILED DESCRIPTION
All publications, patents, and patent applications cited in this Specification are hereby incorporated by reference in their entirety.
The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “a polymer resin” means one polymer resin or more than one polymer resin. Any ranges cited herein are inclusive. The terms “substantially” and “about” used throughout this Specification are used to describe and account for small fluctuations. For example, they can refer to less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%.
Bulk-solidifying amorphous alloys, or bulk metallic glasses (“BMG”), are a recently developed class of metallic materials. These alloys may be solidified and cooled at relatively slow rates, and they retain the amorphous, non-crystalline (i.e., glassy) state at room temperature. Amorphous alloys have many superior properties than their crystalline counterparts. However, if the cooling rate is not sufficiently high, crystals may form inside the alloy during cooling, so that the benefits of the amorphous state can be lost. For example, one challenge with the fabrication of bulk amorphous alloy parts is partial crystallization of the parts due to either slow cooling or impurities in the raw alloy material. As a high degree of amorphicity (and, conversely, a low degree of crystallinity) is desirable in BMG parts, there is a need to develop methods for casting BMG parts having controlled amount of amorphicity.
FIG. 1 (obtained from U.S. Pat. No. 7,575,040) shows a viscosity-temperature graph of an exemplary bulk solidifying amorphous alloy, from the VIT-001 series of Zr—Ti—Ni—Cu—Be family manufactured by Liquidmetal Technology. It should be noted that there is no clear liquid/solid transformation for a bulk solidifying amorphous metal during the formation of an amorphous solid. The molten alloy becomes more and more viscous with increasing undercooling until it approaches solid form around the glass transition temperature. Accordingly, the temperature of solidification front for bulk solidifying amorphous alloys can be around glass transition temperature, where the alloy will practically act as a solid for the purposes of pulling out the quenched amorphous sheet product.
FIG. 2 (obtained from U.S. Pat. No. 7,575,040) shows the time-temperature-transformation (TTT) cooling curve of an exemplary bulk solidifying amorphous alloy, or TTT diagram. Bulk-solidifying amorphous metals do not experience a liquid/solid crystallization transformation upon cooling, as with conventional metals. Instead, the highly fluid, non crystalline form of the metal found at high temperatures (near a “melting temperature” Tm) becomes more viscous as the temperature is reduced (near to the glass transition temperature Tg), eventually taking on the outward physical properties of a conventional solid.
Even though there is no liquid/crystallization transformation for a bulk solidifying amorphous metal, a “melting temperature” Tm may be defined as the thermodynamic liquidus temperature of the corresponding crystalline phase. Under this regime, the viscosity of bulk-solidifying amorphous alloys at the melting temperature could lie in the range of about 0.1 poise to about 10,000 poise, and even sometimes under 0.01 poise. A lower viscosity at the “melting temperature” would provide faster and complete filling of intricate portions of the shell/mold with a bulk solidifying amorphous metal for forming the BMG parts. Furthermore, the cooling rate of the molten metal to form a BMG part has to such that the time-temperature profile during cooling does not traverse through the nose-shaped region bounding the crystallized region in the TTT diagram of FIG. 2. In FIG. 2, Tnose is the critical crystallization temperature Tx where crystallization is most rapid and occurs in the shortest time scale.
The supercooled liquid region, the temperature region between Tg and Tx is a manifestation of the extraordinary stability against crystallization of bulk solidification alloys. In this temperature region the bulk solidifying alloy can exist as a high viscous liquid. The viscosity of the bulk solidifying alloy in the supercooled liquid region can vary between 1012 Pa s at the glass transition temperature down to 105 Pa s at the crystallization temperature, the high temperature limit of the supercooled liquid region. Liquids with such viscosities can undergo substantial plastic strain under an applied pressure. The embodiments herein make use of the large plastic formability in the supercooled liquid region as a forming and separating method.
One needs to clarify something about Tx. Technically, the nose-shaped curve shown in the TTT diagram describes Tx as a function of temperature and time. Thus, regardless of the trajectory that one takes while heating or cooling a metal alloy, when one hits the TTT curve, one has reached Tx. In FIG. 2, Tx is shown as a dashed line as Tx can vary from close to Tm to close to Tg.
The schematic TTT diagram of FIG. 2 shows processing methods of die casting from at or above Tm to below Tg without the time-temperature trajectory (shown as (1) as an example trajectory) hitting the TTT curve. During die casting, the forming takes place substeantially simultaneously with fast cooling to avoid the trajectory hitting the TTT curve. The procssing methods for superplastic foaming (SPF) from at or below Tg to below Tm without the time-temperature trajectory (shown as (2), (3) and (4) as example trajectories) hitting the TTT curve. In SPF, the amorphous BMG is reheated into the supercooled liquid region where the available processing window could be much larger than die casting, resulting in better controllability of the process. The SPF process does not require fast cooling to avoid crystallization during cooling. Also, as shown by example trajectories (2), (3) and (4), the SPF can be carried out with the highest temperature during SPF being above Tnose or below Tnose, up to about Tm. If one heats up a piece of amorphous alloy but manages to avoid hitting the TTT curve, you have heated “between Tg and Tm”, but one would have not reached Tx.
Typical differential scanning calorimeter (DSC) heating curves of bulk-solidifying amorphous alloys taken at a heating rate of 20 C/min describe, for the most part, a particular trajectory across the TTT data where one would likely see a Tg at a certain temperature, a Tx when the DSC heating ramp crosses the TTT crystallization onset, and eventually melting peaks when the same trajectory crosses the temperature range for melting. If one heats a bulk-solidifying amorphous alloy at a rapid heating rate as shown by the ramp up portion of trajectories (2), (3) and (4) in FIG. 2, then one could avoid the TTT curve entirely, and the DSC data would show a glass transition but no Tx upon heating. Another way to think about it is trajectories (2), (3) and (4) can fall anywhere in temperature between the nose of the TTT curve (and even above it) and the Tg line, as long as it does not hit the crystallization curve. That just means that the horizontal plateau in trajectories might get much shorter as one increases the processing temperature.
Phase
The term “phase” herein can refer to one that can be found in a thermodynamic phase diagram. A phase is a region of space (e.g., a thermodynamic system) throughout which all physical properties of a material are essentially uniform. Examples of physical properties include density, index of refraction, chemical composition and lattice periodicity. A simple description of a phase is a region of material that is chemically uniform, physically distinct, and/or mechanically separable. For example, in a system consisting of ice and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the humid air over the water is a third phase. The glass of the jar is another separate phase. A phase can refer to a solid solution, which can be a binary, tertiary, quaternary, or more, solution, or a compound, such as an intermetallic compound. As another example, an amorphous phase is distinct from a crystalline phase.
