Patent Grant
11014147
This application is a U.S. National Phase Application of PCT/EP2016/070963, filed Sep. 6, 2016, which claims priority to European Patent Application No. 15184903.1, filed Sep. 11, 2015, the entireties of which are incorporated by reference herein.
Melt spinning is a technique used for the rapid cooling of liquids. A wheel may be cooled internally, usually by water or liquid nitrogen, and rotated. A thin stream of liquid is then dripped onto the wheel and cooled, causing rapid solidification. This technique is used to develop materials that require extremely high cooling rates in order to form elongate fibers of materials such as metals, inorganic materials and metallic glasses. The cooling rates achievable by melt-spinning are of the order of 104-107 kelvin per second (K/s).
The first proposals for melt spinning originated with Robert Pond in a series of related patents from 1958-1961 (U.S. Pat. Nos. 2,825,108, 2,910,744, and 2,976,590). In U.S. Pat. Nos. 2,825,198 and 2,910,724 a molten metal is ejected through a nozzle under pressure onto a rotating smooth concave surface of a chill block. By varying the surface speed of the chill block and the ejection conditions it is said to be possible to form metal filaments with a minimum cross sectional dimension of 1 μm to 4 μm and lengths from 1 μm to infinity. In U.S. Pat. No. 2,824,198 a single chill block is used, in U.S. Pat. No. 2,910,724 a plurality of nozzles direct flows of metal onto one rotating chill block or a plurality of rotating chill blocks and associated nozzles are provided. In U.S. Pat. No. 2,910,724 no chill block is provided, instead the molten metal is ejected downwardly through nozzles into a vertically disposed cooled chamber containing solid carbon dioxide on ledges provided at the side wall of the chamber. By varying the cross sectional shape of the nozzles the cross-sectional shape of the filaments produced can be varied.
The current concept of the melt spinner was outlined by Pond and Maddin in 1969. Although, liquid was, at first, quenched on the inner surface of a drum, Liebermann and Graham further developed the process as a continuous casting technique by 1976, this time on the drum's outer surface.
The process can continuously produce thin ribbons of material, with sheets several inches in width being commercially available. The dimensions of the bands normally amount to several tens of microns thickness and several centimeters in width and length
References to this process can be found in the following publications:
The melt spinning process has hitherto not been used for the commercial manufacture of micron scale metallic ribbons and fibers on an industrial scale.
In this connection it should be noted that a fiber can be understood as an element of which the length is at least twice its width.
A method of manufacturing microfibers from a metallic melt by depositing the melt on a rotating wheel is described in our as yet unpublished EP application 14 180 273,6 and in the corresponding PCT application PCT/EP2015/068194. There the wheel is provided with a structured surface which modulates the dimensions of the metallic microfibers that are produced.
Metal fiber reinforced composite materials play a central role in a whole series of applications for the improvement of the most diverse properties. Examples of such applications are:
An important aspect for the improvement of fiber based material functions is a large surface area to weight ratio of the metal fibers and the ability to manufacture and process them in an industrially relevant process. This signifies:
Nowadays, the industrially relevant manufacture of functional materials based on metal fibers is restricted to fiber thicknesses of >50 μm. Academic processes exist based on lithographic techniques, glass based template methods and mechanical extrusion processes which enable metallic fibers of <50 μm to be achieved. These methods cannot however be utilized industrially because they are restricted to a few materials and in some cases are not repeatable.
The method and apparatus described in our EP application 14 180 273,6 and in the corresponding PCT application PCT/EP2015/068194 permit the production of micron sized fibers on an industrial scale. However, the need to provide the rotating wheel with a relatively fine and highly precise surface design or topography is a substantial complication and a substantial cost factor in an industrial process.
