Pitch compositions for spinning into carbon products and methods relating thereto

Abstract

Pitch compositions suitable for spinning can include: a pitch having a softening point (SP) of less than 400°C and capable of achieving a pre-break radial Hencky strain of about 0.7 to about 10 at a spinning temperature (T s ) in a range of about SP - 30°C to about SP + 80°C. A method of making carbon fibers from a pitch composition at a temperature in a range of spinning temperatures (T s ) can include determining a temperature range where the maximum radial Hencky strain (εR) lies above a minimum process radial Hencky strain, and where the minimum process radial Hencky strain is in a range of about 0.7 to about 10. The range of spinning temperatures (T s ) can be determined by measuring the pre-break maximum radial Hencky strain (εR) at a range of different temperatures and strain rates. Carbon fiber composites can include the carbon fibers.

Description

Technical Field

[0001] This invention relates to asphalt compositions, their manufacturing methods, and their uses. Background of the Invention

[0003] In recent years, the carbon fiber industry has steadily grown to meet demand from a wide range of sectors, including: automotive (e.g., body parts such as trunk lids, roofs, front ends, bumpers, doors, chassis, suspension systems such as leaf springs, drive shafts), aerospace (e.g., aircraft and space systems), high-performance marine vessels (e.g., yacht and racing boat hulls), aircraft, sports equipment (e.g., golf clubs, tennis rackets, skateboards, skis, helmets, rowing or waterskiing equipment), construction (non-structural and structural systems), military (e.g., flying drones, armor, armored vehicles, military aircraft), wind energy, energy storage applications, refractories, carbon-carbon composites, carbon fibers, and many insulation and sealing materials used in building and road construction (e.g., concrete), turbine blades, lightweight cylinders and pressure vessels, offshore moorings and drilling risers, and medical applications. The non-limiting properties of carbon fiber make it suitable for high-performance applications: high bulk modulus and tensile modulus (depending on the morphology of the carbon fiber), high electrical and thermal conductivity, high specific density, etc. However, the high cost of carbon fiber limits its application and widespread use, despite the material's exceptional performance. Therefore, developing low-cost technologies for manufacturing carbon fibers has been a major challenge for researchers and major manufacturers.

[0004] Carbon fibers can be manufactured from pitch. Pitch is a carbon-containing feedstock that can be divided into isotropic pitch or mesophase pitch. Both isotropic and mesophase pitch can be complex mixtures of aromatic molecules; however, the aromatic molecules in isotropic pitch are randomly oriented, while in mesophase pitch, at least a portion of these aromatic molecules are ordered. Mesophase pitch can have a heterogeneous two-phase structure comprising the ordered aromatic molecules (e.g., anisotropic regions) and isotropic regions.

[0005] Asphalt can be produced from petroleum, coal tar, biomass tar, or by acid-catalyzed oligomerization of small molecules such as naphthalene. Typically, the formation of isotropic asphalt precedes the formation of mesophase asphalt. For example, a fraction from a catalytic cracking or slurry hydrocracking process can be a bottom fraction or “asphalt” fraction. This asphalt fraction can correspond to isotropic asphalt. Alternatively, the fraction can be used as feed to a reaction zone, where the feed is further heat-treated to form isotropic asphalt. If the isotropic asphalt is further processed (e.g., heat-treated), mesophase asphalt can be formed.

[0006] The properties of carbon fiber are greatly influenced by the type of pitch used. General-purpose carbon fibers made from isotropic pitch typically have lower tensile modulus and tensile strength than fibers made from mesophase pitch. Isotropic pitch-based carbon fibers can be used for concrete reinforcement, activated carbon fiber products, and battery casings (to name just a few examples). Mesophase pitch-based carbon fibers, due to their higher tensile modulus, strength, and thermal and electrical conductivity, are suitable for higher-performance applications. Applications for mesophase pitch-based carbon fibers include industrial rollers and robotic arms, sporting goods, building reinforcement, and satellite components.

[0007] The production of carbon fibers from pitch can be achieved through the following steps: melt spinning; stabilization; carbonization; and graphitization. During the melt spinning process, pitch is heated to a sufficiently high temperature to melt it and reduce its viscosity, allowing the heated pitch to pass through a spinneret. The resulting fibers from the pitch can then be wound onto a spinning spool or laid in a fiber mat.

