JP2017528623A - Method and apparatus for making fibers and microstructures from precursors of different molecular mass - Google Patents

Abstract

The disclosed method and apparatus improve the production of solid fibers and microstructures. In many embodiments, one or more low molecular mass precursors are used in combination with one or more high molecular mass precursors, from gases, solids, semisolids, liquids, critical, and supercritical mixtures. Make it. Methods and systems generally use a thermal diffusion / solet effect that concentrates a low molecular mass precursor in the reaction zone, where the presence of a high molecular mass precursor contributes to this concentration and also contributes to the reaction. The reaction zone can be insulated to achieve higher fiber growth rates and / or reduced energy / heat consumption and reduced uniform nucleation. In some embodiments, the present invention also relates to permanent or semi-permanent recording and / or reading of information on or in the fabricated fibers and microstructures. In some embodiments, the present invention also relates to the creation of certain functionally formed fibers and microstructures. In some embodiments, the present invention may also use laser beam profiling to enhance fiber and microstructure fabrication.

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is filed on August 18, 2014, “Method and Apparatus of Fabricating Fibers Displacement Molecular Mass Gasius, Liquid, Liquid,” incorporated herein by reference in its entirety. US Patent Application No. 62 / 038,705 entitled “Supercritical Fluid Mixtures”, “Doped Carbon Fiber and Carbon-Federated Fibers of the United States”, filed November 4, 2014. , An U.S. Patent Application No. 62 / 074,703 entitled "Supercritical Fluid Mixtures", entitled "Method and Apparatus for Recording and Modulated Fibers" on November 4, 2014. Claim the priority and interest of 62 / 074,739.

Statement on research or development supported by the federal government N / A

  The present invention relates to the technical field of the production of fibers and microstructures. In some embodiments, the present invention also relates to permanent or semi-permanent recording and / or reading of information on or in the fibers and microstructures. In some embodiments, the present invention also relates to the manufacture of certain functionally formed and designed short fibers and microstructure materials. In some embodiments, the present invention can also use laser beam profiling to enhance the fabrication of fibers and microstructures.

  In some embodiments, the present invention generally relates to the production of fibers that are commonly used to reinforce composite materials. Often, short strands of fiber are cut to lengths from long rolls of fibers, wires, or rolled strips and then added to the composite matrix material in a random or regular arrangement. These fibers are known in the art as “chopped fibers” and are used in a wide range of applications from carbon fiber reinforced polymers to sprayed metal fiber reinforced insulation, polymer fiber reinforced concrete. In the composite industry, long strands of fiber can also be wound / joined into a tow or rope, which can then be used to create a “fiber layup” to strengthen the composite material.

  Very often, the fibers increase the strength of the composite material and the surrounding matrix material has complementary properties. The overall strength of the composite material depends on both the fiber properties and the matrix properties, but usually the strength is compromised if the fibers are excessively pulled out of the matrix. Thus, one of the biggest challenges associated with composite fiber reinforcement is to optimize the “pull” strength of the fibers within the matrix material. Traditionally, this has been done by (1) increasing the adhesion or bond strength at the fiber-matrix interface, or (2) increasing the surface area for the two materials to contact.

  However, there is basically no existing fiber concept with an optimal fiber concept whose shape is designed to minimize drawing and allow the composite to remain flexible and tough. One reason for this simply arises from the fact that the current manufacturing method is that the raw fiber or wire-based material stretches the fiber material with a die, and in the case of metal strips, these materials are often made from rolled metal sheet material. This is because it is assumed to be disconnected. For many materials, it is difficult to modify the fiber cross-section dynamically using a die or rolling process. Therefore, carbon fiber manufacturers mainly produce carbon fibers with a circular cross section, and often the metal fibers are all chopped from a cylindrical wire having a constant cross section. Of course, the ductile / metal wire / strip may be wound, dented, or mechanically bent to change its shape, such as carbon, silicon carbide, silicon nitride, boron, or boron nitride, Many of the stronger (often brittle) materials desirable for high performance composites are impractical. The forming process increases the overall cost of the process, and the forming process is usually limited to the possible geometries that can be created. Therefore, a method of adjusting the cross-sectional length of the reinforcing fiber is highly desirable, especially when an optimal reinforcing geometry can be created.

  Note that pull-out strength is not the only parameter that must be optimized to reinforce the fiber. In many situations, it is also useful to have fibers that are designed to bend, flex, twist, etc. without breakage or delamination from the matrix. It is desirable in many applications to create fibers in a shape that exhibits more isotropic properties. For example, carbon fibers may have a high tensile strength in one direction and a low compressive or shear strength. This is mainly due to the way the fibers are processed from continuous strands that provide a specific anisotropic microstructure / orientation along the fiber axis. However, changing the nominal geometric orientation of the fiber itself to a non-linear geometry can greatly improve the shear and deflection properties of the resulting composite material. This is difficult to achieve with conventional fiber manufacturing methods.

Traditionally, high pressure laser chemical vapor deposition (HP-LCVD) has been used with simple Gaussian laser beam profiles to grow free-standing three-dimensional fibers from a variety of materials. The Gaussian beam profile is brightest at the center of the beam and the intensity is I (r) = Io * Exp (−2r ² / wo ² )
Accordingly, it gradually decreases in the radial direction with the distance from the central axis of the beam. When focused on the surface by a positive lens, such a Gaussian beam generates a focal point having this same Gaussian distribution. Thus, when the fiber is grown by HP-LCVD using a Gaussian beam, the fiber is most heated at the center of the fiber, but the absorbed energy is reduced in the radial direction. If the thermal conductivity of the fiber material is high, the fiber size is small and the growth rate is slow, and this absorbed thermal energy can be transmitted quickly across the fiber tip, making the temperature profile in the reaction zone at the fiber tip fairly uniform. it can. However, for materials with moderate to low thermal conductivity, the center of the fiber will typically be at a much higher temperature than the fiber edge.

  This creates several problems for rapid fiber growth. First, because the phase and composition of the material being grown can be highly temperature dependent, a non-uniform temperature distribution can create more than one phase or composition of material within the fiber. For example, during carbon fiber deposition from ethylene, depending on the reaction temperature, at least four possible material phases can be deposited: amorphous / particulate carbon, graphitic carbon, spherical carbon, and diamond-like carbon. Therefore, it is very common to grow carbon fibers having a graphitic carbon core with an amorphous or particulate carbon coating using a moderate laser power Gaussian laser beam. This is shown in FIG. 37 (c). The graphite core is often composed of a parabolic or Gaussian graphite shell, which is centrally located on the fiber axis and extends outward toward the outside of the fiber. This material configuration provides strength in the radial direction but is not very strong along the fiber axis. This results in a fiber with very low tensile strength along the primary axis, which is very important for fiber reinforcement applications. To be the most useful / commercially competitive, carbon fibers grown by HP-LCVD are either completely amorphous / glassy or extend in the same direction as the fiber axis. It should have a graphite surface that adds strength along the direction.

  In addition, many desired fibers are binary or ternary compounds or alloys that are deposited using two or more precursors. Each precursor generally deposits differently from other precursors with respect to temperature because it exhibits its own deposition kinetics and activation energy. In the presence of a single temperature, this is less of a problem because the concentration of the vapor phase precursor can compensate for the difference in deposition kinetics. However, in the temperature gradient this causes a compositional change of the deposited elements within the fiber. In the case of a Gaussian beam, this means that a radial composition gradient exists for more than one precursor. This may be advantageous (eg, obtaining a protective coating of the core material in a single step). However, in many cases, a single composition within the fiber is desirable.

  The present invention generally relates to synthesizing fibers from gas, solid, semi-solid, liquid, critical, and supercritical fluid mixtures, where the mixture is composed of precursors having very different molecular masses.

  In one of the simplest forms, the mixture uses one low molecular mass (“LMM”) precursor (eg, silane) and one high molecular mass (“HMM”) precursor (eg, hexamethyldisilane). Using a thermal diffusion / solet effect, the LMM precursor is concentrated in the reaction zone where the fibers are growing. The term “thermal diffusion” is generally understood to refer to a concentration effect that can occur in a gas, and the Soray effect is generally understood to refer to the concentration effect of a liquid, but throughout this specification Uses the term “thermal diffusion” to refer to any example of a concentration effect, regardless of the state of the fluid. It should be understood that the precursor need not necessarily be larger or smaller than a certain molecular mass. Rather, the terms “LMM precursor” and “HMM precursor” are used to contrast the relative molecular masses of different precursors. The difference in precursor molecular mass needs to be sufficient so that the concentration of LMM precursor in the reaction zone increases significantly over the remainder of the chamber volume. Thus, to achieve the desired high concentration effect, the LLM precursor may have a relatively “high” molecular mass if it is sufficiently lower than the molecular mass of the HMM precursor.

  In a preferred embodiment, for a “very different molecular mass”, the molecular mass of the HMM precursor may be at least 1.5 times greater than the LMM and substantially greater than 3 times greater. For example, in one particular embodiment using an alkane, the LMM precursor may be ethane with an approximate mass of 30 amu (atomic mass units) and the HMM precursor may be hexane with an approximate mass of 86 amu. . In this example, the HMM is approximately three times the mass of the LMM. In another example, methane may be used as an LMM with an approximate mass of 16 amu and hexadecane may be used as an HMM with an approximate mass of 226 amu. In this example, the HMM has a mass greater than 14 times that of the LMM. For many precursors, the greater the mass difference between HMM and LMM, the higher the positive effect on fiber growth rate.

As used herein, the term “molecular mass” refers to each precursor species (ie, relative to carbon 12) as determined by mass spectrometry or other standard methods of relative molecular mass (m _r ) determination. it is assumed to refer to the m _r. Since the present invention relies on comparative measurements of very large differences in molecular mass to obtain fairly high fiber growth rates, one method of molecular mass determination can be compared to another (or even different molecular mass definitions). In practice may be ignored in practice for the practice of the present invention. However, if the HMM species or LMM species may be composed of a distribution of various species (eg, for some waxes, kerosene, gasoline, etc.), the meaning of “molecular mass” herein is a mass average molecule It becomes mass. Finally, it should be noted that the present invention applies to both naturally occurring and man-made isotope distributions of molecular mass within each precursor species.

  In addition, the HMM precursor preferably has a lower mass diffusivity and lower thermal conductivity than the LMM precursor, and the lower the diffusivity and thermal conductivity of the HMM precursor, the better . This allows the HMM precursor to thermally insulate the reaction zone, thus reducing heat transfer from the reaction zone to the surrounding gas. Also, the HMM precursor provides a larger Peclet number (general) than the use of the LMM precursor alone and supports large convection. This allows for more rapid convection in a small enclosure chamber and therefore tends to reduce the size of the boundary layer around the reaction zone. This diffusion across the boundary layer often becomes a step limiting rate during the reaction. At the same time, the thermal diffusion effect helps maintain at least a minimal diffusion region in which a concentration gradient exists, allowing the LMM precursor to be maintained at a high concentration in the reaction zone. Note that the HMM precursor may be an inert gas, and the primary function of this inert gas is to concentrate and insulate the LMM precursor.

  Using the systems and methods described herein, LMM precursors can provide rapid fiber growth rates that far exceed that obtained by using LMM precursors alone. In some cases, this results in a growth rate that is one or two orders of magnitude higher than expected for a given laser power and reactor chamber pressure. This effect is not always observed in the case of chemical vapor deposition (CVD) processes, but is evident in microscale CVD processes where the heating means for the reaction is localized.

  Thus, in some embodiments, an aspect of the invention combines the thermal diffusion effect and the use of precursors with very different molecular masses to concentrate at least one of the precursors in the reaction zone and And / or improving the properties of the resulting fiber. In addition, the reaction zone is maintained in the region of the space in the reactor so that the ends of the growing fiber are maintained in the reaction zone, and the growing fiber is moved at a rate similar to the fiber growth rate. A means of translating or winding is disclosed, which can help maintain a stable growth rate and properties of the fiber. Both short (chopped) and wound long fibers can be grown. Along with the method of growing and collecting short (chopped) fibers, a method for winding the long fibers as individual strands or as tows or ropes is disclosed. During fiber length growth, a fiber tensioner is provided to keep the fiber growth edge from moving too much in this reaction zone, so that the fiber can be displaced with respect to the growth zone by winding the fiber. And does not hinder fiber growth. There are various ways of tensioning the fibers known to those skilled in the art. However, the Applicant first developed a means to tension the fiber without retaining the growing edge while keeping the fiber in the center of the reaction zone. Applicants have developed passive, actively controllable electrostatic, magnetic, fluid, and / or mechanical centering / tensioning means.

  In various embodiments described herein, thermal or optical (usually heterogeneous) decomposition of at least one precursor occurs in the reaction zone. Fibers can grow by decomposition of the LMM precursor. However, it is also possible to use LMM precursors that react with HMM precursors in the region of the reaction zone, and the LMM precursors do not independently produce deposits. The decomposition reaction may be triggered by heat or light, but is usually at least partially a heat driven process and therefore there is a thermal diffusion effect if the heating means are small and the surrounding bath is substantially cooler. obtain. In some embodiments, the present invention enhances and controls this thermal diffusion effect, resulting in a more rapid and controlled growth of the fiber. This is useful for reducing manufacturing costs and improving the quality of fibers grown by this method.

  Thermal gradients induced by Gaussian beams can also induce thermal diffusion effects. As described herein, this typically causes the gas phase low molecular mass (LMM) species to diffuse toward the central (hottest) portion of the gradient, with the heavier molecular mass (HMM) species centered. Diffuse away from. Since the by-products of the HP-LCVD reaction are always lower in mass than the precursor, this reduces the precursor at the center of the reaction zone and effectively slows the reaction rate along the center of the fiber axis ( Also called thermal diffusion growth inhibition (TDGS). Thereby, the manufacturing speed of the fiber by HP-LCVD can be reduced significantly.

  Thus, in some embodiments, another aspect of the invention is that two or more fibers can be grown simultaneously in a controlled manner. This can be done by using multiple heating sources, i.e. an array of heating spots or regions. For example, an array of focused laser beams may be created to initiate and continue fiber growth. However, other heating sources are possible, such as by using induction heating of the fibers, using an array of electric arcs, and the like. As described further below, two or more heating means, sometimes referred to herein as “primary” heating means, may be used for each reaction zone.

  In the following, it should be noted that the temperature rise induced by the primary heating means can vary from spot to spot across the array of heated spots, which can cause undesirable variations in growth rate and / or fiber properties from fiber to fiber. . For example, when using an array of focused laser beams, there is often a deviation of several percent or more in the laser power per spot. In addition, fluctuations in the spot waist of each laser spot cause large fluctuations in the temperature rise from spot to spot. Thus, even with precision diffractive optics or beam splitting, laser spot arrangements can cause peak surface temperature variations of more than 20% from spot to spot. These variations must be controlled electro-optically or compensated by other means, or the fiber growth rate will not be similar and the fiber properties will change. If the growth rates are not substantially similar, it becomes difficult to maintain a common growth surface for many fibers at once. In this case, if some of the fibers are delayed and the growth surface is not actively tracked, these fibers may cease to grow overall when they leave the reaction zone.

  Thus, in some embodiments, another aspect of the invention does not require that the thermal diffusion effect be induced only by the primary heating means, but is induced and controlled by another heat source (ie, a “secondary” heating means). Additional parameters used to drive and control reaction rate and fiber properties may be provided. When using only primary heating means, precursor flow rate, pressure, and primary heating rate are the primary tools / parameters that can be used to control reaction and fiber properties (eg, diameter, microstructure, etc.). The ability to change the fiber growth rate and properties independently of the primary heating means, if heat can be applied independently and alternative heating means can be used to control the thermal diffusion gradient and the size of the thermal diffusion region New tools will be provided. In addition, it may be difficult or expensive to control the primary heating means dynamically, such as in the use of electro-optic modulation of many laser beams, but the secondary heating means may be near the reaction zone. It can be very simple, such as a resistance wire across or around the reaction zone. Such wires can be heated inexpensively by passing current through the wires from an amplifier and a data acquisition system that controls the temperature of the wires. Since feedback of the thermal diffusion gradient and the size of the thermal diffusion region is optically obtained by an inexpensive CCD camera, feedback control of the thermal diffusion region becomes possible by adjusting the current flowing through the wire. With existing technology, this can be done in a simple manner which is substantially less expensive than electro-optic modulation. This is especially true when trying to grow many fibers, such as hundreds or thousands of fibers, at once. In order to produce a commercially feasible fabric or fiber tow (ie, untwisted bundles of continuous filaments or fibers), a manufacturing system using thousands of fibers by means of laser induced primary heating means secondary heating means However, active control of thousands of current loops is relatively inexpensive and easy to implement. Thus, in some embodiments, the present invention allows active control of multiple thermal diffusion regions to control fiber growth and properties. Note that adjusting the thermal diffusion region also changes the background temperature of the gas, which can also affect the growth rate.

  Further, in some embodiments, the present invention is not limited to controlling only the thermal diffusion region within a given reaction zone, but from the entry point within the bath to each thermal diffusion region within the sea of HMM precursors. Provides a virtual conduit for the flow of LMM precursors. The heating wire can provide a flow conduit by creating a long heat diffusion region throughout the length of each wire. In addition, in some embodiments, the present invention provides a means for adjusting the flow of LMM precursor to each reaction zone by changing the temperature at a location along the heating wire to the reaction zone. A thermal diffusion valve capable of increasing or decreasing the flow of the LMM precursor is provided. For example, a lead can branch from a heated wire and draw current to other locations, reducing the current through the rest of the wire. Conventional mass flow controllers and diverter valves may be used, but due to the associated length scale, the response time of one preferred method (using a heating wire as a virtual flow conduit) includes a large potential volume. More rapid than that obtained with many conventional mass flow controllers and switching valves. Switching times on the order of sub-milliseconds can be provided to allow rapid control of characteristics. When these wires are continuous beyond the reaction zone, they also provide a way to remove unwanted by-products from the reaction zone and prevent the by-products from substantially mixing with the surrounding gas. The pressure at the entry point of the virtual conduit can encourage flow along the conduit to and beyond the reaction zone.