Further prior art can be found in the following documents: EP 0 055 827 A1, the publication by S. W. Kim et al. titled “Manufacture and Industrial application of Fe-based Metallic Glasses”, published in the Materials Science Forum, in volume 706-709, 2012 on pages 1324 to 1330, the publication by J. K. Sung et al. titled “Theoretical expectations of strip thickness in planar flow casting process”, published in Materials Science and Engineering, volumes A181-A182, 1994 on pages 1237-1242, and the publication by Jech Robert et al. titled: “Rapid Solidification via melt spinning: Equipment and techniques”, published in Journal of Metals, volume 36, no. 4 on Dec. 20, 2013 on pages 41-45.
The object of the present invention is to provide an apparatus and a method by which metallic and more generally inorganic microfibers can be generated on an external surface of a rotating wheel, with the microfibers having a homogenous distribution in the thickness of the fibers and a controllable width having a median value in the range from 200 nm to 50 μm as well as a length of 100 mm to centimeters or longer by depositing the melt onto a rapidly rotating metal or ceramic wheel having a smooth planar surface. The fibers should preferably have a thickness and width of less than one micron and a length of 0.5 mm to 5 mm or larger.
In order to satisfy this object there is provided apparatus for producing elongate fibers of metal, of metallic glasses or of inorganic material, the apparatus comprising a rotatable wheel having a planar external circumferential surface, which is flat in a direction parallel to the axis of rotation of the wheel, at least one nozzle having a nozzle opening for directing a molten material onto the circumferential surface, with the nozzle having a rectangular cross section and a width of a slit of the nozzle opening in the circumferential direction of the wheel being selected to lie in the range from 10 to 500 μm and a collection means for collecting solidified fibers of material formed on the circumferential surface from the molten material and separated from the circumferential surface by centrifugal force generated by rotation of the wheel, wherein the apparatus comprises a further apparatus that is configured to control a gas pressure applied to the molten material which moves the molten material through the nozzle opening and delivers it to the circumferential surface of the rotatable wheel and wherein the further apparatus is further configured to regulate the mass flow of molten material down to a level at which microfibers of the material are formed on the rotatable wheel by controlling and keeping the mass flow per unit area of the wheel surface of the molten material which is deposited per unit of area onto the circumferential surface of the rotatable wheel in the range from 0.01 to 100 g/m2*sec for a surface speed of rotation of the wheel in the range from 10 to 100 m/sec.
The nozzle conveniently has a rectangular cross-section having a width of the nozzle opening in the circumferential direction of rotation of the wheel and a length transverse to the circumferential surface of the wheel which is greater than the width, however this is not essential and the nozzle can in principle be manufactured with the most diverse cross-sectional shapes provided the dimensions and geometry of the nozzle opening permit the flow of molten metal through the opening to be regulated down to a level at which the desired microfibers are produced. As a further example the nozzle could have a crescent shaped opening, or could comprise a row of interconnected generally circular or elliptical or rectangular openings or a row of discrete circular or elliptical or rectangular openings, the row in each case being disposed parallel to the axis of rotation of the wheel or at an angle to the axis of rotation of the wheel. References to the width of the nozzle slit can then be understood as the width or the average width of the circular, elliptical or rectangular openings in a direction parallel to the direction of surface rotation of the wheel.
It should be noted in this connection that the prior art cited in the introduction to the specification does not show that the currently described nozzle widths can produce the desired fibers and that the desired fibers can be produced at the wheel speed ranges respectively at ranges of the surface speed of rotations of the wheel described herein.
The present invention also relates to a method for producing elongate microfibers of metal, or metallic glasses or of inorganic material having a median width of 50 μm or less, a thickness of 5 μm or less and a length at least ten times greater than said width, the method comprising the steps of directing a molten material through a nozzle onto a planar external circumferential surface of a rotating wheel, with the nozzle having a nozzle opening for directing a molten material onto the circumferential surface, with the nozzle having a rectangular cross section and a width of a slit of the nozzle opening in the circumferential direction of the wheel being selected to lie in the range from 10 to 500 μm, by applying a gas pressure to the molten material to move it through the nozzle opening and deliver it to the circumferential surface of the rotatable wheel, and collecting solidified fibers formed on the circumferential surface from the molten material and separated from the circumferential surface by centrifugal force generated by rotation of the wheel, the method further comprising the steps of selecting the dimensions and geometry of the nozzle in combination with the gas pressure (ΔP) to regulate the mass flow of molten material (Mfa) which is deposited per unit of area onto the circumferential surface of the rotatable wheel to a value in the range from 0.1 to 100 g/(m2*sec), especially between 0.5 and 50 g/(m2*sec), particularly between 0.7 and 30 g/(m2*sec) and ideally around 1 g/(m2*sec) for a surface speed of rotation of the wheel in the range from 10 to 100 m/sec to form microfibers of the material on the rotatable wheel by reducing the flow of molten material onto the circumferential surface of the wheel in a material dependent manner to a level at which it is concentrated by the forces that are acting to produce the desired elongate fibers of the material.