Metal, Transition Metal, and Non-metal
The term “metal” refers to an electropositive chemical element. The term “element” in this Specification refers generally to an element that can be found in a Periodic Table. Physically, a metal atom in the ground state contains a partially filled band with an empty state close to an occupied state. The term “transition metal” is any of the metallic elements within Groups 3 to 12 in the Periodic Table that have an incomplete inner electron shell and that serve as transitional links between the most and the least electropositive in a series of elements. Transition metals are characterized by multiple valences, colored compounds, and the ability to form stable complex ions. The term “nonmetal” refers to a chemical element that does not have the capacity to lose electrons and form a positive ion.
Depending on the application, any suitable nonmetal elements, or their combinations, can be used. The alloy (or “alloy composition”) can comprise multiple nonmetal elements, such as at least two, at least three, at least four, or more, nonmetal elements. A nonmetal element can be any element that is found in Groups 13-17 in the Periodic Table. For example, a nonmetal element can be any one of F, Cl, Br, I, At, 0, S, Se, Te, Po, N, P, As, Sb, Bi, C, Si, Ge, Sn, Pb, and B. Occasionally, a nonmetal element can also refer to certain metalloids (e.g., B, Si, Ge, As, Sb, Te, and Po) in Groups 13-17. In one embodiment, the nonmetal elements can include B, Si, C, P, or combinations thereof. Accordingly, for example, the alloy can comprise a boride, a carbide, or both.
A transition metal element can be any of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, rutherfordium, dubnium, seaborgium, bohrium, hassium, meitnerium, ununnilium, unununium, and ununbium. In one embodiment, a BMG containing a transition metal element can have at least one of Sc, Y, La, Ac, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, and Hg. Depending on the application, any suitable transitional metal elements, or their combinations, can be used. The alloy composition can comprise multiple transitional metal elements, such as at least two, at least three, at least four, or more, transitional metal elements.
The presently described alloy or alloy “sample” or “specimen” alloy can have any shape or size. For example, the alloy can have a shape of a particulate, which can have a shape such as spherical, ellipsoid, wire-like, rod-like, sheet-like, flake-like, or an irregular shape. The particulate can have any size. For example, it can have an average diameter of between about 1 micron and about 100 microns, such as between about 5 microns and about 80 microns, such as between about 10 microns and about 60 microns, such as between about 15 microns and about 50 microns, such as between about 15 microns and about 45 microns, such as between about 20 microns and about 40 microns, such as between about 25 microns and about 35 microns. For example, in one embodiment, the average diameter of the particulate is between about 25 microns and about 44 microns. In some embodiments, smaller particulates, such as those in the nanometer range, or larger particulates, such as those bigger than 100 microns, can be used.
The alloy sample or specimen can also be of a much larger dimension. For example, it can be a bulk structural component, such as an ingot, housing/casing of an electronic device or even a portion of a structural component that has dimensions in the millimeter, centimeter, or meter range.
Solid Solution
The term “solid solution” refers to a solid form of a solution. The term “solution” refers to a mixture of two or more substances, which may be solids, liquids, gases, or a combination of these. The mixture can be homogeneous or heterogeneous. The term “mixture” is a composition of two or more substances that are combined with each other and are generally capable of being separated. Generally, the two or more substances are not chemically combined with each other.
Alloy
In some embodiments, the alloy composition described herein can be fully alloyed. In one embodiment, an “alloy” refers to a homogeneous mixture or solid solution of two or more metals, the atoms of one replacing or occupying interstitial positions between the atoms of the other; for example, brass is an alloy of zinc and copper. An alloy, in contrast to a composite, can refer to a partial or complete solid solution of one or more elements in a metal matrix, such as one or more compounds in a metallic matrix. The term alloy herein can refer to both a complete solid solution alloy that can give single solid phase microstructure and a partial solution that can give two or more phases. An alloy composition described herein can refer to one comprising an alloy or one comprising an alloy-containing composite.
Thus, a fully alloyed alloy can have a homogenous distribution of the constituents, be it a solid solution phase, a compound phase, or both. The term “fully alloyed” used herein can account for minor variations within the error tolerance. For example, it can refer to at least 90% alloyed, such as at least 95% alloyed, such as at least 99% alloyed, such as at least 99.5% alloyed, such as at least 99.9% alloyed. The percentage herein can refer to either volume percent or weight percentage, depending on the context. These percentages can be balanced by impurities, which can be in terms of composition or phases that are not a part of the alloy.
Amorphous or Non-crystalline Solid
An “amorphous” or “non-crystalline solid” is a solid that lacks lattice periodicity, which is characteristic of a crystal. As used herein, an “amorphous solid” includes “glass” which is an amorphous solid that softens and transforms into a liquid-like state upon heating through the glass transition. Generally, amorphous materials lack the long-range order characteristic of a crystal, though they can possess some short-range order at the atomic length scale due to the nature of chemical bonding. The distinction between amorphous solids and crystalline solids can be made based on lattice periodicity as determined by structural characterization techniques such as x-ray diffraction and transmission electron microscopy.
The terms “order” and “disorder” designate the presence or absence of some symmetry or correlation in a many-particle system. The terms “long-range order” and “short-range order” distinguish order in materials based on length scales.
The strictest form of order in a solid is lattice periodicity: a certain pattern (the arrangement of atoms in a unit cell) is repeated again and again to form a translationally invariant tiling of space. This is the defining property of a crystal. Possible symmetries have been classified in 14 Bravais lattices and 230 space groups.
Lattice periodicity implies long-range order. If only one unit cell is known, then by virtue of the translational symmetry it is possible to accurately predict all atomic positions at arbitrary distances. The converse is generally true, except, for example, in quasi-crystals that have perfectly deterministic tilings but do not possess lattice periodicity.
Long-range order characterizes physical systems in which remote portions of the same sample exhibit correlated behavior. This can be expressed as a correlation function, namely the spin-spin correlation function:
In the above function, s is the spin quantum number and x is the distance function within the particular system. This function is equal to unity when x=x′ and decreases as the distance |x−x′| increases. Typically, it decays exponentially to zero at large distances, and the system is considered to be disordered. If, however, the correlation function decays to a constant value at large |x−x′|, then the system can be said to possess long-range order. If it decays to zero as a power of the distance, then it can be called quasi-long-range order. Note that what constitutes a large value of |x−x′| is relative.