  During fiber growth from the fluid precursor, it may be seen that the jet of heated gas (often by-products or precursor fragments) leaves the heated reaction zone. In one embodiment, the heated wires exiting the reaction zone can direct these heated gases away from the reaction zone and fiber tips in the desired direction to allow for faster growth.

  In another embodiment, the wire / filament / electrode used to control the thermal diffusion region is charged to the growing fiber and a discharge is generated between the fiber and the wire / filament / electrode. Also good. Electrostatic and electromagnetic can be used to direct precursors, intermediates, and by-product species to and / or from the fibers and / or to heat diffusion channels.

  One aspect of the present invention generally relates to permanently or semi-permanently recording information on or in fibers and fabrics using the fabrication techniques and methods described herein. Information can be recorded on / in these fibers by adjusting the composition, geometry, or surface coating of the fibers. In addition, many fibers may be grown at once to enable massively parallel recording. The present invention also provides a means of reading this information using a simple scanning device.

  The disclosed system and method can create a storage record on / in a high temperature oxidation resistant material to prevent data loss due to fire, floods, natural disasters, and / or electromagnetic pulses. In addition, the system and method provide a means to ubiquitously place random access memory or data in a wide range of daily necessities such as clothing, baggage, in / on composite materials. Information may be written in such a way that it does not include non-linear joints, magnetic films, or metal parts that can be easily detected as electronic equipment or as a recording medium by a high performance security system. For example, data may be encrypted in various physical ways by switching between recording modes (ie, composition, geometry, characteristics, etc. over time). Without a proper reader, decoding will be very time consuming.

  The present invention may be implemented in various ways. The encoded data can take many different forms, e.g. represented within the fiber composition, geometry, or physical / chemical properties.

  One aspect of the present invention generally relates to the manufacture of certain functionally formed and designed short fiber materials of various shapes, configurations, orientations, and compositions. Another aspect of the invention relates to various systems and methods for collecting, reusing and / or storing manufactured fibers.

  In another aspect, some embodiments of the present invention use laser beam profiling and thermal diffusion region control to enhance fiber and microstructure fabrication. In some embodiments, a reaction zone is created in the reaction vessel to decompose at least one precursor, which causes solid fiber growth in the reaction zone. The reaction zone is created by the creation of a temperature zone by the heating means, the temperature zone being controlled to have a specific induced temperature rise of the surface with respect to position and time within the surface of the solid fiber and within the solid fiber. In this way, fibers having specific microstructural characteristics can be grown by controlling the surface induced temperature rise.

  It should be noted that identical features in different figures are generally indicated by the same reference numerals. Various other objects, features, and attendant advantages of the present invention will be more fully understood when considered in conjunction with the accompanying drawings.

FIG. 2 illustrates the thermal diffusion region, reaction zone, fiber, and presence of LMM and HMM precursors in one embodiment of the present invention. FIG. 3 illustrates one embodiment of the present invention showing an array of thermal diffusion zones, reaction zones, and fibers with fiber tensioners and spool devices / mandrels. FIG. 3 shows an embodiment of the invention showing a precursor flowing coaxially towards a reaction (or growth) zone. FIG. 3 shows an embodiment of the invention showing a precursor that is flowed in a flat sheet towards a reaction (or growth) zone and an array of fibers. FIG. 4 illustrates an embodiment of the present invention showing a two-phase (eg, gas + liquid) system having two thermal diffusion regions around each fiber. FIG. 2 illustrates an embodiment of the present invention showing a two-phase (eg, fluid + fluid / solid) system having two heat spreading regions around each fiber. FIG. 3 illustrates one embodiment of the present invention using a solid source of HMM precursor. FIG. 3 illustrates one embodiment of the present invention using a liquid source of HMM precursor. FIG. 2 shows an embodiment of the present invention using primary and secondary heating means, ie wires with partial loops. FIG. 4 shows an embodiment of the present invention using primary and secondary heating means, ie a wire with a coil. FIG. 4 shows an embodiment of the invention using wires near or in front of an array of growing fibers. FIG. 3 shows an embodiment of the present invention using a wire manifold and adjustable individual wires. FIG. 5 shows an embodiment of the invention having a series of wires near or in front of the fibers. It is a flowchart of one Embodiment of this invention. FIG. 6 is a graph showing growth rate charts for certain embodiments of the present invention using methane as the LMM precursor and various higher mass hydrocarbon HMM precursors at different LMM: HMM partial pressures. FIG. 6 is a graph showing growth rate charts for certain embodiments of the present invention using methane as the LMM precursor and xenon (inert gas) as the HMM precursor at different pressures. Figure 6 is a graph of expected gas thermal diffusion region separation for different geometries. FIG. 6 is a graph of expected liquid thermal diffusion region separation for different geometries. FIG. 3 shows an embodiment of the present invention using a baffle. It is a graph which shows the axial direction growth rate of carbon fiber which uses methane as a precursor at different pressures. It is a graph which shows thermal diffusion area | region separation by a mass difference. FIG. 4 is a table of possible combinations of different material states that can be used in various embodiments of the invention. FIG. 2 is a diagram of one embodiment of the present invention for encoding information in or on a fiber. FIG. 2 is a diagram of one embodiment of the present invention for encoding information in or on a fiber. FIG. 2 is a diagram of one embodiment of the present invention for encoding information in or on a fiber. The figure which shows one Embodiment of this invention which creates a fiber using a laser as a primary heating means and a secondary heating means (wire), adjusts the composition of a fiber along the length of a fiber, and records information. It is. FIG. 2 shows an embodiment of the invention in which fibers are created using a laser as the primary heating means and the composition of the fibers is adjusted along the length of the fibers to record information. An embodiment of the invention in which a laser is used as a primary heating means, a laser is used as a secondary heating means to create fibers and the composition of the fibers is adjusted along the length of the fibers to record information. FIG. One embodiment of the present invention, wherein high-pressure discharge heating by an electrode is used to create a fiber by using a laser as a primary heating means and a secondary heating means, and information is recorded by adjusting the composition of the fiber along the length of the fiber. It is a figure which shows embodiment. 1 illustrates one embodiment of a system for reading fiber status. FIG. FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 5 shows different fiber shapes and configurations that can be manufactured using the disclosed system and method (adjusted cross section / profile). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 6 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (one of various / variable cross-sectional shapes). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 illustrates additional fiber shapes and configurations that can be manufactured using the disclosed systems and methods (non-linear orientation and complex examples). FIG. 5 shows an example of an embodiment showing a combination of fiber profile, shape, and geometric orientation in a matrix. FIG. 5 shows smooth fibers having a local smoothness of less than 100 nm per 5 microns. FIG. 5 is a diagram illustrating mixing of materials and anisotropic mixing according to an embodiment of the present invention. FIG. 5 is a diagram illustrating mixing of materials and anisotropic mixing according to an embodiment of the present invention. FIG. 5 is a diagram illustrating mixing of materials and anisotropic mixing according to an embodiment of the present invention. It is a figure of the branched fiber by one Embodiment of this invention. It is a figure which shows the zigzag-like fiber by one Embodiment of this invention. It is a figure which shows the zigzag-like fiber by one Embodiment of this invention. It is a figure which shows one Embodiment of a fiber manufacture and collection system. It is a figure which shows one Embodiment of a fiber manufacture and collection system. It is a figure which shows one Embodiment of a fiber manufacture and collection system. It is a figure which shows one Embodiment of a fiber manufacture and collection system. FIG. 3 shows a flexible substrate rolled with fibers according to one embodiment of the present invention. It is a figure which shows the example of a circular beam profile (circular profile). It is a microscope picture which shows a mode that the microstructure of a fiber is controllable by a beam intensity profile, and the tensile test data obtained as a result. It is a microscope picture which shows a mode that the microstructure of a fiber is controllable by a beam intensity profile, and the tensile test data obtained as a result. It is a microscope picture which shows a mode that the microstructure of a fiber is controllable by a beam intensity profile, and the tensile test data obtained as a result. FIG. 6 is a diagram showing an example of a beam profile for generating a desired intensity profile at a laser focus. FIG. 6 is a diagram showing an example of a beam profile for generating a desired intensity profile at a laser focus. FIG. 6 shows an example of superposition of laser beam spots generated by a diffractive optical element to obtain an approximate intensity profile of the laser focus that is the sum of all beamlet intensity profiles generated by the diffractive optical element. FIG. 5 shows an example of the use of multiple beams to obtain a desired intensity and temperature profile at the fiber tip and sides.

  1-40 show various diagrams and embodiments of the invention, supporting graphs and data. Various embodiments may have one or more of the components outlined below. Reference numerals of components used in the figure are listed.

  FIG. 1 shows a thermal diffusion region 10 (sometimes referred to as a “thermal diffusion region”) 10 surrounding the fiber 25, which occurs when a mixture of two very different molecular mass precursors are mixed together near the fiber 25. A concentration gradient 30 is shown. The concentration gradient 30 is not shown in all figures. The LMM precursor 15 tends to concentrate in the (usually) highest temperature region, which in this case surrounds the reaction zone (sometimes referred to as the growth zone) 35. The 20 HMM precursors tend to displace away from the reaction zone 35 outside the (usually) thermal diffusion region 10 and, as a result, tend to thermally insulate the reaction zone 35. As shown in FIG. 1, some LMM precursors 15 may exist outside the thermal diffusion region 10, and some HMM precursors 20 may exist in the thermal diffusion region 10. In addition, it should be noted that those skilled in the art will appreciate that there is often no clear boundary where the thermal diffusion region 10 ends, and the concentration gradient 30 can gradually decrease.

  One aspect of some embodiments of the present invention is that the reaction zone 35 is thermally isolated by the HMM precursor 20 to greatly reduce heat loss to the surrounding fluid. A much higher growth rate has been observed with a very small input for the power of the primary heating means 40. Thus, one aspect of the utility of the present invention is to make it much more efficient and feasible to grow many fibers 25 at once. For example, when growing 10,000 fibers at a time, if each heated spot receives 200 mW of incident power (common in conventional laser-induced fiber growth), the total energy entering the cell will be 2 kW. This significant heat budget must be addressed or the ambient gas temperature increases over time. The present invention greatly reduces the power required in each reaction zone 35. Thus, for example, if a mixture of HMM precursor 20 and LMM precursor 15 can only require 40 mW in each reaction zone 35, the total energy entering the tank will be only 400 W, greatly reducing the required external cooling. Less, saving energy and making the process more economically feasible.

  In order to prevent excessive uniform nucleation, the gas in the thermal diffusion region 10 may generally be at a temperature below the threshold for rapid (complete) decomposition of the precursor, but this is not necessary Please note that. Since the thermal diffusion region 10 and the reaction zone 35 overlap near the growing fiber 25, the thermal diffusion region 10 may exceed this temperature. In some cases, it may be more useful to induce uniform nucleation to provide a new nucleation site at the tip of the fiber 25, and the present invention may provide an extended heating zone where this can be done.

  The reaction takes place in a reaction vessel, which is any enclosure that contains the precursor and withstands heat from the primary heating means 40 or secondary heating means 110 for the desired lifetime of the system. The reaction vessel may be rigid or flexible. For example, the reaction vessel may be a lithographically patterned silicon microfluidic structure, a molded polymer balloon, or a machined stainless steel vessel, and there are many possible means for implementing the vessel / enclosure. The reaction vessel can include any number of pressure control means for controlling the pressure in the reaction vessel. Non-limiting examples of pressure control means include pumps, variable flow limiters, pistons, diaphragms, screws, or external forces acting on flexible reaction vessels (those that change the internal volume of the reaction vessel) or usable internals Examples thereof include introduction of a solid that effectively changes the volume (for example, introduction of the solid HMM precursor 20).

  As further described herein, the precursor may be introduced in a variety of different ways and configurations. As a non-limiting example, LMM precursor 15 and HMM precursor 20 are (1) flowed together (premixed) into the reaction vessel, (2) flowed coaxially toward the reaction zone, (3) alternating (4) flow from alternate sources and direct to reaction zone, (5) flow from separate sources and direct tangential to reaction zone, and (6) separate Can be directed at an angle relative to each other.

A variety of different LMM precursors 15 and HMM precursors 20 may be used in combination to obtain the desired thermal diffusion region and control effect. For example, in the case of silicon boride deposition, silane and diborane may be used as the gas for LMM precursor 15, and a gas for HMM precursor 20 such as tetraiodosilane, SiI ₄ , or decaborane, B ₁₀ H ₁₄ is used. May be. This list is not exhaustive and is for illustrative purposes only. Significant differences in mass and / or diffusivity are important for obtaining the best results. Other examples of LMM precursor 15 and HMM precursor 20 are outlined in cross-reference applications including US Patent Application No. 62 / 074,703, which is incorporated herein by reference.

  The 20 HMM precursors may be introduced as a gas, liquid, critical / supercritical fluid, solid, semi-solid, soft plastic solid, glassy solid, or very viscous liquid. Depending on the selected precursor, the HMM precursor 20 may liquefy, vaporize, or sublime near the reaction zone 35. The 20 HMM precursors can vary greatly depending on the type of fiber being manufactured. As a non-limiting example, the HMM precursor 20 can be silane, borane, organoaluminum, organosilicon, organoboron, metal halide, organometal, hydrocarbon, fluorocarbon, chlorocarbon, iodocarbon, bromocarbon, or It may be a halogenated hydrocarbon species or a mixture thereof. The HMM precursor 20 may be inert and not decompose, or there may be very limited decomposition in the reaction zone 35. The HMM precursor 20 can also physically or chemically prevent the formation of clusters and particulates near the reaction zone 35.

  As with the HMM precursor 20, the 15 LMM precursors can vary greatly depending on the type of fiber being manufactured: gas, liquid, critical / supercritical fluid, solid, semi-solid, soft plastic solid, glassy It may be introduced as a solid or highly viscous liquid. As non-limiting examples, the LMM precursor 15 can be silane, methylsilane, borane, organoaluminum, organosilicon, organoboron, metal halide, organometal, hydrocarbon, fluorocarbon, chlorocarbon, iodocarbon, bromocarbon. Or a halogenated hydrocarbon species or a mixture thereof. Depending on the HMM precursor 20 and LMM precursor 15, the LMM precursor 15 (a) reacts with at least one HMM precursor 20 to deposit or partially decompose the LMM precursor to produce a new “ A “derived precursor species” is formed and concentrated in the reaction zone 35 (and this derivative precursor decomposes to grow fibers), or (b) the HMM precursor 20 is decomposed to derive the derivative precursor. Acts as a catalyst to form body species (having a lower molecular mass than the HMM precursor), and this derived precursor species is concentrated in the reaction zone 35 (and the derived precursor species decomposes to grow fibers )

  Depending on the desired fiber properties and the HMM precursor 20 and LMM precursor 15 used, the precursor may be in various states. For example, (1) the precursors may all be in a gaseous state, (2) the precursors concentrated in the reaction zone 35 are in a gaseous state, and the precursors outside the reaction zone 35 are in a critical, liquid, or solid state (3) The precursor concentrated in the reaction zone 35 may be at a critical point, and the precursor outside the reaction zone 35 may be in a liquid or solid state. (4) Concentrated in the reaction zone 35 The precursors in the supercritical state and the precursors outside the reaction zone 35 may be in the supercritical, critical, liquid, or solid state, (5) all precursors are at the critical point, or super The precursor in the critical fluid state or (6) the precursor concentrated in the reaction zone 35 may be in the liquid state, and the precursor outside the reaction zone 35 may be in the liquid or solid state. Of course, this is not an exhaustive list. The “liquid” state may include a highly viscous liquid or glass, and the “solid” state may include a soft plastic solid or a semi-solid. See generally FIG. 19, which is a table of possible combinations of different material states.

In some embodiments, an intermediate molecular mass (“IMM”) precursor may be introduced into the reaction vessel. Depending on the desired fiber and the LMM precursor 15 and HMM precursor 20 used, an IMM precursor is introduced to further separate and react with the LMM precursor 15 and / or HMM precursor 20, or This may be disassembled. For example, when the HMM precursor is hexadecane (C ₁₆ H ₃₄ ) [molecular mass = 226.45 g / mol] and the LMM precursor is methane (CH ₄ ) [molecular mass = 16.04 g / mol], four Add IMM precursors such as Fluorocarbon (CF ₄ ) [Molecular Mass = 88.00 g / mol] and react with both methane and hexadecane to produce carbon fiber product and hydrogen + hydrogen fluoride byproduct May be. In some embodiments, an IMM precursor is introduced to react primarily with and degrade the 20 HMM precursors. For example, when HMM is icosane (C ₂₀ H ₄₂ ) [molecular mass = 282.56 g / mol] and LMM is silane (S ₁ H ₄ ) [32.12 g / mol], bromine (Br ₂ ) [ Introducing an IMM precursor, such as molecular mass = 59.80 g / mol], reacts with hydrogen in icosane to produce carbon as a product (ie, deposited as part of the fiber), hydrogen bromide May be produced as a by-product. Silane concentrated in the center of the thermal diffusion zone deposits spontaneously at low temperature without the presence of bromine, but the decomposition of icosane is enhanced through reaction with bromine. In general, the molecular mass of the IMM precursor is between the molecular mass of the LMM precursor and the molecular mass of the HMM precursor.

  By way of example and not limitation, the following types of fibers are used using the systems and methods described herein: boron, boron nitride, boron carbide, carbon, aluminum oxide, aluminum nitride, silicon carbide, silicon nitride, Boron silicon carbide, silicon oxynitride, nickel, iron, titanium, titanium carbide, tantalum carbide, hafnium carbide, tungsten, tungsten carbide fiber, and the like can be produced. Other examples are outlined in cross-reference applications including US Patent Application No. 62 / 074,703, which is incorporated herein by reference.