The flow of material is reduced to a level at which the elongate fibers have a width of 200 μm to <1 μm, preferably of 150 μm to <1 μm and especially of <50 μm to <1 μm. This means that the volume of liquid material Vm which is deposited per unit of area onto the circumferential surface of the rotatable wheel is controlled. The metal strands or fibers thereby produced typically have a thickness of less than or equal to 5 μm to <1 μm.
The length of the fibers is controlled by including grooves or elevations of 5 mm to 1 mm on top of the wheel surface onto which the melt is deposited. The grooves or elevations run parallel to the rotation axis with distances between the grooves and elevations which correspond to the length of the fibers. Practically, these grooves and elevations can be prepared by mechanical machining.
The underlying concept of the invention can be seen from the following calculations based on experimental results:
The quantity of the metallic melt deposited per second (Mf) lies between 0.01 and 10 g/sec; especially between 0.1 and 5 g/sec, particularly between 0.2 and 3 g/sec and ideally around 0.25 g/sec.
The speed of rotation of the wheel surface (U) typically lies between 10 and 100 m/sec; especially between 30 and 80 m/sec, ideally at 60 m/sec.
The mass flow per unit area=Mfa can be calculated as follows, when the speed of rotation of the surface of the wheel is U (m/sec) and the length of the nozzle opening is Ld:
Mf=0.01 g/sec; U=10 m/sec, Ld=1 cm: Mfa=Mf/(U*Ld*sec)=0.1 g/(m2*sec)
Mf=10 g/sec; U=100 m/sec, Ld=1 cm: Mfa=Mf/(U*Ld*sec)=10 g/(m2*sec)
Mf=10 g/sec; U=10 m/sec, Ld=1 cm: Mfa=Mf/(U*Ld*sec)=100 g/(m2*sec)
Mf=0.01 g/sec; U=100 m/sec, Ld=1 cm: Mfa=Mf/(U*Ld*sec)=0.01 g/(m2*sec)
Thus Mfa ranges between 0.01 and 100 g/(m2*sec); ideally at 0.42 g/(m2*sec) for U=60 m/sec and Mf=0.25 g/sec. It will be understood that the Mfa values quoted herein apply per linear centimeter of the nozzle orifice length L.
These Mfa limits can be transformed as follows for the case of steel with a density G of circa 8 g/cm3 to the expected layer thicknesses (d) of the melt on the wheel before separating into fibers:
Mfa=0.01 g/(m2*sec): d=(Mfa/G)*(m2*sec/U*Ld*sec)=⅛ *10−2 mm
Mfa=100 g/(m2*sec): d=⅛ mm
Ideally with
Mfa=0.42 g/(m2*sec): d=0.0875 mm.
It is particularly surprising that it is possible, by providing an apparatus and a method with the above features, to generate metal strands and fibers with dimensions which can be controlled within relatively tight limits using a rotatable wheel with a smooth, polished planar, non-structured surface having a certain surface roughness. The copper wheels used for the experiments detailed below were polished prior to each experiment. It is expected that there is some correlation between the surface roughness and the width of the fibers.