A system can be said to present quenched disorder when some parameters defining its behavior are random variables that do not evolve with time (i.e., they are quenched or frozen)—e.g., spin glasses. It is opposite to annealed disorder, where the random variables are allowed to evolve themselves. Embodiments herein include systems comprising quenched disorder.
The alloy described herein can be crystalline, partially crystalline, amorphous, or substantially amorphous. For example, the alloy sample/specimen can include at least some crystallinity, with grains/crystals having sizes in the nanometer and/or micrometer ranges. Alternatively, the alloy can be substantially amorphous, such as fully amorphous. In one embodiment, the alloy composition is at least substantially not amorphous, such as being substantially crystalline, such as being entirely crystalline.
In one embodiment, the presence of a crystal or a plurality of crystals in an otherwise amorphous alloy can be construed as a “crystalline phase” therein. The degree of crystallinity (or “crystallinity” for short in some embodiments) of an alloy can refer to the amount of the crystalline phase present in the alloy. The degree can refer to, for example, a fraction of crystals present in the alloy. The fraction can refer to volume fraction or weight fraction, depending on the context. A measure of how “amorphous” an amorphous alloy is can be amorphicity. Amorphicity can be measured in terms of a degree of crystallinity. For example, in one embodiment, an alloy having a low degree of crystallinity can be said to have a high degree of amorphicity. In one embodiment, for example, an alloy having 60 vol % crystalline phase can have a 40 vol % amorphous phase.
Amorphous Alloy or Amorphous Metal
An “amorphous alloy” is an alloy having an amorphous content of more than 50% by volume, preferably more than 90% by volume of amorphous content, more preferably more than 95% by volume of amorphous content, and most preferably more than 99% to almost 100% by volume of amorphous content. Note that, as described above, an alloy high in amorphicity is equivalently low in degree of crystallinity. An “amorphous metal” is an amorphous metal material with a disordered atomic-scale structure. In contrast to most metals, which are crystalline and therefore have a highly ordered arrangement of atoms, amorphous alloys are non-crystalline. Materials in which such a disordered structure is produced directly from the liquid state during cooling are sometimes referred to as “glasses.” Accordingly, amorphous metals are commonly referred to as “metallic glasses” or “glassy metals.” In one embodiment, a bulk metallic glass (“BMG”) can refer to an alloy, of which the microstructure is at least partially amorphous. However, there are several ways besides extremely rapid cooling to produce amorphous metals, including physical vapor deposition, solid-state reaction, ion irradiation, melt spinning, and mechanical alloying. Amorphous alloys can be a single class of materials, regardless of how they are prepared.
Amorphous metals can be produced through a variety of quick-cooling methods. For instance, amorphous metals can be produced by sputtering molten metal onto a spinning metal disk. The rapid cooling, on the order of millions of degrees a second, can be too fast for crystals to form, and the material is thus “locked in” a glassy state. Also, amorphous metals/alloys can be produced with critical cooling rates low enough to allow formation of amorphous structures in thick layers—e.g., bulk metallic glasses.
The terms “bulk metallic glass” (“BMG”), bulk amorphous alloy (“BAA”), and bulk solidifying amorphous alloy are used interchangeably herein. They refer to amorphous alloys having the smallest dimension at least in the millimeter range. For example, the dimension can be at least about 0.5 mm, such as at least about 1 mm, such as at least about 2 mm, such as at least about 4 mm, such as at least about 5 mm, such as at least about 6 mm, such as at least about 8 mm, such as at least about 10 mm, such as at least about 12 mm. Depending on the geometry, the dimension can refer to the diameter, radius, thickness, width, length, etc. A BMG can also be a metallic glass having at least one dimension in the centimeter range, such as at least about 1.0 cm, such as at least about 2.0 cm, such as at least about 5.0 cm, such as at least about 10.0 cm. In some embodiments, a BMG can have at least one dimension at least in the meter range. A BMG can take any of the shapes or forms described above, as related to a metallic glass. Accordingly, a BMG described herein in some embodiments can be different from a thin film made by a conventional deposition technique in one important aspect—the former can be of a much larger dimension than the latter.
Amorphous metals can be an alloy rather than a pure metal. The alloys may contain atoms of significantly different sizes, leading to low free volume (and therefore having viscosity up to orders of magnitude higher than other metals and alloys) in a molten state. The viscosity prevents the atoms from moving enough to form an ordered lattice. The material structure may result in low shrinkage during cooling and resistance to plastic deformation. The absence of grain boundaries, the weak spots of crystalline materials in some cases, may, for example, lead to better resistance to wear and corrosion. In one embodiment, amorphous metals, while technically glasses, may also be much tougher and less brittle than oxide glasses and ceramics.
Thermal conductivity of amorphous materials may be lower than that of their crystalline counterparts. To achieve formation of an amorphous structure even during slower cooling, the alloy may be made of three or more components, leading to complex crystal units with higher potential energy and lower probability of formation. The formation of amorphous alloy can depend on several factors: the composition of the components of the alloy; the atomic radius of the components (preferably with a significant difference of over 12% to achieve high packing density and low free volume); and the negative heat of mixing the combination of components, inhibiting crystal nucleation and prolonging the time the molten metal stays in a supercooled state. However, as the formation of an amorphous alloy is based on many different variables, it can be difficult to make a prior determination of whether an alloy composition would form an amorphous alloy.
Amorphous alloys, for example, of boron, silicon, phosphorus, and other glass formers with magnetic metals (iron, cobalt, nickel) may be magnetic, with low coercivity and high electrical resistance. The high resistance leads to low losses by eddy currents when subjected to alternating magnetic fields, a property useful, for example, as transformer magnetic cores.
Amorphous alloys may have a variety of potentially useful properties. In particular, they tend to be stronger than crystalline alloys of similar chemical composition, and they can sustain larger reversible (“elastic”) deformations than crystalline alloys. Amorphous metals derive their strength directly from their non-crystalline structure, which can have none of the defects (such as dislocations) that limit the strength of crystalline alloys. For example, one modern amorphous metal, known as VitreloyTM, has a tensile strength that is almost twice that of high-grade titanium. In some embodiments, metallic glasses at room temperature are not ductile and tend to fail suddenly when loaded in tension, which limits the material applicability in reliability-critical applications, as the impending failure is not evident. Therefore, to overcome this challenge, metal matrix composite materials having a metallic glass matrix containing dendritic particles or fibers of a ductile crystalline metal can be used. Alternatively, a BMG low in element(s) that tend to cause embitterment (e.g., Ni) can be used. For example, a Ni-free BMG can be used to improve the ductility of the BMG.