  FIG. 2 shows an embodiment of the invention that includes an array of thermal diffusion regions 10, reaction zone 35, primary heating means 40, tensioner 45, tension adjustment device 47, and spool device / mandrel 50. The primary heating means 40 is applied to create the reaction zone 35 and the thermal diffusion region 10. The spool device / mandrel 50 rotates to wind the grown fiber 25 around the spool device / mandrel 50. Individual spool devices / mandrels 50 may be used for each fiber 25, or many fibers 25 may be wrapped around a single spool device / mandrel 50 to create a tow. Although shown as an array of growth fibers 25, a similar configuration may be used to grow a single fiber 25. An optional tensioner 45 may be used to apply sufficient tension and alignment to the fiber 25 as the fiber is wound around the spool device / mandrel 50. Other methods of collecting the fibers 25 are known to those skilled in the art. However, the Applicant has developed a new method of tensioning the fiber without retaining the growing edge while keeping the fiber in the center of the reaction zone. Applicants have developed passive, actively controllable electrostatic, magnetic, fluid, and / or mechanical centering / tensioning means.

  The primary heating means 40 may be any number of options known to those skilled in the art that can create localized reaction zones 35 and thermal diffusion regions 10 (alone or in combination with other primary heating means). Please note that. As a non-limiting example, primary heating means 40 may include one or more focused spots or lines of laser light, resistance heating (eg, passing current through the contact with the fiber), induction heating (eg, fiber Current is induced in the fiber by passing current through the coil wire near or around), high pressure discharge (eg, passing current from the electrode to the fiber through the precursor), focused electron beam, focused ion beam, and focused particle It may be an impact (eg from a particle accelerator). For reference, the radiant primary heating means 40 may create a reaction zone using soft x-rays, ultraviolet rays, visible rays, infrared rays, microwaves, millimeter waves, terahertz, or high frequencies (eg, in an electromagnetic cavity). Good. The primary heating means 40 in FIG. 2 is a focused laser beam.

  The secondary heating means is not clearly shown in FIG. 2, but may be used. As described above, the secondary heating means 110 allows further control and enhancement of the thermal diffusion region 10. This allows real-time adjustment and control of the concentration of the 15 LMM precursors in the reaction zone 35, and real-time adjustment and control of the fiber geometry and material properties according to the alignment. By way of non-limiting example, secondary heating means 110 may include one or more focused spots or lines of laser light, a focused electron beam, a focused ion beam, or a focused particle bombardment (eg, from a particle accelerator). A source of energy focused in / on the precursor fluid, wherein the secondary heating means includes resistance heating of the precursor fluid (eg, passing current through the wire), induction heating of the precursor fluid, or the precursor fluid It may take the form of a high-pressure discharge passing through. Any of these secondary heating means 40 may be used individually or in combination with one or more other secondary heating means 40.

  FIG. 3 shows one implementation of the invention having two very different molecular masses coaxially through a coaxial tube 55 having an LMM precursor tube 60 and an HMM precursor tube 65 and directing the flow to the reaction zone 35. The form is shown. In other embodiments, LMM precursor 15 and HMM precursor 20 may be premixed. This embodiment can increase the growth rate of the fibers 25 by supplying directly to the center of the thermal diffusion region 10 and shortening the transport time of the precursor through the fluid. Again, the LMM precursor 15 usually tends to concentrate in the highest temperature region around the reaction zone 35. The 20 HMM precursors tend to displace away from the reaction zone 35 outside the thermal diffusion region 10 and, as a result, tend to thermally insulate the reaction zone 35. Thus, the LMM precursor 15 is decomposed and deposited in the reaction zone 35, causing fiber growth.

  Thus, in one embodiment of the present invention for making fibers using the method of FIGS. 2 and 3, at least one LMM precursor 15 is flowed into the reaction vessel and at least one HMM precursor 20 is introduced into the reaction vessel. Introduce. As described above, the HMM precursor 20 preferably has a molecular mass that is 1.5 to 3 times, more preferably 3 times greater than that of the LMM precursor 15, and preferably significantly higher than the LMM precursor 15. Has low thermal conductivity. One or more reaction zones 35 are created in the reaction vessel by one or more primary heating means 40 to decompose at least one precursor species. Decomposition causes growth of solid fibers 25 in each reaction zone 35. The solid fiber 25 has a first end of the reaction zone 35 or near the reaction zone 35 and a second end, and the second end has a first end in the reaction zone 35. Is pulled back by the tensioner 45 and the spool device / mandrel 50 at a speed that maintains One or more thermal diffusion regions 10 are set in / near the reaction zone 35 and near the reaction zone 35 to use the thermal diffusion effect to remove the 15 LMM precursors from the 20 HMM precursors partially or completely. The 15 LMM precursors are concentrated in each reaction zone 35. In this embodiment, the concentrated LLM precursor 15 significantly enhances the growth of solid fibers 25, and the 20 HMM precursors are from the reaction zone 35 versus those produced using the 15 LMM precursors alone. Reduce heat flow.

  FIG. 4 illustrates another embodiment of the present invention, in which two very different molecular mass precursors are flowed toward a reaction zone 35 of an array of fibers 25 with a precursor planar flow sheet 70. This implementation can increase the growth rate of the fibers 25 by feeding directly to the center of the arrayed thermal diffusion regions 10 to shorten the transport time of the precursor through the fluid. As reaction zone 35 and thermal diffusion region 10 remain substantially stationary in space, fiber 25 is pulled backwards (indicated by arrows). For practical considerations, this arrangement of stationary reaction zones and thermal diffusion regions is often preferred but not necessary. Again, the LMM precursor 15 typically tends to concentrate in the hottest region around the reaction zone 35. The 20 HMM precursors tend to displace away from the reaction zone 35 outside the thermal diffusion region 10 and, as a result, tend to thermally insulate the array of reaction zones 35. Again, the LMM precursor 15 is decomposed and deposited in the reaction zone 35, causing fiber growth.

  As shown in FIG. 4, the flat sheet 70 can alternate between the LMM precursor 15 and the HMM precursor 20, and the LMM precursor 15 flows directly into the thermal diffusion region 10. Any number of fibers 25 can be grown in this configuration. Any of the alternate primary heating means described above may be used, but are not shown in FIGS.

  Thus, it can be seen from FIGS. 3 and 4 that the precursor may be introduced in a variety of different ways and configurations. This method and configuration are not limited, but (1) both (premixed) flow into the reaction vessel, (2) flow coaxially toward reaction zone 35, (3) flow in alternating sheets and react Directed to zone 35 (4) flowing from alternate sources and directed to reaction zone 35, (5) flowing from separate sources and directed tangential to reaction zone 35, and (6) from separate sources For example, it may be directed at an angle with respect to each other. An IMM precursor may be used and introduced as described above. As described above, various HMM and LMM precursors can be used depending on the desired fiber properties. The reaction vessel may optionally include the pressure control means described above.

  It is important to note that the thermal diffusion region 10 need not be in the gas phase only, but may occur in liquid precursors, critical or supercritical fluids, or combinations thereof. Thus, the mixture of LMM precursor 15 and HMM precursor 20 may enter the reaction vessel as a liquid and remain liquid in the thermal diffusion region 10 in the liquid. However, in another implementation, the liquid mixture of HMM precursor 20 and LMM precursor 15 is locally converted to a gas in each reaction zone 35 to form a heat diffusion region 10 in the bubbles and a secondary heat diffusion in the liquid. Region 10 may be created. Alternatively, one or more precursors, often HMM precursors 20, are added to the reaction vessel as viscous liquids (eg, silicone oil), viscoelastic polymers (eg, pitch, rosin), and plastic solids (such as wax or pitch). They may be sent and they create a thermal diffusion region 10 in each reaction zone 35 by evaporating upon heating and surrounding each reaction zone 35. In this case, the LMM precursor 15 may be provided as part of a solid or viscous liquid, or may be separately introduced into the reaction vessel.

  For example, FIG. 5 shows another embodiment of the present invention having a thermal diffusion region present in a two-phase gas + liquid system. In the present embodiment, bubbles 75 are generated. Inside the bubble 75 is an internal thermal diffusion region 80 and a reaction zone 35. There is also a second external heat diffusion region 85 in the liquid. Separation of the HMM precursor and the LMM precursor takes place in both regions 80, 85, and the properties of the precursor (including mass) determine the extent of each separation. Again, in this embodiment, the fibers 25 are pulled backwards (indicated by arrows), but the bubbles 75, thermal diffusion regions 80, 85, and reaction zone 35 remain substantially stationary in the space.

  FIG. 6 shows another embodiment of the present invention having two thermal diffusion regions 10 present in a “two-phase” system, where one fluid 90 (eg, a critical / supercritical fluid) is present around the reaction zone 35. An internal heat diffusion region 80 can be present in this fluid 90. Outside the internal heat diffusion region 80, another external heat diffusion region 85 may be present in another fluid phase or solid phase. Separation takes place in both regions 80, 85 and the properties of the precursor (including mass) determine the extent of each separation. For example, this embodiment may be used when a highly pressurized mixture of liquid or solid precursors is heated by one or more primary heating means 40.

  FIG. 7A shows that the solid heat source of the HMM precursor 20 (wax in FIG. 7A) is converted into a gas thermal diffusion region 10 by one or more primary heating means 40 or secondary heating means 110 (not shown). Fig. 4 shows an embodiment of the invention evaporating nearby. This solid source can be introduced in a number of ways, including at or near the thermal diffusion region 10, including extrusion by vacuum / pressure sealing 95 of the vessel wall 100. Again, in this embodiment, the reaction zone 35 and the thermal diffusion region 10 remain stationary and the fibers 25 are pulled backward (indicated by arrows). The LMM precursor 15 can be separately flowed through the nozzle 105 to the reaction zone 35 and can be arranged in a number of possible orientations, including orientation through a solid source tube of the HMM precursor 20 (not shown). it can. It is also possible to confine the LMM precursor 15 in the solid of the HMM precursor 20 and release both in the thermal diffusion region 10.

  FIG. 7 (b) shows another embodiment of the present invention using a liquid source 102 of HMM precursor. The liquid source may be stationary or may flow under the thermal diffusion region 10 where the liquid evaporates to yield the HMM precursor 20. Also shown is an LMM precursor tube 60 for introducing the LMM precursor 15. It is also possible to dissolve the LMM precursor 15 in the liquid of the HMM precursor 20 or confine it in the liquid of the HMM precursor 20 and release both in the thermal diffusion region 10.

  In the embodiment shown in FIGS. 7 (a) and 7 (b), the primary heating means 40 is shown as a focused laser beam. As described herein, other primary heating means 40 may be used, and secondary heating means 110 (not shown) may be used to control the thermal diffusion region.

  FIG. 8 (a) shows another embodiment of the present invention in which the thermal diffusion region 10 is heated in the reaction zone 35 of the fiber 25 using secondary heating means 110 (resistance wire). In this embodiment, the secondary heating means 110 in the thermal diffusion region 10 is preferably a resistive wire with a small diameter and sufficient resistance to provide the desired heating rate for the applied voltage. Outside this region, the secondary heating means 110 may be of larger diameter and / or conductivity and reduce heating elsewhere. In one embodiment shown in FIG. 8 (a), the secondary heating means 110 (wire) has a single part loop 115. The secondary heating means 110 and the single part loop 115 use resistance heating to heat the fiber and the surrounding gas, creating and / or enhancing the thermal diffusion region 10 and reaction zone 35 around the tip of the fiber 25. To do. FIG. 8 (a) also shows the use of primary heating means 40, which in this embodiment is a focused laser beam.

  FIG. 8 (b) shows another embodiment of the present invention using a secondary heating means 110 composed of a wire coil 120 surrounding the fiber 25. Thereby, the elongate thermal diffusion area | region 125 can be created. If the temperature of the fiber and reaction zone is increased by induction heating, the wire coil 120 can be regarded as a primary heating means.

  Accordingly, in many embodiments (shown in FIGS. 8A and 8B), both the primary heating means 40 and the secondary heating means 110 are used in common. In general, the primary heating means 40 is identified as the primary driving force that induces the decomposition of the precursor in the reaction zone 35, and the secondary heating means generally drives / controls the fluid temperature and the thermal diffusion region 10 surrounding the fibers 25. . In fact, the primary heating means 40 may affect the temperature of the fluid and the heat diffusion region 10 by heat conduction from the fiber to the fluid, and the secondary heating means 110 may cause the fiber 25 by heat conduction from the gas to the fiber. (And reaction zone 35) may be affected. However, in most implementations, the temperature of the reaction zone is higher than the temperature of the ambient fluid and heat tends to flow from the fiber to its surroundings, so that the primary heating means (incident on the fiber) is the local temperature of the reaction zone 35. And the secondary heating means can dominate the control of the size, shape and gradient of the thermal diffusion region 10 (extending outward from the fiber). This control can be enhanced by careful design and arrangement of the secondary heating means.

  As described above, when using the secondary heating means, in addition to affecting the thermal diffusion region, the secondary heating means may cause the HMM precursor 20 or the LMM precursor 15 to partially close near the reaction zone 35. It can be decomposed to create another set of precursor species of lower molecular mass (referred to as “derived precursor species”).

  Thus, in one embodiment of the invention for making fibers, at least one LMM precursor 15 is flowed into the reaction vessel and at least one HMM precursor 20 is introduced into the reaction vessel. As described above, the HMM precursor 20 preferably has a molecular mass that is 1.5 to 3 times, more preferably 3 times greater than that of the LMM precursor 15, and preferably significantly higher than the LMM precursor 15. Has low thermal conductivity. One or more reaction zones 35 are created in the reaction vessel by one or more primary heating means 40 to decompose at least one precursor species. Due to the decomposition, solid fibers 25 grow in each reaction zone 35. The solid fiber 25 has a first end of the reaction zone 35 or near the reaction zone 35 and a second end, and the second end has a first end in the reaction zone 35. Is pulled backward by the tensioner 45 at a speed to maintain the spool device / mandrel 50. Other means may be used to remove the fibers from the reaction zone. One or more thermal diffusion regions 10 are set in / near the reaction zone 35 and near the reaction zone 35 to use the thermal diffusion effect to remove the 15 LMM precursors from the 20 HMM precursors partially or completely. The 15 LMM precursors are concentrated in each reaction zone 35. In the present embodiment, the secondary heating means 110 using a heating wire is configured to penetrate the reaction zone 35 or close to the reaction zone 35, and to / from the heating wire and the reaction zone 35. Further concentration of 15 LMM precursors near 35 and significantly enhanced solid fiber growth by the concentrated LLM precursor 15, while 20 HMM precursors were produced using LMM precursor 15 alone Thus, the heat flow from the reaction zone 35 is reduced. Although one wire is shown in FIGS. 8 (a) and 8 (b), a plurality of wires may be used. A wire may also surround the reaction zone 35. The term “surrounding” is used to describe that the wire surrounds the reaction zone but is not necessarily a circular configuration. For example, the wire can “surround” the reaction zone in a star configuration, a square configuration, a circular configuration, or other desired shape. In this implementation, an IMM precursor may be used. As described above, various HMM precursors 20 and LMM precursors 15 in various forms (gas, liquid, solid, critical, supercritical, etc.) can be used depending on the desired fiber properties. The reaction vessel may also include the above-described pressure control means in some cases. In some related embodiments, each reaction zone 35 has only one primary heating means 40, and in other embodiments, each reaction zone has two or more primary heating means 40.

  FIG. 9 (a) shows another embodiment of the present invention used to make solid fibers. Generally, at least one LMM precursor 15 species is introduced or flowed into the vessel in proximity to at least one secondary heating means 110 (eg, the illustrated heating wire) and at least one HMM precursor 20 species is introduced into the vessel. To introduce. As mentioned above, the HMM precursor 20 preferably has a much larger mass than the 15 LMM precursors and preferably has a much lower thermal conductivity than the 15 LMM precursors. The HMM precursor 20 may be provided by other methods described herein. In this implementation, the thinner high temperature portion of the wire 135 creates an elongated thermal diffusion region 10. This elongated heat diffusion region geometry provides a preferred conduit that follows the secondary heating means 110 (wires in this embodiment) along which the LMM precursor 15 flows and reaches the reaction zone 35. One or more primary heating means 40 (not shown for clarity) create an array of reaction zones 35 in the vessel, resulting in decomposition of at least one of the precursor species. By this decomposition, solid fibers 25 grow in each reaction zone 35. The solid fiber 25 has a first end and a second end of the reaction zone 35, and the second end is pulled backward (indicated by an arrow). The second end may be pulled rearward by a spool device / mandrel 50 (not shown) and may include a tensioner 45 (not shown). Preferably, the second end is pulled at a rate that maintains the first end within the reaction zone 35.

  In the implementation associated with FIG. 9 (a), at least one thermal diffusion region 10 is created or set in / near the reaction zone to use the thermal diffusion effect to convert the 15 LMM precursors into the HMM precursor 20. The LMM precursor 15 species are concentrated in each reaction zone 35 by partial or complete separation from the species. A secondary heating means 110 (in this embodiment, a wire) is passed through the reaction zone 35 or configured close to the reaction zone 35 to use the thermal diffusion effect to flow the 15 species of LMM precursor to the heating wire. A further concentration along the reaction zone 35 creates a selective conduit for the 15 LMM precursors to flow into the reaction zone 35. By concentrating the 15 LMM precursors as described above, the 15 LMM precursors significantly enhance the growth of the solid fibers 25 and the 20 HMM precursors are produced using the LMM precursor 15 alone. In contrast, the heat flow from the reaction zone 35 is considerably reduced.

  FIG. 9 (b) illustrates another embodiment and implementation, in which one or more sources 130 of LMM precursors supply LLM precursor 15 to the manifold of thermal diffusion conduit 140, and the LLM precursor. 15 branch off and flow along the individual heat diffusion conduits. This conduit is created by individual secondary heating means 110 (wires) that are electrically adjustable via switches (represented by transistor symbols). When the current can be switched from the reaction zone 35 to the transistor, the switch connection 145 adjusts the instantaneous flow of the LLM precursor 15 to (or away from) each fiber 25 “thermal diffusion valve”. Acts as In FIG. 9 (b), the HMM precursor 20 is provided by the HMM precursor source 155, but the HMM precursor 20 may be provided by any of the other methods described herein. In addition, reaction by-products are also carried along the secondary heating means 110 (wires) and tend to be removed at a separate outlet manifold 150 in the general flow direction. In this way, the “conduit” of the thermal diffusion zone 10 and secondary heating means 110 may be used to remove by-products that would otherwise affect the reaction. Thus, in some embodiments, by-product species from decomposition flow away from reaction zone 35 along one or more of secondary heating means 110 to remove by-product species from reaction zone 35, and Can be dispersed in the reaction vessel or removed completely from the reaction vessel (eg, via the outlet manifold 150). As shown, a separate inlet is provided for the HMM precursor source 155.