A controller is preferably provided for keeping the speed of rotation of the wheel constant so that the surface speed of the wheel lies in the range from 40 to 60 m/s with a wheel of 20 cm or larger diameter of the external circumferential surface. The production of fiber material is a combination of the material flow from the nozzle and the speed of rotation of the rotatable wheel. If one succeeds in drastically reducing the metal flow from the nozzle then it is also possible to operate with lower speeds of rotation, i.e. surface speeds of the wheel. Accordingly a speed of rotation of 10 Hz with a wheel of 200 mm diameter is also entirely possible providing the amount of molten material issuing from the nozzle is correspondingly reduced. It has proved possible to generate microfibers at speeds of rotation of 60 Hz with a wheel of 200 mm diameter. A surface speed of 100 m/s of a copper wheel is close to the mechanical limit for a copper wheel of 200 mm diameter. However, higher speeds are possible if the material of the wheel is changed, for example speeds of up to 200 m/s for a stainless steel wheel of 200 mm diameter.
Controlling the surface speed of the wheel in this manner makes it possible to ensure the flow of metal from a rectangular orifice of fixed width, or from another suitable orifice can be reduced to a level at which metal fiber of the desired size can be produced.
Although a diameter of the wheel of 20 cm to 35 cm is preferred this is not critical and wheel diameters in the range from 1 to 100 cm can be used. A larger diameter of the circumferential surface of the rotating wheel increases the surface speed of the wheel if the speed of rotation is kept constant. Thus a larger diameter of the wheel results in a smaller width of the metal fibers at constant speed of rotation. The width of the opening of the slit of the nozzle in the circumferential direction of the wheel is preferably selected (for a rectangular nozzle opening or a crescent shaped opening) to lie in the range from 20 to 500 μm and especially in the range from 20 to 100 μm. These are currently the practical size ranges for the width of the nozzle opening. It is however possible that higher peripheral speeds of the wheel will enable greater widths or sizes of the nozzle opening for the production of microfibers. The maximum length of the slit corresponds to the width of the external circumferential surface of the wheel in a direction parallel to the axis of rotation thereof, i.e. is the same as or less than the width of the external circumferential surface of the wheel, e.g. several centimeter shorter than the width of the external circumferential surface of the wheel. In the examples given, the width of the slit was ca. 1 cm and the width of the wheel ca. 4 cm.
For the sake of completeness it should be noted that Liebermann who produced ribbons of 10 to 40 μm thickness used a nozzle with a circular orifice.
The temperature of the melt is preferably kept 100 to 400° C. greater than the melting point of the metal. As the viscosity of the melt reduces with increasing temperature of the melt the reduction in viscosity with increasing temperature must be borne in mind when selecting the operating parameters for a particular metal in order to ensure the rate of delivery of molten metal to the rotatable wheel is kept sufficiently low for fibers of the desired dimensions to be achieved. The viscosity of the melt also depends on the material of the melt.
In addition to the foregoing the pressure exerted on the melt upstream of the nozzle is controlled to be higher than the pressure prevailing in the melt spinning chamber by an amount in the range from 50 to 5000 mbar. Although the aim is to reduce the amount of melt delivered to the rotatable wheel so that the desired sizes of microfibers arise, it nevertheless proves possible, with a nozzle length of 10 mm, to process one gram of metal per second to microfibers, so that the process is industrially relevant.
The rotatable wheel is preferably temperature controlled, e.g. to a temperature in the range of −100° C. to +400° C.
The wheel is usually made of a metal, for example copper or stainless steel, or of a metal alloy or of a ceramic material or is a wheel of a base material having a layer or tire made of a metal or of a metal alloy or of a ceramic material or of graphite or a vapor deposited carbon, for example a copper wheel having a layer of graphite.
The wheel is preferably mounted to rotate within a chamber having an atmosphere, the atmosphere being at least one of air, an inert gas, nitrogen, or helium.
Moreover, the wheel is preferably mounted to rotate within a chamber having an atmosphere at a pressure corresponding to the ambient atmospheric pressure, or to a lower pressure than ambient pressure.
Generally speaking the thickness and width of the microfibers can be controlled by dispensing a metallic melt from a crucible standing under a pressure P through a rectangular slot of area A onto a rapidly rotating planar wheel. In this connection the following process parameters have been found to be the determining factors:
Mfa—the mass of liquid metal dispensed per unit of area per second onto the surface of the rotating wheel, should be controlled and kept very low, typically below 10 g/(m2*sec).