[0008] The viscosity of many types of pitch materials is highly temperature-dependent. During fiber formation, even small temperature fluctuations can cause significant changes in fiber diameter and / or tensile stress within the filaments. To overcome this challenge, conventional methods of manufacturing carbon fibers from pitch require operating the process within a narrow temperature window, which is difficult to maintain under commercial manufacturing conditions. Furthermore, the difficulty in maintaining the manufacturing process within the desired temperature window can also limit the yield of fibers produced. In some cases, the sensitivity of the fiber formation process to minute temperature changes in a steady state can lead to fiber breakage because the pitch cannot flow through the spinneret and / or due to structural weaknesses caused by dimensional changes and / or tensile stress. Therefore, it is crucial to predict / evaluate the spinnability of pitch and determine the optimal spinning conditions based on its material properties.

[0009] Various spinning conditions (e.g., temperature, die design, draw ratio (DDR), etc.) have been used, and based on performance under these conditions, pitch is characterized as having good or poor spinnability. Traditional pitch specifications such as softening point and mesophase content (volume %) are used as predictive indicators of spinnability. However, such specifications are insufficient to guarantee spinnability. To evaluate spinnability, large quantities of pitch are needed to assess various spinning conditions. Therefore, there is an urgent need for a method that can evaluate and establish the properties of materials (e.g., pitch) directly related to the spinning process and enable the manufacture of materials with customized properties to achieve good spinnability. Summary of the Invention

[0010] This invention provides a pitch composition suitable for spinning. The pitch composition comprises: a pitch having a softening point (SP) below 400°C and a spinning temperature (T) in the range of about SP-30°C to about SP+80°C. sIt can achieve radial Hencky strain of about 0.7 to about 10 before fracture.

[0011] This invention provides a method for preparing a pitch composition suitable for spinning. The method includes: at a spinning temperature (T... s Carbon fibers are manufactured from a pitch composition at temperatures within the range of ) , wherein the spinning temperature (T) s The range is determined by varying the temperature (°C) and strain rate (s). -1 The maximum radial Hengyi strain (ε) before fracture was measured. R To determine; and to determine the temperature range in which the maximum radial Hengyi strain (ε) is found. R It is located above the minimum process radial Hengi strain, and the minimum process radial Hengi strain is in the range of about 0.7 to about 10.

[0012] This invention provides a carbon fiber composite material. The carbon fiber composite material comprises carbon fibers manufactured from a pitch composition, wherein the pitch composition comprises: a pitch having a softening point (SP) below 400°C and a spinning temperature (T) in the range of about SP-30°C to about SP+80°C. s It can achieve radial Hengi strain of about 0.7 to about 10 before fracture. Attached Figure Description

[0013] The accompanying drawings, which illustrate specific aspects of the invention, should not be considered as exclusive embodiments. The disclosed subject matter is capable of numerous variations, changes, combinations, and equivalents in form and function, as will be apparent to those skilled in the art and those who benefit from the invention.

[0014] Figure 1A It describes isotropic asphalt at 150℃ under different strain rates (s) -1 The tensile viscosity η at ) + (Pa·s) Plot of radial Hengi strain.

[0015] Figure 1B It describes isotropic asphalt at 150℃ under different strain rates (s) -1 A graph of stress (Pa) versus radial Hengi strain at 0.

[0016] Figure 2 It is the maximum radial Hengyi fracture strain ε that describes various types of asphalt. R、C A graph showing the temperature difference corresponding to its glass transition temperature (°C).

[0017] Figure 3 It describes the maximum axial Henji fracture strain ε of various asphalts. 轴向,CA graph showing the temperature difference corresponding to its glass transition temperature (°C).

[0018] Figure 4 It is a graph depicting the temperature difference between the maximum stress and critical fracture stress (Pa) of various asphalts and their corresponding glass transition temperature (°C).

[0019] Figure 5 It describes the axial Hengyi strain ε of asphalt containing 0.5 vol% mesophase at various temperatures (°C) based on the total volume of asphalt. 轴向,C For radial Hengi strain ε R The image.

[0020] Figure 6 This describes the axial Hengyi strain ε of asphalt containing 14 vol% mesophase at various temperatures (°C) based on the total volume of asphalt. 轴向,C For radial Hengi strain ε R The image.

[0021] Figure 7 This is a graph depicting the average molecular weight distribution of three asphalt samples with 0 vol% mesophase, 0.5 vol% mesophase, and 14 vol% mesophase based on the total volume of asphalt.

[0022] Figure 8 This is a chart showing the most abundant substances present in three asphalt samples with a total volume of 0%, 0.5%, and 14% mesophase, respectively. HC represents substances containing only carbon and hydrogen, 1N represents hydrocarbons containing one nitrogen atom, 1O represents hydrocarbons containing one oxygen atom, and 2O represents hydrocarbons containing two oxygen atoms.