  The embodiment of FIG. 9 (b) is used to control the current in the wire and adjust the concentration of LMM precursor 15 and HMM precursor 20 in the reaction zone 35 to make the primary heating means 40 (clarified). It should also be noted that the decomposition and growth of the solid fibers 25 may be controlled independently from the (not shown). By adjusting the concentration of the precursor, the desired geometry, diameter, microstructure, composition, physical properties, chemical properties, coating (including the presence or absence of coating or coating thickness), and growth rate (herein) Solid fibers having a general term in the book called “fiber properties”) can be grown.

  In the embodiment similar to the present invention of FIG. 9 (a), each secondary heating means 110 (wire) is composed of two or more thin wire portions with a thicker (lower resistance) shorter portion in between. Also good. This intermediate part is heated by a laser beam (or other heating means) to effectively create a structure similar to a “thermal diffusion transistor” by adjusting the flow of the LMM precursor 15 to the reaction zone 35. can do. In another implementation, one or more portions may be fitted with cooling fins that are resistively heated and LMM precursor 15 to reaction zone 35 (another form of thermal diffusion switch / transistor). Can be used to regulate the flow of In another implementation, one or more of the secondary heating means 110 (wire) portions may be attached with a dispersion wire that is resistively heated to disperse the LMM precursor 15 species elsewhere. , Can be used to regulate the flow of 15 LMM precursors to the reaction zone 35 in real time (ie, the dispersion wire acts as a reverse heat diffusion valve). The heating wire may be in the form of a microtube that is heated by passing a hot fluid through the microtube.

  In most embodiments, the present invention incorporates a feedback means to measure the properties of the fiber 25 being produced, and this feedback is used to use one or more aspects of the production process and ultimately the fiber properties / characteristics. To control. As the fiber grows, measurements of the fiber geometry, microstructure, composition, and physical properties can be made. This feedback may be used to control the primary heating means 40 and / or the secondary heating means 110. For example, in FIG. 9 (b), the current through the secondary heating means 110 (forming the conduit of the manifold 140) can be controlled to change the production of the fiber 25 in progress. This may be done independently of the primary heating means 40 being used, or at least partly independently. For example, if the feedback means detects the composition of the fiber resulting from suboptimal LMM precursor concentration in the reaction zone 35, increasing the current through the wire will increase the temperature of the wire, resulting in additional LMM precursor. The body is flowed through a conduit to obtain the desired fiber composition.

  The feedback means (not shown in FIG. 9 (b)) includes electromagnetic sensing devices and may be of various types known to those skilled in the art. A non-exhaustive list of examples of feedback means includes real-time FT IR spectroscopy, Raman spectroscopy, fluorescence spectroscopy, X-ray analysis, two- and three-color pyrometry, and optics, UV, and IR imaging, emission line / Examples include narrow band detection of absorption lines, reflectance / absorbance measurement, and the like. Similarly, concentration / density feedback means of LMM precursor 15 and 20 HMM precursors in thermal diffusion region 10 and / or reaction zone 35 are obtained using real-time shadow graph, schlieren, and spectroscopy. be able to. In other embodiments, the feedback means may be an acoustic sensing device. This is not an exhaustive list. Various feedback means can be used individually or in combination.

  Other devices and methods may be used to obtain process feedback and control fabrication. In some embodiments, the HMM precursor 20 may be measured by real-time shadow graph or schlieren imaging with the thermal diffusion region 10 and / or the reaction zone 35 alone or in combination with one or more of the options described above. Feedback on the relative concentration / density of the 15 LMM precursors to the species can be obtained. Therefore, in this embodiment, the feedback means is to measure the thermal diffusion region 10 and / or the reaction zone 35 rather than the fiber properties. This feedback can be used as an input to control one or more aspects of the fabrication process, for example, to modify the primary heating means 40 or the secondary heating means 110 to produce a desired solid fiber having the desired fiber properties. Can be obtained at speed.

  FIG. 10 shows another embodiment of the present invention. In this embodiment, a series of secondary heating means 110 (in the form of a wire) is connected to a current source (not shown), and the secondary heating means 110 collects in and surrounds the reaction zone 35 of the fibers 25. The current flow through any particular wire 110 may be adjusted to control the heating rate of that wire. In one embodiment where LMM precursor 15 and HMM precursor 20 are in a gas mixture, the concentration of LMM precursor 15 may be varied by adjusting the amount of current in wire 110. As all wires 110 are heated, LMM precursor 15 is withdrawn from the ambient gas mixture and concentrates in reaction zone 35. When the wire is turned off, the concentration of LMM precursor 15 gradually decreases. The primary heating means 40 of this embodiment is a focused laser beam. A return conductor 112 provides a return path for current from the wire 110.

  FIG. 11 shows an embodiment of the invention having feedback means 156 used to control the growth of multiple fibers by adjusting the reaction zone 35 (shown) and the thermal diffusion region 10 (not shown). FIG. In this particular implementation, a visual system that can track the growth and properties of many fibers at once is used as feedback means 156. Based on input from the vision system, the controller 160 determines what changes need to be made to achieve the desired fiber growth rate and characteristics, if there are parameter changes in the fabrication process. The controller 160 includes the necessary hardware and software that receives the input of the vision system and sends appropriate signals to the multi-output analog amplifier 165 and / or the motor controller driver 170. Here, the analog amplifier 165 supplies current to the secondary heating means 110 (in the form of a wire). The current in the wire controls the concentration of LMM precursor in the thermal diffusion region (not shown) and reaction zone 35. The return path of the current in each wire is not shown. By input from the controller 160, the motor controller driver 170 controls the spool device / mandrel 50 and the winding speed of the fiber. In this way, the controller 160 adjusts / controls the fiber growth rate and properties such as diameter, composition, microstructure, bulk material properties, and process parameters such as precursor concentration, flow rate, pressure, and induction temperature. Can do. The interaction of the controller 160 and its various configurations and other elements used to control fiber growth and properties can be referred to herein as “control means”.

  Thus, in one embodiment, the present invention includes a system for making solid fibers 25 having one or more reactors, each reactor having an associated one or more primary heating means 40 and It includes or has one or more secondary heating means 110. In use, the primary heating means and secondary heating means create one or more reaction zones 35 and thermal diffusion regions 10 in each reaction vessel in which the fibers 25 are grown. The system may incorporate one or more spool devices / mandrels 50 and tensioners 45 for the grown fibers 25. The system may include one or more precursor inlet channels and one or more byproduct outlet channels. In practice, the precursor inlet channel allows the flow of LMM precursor 15 and HMM precursor 20 to enter the reactor. The primary heating means 40 may remain activated and may provide a relatively stable temperature for the reaction zone 35 and the thermal diffusion region 10. Thereafter, secondary heating means 110 may be used to adjust / control the concentration of LMM precursor 15 relative to HMM precursor 20 in thermal diffusion region 10 and reaction zone 35. As described above, any of the heating means described herein may be used for the primary heating means 40 and the secondary heating means 110.

  In one embodiment, the secondary heating means 110 is selected from the group of resistive heating wires or focused infrared, microwave, millimeter wave, terahertz, or high frequency electromagnetic radiation. When using a resistance heating wire, in some embodiments, the heating wire passes through or surrounds the reaction zone 35. In other embodiments, the heating wires are interconnected to create at least one heat diffusion valve. In some embodiments, the heating wire extends to the precursor inlet channel to create a thermal diffusion conduit leading to the reaction zone 35 and the thermal diffusion region 10, and / or the heating wire extends to the byproduct outlet channel. Create a heat diffusion conduit (see, eg, FIG. 9B). The same feedback means and control device as described above can be used to control the process (eg secondary heating means) and to control the fiber properties of the fiber 25 being made.

  FIG. 12 is a graph showing growth rate charts for certain embodiments of the present invention using methane as LMM precursor 15 and various higher mass hydrocarbon HMM precursors 20 at different LMM: HMM partial pressures. is there. The vertical axis 200 represents the fiber growth rate relative to the expected growth rate of pure methane at the same methane partial pressure. The horizontal axis 205 represents the ratio of methane to the hydrocarbon HMM precursor partial pressure. Data 210 shows that when the partial pressure of the HMMP precursor is sufficiently large (ie, greater than 1/4 of the partial pressure of methane), at least an order of magnitude growth enhancement occurs for pure methane growth. Indicates. Line 215 is a curve fit to this data and approaches the growth rate of pure methane as the HMMP partial pressure approaches zero.

FIG. 13 is a graph showing growth rate charts for certain embodiments of the present invention using methane as LMM precursor 15 and xenon as HMM precursor 20 at different pressures. Results # 1 220 shows a graph of CH ₄ at 15 PSI, the result # 2 225 shows a graph of CH ₄ at 30 PSI, the result # 3 230 shows a graph of CH ₄ at 45 PSI. The vertical axis indicates the growth rate of the fiber 25 in μm / second, and the horizontal axis indicates the xenon pressure in PSI. This result also shows a significant increase in the growth rate of methane by simply adding a much higher mass of inert HMM precursor than the LMM precursor.

  FIG. 14 is a graph of the expected gas thermal diffusion region separation. These graphs show the (normalized) separation expected during fiber growth for different mass gas precursors (one LMM precursor 15 and one HMM precursor 20) with a constant flow rate. Indicates the degree. Two thermal diffusion region 10 geometries (cylindrical and spherical) having various sizes of thermal diffusion regions 10 (depending on pressure and induction temperature by primary and secondary heating sources 40 and 110, for example). Is given. Changing the size of the thermal diffusion region 10 directly affects the concentration of LMM precursor and HMM precursor near / in the reaction zone 35, thereby affecting the growth rate of the fibers 25.

  FIG. 15 is a graph of the expected thermal diffusion region separation of the liquid. These graphs show the (normalized) separation expected during fiber growth for different mass liquid precursors (one LMM precursor 15 and one HMM precursor 20) with a constant flow rate. Indicates the degree. Two thermal diffusion region 10 geometries (cylindrical and spherical) having various sizes of thermal diffusion regions 10 (depending on pressure and temperature induced by primary and secondary heating means 40 and wires 110, for example). Is given. Changing the size of the thermal diffusion region 10 directly affects the concentration of LMM precursor and HMM precursor near / in the reaction zone 35, thereby affecting the growth rate of the fibers 25.

  FIG. 16 shows one embodiment of the present invention using a baffle. In this embodiment, the thermal diffusion region 10 can be protected by a woolen webbing 235 and / or a baffle 240 that prevents advection from overcoming the thermal diffusion region 10. The baffle 240 may be a solid structure or a solid structure having holes or perforations. In embodiments where the woolly webbing 235 is used with a baffle 240 “conduit”, the woolen webbing 235 may be on the outside or inside of the baffle 240 “conduit”. Means for cooling the gas outside the heat diffusion region 10 or outside the heat diffusion region 10 may be used, such as heat sinks, heat pipes, or near the boundary of the heat diffusion region 10 / The use of actively cooled porous surface locations at the boundary is mentioned. FIG. 16 shows the cooling fluid flow through the channels of the baffle 240 for cooling.

  FIG. 17 is a graph showing the axial growth rate of carbon fibers using pure methane as a precursor at different pressures.

  FIG. 18 is a graph showing thermal diffusion region separation due to mass difference. This shows the degree of separation (normalization) expected during fiber growth in the case of a spherical geometry with all precursors as gas in the thermal diffusion region and a constant flow rate. This model assumes that all precursors are ideal gases and that the thermal diffusion constant (alpha) is independent of temperature, intermolecular forces, etc. Note that very large separations can occur as the ratio of HMM mass to LMM mass increases.

  FIG. 19 is a table of possible combinations of different material states that can be used in various embodiments of the invention. This does not take into account combinations that are not practically feasible due to the normal shape of the pressure-temperature phase diagram for most materials.

  Although the above disclosure primarily describes the decomposition and dissociation of the precursor using various heating means, it should be understood that other methods may be used. For example, the precursor may be chemically decomposed using x-rays, gamma rays, neutron beams, or other systems and methods. In addition, many embodiments describe the pulling of the fibers backwards during fabrication, mainly leaving the reaction zone stationary, but leaving the fibers stationary, the reaction zone 35 and / or heat It should be understood that the diffusion region 10 may be moved. For example, the arrangement of the primary heating means 40 may be moved. In one embodiment using stationary fibers, when using a laser beam as the primary heating means 40, the direction / orientation of the laser beam may be varied and the laser is placed on a movable translationally movable platform. Alternatively, various optical elements and lenses may be used to change the focus of the laser. Similarly, when a heating wire is used as the primary heating means 40, the wire may be movable and translatable, allowing movement of the thermal diffusion region 10 and / or reaction zone 35.

  In addition, the disclosure primarily relates to and uses LMM precursors and HMM precursors having very different molecular masses, although the thermal diffusion regions 10 and / or reaction zones 35 may be used even though their molecular masses are significantly different. Adjustments can be used and can be very advantageous for many different types of precursors.

Recording of information about conditioned fibers, microstructures, and fabrics, and devices for reading the same As described further in some embodiments herein, conditioned fibers, microstructures, and fabrics A method and system for recording information and reading the information stored therein is disclosed. Depending on the desired properties of the fiber, the HMM precursor species and LMM precursor species described above may be used as precursors for recording information in the conditioned fiber described below, It should be noted that it is not necessary to share the same properties described above with respect to the difference between the HMM precursor and the LMM precursor. Indeed, some embodiments of systems and methods for recording information on fibers and microstructures do not require the use or manipulation of a thermal diffusion region. Decompose and grow fibers using any number of systems and methods, including high pressure laser chemical vapor deposition and chemical vapor deposition, high pressure laser chemical vapor deposition, electron beam deposition, ion beam, photolysis, and various focused energy sources Can be made. The recording and reading of information in a fiber-based format is new per se.

  FIG. 20 shows different means for encoding information on or in the fiber 25. In one implementation, the data can be represented as discrete or analog changes in the surface coating of the fiber (FIG. 20 (a)). For example, “0” may be represented by the first coating composition portion 425 and “1” may be represented by the second coating composition portion 430. In one embodiment, only one coating composition is used on only a portion of the fiber, and the data is encoded by the presence or absence of a surface coating that occurs during or after fiber growth, or by the variable properties of the surface coating of the fiber. Also good. For example, the difference in activation energy between the two precursors allows the precursors to grow selectively in the fiber. However, depending on the radial distribution of the primary heating means (relative to the fiber axis), one material grows on the fiber core and the other material concentrates as a coating on the outside of the core. By carefully manipulating the radial distribution of heating, the coating can appear and disappear. This can be achieved by using another heating means (eg after the first heating means), so that the core grows only one material while the second material is the first material. Is added as a coating on top of (or not added).

  In another embodiment of the coating method of FIG. 20 (a), more than one coating composition portion may be used. They can be grown from different precursors on existing fibers or from a mixture of precursors, and when the primary (or secondary) heating means are changed, the two coating compositions are selected alternately on the surface of the fibers. The In another embodiment, the precursor is delivered at the nozzle and alternates rapidly, producing an alternating coating.

  Importantly, in all of these methods of FIG. 20, the length of the coating composition portion can also vary, which can also represent a digital or analog value. Also, although the illustrated main embodiment is encoded as a digital pattern, the information is encoded with an analog composition gradient or a geometric gradient (eg, the coating composition varies slowly along the length). Also good. In addition, it should be noted that more than two materials or geometries may be used to encode information.

  In another implementation, as shown in FIG. 20 (b), the fiber composition itself may be varied in a discrete or mixed (analog) manner. For example, “0” may be represented by the first composition portion 410 and “1” may be represented by the second composition portion 415. Particular examples are a first composition portion 410 composed of silicon and a second composition portion 415 composed of silicon carbide. Many other materials may be used and this example is for illustration only. In addition, more than two types of composition parts may be used and the length of the composition part may vary.

One means of encoding alternating materials for length is to simultaneously grow fibers using two precursors (as mentioned above, incorporated herein by reference, 2014-11 Filed on May 4, entitled “Doped Carbon Fiber and Carbon-Alloy Fibers and Method of Fabricating Therof from Displace-Molecular Mass Gasoid, United States 74 and United States. , They decompose at different temperatures (eg, due to differences in rate constants or activation energies), and temperature changes may be selected from material to material. For example, silicon fibers such as disilane (Si ₂ H ₆ ) may be used to grow silicon fibers, but carbon precursors such as benzene may be used to provide silicon carbide deposits. Disilane begins to decompose significantly at 690-920K, while benzene decomposes at 950-1200K. By varying the reaction zone temperature during growth, the amount of carbon in the deposit relative to length varies. Because the reaction zone length scale is small, this temperature may change rapidly (on the order of femtoseconds to milliseconds). For example, in some embodiments using a laser as the primary heating means, the temperature may be varied by controlling the timing of the laser beam (or the output of the laser beam). In a similar implementation, a single precursor having two or more elements may be used to deposit one element at one temperature and another element at a higher temperature. For example, the precursor ferrocene, Fe (C ₅ H ₅ ) ₂ is composed of an iron atom having two attached cyclopentadienyl ligands (C ₅ H ₅ ). At low temperatures, the iron is separated from the _C 5 _{H 5 ligand,} deposited without C 5 _{H 5} ligand itself is decomposed. However, at higher temperatures, the C ₅ H ₅ ligand also decomposes and carbon is added to the iron deposit. In another implementation, using two precursors with very different mass or diffusion properties, having a high concentration of the desired material in the reaction zone during writing (e.g., fiber creation) and exclusion of the other, One material can be selected for another material. For example, because disilane has a molecular mass of 78 amu and methane has a molecular mass of 16 amu, these different thermal diffusivities can be used to select methane in the reaction zone due to thermal diffusion effects. Such same characteristics of different reactions at different temperatures, different masses, and different thermal diffusivities are described in the above-mentioned “Doped Carbon Fiber and Carbon-Alloy Fibers and Method of Fabricating Thermof From Dispense”. -Molecular Mass Gaseous, Liquid, and Supercritical Fluid Mixtures ", present by different precursors disclosed in US Provisional Patent Application No. 62 / 074,703, and used herein depending on the particular properties desired. be able to.