In detail it has been found that the width of the fibers can be set in that a lower value of Vm results in a lower width of the metal fibers
Mfa can be set by adjusting the following process parameters:
U—the surface speed of rotating wheel B on which the metallic melt is deposited.
In the experiments U was varied between 18 and 60 m/sec and it was found that higher speeds resulted in a lower width of the fibers. Speeds between 10 and 100 m/sec are readily conceivable.
A—the aperture area of the slit of the rectangular slit of the crucible through which the metallic melt is distributed onto the surface of the wheel. Reducing the width of the slit in the circumferential direction of the wheel results in a reduced value of Vm. The width W of the slit can be selected to lie at a value between 10 and 500 μm.
T—the temperature of the melt. As noted above the viscosity of the melt sinks with increasing temperature. A lower viscosity results in a higher Vm under constant conditions. Hence controlling T allows Vm to be reduced. It must be borne in mind that T has to be selected in dependence on the metal that is being used. Temperatures in the range from 100 to 400° C. above the melting point of the metal being used have been found to be useful.
P—the excess pressure which is used to expel the melt through the nozzle opening of the crucible. A higher value of ΔP, i.e. of the pressure difference between the pressure acting on the melt in the crucible and the pressure prevailing within the processing chamber, results in a higher Vm, however it must be borne in mind that a narrow value of the width of the nozzle may require higher values of pressure ΔP to partly compensate for the reduction in Vm due to the narrower width. In the experiments conducted pressures ΔP between 50 and 2000 mbar were found to be useful.
It is not easy to understand or predict why the metallic melt is split up into microfibers if Mfa is appropriately selected. A possible academic explanation is as follows:
Dewetting of thin liquid films on solid supports may appear by two different mechanisms:
These forces can destabilize a thin film by causing surface fluctuations to grow exponentially. Rupture takes Place on a length scale corresponding to the wavelength of the surface undulation whose amplitude increases most rapidly till it reaches the thickness of the film, also called critical film thickness.
In the case of an ideally flat surface no heterogeneous hole nucleations due to defects is expected.
Therefore, for dewetting to occur, a reduced film thickness less than the critical film thickness of the liquid film on a flat substrates needs to be provided. In the case of a non-moving substrate, surface forces which appear on the air-liquid and liquid-solid interface pull undulations in the thin film which eventually cause dewetting, i.e. holes. Such dewetting occurs within microseconds.
For moving solid substrates such as in the case of a rotating wheel which gets coated by ejection of a metal liquid film through the opening of a crucible the situation is drastically different.
The ejection direction is perpendicular to the movement of the surface of a rotating wheel. Upon contact of the liquid film with the moving solid support two additional forces pull on the air-liquid and liquid-solid interface: a tangential traction forces which pulls the liquid film with the moving solid support and a centrifugal force which pulls vertically away from the solid interface. These two forces may be enormous since the circular movement of the solid support is in the range of 60 m/sec or more. The traction forces cause the film to spread thinly and eventually to dewet if the film thickness is less than the critical film thickness of the material. The centrifugal force pulls on the appearing surface film undulations and promotes the dewetting structure even more. Since the traction force and the centrifugal force are one dimensional forces which respectively act tangentially and vertically to the liquid film surface, the undulations appear in stripe pattern in the direction of the traction force. This process may take a time in the range of microseconds. The cooling rate of melt spinning is in the range of 104-10 microseconds per 100 degree centigrade—rather 1-10 microseconds—considering the little material which needs to be cooled in case of microfiber fabrication. Therefore, cooling rate and spinodal dewetting cover similar time ranges! If the temperature of the liquid film drops below its melting temperature slower than the dewetting time, solidified microfibers are spun-off the wheel. Therefore, macroscopic long fibers with microscopic width are fabricated where the width of the fiber depend on the amount of liquid material which is cast onto the rotating wheel area per unit time. A defect on the surface of the rotating wheel, such as topographic domains or surface roughness act as a nucleation site for the liquid film in addition to the spinodal dewetting. Regular domains along the surface of the wheel and perpendicular to the rotation axis may support to form a more homogeneous distribution of the fiber width and length. In the case of conical shaped domains centrifugal forces will force the liquid film to accumulate at the tip of the cones. This will impact the shape and uniformity of such fabricated microfibers.