Another useful property of bulk amorphous alloys is that they can be true glasses; in other words, they can soften and flow upon heating. This can allow for easy processing, such as by injection molding, in much the same way as polymers. As a result, amorphous alloys can be used for making sports equipment, medical devices, electronic components and equipment, and thin films. Thin films of amorphous metals can be deposited as protective coatings via a high velocity oxygen fuel technique.
A material can have an amorphous phase, a crystalline phase, or both. The amorphous and crystalline phases can have the same chemical composition and differ only in the microstructure—i.e., one amorphous and the other crystalline. Microstructure in one embodiment refers to the structure of a material as revealed by a microscope at 25× magnification or higher. Alternatively, the two phases can have different chemical compositions and microstructures. For example, a composition can be partially amorphous, substantially amorphous, or completely amorphous.
As described above, the degree of amorphicity (and conversely the degree of crystallinity) can be measured by fraction of crystals present in the alloy. The degree can refer to volume fraction of weight fraction of the crystalline phase present in the alloy. A partially amorphous composition can refer to a composition of at least about 5 vol % of which is of an amorphous phase, such as at least about 10 vol %, such as at least about 20 vol %, such as at least about 40 vol %, such as at least about 60 vol %, such as at least about 80 vol %, such as at least about 90 vol %. The terms “substantially” and “about” have been defined elsewhere in this application. Accordingly, a composition that is at least substantially amorphous can refer to one of which at least about 90 vol % is amorphous, such as at least about 95 vol %, such as at least about 98 vol %, such as at least about 99 vol %, such as at least about 99.5 vol %, such as at least about 99.8 vol %, such as at least about 99.9 vol %. In one embodiment, a substantially amorphous composition can have some incidental, insignificant amount of crystalline phase present therein.
In one embodiment, an amorphous alloy composition can be homogeneous with respect to the amorphous phase. A substance that is uniform in composition is homogeneous. This is in contrast to a substance that is heterogeneous. The term “composition” refers to the chemical composition and/or microstructure in the substance. A substance is homogeneous when a volume of the substance is divided in half and both halves have substantially the same composition. For example, a particulate suspension is homogeneous when a volume of the particulate suspension is divided in half and both halves have substantially the same volume of particles. However, it might be possible to see the individual particles under a microscope. Another example of a homogeneous substance is air where different ingredients therein are equally suspended, though the particles, gases and liquids in air can be analyzed separately or separated from air.
A composition that is homogeneous with respect to an amorphous alloy can refer to one having an amorphous phase substantially uniformly distributed throughout its microstructure. In other words, the composition macroscopically comprises a substantially uniformly distributed amorphous alloy throughout the composition. In an alternative embodiment, the composition can be of a composite, having an amorphous phase having therein a non-amorphous phase. The non-amorphous phase can be a crystal or a plurality of crystals. The crystals can be in the form of particulates of any shape, such as spherical, ellipsoid, wire-like, rod-like, sheet-like, flake-like, or an irregular shape. In one embodiment, it can have a dendritic form. For example, an at least partially amorphous composite composition can have a crystalline phase in the shape of dendrites dispersed in an amorphous phase matrix; the dispersion can be uniform or non-uniform, and the amorphous phase and the crystalline phase can have the same or a different chemical composition. In one embodiment, they have substantially the same chemical composition. In another embodiment, the crystalline phase can be more ductile than the BMG phase.
The methods described herein can be applicable to any type of amorphous alloy. Similarly, the amorphous alloy described herein as a constituent of a composition or article can be of any type. The amorphous alloy can comprise the element Zr, Hf, Ti, Cu, Ni, Pt, Pd, Fe, Mg, Au, La, Ag, Al, Mo, Nb, Be, or combinations thereof. Namely, the alloy can include any combination of these elements in its chemical formula or chemical composition. The elements can be present at different weight or volume percentages. For example, an iron “based” alloy can refer to an alloy having a non-insignificant weight percentage of iron present therein, the weight percent can be, for example, at least about 20 wt %, such as at least about 40 wt %, such as at least about 50 wt %, such as at least about 60 wt %, such as at least about 80 wt %. Alternatively, in one embodiment, the above-described percentages can be volume percentages, instead of weight percentages. Accordingly, an amorphous alloy can be zirconium-based, titanium-based, platinum-based, palladium-based, gold-based, silver-based, copper-based, iron-based, nickel-based, aluminum-based, molybdenum-based, and the like. The alloy can also be free of any of the aforementioned elements to suit a particular purpose. For example, in some embodiments, the alloy, or the composition including the alloy, can be substantially free of nickel, aluminum, titanium, beryllium, or combinations thereof. In one embodiment, the alloy or the composite is completely free of nickel, aluminum, titanium, beryllium, or combinations thereof.
For example, the amorphous alloy can have the formula (Zr, Ti)a(Ni, Cu, Fe)b(Be, Al, Si, B)c, wherein a, b, and c each represents a weight or atomic percentage. In one embodiment, a is in the range of from 30 to 75, b is in the range of from 5 to 60, and c is in the range of from 0 to 50 in atomic percentages. Alternatively, the amorphous alloy can have the formula (Zr, Ti)a(Ni, Cu)b(Be)c, wherein a, b, and c each represents a weight or atomic percentage. In one embodiment, a is in the range of from 40 to 75, b is in the range of from 5 to 50, and c is in the range of from 5 to 50 in atomic percentages. The alloy can also have the formula (Zr, Ti)a(Ni, Cu)b(Be)c, wherein a, b, and c each represents a weight or atomic percentage. In one embodiment, a is in the range of from 45 to 65, b is in the range of from 7.5 to 35, and c is in the range of from 10 to 37.5 in atomic percentages. Alternatively, the alloy can have the formula (Zr)a(Nb, Ti)b(Ni, Cu)c(Al)d, wherein a, b, c, and d each represents a weight or atomic percentage. In one embodiment, a is in the range of from 45 to 65, b is in the range of from 0 to 10, c is in the range of from 20 to 40 and d is in the range of from 7.5 to 15 in atomic percentages. One exemplary embodiment of the aforedescribed alloy system is a Zr—Ti—Ni—Cu—Be based amorphous alloy under the trade name VitreloyTM, such as Vitreloy-1 and Vitreloy-101, as fabricated by Liquidmetal Technologies, CA, USA. Some examples of amorphous alloys of the different systems are provided in Table 1 and Table 2.