  The composition variation technique (FIGS. 20A and 20B) can provide multiple means of encoding and reading information according to changing material properties. For example, due to compositional changes, specific conductivity, dielectric constant, thermal conductivity / heat capacity, light transmission, reflectance, and / or absorbance, or selective chemical reactivity / bonding, dangling bonds, or fibers Bits / bytes encoded as surface wetting characteristics are obtained. A change in composition may be performed to add a small amount of dopant to the semiconductor fiber, and the addition of a small amount of dopant may cause a very large change in local conductivity. These various material properties obviously need to be read in different ways including optical, capacitive, resistive, inductive, chemical, mechanical, etc. Two or more reading methods may be used to improve reading accuracy. The change in composition need only be sufficient to produce a detectable difference in the desired property. For example, if conductivity is a property to be read, the material deposited as part of the fiber preferably has a conductivity that is sufficiently different to allow detection. For example, dielectric properties, thermal conductivity / heat capacity, light transmission, reflectance, and / or absorbance, or other properties such as selective chemical reactivity / bonding, dangling bonds, or wetting properties of the fiber surface The same is true.

  While using one or more precursors to locally change the microstructure of the fiber, for example, by various means, eg, more than for sp2 bonded carbon, which is optically readable by relative Raman peaks. Many sp3 bonded carbons can also be created. Graphite carbon (reflection) and glassy carbon (absorption) can also have different optical properties that are optically readable. There are many different ways in which information can be encoded using microstructural changes.

  As shown in FIG. 20 (c), the geometry of the fiber 25 may be used to encode discrete or analog information, for example, by changing the fiber diameter along the fiber length, eg, smaller The diameter portion 400 can represent “0” and the larger diameter portion 405 can represent “1”. Alternatively, different geometric configurations may be used, for example using a circular cross-section for one part and a square cross-section for another part. Any of the different types of geometries described herein may be used. Other discrete geometric representations, for example a defined diameter representing an integer from 0 to 255 (ie one diameter = 8 bit binary data where 1 byte), or an integer from 0 to 9 or some letter (eg a, b , C, etc.), the specified diameter of the decimal encoding system may be used. Thus, not only bits but all bytes of data may be stored in a single diameter. There may be tolerances in these diameters so that small changes in diameter do not cause erroneous measurements similar to the CMOS or TTL voltage specifications for microelectronic signals.

  Provide a given length for each bit or byte similar to the clock timing of microelectronic data, creating start and stop bits with unique diameters or lengths so that no errors are accumulated Length measurements may be re-registered periodically. An analog method of data representation may be implemented in which the analog voltage vs. time can be encoded as fiber diameter vs. length. Again, a calibration start / stop bit may be used to read such data more accurately. In this implementation, only a single precursor may be required to produce the fiber, but it is possible to use two or more precursors to provide a fiber with a binary or more complex composition. is there. Similar analog and / or digital representations may be performed on fibers having a specific composition and / or coating.

  Encoding circular or spiral patterns on the fibers may be used (as a coating, composition, or geometry), which can increase data density, which can be difficult to read. Another means of achieving fiber data encoding is to represent the numbers by zigzaging the fibers individually or gradually. In this case, as the fiber axis grows, it deviates from a known reference axis, and the distance, orientation, or angle with respect to the reference axis provides an indication that represents a number. However, this technique usually results in a lower encoding rate than diameter adjustment.

  It is important to note that the secondary heating means (in addition to the primary means) are used to locally heat the gas and rapidly change the fiber deposition results. Thus, for example, a focused laser beam may be combined with a heating coil, where the laser beam induces primary growth, and the coil induces local heating of the fiber to locally alter the composition, microstructure, or geometry. Can be changed. In this example, the coil can be subjected to particle refinement that changes the microstructure, or zone refinement of dopants in the fiber or as a coating of the fiber. With small sized fibers, these processes can be performed rapidly. The secondary heating means can take many forms including wires, electrodes, laser beams and the like. Some possible implementations of the heating means are shown in FIGS. When provided as a coil wire geometry, the secondary heating means can induce a magnetic field and encode this magnetic field into the orientation of the material in / on the growing fiber (or coating).

  For example, FIG. 21 uses the laser as the primary heating means 40 and the wire 110 as the secondary heating means 40 to create the fiber 25, and the fiber composition is adjusted along the length of the fiber for information. 1 illustrates one embodiment of the present invention that is recorded. In FIG. 21, a first composition portion 410 and a second composition portion 415 are used to change the composition of the fiber 25 along its length. One end of the fiber 25 is attached to the substrate 320 and the other end is in the reaction zone 35. Optionally, the substrate 320 may be removed if the relative position of the fibers is maintained in some other way.

  FIG. 22 shows an embodiment of the invention in which a laser is used as primary heating means 40 to create fiber 25 and the composition of the fiber is adjusted (by the laser) along the length of the fiber to record information. . In FIG. 22, a first composition portion 410 and a second composition portion 415 are used to change the composition of the fiber 25 along its length. One end of the fiber 25 is attached to the substrate 320 and the other end is in the reaction zone 35. Optionally, the substrate 320 may be removed if the relative position of the fibers is maintained in some other way.

  FIG. 23 uses the laser as the primary heating means 40 and uses the laser as the secondary heating means 40 to create the fibers 25 and the fiber composition is adjusted along the length of the fibers to record information. 1 illustrates one embodiment of the present invention. In FIG. 23, a first composition portion 410 and a second composition portion 415 are used to change the composition of the fiber 25 along its length. One end of the fiber 25 is attached to the substrate 320 and the other end is in the reaction zone 35.

  FIG. 24 uses the laser as the primary heating means 40 and creates the fibers 25 using the secondary heating means 40 using high pressure discharge heating with electrodes, and the composition of the fibers is adjusted along the length of the fibers. 1 shows an embodiment of the present invention for recording information. In FIG. 24, first composition portion 410 and second composition portion 415 are used to change the composition of fiber 25 along its length. One end of the fiber 25 is attached to the substrate 320 and the other end is in the reaction zone 35. In any of the embodiments shown in FIGS. 21-24, changing properties other than the fiber composition may be used, for example, the fiber geometry may be changed, or the fiber may be coated as described above. May be added.

One implementation to increase data encoding rate is at least one LMM precursor (eg, silane, SiH ₄ ), and at least one HMM precursor (eg, n icosane, C ₂₀ H ₄₂ , or n tetracontane, C ₄₀ H ₈₂ ). Implementation may use a high-mass reactive gas (eg, iodine), which does not add deposition elements / compounds to the reaction, but its presence, eg, an sp3 binding element for sp2 bonded carbon This can modify the microstructure or the fiber geometry. This particular implementation uses the thermal diffusion effect to concentrate the LMM precursor in the thermal diffusion region 10 and reaction zone 35 described above. Information may be recorded on the fiber using any of the various embodiments described above (eg, FIGS. 1-11), which are not limited to reaction and fiber properties (eg, diameter, microstructure). Etc.) including primary and / or secondary heating means used to control.

  In some embodiments, another aspect of the invention may include a calibration code where each fiber is (optionally) located at the intended location of the fiber, which makes the fiber unique compared to other fibers. The fiber can be read accurately. This also provides another means of encrypting the data and making unauthorized reading of the data more difficult. The calibration code provides information about the type of property being read, detected, or measured, and the code, eg, conductivity, dielectric constant, thermal conductivity / heat capacity, light transmittance, reflectance, and / or absorbance Or selective chemical reactivity / bonding, dangling bonds, or wetting properties of the fiber surface, or length of each bit, start / stop bit, fiber diameter versus length, calibration start / stop bit, etc. Decipher. The calibration code may include a code key (described below). A calibration code and / or code key is placed in a predetermined position in or along the fiber so that the calibration code and / or code key can be detected and read.

  To the best of Applicants' knowledge, the sequential recording of information on or into the fiber, including recording using active control of multiple thermal diffusion regions, has not occurred prior to the present invention.

  Using selective conduits or switches / valves to provide information to the fiber using the various embodiments described above that use or implement regulation in or around the reaction zone or thermal diffusion region or precursor flow. Can be recorded. Examples of adjustments in or around the thermal diffusion region or precursor flow are shown and described by way of example with reference to FIGS. 9 (a), 9 (b), and 10. FIG. The ability to switch heat diffusion valves rapidly provides a means to rapidly adjust the composition and / or geometry of the growing fiber, especially the fibers that grow rapidly on the order of millimeters per second. Thus, information can be encoded in / on the fiber as the fiber grows and a permanent or semi-permanent recording of that information can be made using only secondary heating means. This may be done using only the primary heating means. When hundreds and thousands of fibers are grown simultaneously, a parallel system of information encoding / writing can be realized. For example, if the thermal diffusion valve is adjusted at 1 millisecond intervals, the fibers are 8-bit diameter encoded fibers that grow at 2 mm / sec, and 20,000 fibers grow at the same time, at a rate of 320 Mb per second. Information can be encoded / written. This may be slower than some currently available hard drives, but is approximately equal to the USB data transfer rate and can be written in a more permanent storage format than magnetic or magneto-optical drives.

  Significantly, data can be encoded with a physically and chemically very stable material to preserve a record of information. For example, in the composition coding approach, a fiber composed of tantalum carbide having a melting point of 3153-4100 K may be coded by changing the carbon concentration in the deposit up to 2: 1 (TaC vs. TaC 0.5). Good. Alternatively, the titanium oxide fiber may be grown by changing the concentration of oxygen that changes the fiber impermeability to light, and the data may be read optically. Alternatively, the same system may be read by measuring the dielectric constant or resistivity of the deposit over length.

  A variety of different LMM precursors and HMM precursors may be used in combination to obtain the desired thermal diffusion region and control effect. For example, for silicon deposition from LMM precursors, hydrides including silane and disilane may be used. In the case of HMM gas, precursors such as tetraiodomethane or wax may be used. This list is not exhaustive and is for illustrative purposes only. For example, there are many possible silicon precursor and wax combinations. Again, the use of LMM precursors and HMM precursors is optional.

  A device for reading information recorded or encoded on a fiber is also disclosed. In some embodiments, such as the example shown in FIG. 25, the reading system includes a sensing means (or sensor) 450, a translational movement means 455 (indicated by an arrow) that moves the sensor support surface 465, a hole / aperture 460 through which the fiber passes, A sensor support surface 465 (eg, some type of plane, surface, or grid that supports the sensor) and an analog / digital (“A / D”) system 470 that records data for later use. Sensing means (or sensor) 450 may be any known or future developed sensor capable of sensing, detecting or reading various properties of the fibers described herein, eg, conductive, dielectric Rate, thermal conductivity / heat capacity, light transmittance, reflectance, and / or absorbance, or selective chemical reactivity / bonding, dangling bonds, or wetting properties of the fiber surface, or fiber length or diameter It may be a sensor or detector that can sense, detect, read or measure. The sensing means 450 may be electrically connected to the analog / digital system 470 and other means may be used to communicate readings to the analog / digital system 470. Examples of various sensing means are described above (and described as “feedback means” in the context of fiber production), but when used to read an already manufactured fiber, the sensing means used for fiber production (Or feedback means) may be different. The analog / digital system 470 may be computer hardware, software, or firmware that can interpret and decode readings from the sensing means (or sensor) 450 and will be well understood by those skilled in the art. For example, if different conductivities are used for the encoded information, the analog / digital system 470 interprets the readings of values A-B as “0” and the readings of values C-D as “1”. (In binary application). Dielectric constant, thermal conductivity / heat capacity, light transmission, reflectance, and / or absorbance, or selective chemical reactivity / bonding, dangling bonds, or wetting properties of the fiber surface, or fiber length or diameter The same applies to the measurement of as well as to other embodiments. As described above, other discrete representations may be used and implemented by the analog / digital system 470, eg, a value or reading is an integer from 0 to 255 (ie, one diameter = 8 bytes where 1 byte is 1 byte). Bit binary data), an integer from 0 to 9 may be encoded, or may be associated with or represented by a decimal number representing a character (eg, a, b, c, etc.). The analog / digital system 470 has non-transitory memory, may be programmable, and is also referred to as a “code key”, a value associated with a particular reading from the sensing means (or sensor) 450, a number Or memorize characters. In this embodiment, the detection means 450 is on the sensor support surface 465, and the sensor support surface 465 has a hole / aperture 460 through which the fiber 25 can pass. The fiber 25 may be translated or moved so that different portions of the fiber 25 pass through or enter the detection area of the sensing means 450. Thereafter, the reading from the sensing means 450 is sent to the analog / digital system 470 for further processing. Obviously, other arrangements for reading the fibers are possible, for example arrangements in which the fibers pass through the sensing means 450 without passing through the holes 460 of the sensor support surface 465.

  Various code keys (if used) may be used in conjunction with the feedback means and control means during fiber manufacture when encoding information is applied. With a suitable control system for fiber production, the operating parameters are changed and the desired information is encoded using code keys. For example, if different conductivity is used, the code key may represent a conductivity between values A and B of “0” and a conductivity between values C and D of “1”. If the user wants to attach encoded information representing the data string 010010011, the control system of the manufacturing process (e.g. laser power, primary heating means, secondary heating means, amount of precursor, precursor flow to the reaction zone, Pressure, etc.) to ensure that the right material is deposited at the right location causing the right sensor reading. The code key may be made on the fiber itself and read and used by the analog / digital system 470.

  Accordingly, in one embodiment, a recording medium comprising fibers is provided, the fibers having a specific fiber state along the length of the solid fiber, the fiber state corresponding to a known length (signal period). And the fiber state value represents a digital or analog value (corresponding to the signal amplitude), and the combination of the known state and value of the fiber state provides digital or analog information along the solid fiber Are sequentially encoded. “Fiber state” includes (1) fiber geometry, (2) fiber diameter, (3) fiber composition, (4) fiber microstructure, (5) fiber microstructure and fiber composition, (6) physical properties, ( 7) chemical properties, and (8) various different properties including the presence or thickness of the coating on the surface of the solid fibers, or any combination of the foregoing.

  In embodiments where the “fiber state” is a fiber geometry, various alternatives can be used: (a) the slope of the surface of the solid fiber relative to the fiber axis, (b) the orientation of the fiber growth direction relative to the known axis. Position and / or (c) orientation of the fiber growth direction relative to a known axis.

  In embodiments where the “fiber state” is a fiber composition, various alternatives can be used: (a) the fiber composition includes two or more different elements / compounds, wherein the different elements / compounds have different degradation rate pairs. (B) at least one wherein the fiber composition comprises two or more different elements / compounds, the different elements / compounds providing different element / compound pairs temperatures, comprising depositing from two or more precursors having a temperature Including depositing from one multi-element containing precursor.

  In embodiments where the “fiber state” is a fiber microstructure, various alternatives can be used, where the fiber microstructure includes (a) two or more allotropes and (b) two or more solid phases. Can be mentioned.

  In embodiments where the “fiber state” is a physical property of the fiber, various alternatives can be used, including optical, electrical, thermal, acoustic, physical adsorption, adhesion, or mechanical properties.

  In embodiments where “fiber state” is a chemical property, various alternatives can be used, including chemisorption, oxidation, reduction, reaction, bonding, dangling bonds, or wetting properties.

  In another embodiment, a method of recording digital and / or analog information in fibers and / or arrays of fibers, wherein: (1) in a vessel in which decomposition of at least one precursor species takes place by primary heating means Creating said array of reaction zones comprising the step of decomposition causing solid fiber growth in each reaction zone; (2) a first end where said solid fibers are in said reaction zone; And the second end is pulled backward by the tensioner 45 and the spool device / mandrel 50 at a rate that maintains the first end within (or near) the reaction zone. (3) the degradation is adjusted over time by the control means to create a specific fiber state for the length along the growth direction of the solid fibers, and (4) the fiber state is a known length (signal Period of (5) the fiber state value represents a digital or analog value (corresponding to the signal amplitude), and (6) a combination of the known length and the fiber state value provides a digital Alternatively, a method for sequentially encoding analog information along the solid fibers is provided. Thus, in some embodiments, the solid fibers can form an array that allows for massively parallel encoding of digital and / or analog information.

  In another embodiment, a method of recording digital and / or analog information in a fiber and / or an array of fibers, comprising: (1) introducing at least one low molecular mass (LMM) precursor species into a bath; (2) introducing at least one high molecular mass (HMM) precursor species having a significantly larger mass than the LMM precursor species and having a thermal conductivity significantly lower than the LMM precursor species into the vessel; (3) creating an array of reaction zones in the vessel by primary heating means and decomposing at least one precursor species; and (4) in the reaction zone / in the reaction zone by secondary heating means Setting a thermal diffusion region (TDR) nearby to partially or completely separate the LMM precursor species from the high molecular mass precursor species using thermal diffusion effects, and (5) before Decomposition causes solid fiber growth in each reaction zone, the solid fiber is composed of at least one element of the precursor species, and (6) a first end where the solid fiber is in the reaction zone; And a second end that is rearwardly driven by a tensioner 45 and a spool device / mandrel 50 at a rate that maintains the first end within the reaction zone (or near the reaction zone). (7) the degradation is adjusted over time to create a specific fiber state for the length along the growth direction of the solid fibers, and by the secondary heating means (independent of the primary heating means) The adjustment is performed by controlling the TDR, and (8) the fiber state has a known length (corresponding to the duration of the signal), and (9) the value of the fiber state is digital or Analog value (signal amplitude Represent corresponding), (10) by a combination of the value of the known length and the fiber state, a method of sequentially coding along the digital or analog information to said solid fibers are provided.