The invention will now be described in further detail and by way of example only with reference to the accompanying drawings and various examples of the method of the invention. In the drawings there are shown:
Turning now to the schematic drawing of the melt spinning process shown in
The pressure P applied to the molten metal can also be used to change the flow rate. Clearly a relatively large pressure leads to a higher flow rate than a relatively lower pressure. A minimum pressure P is always required in order to force the molten metal through the nozzle N, as gravity alone is not normally sufficient to ensure adequate flow, particularly with a relatively small width W of the nozzle opening. In fact this is advantageous because otherwise some form of valve would be necessary and a valve for regulating the flow of molten metal is technically challenging. It should be noted that the pressure difference ΔP between the pressure applied to the melt and the pressure prevailing in the chamber 12 is dependent on the metal used and on the width of the nozzle opening in the circumferential direction. It is also dependent on the length of the nozzle opening in a direction parallel to the axis of rotation of the wheel. The length of the nozzle opening can be varied within wide limits. For laboratory experiments values of 10 to 12 mm have been found useful. In production much greater lengths could be selected in dependence on the axial width of the circumferential surface of the wheel.
The actual apparatus used is shown in
The cover for closing the port 16 can be a hinged or removable glass cover permitting the material collected in the cylindrical extension 18 to be observed, removed and filmed as required. In all experiments the copper wheel was not cooled.
The following experiments were conducted:
In the first experiment melt spun ribbons were generated on a standard copper wheel B with a diameter of 200 mm and a smooth circumferential surface 32 (indicated at S n
In the following examples will be given of fibers produced by melt spinning using a smooth flat wheel and an Fe40Ni40B20 metallic glass (examples 3 to 7 and 9 to 14), for stainless steel (V2A example 8) as well as for Zn and Al (examples 15 and 16). Where reference is made to the median width this value is obtained in accordance with the usual definition. In all cases the thickness of the majority of the fibers was less than 5 μm. As yet no attempts have been made to more accurately determine the thicknesses
The values for both the comparative example 1 and for the inventive examples 2 to 8 are summarized—together with other relevant values—in the Table of
The Table of
Although the spacing between the nozzle opening and the wheel was 300 μm in the Examples given experiments have shown that choosing spacings between 100 and 300 mm; has not had any measurable influence on the microfibers produced.
In all experiments the diameter of the wheel was 200 mm.
| Number | Date | Country | Kind |
|---|---|---|---|
| 15184903 | Sep 2015 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2016/070963 | 9/6/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/042155 | 3/16/2017 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 2825108 | Pond | Mar 1958 | A |
| 2825198 | Pond | Mar 1958 | A |
| 2910724 | Grajeck | Nov 1959 | A |
| 2910744 | Pond | Nov 1959 | A |
| 2976590 | Pond | Mar 1961 | A |
| 4454908 | Kodama | Jun 1984 | A |
| 4523966 | Tsuya | Jun 1985 | A |
| 5096513 | Sawa | Mar 1992 | A |
| 5213151 | Hackman | May 1993 | A |
| 6626228 | Bewlay et al. | Sep 2003 | B1 |
| 20150027592 | Shibasaki | Jan 2015 | A1 |
| 20170209918 | Spatz et al. | Jul 2017 | A1 |
| Number | Date | Country |
|---|---|---|
| 0 055 827 | Jul 1982 | EP |
| 2 982 460 | Feb 2016 | EP |
| H0655247 | Mar 1994 | JP |
| 2000-42694 | Feb 2000 | JP |
| Entry |
|---|
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| Number | Date | Country | |
|---|---|---|---|
| 20180178275 A1 | Jun 2018 | US |