TABLE 1







Exemplary amorphous alloy compositions















Alloy
Atm %
Atm %
Atm %
Atm %
Atm %
Atm %
Atm %
Atm %





1
Fe
Mo
Ni
Cr
P
C
B




68.00%
5.00%
5.00%
2.00%
12.50%
5.00%
2.50%


2
Fe
Mo
Ni
Cr
P
C
B
Si



68.00%
5.00%
5.00%
2.00%
11.00%
5.00%
2.50%
1.50%


3
Pd
Cu
Co
P



44.48%
32.35% 
4.05%
19.11% 


4
Pd
Ag
Si
P



77.50%
6.00%
9.00%
7.50%


5
Pd
Ag
Si
P
Ge



79.00%
3.50%
9.50%
6.00%
 2.00%


5
Pt
Cu
Ag
P
B
Si



74.70%
1.50%
0.30%
18.0%
 4.00%
1.50%
















TABLE 2







Additional Exemplary amorphous alloy compositions (atomic %)













Alloy
Atm %
Atm %
Atm %
Atm %
Atm %
Atm %
















1
Zr
Ti
Cu
Ni
Be




41.20%
13.80%
12.50%
10.00%
22.50%


2
Zr
Ti
Cu
Ni
Be



44.00%
11.00%
10.00%
10.00%
25.00%


3
Zr
Ti
Cu
Ni
Nb
Be



56.25%
11.25%
 6.88%
 5.63%
 7.50%
12.50%


4
Zr
Ti
Cu
Ni
Al
Be



64.75%
 5.60%
14.90%
11.15%
 2.60%
 1.00%


5
Zr
Ti
Cu
Ni
Al



52.50%
 5.00%
17.90%
14.60%
10.00%


6
Zr
Nb
Cu
Ni
Al



57.00%
 5.00%
15.40%
12.60%
10.00%


7
Zr
Cu
Ni
Al



50.75%
36.23%
 4.03%
 9.00%


8
Zr
Ti
Cu
Ni
Be



46.75%
 8.25%
 7.50%
10.00%
27.50%


9
Zr
Ti
Ni
Be



21.67%
43.33%
 7.50%
27.50%


10
Zr
Ti
Cu
Be



35.00%
30.00%
 7.50%
27.50%


11
Zr
Ti
Co
Be



35.00%
30.00%
 6.00%
29.00%


12
Zr
Ti
Fe
Be



35.00%
30.00%
 2.00%
33.00%


13
Au
Ag
Pd
Cu
Si



49.00%
 5.50%
 2.30%
26.90%
16.30%


14
Au
Ag
Pd
Cu
Si



50.90%
 3.00%
 2.30%
27.80%
16.00%


15
Pt
Cu
Ni
P



57.50%
14.70%
 5.30%
22.50%


16
Zr
Ti
Nb
Cu
Be



36.60%
31.40%
 7.00%
 5.90%
19.10%


17
Zr
Ti
Nb
Cu
Be



38.30%
32.90%
 7.30%
 6.20%
15.30%


18
Zr
Ti
Nb
Cu
Be



39.60%
33.90%
 7.60%
 6.40%
12.50%


19
Cu
Ti
Zr
Ni



47.00%
34.00%
11.00%
 8.00%


20
Zr
Co
Al



55.00%
25.00%
20.00%









Other exemplary ferrous metal-based alloys include compositions such as those disclosed in U.S. Patent Application Publication Nos. 2007/0079907 and 2008/0118387. These compositions include the Fe(Mn, Co, Ni, Cu) (C, Si, B, P, Al) system, wherein the Fe content is from 60 to 75 atomic percentage, the total of (Mn, Co, Ni, Cu) is in the range of from 5 to 25 atomic percentage, and the total of (C, Si, B, P, Al) is in the range of from 8 to 20 atomic percentage, as well as the exemplary composition Fe48Cr15Mo14Y2C15B6. They also include the alloy systems described by Fe—Cr—Mo—(Y,Ln)—C—B, Co—Cr—Mo—Ln—C—B, Fe—Mn—Cr—Mo—(Y,Ln)—C—B, (Fe, Cr, Co)—(Mo,Mn)—(C,B)—Y, Fe—(Co,Ni)—(Zr,Nb,Ta)—(Mo,W)—B, Fe—(Al,Ga)—(P,C,B,Si,Ge), Fe—(Co, Cr,Mo,Ga,Sb)—P—B—C, (Fe, Co)—B—Si—Nb alloys, and Fe—(Cr—Mo)—(C,B)—Tm, where Ln denotes a lanthanide element and Tm denotes a transition metal element. Furthermore, the amorphous alloy can also be one of the exemplary compositions Fe80P12.5C5B2.5, Fe80P11C5B2.5Si1.5, Fe74.5Mo5.5P12.5C5B2.5, Fe74.5Mo5.5P11C5B2.5Si1.5, Fe70Mo5Ni5P12.5C5B2.5, Fe70Mo5Ni5P11C5B2.5 Si 1.5, Fe68Mo5Ni5Cr2P12.5C5B2.5, and Fe68Mo5Ni5Cr2P11C5B2.5Si1.5, described in U.S. Patent Application Publication No. 2010/0300148.
The amorphous alloys can also be ferrous alloys, such as (Fe, Ni, Co) based alloys. Examples of such compositions are disclosed in U.S. Pat. Nos. 6,325,868; 5,288,344; 5,368,659; 5,618,359; and 5,735,975, Inoue et al., Appl. Phys. Lett., Volume 71, p 464 (1997), Shen et al., Mater. Trans., JIM, Volume 42, p 2136 (2001), and Japanese Patent Application No. 200126277 (Pub. No. 2001303218 A). One exemplary composition is Fe72Al5Ga2P11C6B4. Another example is Fe72Al7Zr1 0Mo5W2B15. Another iron-based alloy system that can be used in the coating herein is disclosed in U.S. Patent Application Publication No. 2010/0084052, wherein the amorphous metal contains, for example, manganese (1 to 3 atomic %), yttrium (0.1 to 10 atomic %), and silicon (0.3 to 3.1 atomic %) in the range of composition given in parentheses; and that contains the following elements in the specified range of composition given in parentheses: chromium (15 to 20 atomic %), molybdenum (2 to 15 atomic %), tungsten (1 to 3 atomic %), boron (5 to 16 atomic %), carbon (3 to 16 atomic %), and the balance iron. The aforedescribed amorphous alloy systems can further include additional elements, such as additional transition metal elements, including Nb, Cr, V, and Co. The additional elements can be present at less than or equal to about 30 wt %, such as less than or equal to about 20 wt %, such as less than or equal to about 10 wt %, such as less than or equal to about 5 wt %. In one embodiment, the additional, optional element is at least one of cobalt, manganese, zirconium, tantalum, niobium, tungsten, yttrium, titanium, vanadium and hafnium to form carbides and further improve wear and corrosion resistance. Further optional elements may include phosphorous, germanium and arsenic, totaling up to about 2%, and preferably less than 1%, to reduce melting point. Otherwise incidental impurities should be less than about 2% and preferably 0.5%.
In some embodiments, a composition having an amorphous alloy can include a small amount of impurities. The impurity elements can be intentionally added to modify the properties of the composition, such as improving the mechanical properties (e.g., hardness, strength, fracture mechanism, etc.) and/or improving the corrosion resistance. Alternatively, the impurities can be present as inevitable, incidental impurities, such as those obtained as a byproduct of processing and manufacturing. The impurities can be less than or equal to about 10 wt %, such as about 5 wt %, such as about 2 wt %, such as about 1 wt %, such as about 0.5 wt %, such as about 0.1 wt %. In some embodiments, these percentages can be volume percentages instead of weight percentages. In one embodiment, the alloy sample/composition consists essentially of the amorphous alloy (with only a small incidental amount of impurities). In another embodiment, the composition includes the amorphous alloy (with no observable trace of impurities).
In one embodiment, the final parts exceeded the critical casting thickness of the bulk solidifying amorphous alloys.
In embodiments herein, the existence of a supercooled liquid region in which the bulk-solidifying amorphous alloy can exist as a high viscous liquid allows for superplastic forming. Large plastic deformations can be obtained. The ability to undergo large plastic deformation in the supercooled liquid region is used for the forming and/or cutting process. As oppose to solids, the liquid bulk solidifying alloy deforms locally which drastically lowers the required energy for cutting and forming. The ease of cutting and forming depends on the temperature of the alloy, the mold, and the cutting tool. As higher is the temperature, the lower is the viscosity, and consequently easier is the cutting and forming.
Embodiments herein can utilize a thermoplastic-forming process with amorphous alloys carried out between Tg and Tx, for example. Herein, Tx and Tg are determined from standard DSC measurements at typical heating rates (e.g. 20° C./min) as the onset of crystallization temperature and the onset of glass transition temperature.
The amorphous alloy components can have the critical casting thickness and the final part can have thickness that is thicker than the critical casting thickness. Moreover, the time and temperature of the heating and shaping operation is selected such that the elastic strain limit of the amorphous alloy could be substantially preserved to be not less than 1.0%, and preferably not being less than 1.5%. In the context of the embodiments herein, temperatures around glass transition means the forming temperatures can be below glass transition, at or around glass transition, and above glass transition temperature, but preferably at temperatures below the crystallization temperature Tx. The cooling step is carried out at rates similar to the heating rates at the heating step, and preferably at rates greater than the heating rates at the heating step. The cooling step is also achieved preferably while the forming and shaping loads are still maintained.
Electronic Devices
The embodiments herein can be valuable in the fabrication of electronic devices using a BMG. An electronic device herein can refer to any electronic device known in the art. For example, it can be a telephone, such as a cell phone, and a land-line phone, or any communication device, such as a smart phone, including, for example an iPhoneTM, and an electronic email sending/receiving device. It can be a part of a display, such as a digital display, a TV monitor, an electronic-book reader, a portable web-browser (e.g., iPadTM), and a computer monitor. It can also be an entertainment device, including a portable DVD player, conventional DVD player, Blue-Ray disk player, video game console, music player, such as a portable music player (e.g., iPodTM), etc. It can also be a part of a device that provides control, such as controlling the streaming of images, videos, sounds (e.g., Apple TVTM), or it can be a remote control for an electronic device. It can be a part of a computer or its accessories, such as the hard drive tower housing or casing, laptop housing, laptop keyboard, laptop track pad, desktop keyboard, mouse, and speaker. The article can also be applied to a device such as a watch or a clock.
Embodiments