  The primary heating means includes a focused laser beam, an array of focused laser beams, inductive heating of solid fibers, a high voltage electrical discharge (eg, plasma), and current through the precursor, a focused line of laser light, and any of those described above It may be a combination. Other primary heating means are known to those skilled in the art and are described herein.

  The secondary heating means may be a heating wire, and the heating wire is heated and resisted by passing a current through the wire. The secondary heating means may also be a current through the focused laser beam, an array of focused laser beams, a high pressure discharge and / or a precursor. Other secondary heating means are known to those skilled in the art and are described herein. In some embodiments, a heated wire may be used to “sink” by-product species from decomposition in the reaction zone. The heating wire can take a variety of configurations, including but not limited to: (a) at least two heating wires are joined but are composed of electrically separate parts, The flow of low molecular mass precursor species to the reaction zone is adjusted in real time using current passing through (ie, the portion acts as a thermal diffusion valve); (b) at least one portion of the heating wire is Heated by a laser beam and using this part to regulate the flow of low molecular mass precursor species to the reaction zone in real time (ie, the part acts as a thermal diffusion valve), (c) the heating At least one part of the wire is fitted with a cooling fin that can be resistively heated at the base, and this part is used to flow the low molecular mass precursor species to the reaction zone in real time. And (d) at least one portion of the heating wire is resistively heated to disperse the low molecular mass precursor species along the heat diffusion conduit. A configuration in which a dispersible wire is attached and this part is used to regulate the flow of low molecular mass precursor species to the reaction zone in real time (that is, the disperse wire acts as a reverse heat diffusion valve). .

  In some embodiments, as described above, the tank into which the precursor is introduced may have pressure control means. As previously mentioned, the species introduced into the bath may be in various forms. In some embodiments, all species are in the gaseous state. In other embodiments, species concentrated in the reaction zone are in a gaseous state, but all other species are in a liquid state. In other embodiments, species concentrated in the reaction zone are in a critical point or supercritical state and all other species are in a liquid or solid state. In other embodiments, all species are in a critical point or supercritical fluid state.

  As described above, sensing means (or sensors) are used to obtain feedback on precursor degradation and fiber growth and control secondary heating means to control solid fiber degradation, growth, and composition. Digital and / or analog information can be encoded. The sensing means (or sensor) may be a variety of sensing devices / spectrometers known to those skilled in the art, including acoustic, mechanical, optical, ultraviolet, infrared, and x-ray.

  In yet another embodiment, an apparatus for reading information from an array of one or more solid fibers, wherein (a) the fibers have a particular fiber state along the length of the solid fibers; b) the fiber state has a known length (corresponding to the duration of the signal), (c) the value of the fiber state represents a digital or analog value (corresponding to the signal amplitude), and (d) the fiber state Sequentially encodes digital or analog information along the solid fiber according to the known length and value combination of: (e) the device comprises a number of sensors located on a surface / grid; and (f) the The surface / grid has holes / passages through which fibers can penetrate, and (g) the surface / grid is translatable along the length of the solid fibers (along the direction of fiber growth) And (h) the multiple sensors are compiled. Is electrically connected to the over data or data acquisition system, said surface when translating, all the sensors, devices that can be read at speeds in excess of the Nyquist sampling criteria are provided. In some embodiments, the translational motion can be cycled to obtain multiple readings of the fiber.

Functionally shaped and engineered short fibers and microstructured materials In one aspect, the present invention uses a novel, very flexible manufacturing process to grow short fibers from precursors. Create precise functionally shaped and designed short fibers as described herein by controlling process characteristics such as heating means characteristics, precursor flow geometry and flow, local pressure, etc. Can do. The aforementioned HMM precursor species and LMM precursor species (with the use of thermal diffusion regions) as precursors to create precise functionally shaped and designed fibers, depending on the desired properties of the fibers It should be noted that the precursors may be used and the precursors need not share the same properties described above with respect to the difference between the HMM precursor and the LMM precursor. Indeed, some embodiments of systems and methods for creating precise functionally formed fibers and microstructures do not require the use or manipulation of heat diffusion regions. Using any number of systems and methods, including high pressure laser chemical vapor deposition and chemical vapor deposition, high pressure laser chemical vapor deposition, electron beam deposition, ion beam, photolysis, and various focused energy sources; Can be grown.

  In many cases, the primary heating means is a focused electromagnetic beam or other directed energy source such as a laser, ion or electron beam. However, other primary heating means such as inductive or microwave coupling to the fiber material may be used. The primary heating means may be adjusted, formed, or oriented to create specific geometries in the solid fibers as they are grown, rather than as a post-additional process that modifies existing fibers. In addition, more than one fiber may be grown at a time by using multiple primary heating means. For example, a general primary heating means is an array of focused laser beams, an array of focused laser beams and a focusing line of laser light, an array of high-voltage discharges, an array of electrodes for passing a current through a precursor, an array of inductive primary heating means As well as a set of resistance heating wires. Two or more primary heating means may be used to provide additional processing flexibility.

  The present invention also provides feedback control of desired fiber properties including the shape, composition and microstructure of the fiber material so that these properties can be controlled during the growth process (see FIG. 11 as an example). This provides a way to obtain the correct fiber length without using a cutting process. The fibers can be grown to a specific length with a specific diameter versus length and into a curved pattern rather than just a straight cylinder. Several real-time feedback and / or control means are used, such as interference pattern feedback (eg Fabry-Perot interferometer), adaptive optical focal plane recognition, secondary laser beam attenuation, fiber length slits Imaging / sensing, knife-edge and chopper methods (eg, attenuation or shadow graph methods), ultrasonic measurements, and thermal measurements. This is not a complete or exhaustive list.

  In addition to straight lines (cylindrical fibers), some specific fiber shapes versus lengths are also suitable for composites, such as sinusoidal diameter versus length profiles (see FIG. 26 (a)), or other more complex geometries. Important for fibers having a shape. These profiles may be specially designed for specific fiber matrix combinations. A number of commercially beneficial periodic precision profiles are shown in FIG. 26, including (a) sinusoidal profile versus length (FIG. 26 (a)), (b) elliptical profile versus length (see FIG. 26 (b)), (c) Parabolic profile versus length (FIG. 26 (c)), (d) Hyperbolic profile versus length (FIG. 26 (d)), (e) Gaussian profile versus length (FIG. 26). (E)), (f) sawtooth / ramp profile versus length (FIG. 26 (f)), (g) dogbone profile versus length (FIG. 26 (g)), and (h) bed strut profile. The pair length (FIG. 26 (h)) is included. Significantly, these profiles are periodically applied to straight fibers as in the typical example shown in FIG. 26 (i) having a periodic sinusoidal shape, a periodic elliptical shape, a periodic multifrequency shape, a periodic parabolic shape, and the like. May be added. One or more profile geometries may also be adjusted on another profile to create more complex profiles with additional functionality. For example, sinusoidal variations may be superimposed on the hyperbolic profile (ie, sinusoidal hyperbolic geometry) to create a fiber as shown in FIG. 26 (j). This fiber has a high pull-out strength due to the dogbone shape (the protrusions must be cut off in order for the protrusions to come off), and at the same time has a large surface area due to sinusoidal variations, at the interface Create additional adhesion. Finally, any profile with a random diameter may be created (FIG. 26 (k)), resulting in statistical randomization of the adhesion of the fibers within the matrix (randomization of other properties). A simpler fractal profile is possible, in which at least one pattern is repeated on different length scales (see FIG. 26 (1)). Additional variable shapes may be combined as shown in FIG.

  In addition, the cross section of the fiber need not be circular, and may be grown in various shapes as shown in FIG. For example, the cross section is an I-shaped beam (FIG. 27A), an X-shaped beam (cross) (FIG. 27B), an L-shaped beam (FIG. 27C), and a T-shaped beam (FIG. 27D). ), Or a star shape (ie, a multi-point star shape and / or a multi-point star shape having a T-point) (FIG. 27 (e)). Furthermore, a circle (FIG. 27 (f)), an ellipse, a triangle (FIG. 27 (g)), a rectangle (FIG. 27 (h)), a hexagon (FIG. 27 (i)), a polygon, an arbitrary shape (FIG. 27). (J)) and / or an adjusted (FIG. 27 (k)) cross section may be grown. This is not an exhaustive list of different cross sections that can be used. Thereby, depending on the case, the ratio of strength and mass of the reinforcing fiber can be increased in a desired direction.

  In addition, the fiber growth direction may be continuously reoriented during deposition to create geometries that are not possible through spinning or extrusion processes. By way of example only, the position of the reaction zone may be changed (as described herein), or the substrate on which the fibers are grown may be moved, or the substrate may be reoriented. There are many possible shapes resulting from reorientation as shown in FIG. 28A shows a curved shape, FIG. 28B shows a gentle curve, FIG. 28C shows a sinusoidal shape, FIG. 28D shows a parabolic shape, and FIG. ) Shows a hyperbolic shape, FIG. 28 (f) shows a U-shape, and so on. These curvilinear shapes grow to the desired shape without residual stress, but produce fibers that are very difficult to “draw” in either direction. As also shown in FIG. 28, fibers with “hooks” or “barbs” that entangle with other fibers in the composite can be created to transfer local stress from one fiber to the next (hook). (See FIG. 28 (g) for the shape, and FIG. 28 (h) for the return shape). In order to further increase the pulling strength, zigzag fibers (FIG. 28 (i)) and ramp-like fibers (FIG. 28 (j)) may be grown. An example of a grown zigzag fiber is shown in FIG. In another embodiment, a coiled fiber is produced that is more flexible than a simple straight cylinder with the same volume and a given Young's modulus (having a larger surface area), possibly stronger, stronger and more flexible A route for obtaining a highly composite material is provided (see FIG. 28 (k)). Finally, two or more patterns may be superimposed on the orientation geometry to produce an adjusted orientation (FIG. 28 (I)).

  Even when the primary heating means and / or the secondary heating means are reoriented, more complex shapes can be created by changing the strength of the primary heating means and / or the secondary heating means. For example, a complex curved fiber having a periodic waveform along the length may be created (see FIG. 29). The cross-sectional shape can also be changed when the cross-sectional size and orientation of the fibers change.

  Another aspect of the invention inherently provides local smoothness of less than 100 nanometers on the growing surface and can improve bonding at the fiber matrix interface (eg, by van der Waals or covalent bonds). It is. During the growth process described above, this can be made even more accurate by feedback control of the primary and / or secondary heating means and other process parameters. The carbon fibers shown in FIG. 30 are examples of fibers grown with local surface smoothness of less than 100 nanometers. Since the fibers are not pulled by mechanical spinning or drawing processes, they exhibit very little (if any) voids / cracks and the material can be grown as a sufficiently dense material. In addition, the microstructure of the material can be designed to be amorphous or glassy, resulting in strong fibers with more uniform properties. The microstructure of the material may be a single crystal fiber / whisker microstructure and may have a strength that is much greater than the polycrystalline form of the same material.

  Another aspect of the present invention is to grow multiple materials simultaneously to create functionally gradual fibers. For example, if two materials are deposited simultaneously under a Gaussian laser focus, with different threshold deposition temperatures and kinetics, one material will naturally concentrate more on the fiber core and the other toward the outside of the fiber. Tend to grow preferentially. However, these materials can be mixed together with a gradual transition from the core to the outer material, rather than having individual step transitions from material to material, such as present in the coating. This can result in a stronger transition from the core to the outer material without separation. This allows a very strong material that would otherwise react or degrade in contact with the matrix material to be permanently protected by the outer material in contact with the matrix material. This can optionally improve the bond between the fiber and the matrix material, allowing a flexible transition between the fiber and the matrix and preventing undesirable alloying or chemical reactions. There are many possible implementations of this multiple material approach, and the fibers may change functionally and gradually in the radial and axial directions. The method of applying the precursor may be varied. For example, the precursors may be premixed or flowed separately to cause anisotropy variation in the composition (see FIG. 31). FIG. 31 (a) shows the radial mixing of the deposited material shown as a cross section of the fiber. In this embodiment, the first material 280 concentrates on the fiber core and the second material 285 concentrates on the outside of the core. In most cases, there is a gradual transition 290 that causes the deposited material to transition from the first material 280 to the second material 285 as it moves away from the core. Additional material may be deposited in this manner with radial mixing of the plurality of materials.

  FIG. 31 (b) shows the axial mixing of the deposited material. In this embodiment, the first material 280 is deposited as a fiber. The fiber then has a transition 290 where the fiber transitions to the second material 285. Again, additional material may be deposited. FIG. 31 (c) shows anisotropic mixing of the deposited material. In this embodiment, the first material 280 is deposited on one portion of the fiber cross section, the second material 285 is deposited on another portion of the fiber cross section, and the transition 290 separates the two materials. To do. It should be noted that the transition 290 is optional and may not be required depending on the desired fiber properties, the precursor used, heating conditions, and the like.

  Importantly, the fibers may be branched to provide additional resistance to fiber drawing. The fibers may form a network of connected strands, an example being shown in FIG. The branched fibers shown in FIG. 32 are created using two overlapping primary heating means (laser beams), and then separate these fibers during growth to make the reaction (or growth) zone into two reaction zones. To separate.

  In some embodiments, the present invention also provides a means for collecting and removing fibers after growth, including recirculation or reuse of an optional initial substrate (see FIGS. 34 (a), 34 (d)). . The term “substrate” is used broadly herein and includes wires, wire mesh, plates, wafers, flexible films, disks, drums, belts, coils, and the like. For example, in one implementation, the fiber may be grown on a substrate that has minimal adhesion to the growth material (ie, the fiber), and the wiper blade may be used to “knock” the fiber from the substrate. Good (FIG. 34 (a)). In FIG. 34 (a), a spinning mandrel or drum 300 on which the fibers are grown is shown. The primary heating means and secondary heating means can control the reaction zone 35 and other parameters of fiber growth using the systems and methods described above. The embodiment shown in FIG. 34 (a) shows a plurality of primary heating means 40 (lasers in this embodiment) for growing a plurality of fibers. As the mandrel / drum 300 rotates, the grown fibers 25 rotate toward the wiper 310 to remove the fibers from the substrate and collect the fibers in the fiber bin 315. The movement of the mandrel / drum 300 may be controlled by the control means described above using conventional industrial equipment.

  In another embodiment shown in FIG. 34 (b), the fibers 25 may be grown on a movable substrate 320 that can move or vibrate vertically, for example, which is based on wiper 310 or fibers. It has a knife edge that “disconnects” from the material 320. The movable substrate 320 may be a drum or belt, or any other suitable configuration including a stand-alone substrate as shown in FIG. 34 (b) (eg, a configuration that is not “continuous” like a belt or drum). ). The manufactured fibers 25 may be collected in the fiber bottle 315.

  In another embodiment shown in FIG. 34 (c), the fibers 25 may be grown on a flexible substrate 320 configured as a belt that translates and rotates. The movement of the belt may be controlled by the control means described above using conventional industrial equipment. The belt may be stopped (if necessary), the fibers 25 may be grown in one or more reaction zones, and / or the heating means is moved or redirected as the flexible substrate 320 moves. Thus, the heating means can be moved or redirected in such a way as to maintain a suitable reaction zone in which the fibers are growing. When the desired growth is complete, the fiber 25 can be removed. In some embodiments, rotation of the flexible substrate 320 around the end of the belt causes the fibers 25 to fall (shown in FIG. 34 (c)) or using a wiper 310 or knife edge. It is good (not shown).

  In another embodiment, the fiber may be grown on the wire, and the wire can be vibrated (by ultrasound) to remove the fiber after growth. In another embodiment, the fibers may be removed by flowing fluid over the fibers. In another embodiment, electrostatic forces may be used to remove the fibers from the surface. Finally, in another embodiment, the temporary coating may be dissolved from the substrate and the fiber attachment point removed.

  In another embodiment shown in FIG. 34 (d), the fiber 25 may be removed by centrifugal force. In FIG. 34 (d), a spinning mandrel or drum 300 on which the fibers are grown is shown. Heat sources, reaction zones, and other parameters of fiber growth may use the systems and methods described above. The embodiment shown in FIG. 34 (d) shows how a plurality of primary heating means 40 (in this embodiment, a laser directed through the reaction vessel window 330) grows a plurality of fibers 25. As the mandrel / drum 300 rotates, the grown fibers can be removed by centrifugal force and collected in the fiber bottle 315. The movement of the mandrel / drum 300 may be controlled by the control means described above using conventional industrial equipment. There are many possible implementations for removing the fibers. Those skilled in the art will appreciate that the substrate on which the fibers are grown may remain stationary even if moved during fiber growth. When the substrate is moving during fiber growth, the heating means can be made movable or divertable as needed to maintain the reaction zone for fiber growth.

  After removal, the short fibers may be collected in a bottle and aspirated from the growth system by a vacuum or similar device. In another embodiment, the fibers can pass through a vapor lock that prevents the precursor from exiting the reaction vessel but moves the solid fibers out of the growth system through another fluid. In another embodiment, the fibers may be collected in a bin and removed by a conventional load lock. There are many possible ways to collect and remove large quantities of fiber, and this is not an exhaustive list.

  It is also possible to use a reusable substrate in the form of a tape, mesh or lattice on which the fibers are grown. The substrate may be flexible and can be rolled and stored for later use, as shown in FIG. This roll can then be applied directly to the composite matrix material or cut / stacked to allow the matrix to penetrate, creating a new interwoven composite material with the fibers crossing the substrate surface.

  Thus, in one embodiment of the present invention, the designed solid fiber material can be grown from a fluid-based chemical precursor by heating means, the fiber material having a cross-sectional size / diameter of less than 4 mm Have a defined cross-sectional fiber shape and size that can grow and vary along the length, have a defined composition versus radius, and have a defined geometric orientation versus length. And has a defined microstructure.