A preferred embodiment provides a connection or joint between parts that move with respect to one another, wherein at least one first part is at least partially enclosed by at least one second part. The method includes forming at least one first part having at least one contact surface, depositing an etchable material on at least the one contact surface of the at least one first part, and forming at least one second part at least on the etchable material, wherein the at least one second part at least partially encloses the at least one first part. The method further includes etching away the etchable material to form a space between the at least one first part and the at least one second part such that the at least one first part and the at least one second part move with respect to one another.
In accordance with another embodiment, there is provided a method of forming a connection or joint between parts that move with respect to one another, wherein at least one part is at least partially enclosed by at least one second part. The method includes forming at least one first part having at least one contact surface, depositing an etchable material on at least the one contact surface of the at least one first part, and forming at least one second part at least on the etchable material, wherein the at least one second part at least partially encloses the at least one first part. The at least one first part and/or the at least one second part is formed of a bulk-solidifying amorphous alloy material. The method further includes etching away the etchable material to form a space between the at least one first part and the at least one second part such that the at least one first part and the at least one second part move with respect to one another.
Another embodiment includes a method of molding a movable joint made of bulk-solidifying amorphous alloy using a mold, the movable joint including a first mold part configured to move within a second mold part. The method includes providing a first mold part formed of a bulk-solidifying amorphous alloy material having at least one contact surface, and applying an etchable material on the at least one contact surface. The method further includes overmolding a second mold part formed of a bulk-solidifying amorphous alloy material over at least the etchable material on the at least one contact surface of the first mold part. The method also includes removing the etchable material such that at least a portion of the first mold part is configured to move freely within the second mold part.
Bulk-solidifying amorphous alloy materials are capable of being shaped and formed, using a variety of forming techniques such as extrusion molding, die casting, injection molding, and the like, to form intricately shaped metal objects that can be used in virtually limitless applications. When formed and cooled in accordance with the guidelines provided herein, the bulk-solidifying amorphous alloy metal objects can form extremely hard, intricately shaped parts that can be used for a variety articles, such as electronic devices, machine parts, engines, pump impellers, rotors, rotating drums, knives, cutting devices, and the like. These parts typically are assembled and connected to other parts that may or may not be made from bulk-solidifying amorphous alloys. In some instances it is desirable that the parts joined to one another be movable with respect to one another, and that it be difficult for the joined parts to come apart from one another. The preferred embodiments therefore provide methods for making a connection mechanism between two parts, at least one of which is comprised of a bulk-solidifying amorphous alloy material, and wherein at least a second part at least partially encloses all or a portion of an at least first part.
One preferred method can be described with reference to FIGS. 3-5, which show a method 300 of forming a movable joint between an at least one first part 310 and an at least one second part 320. FIG. 3 is a cross-sectional view of a portion of the method 300 in which an at least one first part 310, preferably at least a portion of which is made from a bulk-solidifying amorphous alloy material is provided. The at least one first part 310 optionally may include a connection feature 350 in the form of a threaded bore or other connection mechanism known in the art (e.g., friction fit connections, seating a threaded nut or other threaded connector to receive a mating connector, seating a bolt with extending threads to accommodate connection with another object, insert casting a soft metal into a cavity and self threading a connector). The at least one first part 310 may be in any size or shape, depending on the final desired product, and may be spherical, oblong, ovoid, triangular, rectangular, cylindrical, pyramidal, rod-like, or any other shape. The shape of the at least one first part 310 is not critical to the embodiments described herein.
In accordance with the method 300, the at least one first part 310 has at least one contact surface 315 that is intended to ultimately provide movement between the at least one first part 310 and an at least one second part 320. The at least one contact surface 315 may be formed on the entire periphery of the at least one first part 310, or only on select portions thereof, depending on the size and shape of the respective first and second parts 310, 320, and the desired movement. The method includes depositing on the at least one contact surface 315 an etchable material 330. Depositing may include spray coating, spraying, plasma coating, chemical vapor deposition, overmolding, or any other technique known that is capable of positioning a layer of etchable material 330 on the at least one contact surface 315. The particular technique employed is not critical to the embodiments, and will depend, for example, on the chemical make up of the at least one first part 310, the etchable material 330, whether any additional treatments have been carried out on the at least one contact surface 315, and the final thickness of the etchable material 330.
The at least one contact surface 315 may optionally be treated to facilitate a metal-to-etchable material bond, such as a thin foil that will deform, melt, or otherwise fuse to the bulk-solidifying amorphous alloy 310, or depositing adhesive, or by a blasting treatment with a nonmetallic abrasive, or using a surface roughening treatment such as contact with an acid. The thickness of the etchable material 330 deposited on the at least one first part 310 depends on the desired degree of movement between the respective parts 310, 320. For example, if it is desired that the respective parts be capable of moving, for example, at least 10 mm with respect to one another, then the thickness of the etchable material 330 should be about 10 mm. Those skilled in the art will be capable of applying a suitable thickness of a suitable etchable material 330 on the at least one first part 310, using the guidelines provided herein.
Any material that can be subsequently removed from in between the at least one first part 310 and the at least one second part 320 can be used as the etchable material 330. It is preferred that the etchable material not be comprised of a meltable solder or metal alloy since such a material likely would melt upon overmolding of the at least one second part 320 over the etchable material 330. In addition, if a meltable metal layer were used as the etchable layer, subsequently heating the respective first and second parts 310, 320, may influence their crystal structure. It therefore is preferred in the embodiments that the etchable material 330 not be comprised of a meltable metal layer.
Suitable etchable layers include those that are “wet” etchable and those that are “dry” etchable. Dry-etchable materials are those that can be etched with a particular gas, such as a chlorine based gas, or a fluorine based gas. Suitable materials for dry etching include, for example, chromium, chromium nitride, chromium oxide, chromium oxynitride, and chromium oxycarbonitride, tantalum nitride, tantalum oxide, and mixtures thereof. Other suitable etchable materials that may be wet-etched include, for example, metal oxides and nitrides of Zr, Hf, La, Si, Y, Indium, and Al, photoresist resins, brass, gold, copper, beryllium-copper, molybdenum, nickel, nickel silver, phosphorous-Bronze, platinum, silicon, Carbon Steel, stainless steel, spring steel, titanium, titanium nitride, tungsten, zinc, Monel, and alloys and mixtures thereof. Any suitable etching material may be used, depending on whether the etchable material 330 is a dry-etchable material or a wet-etchable material. Suitable wet-etching materials include acids such as hydrofluoric acid, sulfuric acid, or other etchants such as sodium hydroxide, ethylene diamine pyrocatechol (EDP), potassium hydroxid/isopropyle alcohol (KOH/IPA), tetramethylammonium hydroxide (TMAH), and the like. Dry-etchants and dry-etching processes, or those used in plasma etching, may include gases containing chlorine or fluorine, such as, for example, carbon tetrachloride, oxygen (for etching ash photoresist), ion milling or sputter etching using noble gases such as argon, reactive-ion etching, and deep reactive-ion etching. The following table provides suitable etchants (wet and dry) that can be used to etch various etchable materials.










Etchants for Specified material









Material to be

Plasma


etched
Wet etchants
etchants





Aluminium (Al)
80% phosphoric acid (H3PO4) + 5% acetic acid +
Cl2, CCl4,



5% nitric acid (HNO3) + 10% water (H2O) at 35-45° C.;
SiCl4, BCl3



or sodium hydroxide



Indium tin oxide
Hydrochloric acid (HCl) + nitric acid (HNO3) + water



[ITO] (In2O3:SnO2)
(H2O) (1:0.1:1) at 40° C.



Chromium (Cr)
Chrome etch: ceric ammonium nitrate ((NH4)2Ce(NO3)6) +




nitric acid (HNO3)




Hydrochloric acid (HCl)



Copper
Cupric oxide, ferric chloride, ammonium persulfate,




ammonia, 25-50% nitric acid, hydrochloric acid, and




hydrogen peroxide



Gold (Au)
Aqua regia



Molybdenum (Mo)

CF4


Organic residues and
Piranha etch: sulfuric acid (H2SO4) + hydrogen peroxide
O2 (ashing)


photoresist
(H2O2)



Platinum (Pt)
Aqua regia



Silicon (Si)
Nitric acid (HNO3) + hydrofluoric acid (HF)
CF4, SF6, NF3




Cl2, CCl2F2


Silicon dioxide
Hydrofluoric acid (HF)
CF4, SF6,


(SiO2)
Buffered oxide etch [BOE]: ammonium fluoride
NF3



(NH4F) and hydrofluoric acid (HF)



Silicon nitride
85% Phosphoric acid (H3PO4) at 180° C. (Requires
CF4, SF6,


(Si3N4)
SiO2 etch mask)
NF3


Tantalum (Ta)

CF4


Titanium (Ti)
Hydrofluoric acid (HF)
BCl3


Titanium nitride
Nitric acid (HNO3) + hydrofluoric acid (HF)



(TiN)
SCl




Buffered HF (bHF)



Tungsten (W)
Nitric acid (HNO3) + hydrofluoric acid (HF)
CF4



Hydrogen Peroxide (H2O2)
SF6









Etchable materials 330 and the etchants that can be used to selectively remove them are described, for example, in Wolf, S.; R. N. Tauber (1986), Silicon Processing for the VLSI Era: Volume 1- Process Technology. Lattice Press. pp. 531-534, 546; Walker, Perrin; William H. Tarn (1991), CRC Handbook of Metal Etchants. pp. 287-291; and Kohler, Michael (1999). Etching in Microsystem Technology. John Wiley & Son Ltd. p. 329. Those having ordinary skill in the art will be capable of utilizing a suitable etchable material 330 depending on the desired thickness, the geometry, and the make-up of the at least one first part 310 and the at least one second part 320, using the guidelines provided herein.
An advantage of using an etchable material, when compared to using a low-melting metal is that the etchable material can be removed using gas or liquid without significantly damaging the bulk-solidifying amorphous metal parts 310, 320. Use of a low-melting metal makes it difficult to overmold a bulk-solidifying amorphous second part 310 because the metal interlayer would melt during the molding process. If a higher melting point metal were used, then the heat needed to melt the metal to remove it would damage the first and second parts 310, 320. Etchable materials that can withstand the molding conditions when the at least one second part 320 is molded over the at least one first part 310 therefore provide a unique advantage in the present embodiments.
The movable joint that includes at least one first part 310 at least partially encased or enclosed by an at least one second part 320 can be fabricated by overmolding or molding an at least one second part 320 onto the etchable material 330, as shown in FIG. 4. Any method can be used to mold the at least one second part 320 including, but not limited to, injection molding, casting, insert casting, and the like. It is preferred that the at least one second part 320 be fabricated at least in part of a bulk-solidifying amorphous alloy.
The movable joint can be completed by etching away the etchable material 330 as shown in FIG. 5, thereby forming a space 360 between the at least one first part 310 and the at least one second part 320. This space permits the at least one first and second parts 310, 320, to move with respect to one another in both the x and y directions. The amount of movement permitted between the respective parts can be varied widely by modifying the thickness of etchable material 330.
As an alternative embodiment, instead of a space 360 positioned between the respective parts 310, 320, a compressible material or fluid may be injected into the space 360 to provide damped or cushioned movement. Any compressible material or fluid can be used including, for example, curable resins such as polyurethane foams, curable rubber materials, gels, hydrogels, hyaluronic acid, polyacrylates, and any known compressible material that can be injected into the space 360 to provide a compressible structure therein. Another alternative embodiment includes injecting a solder or soft metal into space 360, including lead or babbitt type materials that can permit the respective parts 310, 320 to move with respect to one another.
The particular size and shape of the at least one first part 310 and the at least one second part 320 are not critical to the embodiments. For example, the at least one first part 310 may be in the form of a cylinder with an extending shaft as shown in FIG. 6. The method of forming a movable joint 600 in accordance with the embodiment shown in FIGS. 6-8 provides a movable joint in which the at least one first part 610 is nearly fully encased by the at least one second part, and is rotatable within the at least one second part 620.
FIG. 6 illustrates a cross-sectional view of a cylindrically-shaped at least one first part 610 with an at least one contact surface 615 having positioned thereon an etchable material 630. The embodiment illustrated in FIG. 6 shows etchable material 630 applied only partially around the at least first part 610 for purposes of clarity. It is preferred that etchable material 630 completely surrounds the upper cylindrical portion of the at least first part 610, and optionally a portion of the stem. Again, the amount of etchable material 630 applied to the at least one contact surface 615 will depend on the degree of movement desired. If the at least one first part 610 is to be freely rotated within the at least one second part 620, then the portions of the at least one part 610 that are enclosed or otherwise encased by the at least one second part 620 should be covered with the etchable material 630.
FIG. 7 illustrates a cross-sectional view of an additional processing of the method of forming a rotatable joint 600 in which an at least one second part 620 is overmolded or otherwise deposited over the etchable material 630 and the at least one first part 610. The final processing of the method 600 is illustrated in FIG. 8 whereby the etchable material 630 is removed, leaving a space 660 that permits the at least one first part 610 to freely rotate in the direction of arrows A. FIG. 8 shows space 660 completely surrounding the portion of the at least one first part 610 that is surrounded or otherwise enclosed by the at least second part 620. It is preferred in this embodiment, although not necessary, that space 660 not be filled with a compressible material as described above with reference to FIGS. 3-5 so that the at least one first part 610 can freely rotate within the at least one second part 620.
The lower stem portion 625 of the at least one first part 610 can be adapted to connected to a device that provides the motive force to rotate the at least one first part 610 within the at least one second part 620. The particular connection is not critical to the embodiments, and may include for example, a threaded bore or threads on the outer surface of stem 625, friction fitting stem 625 into or onto a rotatable shaft, a groove to accept a band connected to a rotating device, and the like.
A method of forming a movable joint 900 in accordance with the embodiment shown in FIGS. 9-11 provides a movable joint in which the at least one first part 910 is nearly fully encased by the at least one second part, and is rotatable within the at least one second part 920.
FIG. 9 illustrates a cross-sectional view of a ball-shaped at least one first part 910 with an at least one contact surface 915 having positioned thereon an etchable material 930. The ball-shaped at least one first part 910 includes a stem portion 925, similar to the stem portion 625 shown in the embodiment of FIG. 8. It is preferred that etchable material 930 completely surrounds the upper ball portion of the at least first part 910, and optionally a portion of the stem 925. Again, the amount of etchable material 930 applied to the at least one contact surface 915 will depend on the degree of movement desired. If the at least one first part 910 is to be freely rotated within the at least one second part 920, then the portions of the at least one part 910 that are enclosed or otherwise encased by the at least one second part 920 should be covered with the etchable material 930.
FIG. 10 illustrates a cross-sectional view of an additional processing of the method of forming a rotatable joint 900 in which an at least one second part 920 is overmolded or otherwise deposited over the etchable material 930 and the at least one first part 910. The at least one second part may include through-bores 927 (threaded or otherwise) to facilitate its attachment to another, possibly stationary, part or object (e.g., circuit board, beam, bone, or the like). The final processing of the method 900 is illustrated in FIG. 11 whereby the etchable material 930 is removed, leaving a space 960 that permits the, at least one first part 910 to freely rotate within the at least one second part 920. FIG. 11 shows space 960 completely surrounding the portion of the at least one first part 910 that is surrounded or otherwise enclosed by the at least second part 920. It is preferred in this embodiment, although not necessary, that space 960 not be filled with a compressible material as described above with reference to FIGS. 3-5 so that the at least one first part 910 can freely rotate within the at least one second part 920.
The lower stem portion 625 of the at least one first part 610 can be adapted to connected to a device that provides the motive force to rotate the at least one first part 610 within the at least one second part 620. The particular connection is not critical to the embodiments, and may include for example, a threaded bore or threads on the outer surface of stem 625, friction fitting stem 625 into or onto a rotatable shaft, a groove to accept a band connected to a rotating device, and the like.
The embodiments preferably include an at least one second part at least partially enclosing or otherwise encasing an at least one first part. The amount by which the at least one second part encases the at least one first part will depend in the desired degree of relative motion between the respective parts, and the shape of the parts so that the at least one first part will not become dislodged from the at least one second part during ordinary operation of the movable joint. It is preferred that the at least one second part surround at least 50% of the portion of the at least one first part that moves relative to the at least one second part, more preferably, surrounds at least 75% of the portion of the at least one first part that moves relative to the at least one second part, or even more preferably, surround at least 90% of the at least one first part, and even more preferably entirely surround the portion of the at least one first part that moves relative to the at least one second part.
While the invention has been described in detail with reference to particularly preferred embodiments, those skilled in the art will appreciate that various modifications may be made thereto without significantly departing from the spirit and scope of the invention.