  As described above, in some embodiments, the cross-section of the fiber is circular, elliptical, triangular, X-shaped (cross), I-shaped, L-shaped, T-shaped, multi-point star, T-shaped. It may be a multi-point star, rectangle, hexagon, polygon, any and / or adjusted cross section. The cross-sectional fiber shape may vary along the length or may be constant. In some embodiments, the cross-sectional fiber shape may vary along the length or repeat periodically. In some embodiments, the cross-sectional fiber shape varies along the length and repeats periodically, the cross-sectional fiber shape is a composite of two or more repetitive profiles, and at least one profile is another The profile is adjusted. In some embodiments, the cross-sectional fiber size varies along the length, and in other embodiments, the fiber size is constant along the length. In some embodiments, the cross-sectional fiber size varies along the length to: (a) sinusoid, (b) ellipse, (c) parabola, (d) hyperbola, (e) gauss Forming a profile selected from at least one of: (f) sawtooth / ramp, (g) dogbone, and (h) bed strut. In some embodiments, the cross-sectional fiber size varies along the length and repeats periodically, with the following profiles: (a) sinusoid, (b) ellipse, (c) parabola, (d) A repetitive profile is formed that includes at least one of a hyperbola, (e) gauss, (f) sawtooth / ramp, (g) dogbone, and (h) bed strut. In other embodiments, the cross-sectional fiber size varies along the length and repeats periodically, with the following profiles: (a) sinusoid, (b) ellipse, (c) parabola, (d) hyperbola , (E) Gaussian, (f) sawtooth / ramp shaped, (g) dogbone shaped, and (h) a rectilinear profile comprising a straight section having a bed strut shape.

  In some embodiments, the cross-sectional fiber size varies along the length and periodically repeats at two or more frequencies to form a complex multi-frequency repeat profile. In some embodiments, the cross-sectional fiber size varies along the length, forms a profile, repeats periodically, the profile is a composite of two or more repeating profiles, and at least one profile Adjusts (or superimposes on) another profile. In some embodiments, the cross-sectional fiber size varies randomly along the length, forming an arbitrary profile that does not repeat in a particular pattern. In some embodiments, the cross-sectional fiber size varies along the length and repeats periodically, the profile having self-similar repeating profiles (fractal profiles) of different length scales.

  As described herein, the fiber composition may be varied depending on the desired properties. Thus, in some embodiments, the defined composition versus radius is a constant. In some embodiments, the defined composition versus radius varies from one or more core materials in the fiber center to one or more outer materials on the outer surface of the fiber. In some embodiments, the defined composition versus radius varies continuously from the fiber core one or more core materials to the fiber outer surface one or more outer materials according to a defined concentration function. In some embodiments, the composition is a radial mix from the core material to the outer material. In some embodiments, the composition is an axial mix from one material to another. In some embodiments, the composition varies along a direction perpendicular to the axis of the solid fibers (eg, bimorph).

  As explained herein, the microstructure of the fibers may be varied depending on the desired properties. Thus, in some embodiments, the defined microstructure of the fiber is amorphous or glassy. In some embodiments, the defined microstructure is a single crystal.

  Also, as described herein, the fiber orientation may be varied according to the desired properties. Thus, in some embodiments, the defined orientation varies along the length of the fiber material. In some embodiments, the defined orientation is the following pattern along the length of the fiber material: curvilinear shape, gentle curve, sinusoidal curve, parabola, hyperbola, U-shape, hook shape, barb shape, It varies according to at least one of a zigzag shape, a lamp shape, a coil shape, and an adjusted shape. In some embodiments, the fiber material branches (divides) from one fiber to two or more fibers during growth. In some embodiments, the fiber material is locally smooth so as to be better than an RMS roughness of 500 nm over a length of at least 5 microns. In some embodiments, the fiber material is grown to a defined length to be better than 5 microns accuracy.

  In another embodiment, the present invention relates to a method for growing one or more designed solid fibers from chemical precursors in a reaction zone. The fibers may be grown on a reusable substrate. The solid fibers can have a first end and at least one second end, wherein the first end is temporarily attached to a reusable substrate, and the second end is Within the reaction zone. The reaction zone can be created by primary heating means and optionally by secondary heating means. In some embodiments, the reaction zone can be adjusted and controlled in real time to produce a specific fiber cross section, profile, geometric orientation versus length. Specific fiber cross-sections, profiles, and geometric orientation versus length may be monitored in real time by a monitoring system (or feedback means) and used to control the manufacturing process and reaction zone characteristics. The length of the solid fiber is monitored in real time by a monitoring system (or feedback means) and is used to grow the solid fiber to a predetermined end length by controlling the characteristics of the manufacturing process and reaction zone. You may let them. The collection mechanism allows the fibers to be collected off the substrate after growth, for example by recycling / reusing the substrate for further solid fiber growth by means of a recycling mechanism (eg a rotating drum or belt). Also good.

  As described above, the precursor may be in various forms including a gaseous fluid, a liquid fluid, a critical fluid, or a supercritical fluid. The substrate is preferably reusable, preferably providing sufficient adhesion during growth to secure the first end to the reusable substrate and providing a sufficiently limited adhesion. And having a texture, composition, or surface coating that allows the first end to be removed by a collection mechanism (eg, wiper or knife blade). The substrate can be in various forms including, but not limited to, wires, wire mesh, plates, wafers, flexible films, disks, drums, belts, helical coils, and the like.

  As described herein, in some embodiments, the reaction zone may be divided, creating an additional second end of each fiber that branches off from each fiber. The primary heating means includes, but is not limited to, an array of focused laser beams, an array of focused laser beams and lines of focused laser light, two or more arrays of focused laser beams, a high pressure discharge, a current through the precursor, Any of the heating means described above, including induction heating, coupled electromagnetic radiation, and / or resistance heating wires.

  As described herein, in some embodiments, using the systems and methods described above, but not limited to, the reaction zone shape, size, position, and geometric orientation, and across the reaction zone The characteristics of the reaction zone including the reaction rate may be varied. In some embodiments, the reaction zone is created, adjusted in real time by (1) primary heating means, (2) flow rate of the chemical precursor, and (3) local concentration of the chemical precursor, and Controlled to adjust the cross-sectional shape, size, composition, and microstructure of the second end in real time, and to adjust the specific fiber cross-section, profile, geometric orientation, composition, and microstructure vs. length Achieve.

  In some embodiments of the method for growing fibers, the fiber cross-section is controlled to a desired size with a tolerance better than 500 nm over a length of 5 microns, and the end length is accurate to 5 microns or less. Yes, the fibers may have the cross-sectional shape, profile, geometric orientation, composition, and variation described above (eg, changing along the length of the fiber, or constant, repeating, or arbitrary). .

  In some embodiments, as described above, the reaction zone may be adjusted and controlled in real time by secondary heating means, including but not limited to resistance heating, induction heating, or coupled electromagnetic radiation. It may be at least one heating wire heated by.

  In some embodiments, the reaction zone may be tuned and controlled in real time by introducing at least one high molecular mass precursor and at least one low molecular mass precursor, the mixture within the reaction zone The reaction rate across the reaction zone is adjusted when the thermal gradient or concentration of any precursor changes, by at least partially separating in the presence of a thermal gradient. It should be understood that the use of the high and low molecular mass precursors described herein is not necessary to create the functionally formed and engineered fibers described herein. It is.

  In some embodiments, the monitoring system (or feedback means) includes the following: interference pattern measurement (eg, Fabry-Perot interferometer), adaptive optical focal plane recognition, secondary laser beam attenuation, fiber length slit imaging / Selected from at least one of sensing, knife-edge and chopper methods (e.g. attenuation or shadow graph methods), ultrasonic measurements and thermal measurements (e.g. heat conduction to sensors in the substrate).

  In some embodiments, a collection mechanism is used to remove the solid fibers from the reusable substrate. The collection mechanism (or “collection means”) includes, but is not limited to: (1) driving the solid fibers relative to the wiper / blade by translational movement and / or rotation of the reusable substrate; (2) moving the wiper / blade across the reusable substrate, (3) bending the flexible substrate, (4) vibrating / shaking the substrate, (5) rotating the substrate. Generating a centrifugal force to remove the solid fibers; (6) flowing fluid over the substrate to carry away the solid fibers; (7) removing the fibers using electrostatic force / magnetic force; And (8) can take various forms, including dissolving / etching the temporary coating on the reusable substrate.

  In some embodiments, after growing a bundle of the solid fibers, a recyclable mechanism is used to translate, rotate, or reorient the reusable substrate to recycle the reusable substrate. The substrate may be returned to alignment with the reaction zone and additional solid fibers may be grown. In some embodiments, after growing a bundle of the solid fibers, the recycling mechanism may coat a reusable substrate with a temporary coating and grow additional solid fibers on the temporary coating. Good. The recycling mechanism is not limited, but (1) collection in the bin and removal by load lock, (2) collection in the bin / tube and suction by flowing fluid, (3) in the filter using flowing fluid (4) electrostatic collection on charged materials, (5) magnetic collection using magnetic materials / devices, and (5) collection surfaces with van der Waals forces and large surface areas Can take various forms, including the use of

  In some embodiments, the substrate may be reusable. In some embodiments, the reusable substrate is a flexible tape or grid that is wrapped around to leave the solid fibers on the flexible substrate and directly or in a composite layup It may be stored in a roll for indirect use.

Beam intensity profiling and control of fiber internal microstructure and properties Means to control both the beam intensity profile and the shape of the thermal diffusion region can be important to obtain the desired microstructure of high quality fibers. This part of the invention focuses on creating a strength profile of a useful primary heating means that provides useful fiber properties.

  There are many advantageous intensity profiles that can be generated. 36, 38, 39, and 40 show some examples. The simplest intensity profiles are beamforming and holography, ie single mode and multimode Gaussian beams, inverse Gaussian beams, Bessel beams, Laguerre Gaussian beams, flat top beams, super Gaussian beams, etc. Those known to those skilled in the art. In addition, these intensity profiles may be superimposed on the overall beam focus geometry, such as a circular (donut-like) beam, a linear beam, a rectangular beam, a cross beam, and the like.

  There are many methods that can be used to generate the desired beam intensity profile for fiber growth, some of which are known to those skilled in the art and some are less well known. The methods included in the present invention include controlled phase plane manipulation, grating and diffractive optics, vortex beam shaper, diode laser beamlet superposition, microlens diffuser, adaptive optics, spatial light conditioner, liquid crystal adjustment A refraction and reflection field mapper that uses an instrument or the like. This is not an exhaustive list.

  The incident (laser) beam intensity profile can then affect the temperature rise at the fiber surface in the reaction zone 35 and the shape of the thermal diffusion region 10 by heat transfer. For example, a circular laser intensity profile can heat a fiber tip around it, creating a reaction zone that is hotter around the center and a heat diffusion region that is hottest in the ring in the surrounding fluid near the fiber circumference. Bring. Conversely, the Gaussian beam intensity profile results in a thermal diffusion region that is hottest in the center. By using a circular laser intensity profile, the fiber can grow more rapidly in the center by the thermal diffusion effect pushing the reaction byproducts to the fiber edge rather than the fiber center. This eliminates the TDGS described above.

  For example, as shown in FIG. 36, the laser beam 500 passes through a focus lens 505 to create a focused profile laser beam 510 that produces a beam intensity profile 515 at that focus. The beam intensity profile 515 has an induced temperature rise associated with the surface 520, where the most intense portion of the laser beam profile is associated with a higher temperature rise on the surface. The beam intensity profile 515 shown in FIG. 36 is an example of a particularly useful beam profile (circular profile) because it can change the position at which a phase occurs in the fiber. In the example of carbon fiber growth shown in FIG. 36, the resulting fiber 25 may have amorphous carbon 525 in the core and graphitic carbon 530 around (or around) the edges. As described herein, this is in contrast to the morphology of fibers grown using a Gaussian beam profile, with the graphite core at the center and the finer particle phase around. Thus, it is expected that the circular beam intensity profile will provide stronger fiber material properties than those provided by the Gaussian beam intensity profile.

  One subset of such circular profiles are Bessel-like beams that are represented by Bessel functions of the first kind. Only mode 1 is shown in FIG. 36, but additional modes may be used.

  Most embodiments of the present invention use such a beam profile / shape to initially grow a three-dimensional fiber by HP-LCVD and control the fiber microstructure to provide optimal material properties. Note that changing the beam profile as the fiber grows may result in phase and composition changes that can be used to record information (as described elsewhere in this application). Should.

  Consider the three fibers shown in FIGS. 37 (a)-(c), which show scanning electron micrograph cross sections of carbon fibers grown using three different axisymmetric beam profiles. FIG. 37 (a) shows carbon fibers grown under a focused Gaussian beam intensity profile. The fiber has a graphite center core and an outer coating. The graphite core is composed of a parabolic sheet of graphite, and its central axis is aligned parallel to the fiber axis. This allows the parabolic sheets to be cut from one another across the fiber axis, or pulled away along the axis, so there is little lateral or axial strength. The outer coating is a fine-grained carbon that has increased strength but contains little cross-fiber area. The result is a fiber with a weak tensile strength of only 0.598 GPa. FIG. 37 (b) shows carbon fibers grown under a substantially flat beam intensity profile. This also provides the core and outer fiber shell. However, this time, the graphite surface is no longer an extremely parabolic shape, and the sheet is slightly bowed in a plane perpendicular to the fiber axis. Even with the orientation of the graphite, the strength along the fiber axis is almost eliminated. The outer coating is fine, but again it contains little cross-fiber area. The result is a strength of only 0.377 GPa, less than the optimum tensile strength of the fiber. Finally, FIG. 37 (c) shows a cross section of carbon fiber grown using a circular beam profile. This again yields a biphasic fiber having an inner core and an outer shell. However, the graphite of the outer shell is now aligned coaxially with the fiber axis, and the fiber core becomes more finely divided carbon. This provides a carbon fiber with greatly improved strength. The applicant has recently tested carbon fibers having a tensile strength of 2.5 GPa, which has been found to be fully useful in the high strength carbon fiber industry. This fiber is 4-6 times the strength of the flat top and Gaussian profile. This shows how the strength profile of a particular primary heating means can result in improved microstructural properties and material phases within the fiber, thereby differentiating the commercial usefulness of the fiber.

  Similarly, the strength of silicon carbide fibers grown by this technique can vary greatly depending on the beam intensity profile. This is because SiC can grow in three phases, that is, amorphous SiC, βSiC, and αSiC in order of increasing deposition temperature. Thus, if the induced temperature rise on the surface can cross the phase boundary, more than one phase is produced in the SiC fiber. If the strengths of these phases are not the same (and are not isotopes in the crystalline phase), the value of the SiC fiber for fiber reinforcement depends on how well the primary heating means is profiled Determined. This applies not only to carbon and SiC fibers, but to most materials, especially binary, ternary, quaternary and more complex compounds / alloys.

  In the present invention, Applicants provide several novel ways of generating strength profiles / geometry of useful primary heating means for fiber growth. Examples are seen in FIGS.

  In the embodiment shown in FIG. 38 (a), a two- and one-mode Laguerre Gaussian is focused on the fiber tip 495 by the focused profile laser beam 510, producing a beam intensity profile 515 and an induced temperature rise on the illustrated surface 520. . This beam intensity profile 515 is useful for producing multiphase fibers having different phases aligned with the fiber axis. For example, when carbon fibers are grown, the outer and inner layers can have a graphitic carbon 530 layer, and as shown, both the outer and inner layers are aligned with the fiber axis and either amorphous carbon 525 or particulate carbon Separated by This can give further strength to such fibers. Alternatively, two or more beam modes may be combined from different beams to create a similar intensity profile. In the embodiment shown in FIG. 38 (b), a beam intensity profile 515 similar to that of FIG. 38 (a) is created by two means of superimposing two or more beams 500 on different beam intensity profiles 515. In this case, beam # 1 is a focused Laguerre Gaussian (mode 1, 0) beam, and beam # 2 is a Laguerre Gaussian (mode 2, 0) beam. By superimposing these two beam intensity profiles 515, Applicants create a double ring intensity profile (also called a composite beam intensity profile) at the focus, thereby providing the multiphase fibers described above. Can do.

  The embodiment shown in FIG. 39 illustrates how to use a superposition of many beamlets 540 to approximate a more complex profile. As shown in this figure, only 8 laser spots are created by beamlets 540, and the number of beamlets 540 can be increased until a substantially uniform “ring” is created. Heat transfer within the fiber tip 495 and in the reaction zone tends to spread the energy imparted by each beamlet 540, thereby tending to smooth the induced temperature rise on the surface 520 (as shown). This technique is well suited for the use of diffractive optical elements 545, micro-optical elements, and spatial light modulators to generate beamlets. As shown in FIG. 39, one or more lenses 505 or diffractive optical elements 545 may be used.

  In addition, a very rapid scan of one or more “microbeamlets” over the fiber surface may simulate a complex beam profile over the extended region. In this case, the time to cool the surface to below the deposition threshold should be much longer than the repetition rate of the micro beamlet pattern. If the repetition rate is sufficient, a pulsed laser may be used.