## Claims

1. A method of making a connection or joint between parts that move with respect to one another, wherein at least one first part is at least partially enclosed by at least one second part, comprising:
forming at least one first part comprising a bulk-solidifying amorphous alloy having at least one contact surface, said forming including a technique selected from one of extrusion molding, die casting, or injection molding;
depositing an etchable material on at least the at least one contact surface of the at least one first part;
injection molding at least one second part comprising a bulk-solidifying amorphous alloy at least on the etchable material, wherein the at least one second part at least partially encloses the at least one first part; and
removing the etchable material to form a space between the at least one first part and the at least one second part such that the at least one first part and the at least one second part move with respect to one another.

2. The method of claim 1, wherein the at least one second part is formed on at least the etchable material using a mold apparatus.

3. The method of claim 1, wherein the etchable material is removed by a dry or wet etching process.

4. The method of claim 1, further comprising inserting a compressible material into the space formed between the at least one first part and the at least one second part.

5. The method as claimed in claim 1, wherein the alloy is described by the following molecular formula: (Zr, Ti)a(Ni, Cu, Fe)b(Be, Al, Si, B)c, wherein “a” is in the range of from 30 to 75, “b” is in the range of from 5 to 60, and “c” is in the range of from 0 to 50 in atomic percentages.

6. The method as claimed in claim 1, wherein the alloy is described by the following molecular formula: (Zr, Ti)a(Ni, Cu)b(Be)c, wherein “a” is in the range of from 40 to 75, “b” is in the range of from 5 to 50, and “c” is in the range of from 5 to 50 in atomic percentages.

7. The method as claimed in claim 1, wherein the bulk solidifying amorphous alloy can sustain strains up to 1.5% or more without any permanent deformation or breakage.

8. The method as claimed in claim 1, wherein the at least one first part comprises threaded bore or a connection mechanism selected from the group consisting of a friction fit connection, a threaded connector, a bolt with extending threads, a self-threading connector, and a combination thereof.

9. The method as claimed in claim 1 wherein depositing includes a technique selected from one of spray coating, spraying, plasma coating, chemical vapor deposition, or overmolding.

10. The method as claimed in claim 1 wherein the etchable material consists of at least one material selected from among: aluminum (Al); Indium Tin Oxide (ITO) In2O3; SnO2; Chromium (Cr);Copper(Cu);Gold (Au); Molybdenum (Mo); Organic residues and photoresist; Platinum(Pt); Silicon (Si); Silicon dioxide (SiO2); Silicon Nitride (Si3N4);Tantalum (Ta); Titanium (Ti); titanium Nitride (TiN); and Tungsten (W).

11. A method of forming a connection or joint between parts that move with respect to one another, wherein at least one part is at least partially enclosed by at least one second part, comprising:
forming at least one first part comprising a bulk-solidifying amorphous alloy having at least one contact surface;
the operation of forming including a technique selected from one of extrusion molding, die casting or injection molding;
treating the at least one contact surface to facilitate a metal to etchable material bond;
depositing an etchable material on at least the at least one contact surface of the at least one first part;
injection molding at least one second part comprising a bulk-solidifying amorphous alloy at least on the etchable material;
wherein the at least one second part at least partially encloses the at least one first part; and
removing the etchable material to form a space between the at least one first part and the at least one second part such that the at least one first part and the at least one second part move with respect to one another.

12. The method of claim 11, wherein the at least one second part is formed on at least the etchable material using a mold apparatus.

13. The method of claim 11, wherein the etchable material is removed by a dry or wet etching process.

14. The method of claim 11, further comprising inserting a compressible material into the space formed between the at least one first part and the at least one second part.

15. The method of claim 11, wherein the at least one first part rotates within the at least one second part.

16. The method of claim 11, wherein the at least one first part moves in at least one direction with respect to the at least one second part.

17. The method of claim 11, wherein the at least one second part surrounds at least 75% of the portion of the at least one first part that moves relative to the at least one second part.

18. The method of claim 11, wherein the connection or joint permits the relative movement of the at least one first part with respect to the at least one second part, without the respective parts becoming separated during normal operation.

19. The method of claim 11, wherein the at least one second part moves relative to the at least one first part.

20. The method as claimed in claim 11, wherein the alloy is described by the following molecular formula: (Zr, Ti)a(Ni, Cu, Fe)b(Be, Al, Si, B)c, wherein “a” is in the range of from 30 to 75, “b” is in the range of from 5 to 60, and “c” is in the range of from 0 to 50 in atomic percentages.

21. The method as claimed in claim 11, wherein the bulk solidifying amorphous alloy can sustain strains up to 1.5% or more without any permanent deformation or breakage.

22. The method as claimed in claim 11, wherein the at least one first part comprises threaded bore or a connection mechanism selected from the group consisting of a friction fit connection, a threaded connector, a bolt with extending threads, a self-threading connector, and a combination thereof.