  FIG. 40 shows three examples of incident beams: (a) a first beam 560 that passes through a focusing lens 505 and enters the fiber tip to generate a reaction zone and uses a flat-top beam intensity profile 515; (B) A second beam 565 that is incident on the fiber using a beam splitter 590 and is focused at a distance from the first beam 560 by the beam intensity profile 515 on the side of the fiber. One possible implementation with a second beam 565 that can be made is shown. The second beam 565 may be coaxial with the first beam 560 or may have an angle. A third beam 570 may be used, which is incident on the side of the fiber at a distance from the first beam 560 and / or the second beam 565 (circular beam intensity profile). 515), the fiber material structure can be modified, or a coating 420 can be applied to the fiber surface, and a focal reflective or refractive optical element 585 can be used. The third beam 570 can provide symmetric axial heating to produce a coating 420 or surface modification. The third beam 570 of this embodiment uses a flat top beam intensity profile 515. In the case of the coating 420, an optional aperture 575 is provided, and the gas before the aperture (in the case of the induced reaction zone of the first beam 560 and the second beam 565) may be different from the gas behind the aperture 575. The fibers can be coated with a material different from the original fiber material grown by the first beam 560 or the second beam 565 (FIG. 40 shows two different coatings 420). Optional nozzles 580 or gas delivery means are provided to supply precursors to the respective reaction zones. The optical element 585 that provides the third beam 570 may be reflective (as shown), refracted, or diffracted. In all three cases, first beam 560, second beam 565, and third beam 570, using different beam intensity profiles 515 (each having an induced temperature rise associated with surface 520) Optical material phases, microstructures and properties can be obtained. This example is not exhaustive of the various possible implementations, and multi-step fiber extrusion / spinning, firing, and coating, common in the industry today, when multiple beams, each profiled, are used simultaneously It shows how a deposition system can be provided that is sufficiently sophisticated to replace the system. Within the initial reaction zone of a few millimeters of the first beam 560, the fibers have already reached the final structure and shape. Other implementations use alternative primary heating means (different from the focused laser beam), use each of the previously described incident beams 560, 565, 570, and use different orientations and profiles. To obtain the desired surface topology, internal microstructure / phase, and fiber material properties. These profile beam examples may be used to modify the thermal diffusion region in each reaction zone to obtain optimal growth rates, accurate coating thicknesses, and the like. Of course, as described elsewhere in this application, each of these can be adjusted in real time to obtain a patterned and adjusted fiber. The embodiment shown in FIG. 40 has an amorphous carbon 525 core material.

  Recall that secondary heating means may be used with all of the profile laser beam methods described herein. The secondary heating means may affect the temperature profile of the fiber surface in some cases due to heat transfer. For example, a wire coil around the fiber (as in FIG. 8 (b)), when held close to the fiber, raises the overall temperature of the fiber, thereby causing primary heating means to cause growth. The required output can be reduced.

  Accordingly, the fiber deposition system is preferably designed to optimize the primary heating means profile / geometry (eg, focused beam) and the secondary heating means geometry / profile (eg, conductive wire assembly). In addition, the placement of these means on the fibers can be important. In many embodiments, these means are used simultaneously to control both the reaction zone and the thermal diffusion region.

  In some embodiments, a reaction zone is created in the reaction vessel to decompose at least one precursor, causing decomposition to cause solid fiber growth in the reaction zone. The reaction zone is such that the temperature rise of the surface is generated by the primary heating means and the temperature region is controlled to have a specific induced temperature rise of the surface with respect to the surface of the solid fiber and the position and time within the solid fiber. Arise. In this way, fibers having specific microstructural characteristics can be grown by controlling the surface induced temperature rise.

  In some embodiments, the microstructural characteristics may be uniform across any cross section of the fiber. The cross-section may have more than one microstructural characteristic, and the desired physical and / or chemical properties of the solid fiber, such as Young's modulus, Poisson's ratio, tensile strength, compressive strength, shear strength May be arranged to provide corrosion resistance and / or oxidation resistance.

  In some embodiments, the fibers may be composed of at least 60 atomic percent (at%) carbon.

  Various embodiments use a specific beam intensity profile versus radial position (resulting in an induced temperature rise in the reaction zone), which has the following shapes: (a) flat top profile, (b) centered It can be represented approximately by a contour having a minimum value, (c) a contour having a center drop and a local center peak, (d) a plurality of ring shapes, and (e) a function having a toroidal shape. The specific excitation beam intensity profile versus radial position is also represented by the following functions: (a) sinusoidal function, (b) polynomial, (c) Bessel function, (d) Laguerre Gaussian function, (e) associated Laguerre polynomial, And (f) can be schematically represented by a superposition of Hermitian Gaussian functions. Various modes of these above beams (functions) can be used alone or simultaneously to generate the desired intensity profile and surface temperature rise. For example, a beam intensity profile can be generated from a plurality of superimposed Gaussian beam intensity profiles to obtain a more uniform temperature distribution overall.

  The use of laser beam profiling to enhance the fabrication of fibers and microstructures is performed in any of the embodiments described herein, including the use of LMM precursors, HMM precursors, and thermal diffusion regions. May be. This use may be carried out for use in recording information on or in fibers and microstructures and functionally formed and designed fibers. Thus, in one embodiment, LMM precursors and HMM precursors having substantially different molecular masses are introduced into the reactor, and the HMM precursor also has a substantially lower thermal conductivity than the LMM precursor. A thermal diffusion region is created at or near the reaction zone to react the LMM precursor species by partially or completely separating the LMM precursor from the HMM precursor using thermal diffusion effects. The HMM precursor species reduce the heat flow from the reaction zone, as compared to those concentrated in the zone, enhancing solid fiber growth and resulting from the use of the LMM precursor alone. The thermal diffusion region may be created at least in part by an array of focused laser beams, where the focused laser beam is ring shaped, with a maximum value in a circle and a local minimum value at the center. Any of the laser beam profiles described herein may be used.

DESCRIPTION OF SYMBOLS 10 Thermal diffusion area | region 15 Low molecular mass (or LMM) precursor 20 High molecular mass (or HMM) precursor 25 Fiber 30 Concentration gradient 35 Reaction zone 40 Primary heating means 45 Tensioner 47 Tension adjustment device 50 Spool device / mandrel 55 Coaxial Tube 60 Low molecular mass (or LMM) precursor tube 65 High molecular mass (or HMM) precursor tube 70 Flat flow sheet of precursor 75 Bubble 80 Internal thermal diffusion region 85 External thermal diffusion region 90 Fluid (in two-phase system)
95 Bath Seal 100 Bath Wall 101 Solid Source of HMM Precursor (eg Wax) 102 Liquid Source of HMM Precursor 105 Nozzle 110 Secondary Heating Means 112 Return Conductor 115 Single Partial Loop 120 Coil 125 Elongated Thermal Diffusion Area 130 LLM Precursor Source 135 Wire hot section 140 Wire manifold 145 Switch connection 147 Control signal 150 Outlet manifold 155 HMM precursor source 156 Feedback means 160 Controller 165 Multi-output analog amplifier 170 Motor controller driver 200 Vertical axis 205 Horizontal axis 210 LMM Growth rate data for a mixture of precursor and HMM precursor 215 Curve fit to 215 data 220 Result # 1 (CH _{4 at} 15 PSI with xenon)
225 Result # 2 (CH _{4 at} 30 PSI with xenon)
230 Result # 3 (CH _{4 at} 45 PSI with xenon)
235 Wool-like webbing 240 Baffle 280 First material 285 Second material 290 Transition part 300 Mandrel / drum 310 Wiper 315 Fiber bottle 320 Base material 330 Window 400 Small diameter part 405 Large diameter part 410 First composition part 415 Second Composition part 420 Fiber coating 425 First coating composition part 430 Second coating composition part 450 Detection means (or sensor)
455 translational motion means 460 hole / aperture 465 sensor support surface (or detection means support surface)
470 Analog / digital and / or multiplexing system 495 Fiber tip 500 Laser beam 505 Focus lens 510 Focus profile laser beam 515 Beam intensity profile 520 Surface temperature rise 525 Amorphous carbon 530 Graphite carbon 540 Beamlet 545 Diffraction Optical element 560 First beam 565 Second beam 570 Third beam 575 Aperture 580 Nozzle 585 Focal reflection or refractive optical element 590 Beam splitter

Claims (39)

A method of making a fiber,
a. Introducing a low molecular mass precursor species into the reaction vessel;
b. Introducing a high molecular mass precursor species having a molecular mass at least 1.5 times greater than the low molecular mass precursor species into the reaction vessel;
c. (I) creating a reaction zone in the reaction vessel; (ii) creating a thermal diffusion region in or near the reaction zone, wherein the thermal diffusion region and the reaction zone are At least one is at least partially created by primary heating means, and the thermal diffusion region at least partially separates the low molecular mass precursor species from the high molecular mass precursor species, wherein at least one of the precursor species Concentrating one in the reaction zone;
d. Decomposing the at least one precursor species concentrated in the reaction zone within the reaction zone and depositing it as solid fibers in the reaction zone, wherein the solid fibers are in the reaction zone; Having an end and a second end, wherein the second end is separated from the reaction zone, or the reaction zone is separated from the second end;
Including methods. The primary heating means is
a. Induction heating,
b. Laser beam focusing line,
c. High pressure discharge through the precursor species,
d. Current through the precursor species,
e. One or more laser beams;
f. One or more laser beams and induction heating;
g. A high pressure discharge through the precursor species and one or more laser beams;
h. Current through the precursor species and one or more laser beams;
i. A focusing line of laser light and one or more laser beams;
j. A focusing line of laser light and one or more laser beams and induction heating;
k. A high pressure discharge through the precursor species and a focused line of laser light and one or more laser beams, or
l. A focusing line of current and laser light and one or more laser beams through the precursor species;
The method of claim 1, wherein the method is at least one of:   The high molecular mass precursor species has a lower thermal conductivity than the low molecular mass precursor species, and the high molecular mass precursor species results from using the low molecular mass precursor species alone. The process of claim 1, wherein the heat flow from the reaction zone is reduced.   The method of claim 1, wherein the low molecular mass precursor species are concentrated in the reaction zone.   The method of claim 1, wherein the high molecular weight precursor species are concentrated in the reaction zone. Introduction of the low molecular mass precursor species and the high molecular mass precursor species into the reaction vessel,
a. Premix the low molecular mass precursor species and the high molecular mass precursor species;
b. Directing the low molecular mass precursor species and the high molecular mass precursor species coaxially toward the reaction zone;
c. Flowing the low molecular mass precursor species and the high molecular mass precursor species in alternating sheets and directing them to the reaction zone;
d. Flowing the low molecular mass precursor species and the high molecular mass precursor species from separate sources and directing them to the reaction zone;
e. Flowing the low molecular mass precursor species and the high molecular mass precursor species from separate sources and directing them tangential to the reaction zone, or
f. Flowing the low molecular mass precursor species and the high molecular mass precursor species from separate sources and directing them at an angle to each other;
The method of claim 1, wherein the method is at least one of:   Molecules smaller than the low molecular mass precursor species by using secondary heating means to at least partially decompose the high molecular mass precursor species or the low molecular mass precursor species near the reaction zone The method of claim 1, further comprising creating a derived precursor species having a mass.   Further comprising introducing an intermediate molecular mass precursor species, wherein the intermediate molecular mass species separates the low molecular mass precursor species and the high molecular mass precursor species, or the high molecular mass precursor species or The method of claim 1, wherein the method reacts with at least one of the low molecular mass precursor species.   The method of claim 1, wherein the high molecular weight precursor species is inert.   Derived precursor in which the low molecular mass precursor species reacts with the high molecular mass precursor species, deposits the low molecular mass precursor species as solid fibers, or partially decomposes and concentrates in the reaction zone The method of claim 1, wherein the seed is formed.   A derivative precursor in which the low molecular mass precursor species reacts with the high molecular mass precursor species, deposits the high molecular mass precursor species as solid fibers, or partially decomposes and concentrates in the reaction zone The method of claim 1, wherein the seed is formed.   The method of claim 1, wherein the high molecular mass precursor species physically or chemically inhibits the formation of clusters and particulates near the reaction zone.   The method of claim 1, wherein the pressure of all precursor species in the reaction vessel is controlled by pressure control means. The pressure control means;
a. piston,
b. Diaphragm,
c. A screw that effectively changes the internal volume of the reaction vessel;
d. A pump and a flow rate limiter at the reaction vessel outlet,
e. An external force applied to the reaction vessel to change the internal volume of the reaction vessel, or
f. Introduction of a solid that effectively changes the internal volume of the reaction vessel;
The method of claim 13, wherein the method is at least one of the following:   The method of claim 1, wherein all precursor species are in a gaseous state.   The method of claim 1, wherein the precursor species concentrated in the reaction zone are in a gaseous state and the precursor species not concentrated in the reaction zone are in a liquid state.   The method of claim 1, wherein the precursor species concentrated in the reaction zone are in a critical point or supercritical state, and the precursor species not concentrated in the reaction zone are in a liquid or solid state.   The method of claim 1, wherein all precursor species are at a critical point or in a supercritical fluid state. The high molecular mass precursor species is
a. liquid,
b. Soft plastic solid,
c. A glassy solid, or d. Highly viscous liquid,
One of the
The method of claim 1, wherein the high molecular weight precursor species liquefies, vaporizes, or sublimes near the reaction zone.   The low molecular mass precursor species is silane, borane, organoaluminum, organosilicon, organoboron, metal halide, organometal, hydrocarbon, fluorocarbon, chlorocarbon, iodocarbon, bromocarbon, or halogenated hydrocarbon The method of claim 1, wherein the method is at least one of a seed or a mixture.   The high molecular mass precursor species is silane, borane, organoaluminum, organosilicon, organoboron, metal halide, organometal, hydrocarbon, fluorocarbon, chlorocarbon, iodocarbon, bromocarbon, or halogenated hydrocarbon The method of claim 1, wherein the method is at least one of a seed or a mixture. A method of making a fiber,
a. Introducing a low molecular mass precursor species into the reaction vessel;
b. Introducing a high molecular mass precursor species having a molecular mass at least 1.5 times greater than the low molecular mass precursor species into the reaction vessel;
c. (I) creating a reaction zone in the reaction vessel; (ii) creating a thermal diffusion region in or near the reaction zone, wherein the thermal diffusion region and the reaction zone are At least one is at least partially created by primary heating means, the thermal diffusion region at least partially separates the low molecular mass precursor species from the high molecular mass precursor species, and the low molecular mass precursor is Concentrating on the reaction zone;
d. Decomposing the low molecular mass precursor species concentrated in the reaction zone within the reaction zone and depositing them as solid fibers in the reaction zone, wherein the solid fibers are in the reaction zone; Having an end and a second end, wherein the second end is separated from the reaction zone, or the reaction zone is separated from the second end;
e. Adjusting the flow of low molecular mass precursors to the reaction zone or to the reaction zone to alter the fiber properties of the solid fibers growing in the reaction zone;
Including methods.   Using a heating wire proximate to the reaction zone, the flow of the reaction zone or low molecular mass precursor is adjusted to direct the low molecular mass precursor species to the heating wire and reaction zone or to the heating. 23. The method of claim 22, further concentrated near the wire and reaction zone.   24. The method of claim 23, wherein the heating wire penetrates the reaction zone.   24. The method of claim 23, wherein the heating wire surrounds the reaction zone.   26. The method of claim 25, wherein the surrounding heating wire is at least one of diamond, rectangle, circle, or star.   23. The method of claim 22, wherein the adjustment is by infrared, microwave, millimeter wave, terahertz, or high frequency radiation.   A low molecular mass precursor species is introduced into the reactor adjacent to the heating wire, the low molecular mass precursor is concentrated along the heating wire, and the heating wire is a flow conduit for the low molecular mass precursor species. 24. The method of claim 23, wherein the low molecular mass precursor species flows to or near the reaction zone, acting as:   23. The method of claim 22, wherein the by-product species from the decomposition flow away from the reaction zone along at least one heating wire to remove the by-product species from the reaction zone.   30. The method of claim 29, wherein the byproduct species are removed from the reaction vessel by a byproduct outlet manifold.   The heating wire is composed of at least two bonded but electrically separate parts, and the current through one of the parts is used to real-time the flow of low molecular mass precursor species to the reaction zone. 24. The method of claim 23, wherein the adjustment is made at   24. The method of claim 23, wherein at least one portion of the heating wire is heated by a laser beam to condition the flow of low molecular mass precursor species to the reaction zone in real time.   At least one portion of the heating wire is attached to a dispersion wire, and the dispersion wire is resistively heated to disperse the low molecular mass precursor species and to flow the flow of low molecular mass precursor species to the reaction zone in real time. 24. The method of claim 23, wherein the adjustment is made at   Using a feedback means for obtaining feedback on one or more fiber properties of the growing solid fiber, and using the feedback, the reaction zone or a low molecular mass precursor to the reaction zone 23. The method of claim 22, further comprising controlling the adjustment of flow.   35. The method of claim 34, wherein the feedback means is selected from the group of FT-IR spectroscopy, Raman spectroscopy, fluorescence spectroscopy, band filters with electro-optic sensors, pyrometers, and X-ray probes.   35. The method of claim 34, wherein the feedback means is an acoustic sensing device.   Determining a relative concentration of the low molecular mass precursor species and the high molecular mass precursor species in the thermal diffusion region or the reaction zone using feedback means; and using the relative concentration, the reaction zone Or altering the fiber properties of the growing solid fibers by adjusting the flow of low molecular mass precursors to the reaction zone. A method of making a fiber,
a. Introducing a first precursor species into the reaction vessel;
b. Introducing a second precursor species having a molecular mass greater than the first molecular mass precursor species into the reaction vessel;
c. (I) creating a reaction zone in the reaction vessel; (ii) creating a thermal diffusion region in or near the reaction zone, wherein the thermal diffusion region and the reaction zone are At least one is at least partially created by primary heating means, the thermal diffusion region at least partially separates the first precursor species from the second precursor species, and the first precursor is Concentrating on the reaction zone;
d. Decomposing the first precursor species concentrated in the reaction zone within the reaction zone and depositing them as solid fibers in the reaction zone, wherein the solid fibers are in the reaction zone; Having an end and a second end, wherein the second end is separated from the reaction zone, or the reaction zone is separated from the second end;
e. Adjusting the flow of the first precursor species to the reaction zone or to the reaction zone to alter the fiber properties of the solid fibers growing in the reaction zone;
Including methods. An apparatus / system for making one or more solid fibers comprising:
a. At least one reactor, at least one precursor fluid inlet channel for introducing a low molecular mass precursor species and a high molecular mass precursor species into the reactor, and the precursor species in the reactor A reaction vessel having at least one by-product outlet channel for removing by-products from decomposition of
b. Primary heating means;
c. Secondary heating means;
Including
At least one of the primary heating unit and the secondary heating unit is configured to create a thermal diffusion region and a reaction zone in the reaction tank, and the secondary heating unit is adjusted to adjust the thermal diffusion region. And an apparatus / system for controlling the concentration of the low molecular mass precursor species relative to the high molecular mass precursor species in the reaction zone.

Images