[0023] Figure 9 This is a graph showing the Z-number distribution of hydrocarbons (HC), hydrocarbons containing one oxygen (1O), and hydrocarbons containing two oxygens (2O) present in three asphalt samples with a total volume of 0 vol% mesophase, 0.5 vol% mesophase, and 14 vol% mesophase, relative to the mass-to-charge ratio (m / z).

[0024] Figure 10A It is a graph depicting the critical draw ratio (DDR) of isotropic pitch at different strain rates and the corresponding fiber spinning data.

[0025] Figure 10B It is a graph depicting the critical draw ratio (DDR) of mesophase pitch at different strain rates (based on a total pitch volume content of 3% mesophase) and the corresponding fiber spinning data.

[0026] Figure 10CIt is a graph depicting the critical draw ratio (DDR) of mesophase pitch at different strain rates (based on a total pitch volume content of 17% mesophase) and the corresponding fiber spinning data. Detailed Implementation

[0027] This invention relates to asphalt compositions, their manufacturing methods, and their uses.

[0028] For example, as mentioned above, the demand for carbon fiber, especially high-quality carbon fiber, is constantly growing across various industries, such as those suitable for manufacturing wind turbine blades or automotive products. Currently, there are some qualitative analytical options available for evaluating the spinnability of pitch, but no quantitative analytical property can accurately define whether pitch is spinnable. Furthermore, the options available for manufacturing spinnable pitch compositions are limited, particularly in terms of the ability to adjust the physical properties of the pitch to meet the specific requirements of a particular application. This invention demonstrates that certain quantitative measures of material properties (e.g., pitch) can be used as a means of evaluating and establishing the spinnability of pitch. This approach provides new techniques and tools for predicting the spinnability of pitch, enabling the custom design of pitches with desired spinning properties (e.g., blends), determining suitable process conditions for spinning pitches, and the ability to adjust process conditions to produce stronger and more stable spinnable pitches for manufacturing carbon fibers, and providing product applications for these pitches.

[0029] The pitch composition suitable for spinning according to the present invention may comprise a pitch having a softening point (SP) below 400°C and a spinning temperature (T) from about SP-30°C to about SP+80°C. s Within the range of about 0.7 to about 10, radial Henkel strain before fracture can be achieved. Advantageously, such compositions provide improved ability to be spun into carbon fibers. Due to these improved properties, the pitch compositions described herein can be used to manufacture higher quality carbon fiber composites for applications such as automotive body parts, drilling risers, or wind turbine blades. Preferably, the pitch has: an interphase content of less than about 5% by volume based on the total volume of the pitch; an axial Henkel strain in the range of about 0.1 to about 8; and a radial strain in the range of about 0.1s. -1 approximately 100s -1 The tensile strain rate is within the range of about 1,000 Pa to about 10,000,000 Pa; the maximum critical stress is within the range of about 5 Pa·s to about 500,000 Pa·s; and / or the tensile viscosity is within the range of about 5 Pa·s to about 500,000 Pa·s. Alternatively, the asphalt has: an intermediate phase content based on the total volume of the asphalt, ranging from about 5 vol% to about 100 vol%; an axial Hengyi strain ranging from about 0.1 to about 8; and a tensile viscosity within the range of about 0.1 s. -1 approximately 100s -1The tensile strain rate in the range of about 1,000 Pa to about 10,000,000 Pa; and / or the tensile viscosity in the range of about 5 Pa·s to about 500,000 Pa·s.

[0030] This invention also relates to a method for manufacturing carbon fiber composite materials, the method comprising combining one or more carbon fibers derived from bitumen with one or more matrices. The matrices used herein can be manufactured from substances such as thermosetting polymers (e.g., cyclopentadiene, dicyclopentadiene, epoxy resins, bitumen, phenolic resins, vinyl esters, polyimides, and polyesters), thermoplastic polymers (e.g., thermoplastic polymers including one or more of polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyamide, polyvinyl chloride, polyetheretherketone, polyetherketoneketone, polyaryletherketone, polyetherimide, and polyphenylene sulfide), cement, concrete, ceramics, metals, metal alloys, or combinations thereof. For example, bitumen itself can be used as a matrix and / or binder for manufacturing carbon fibers, thereby enabling the manufacture of carbon-carbon composite materials.

[0031] Furthermore, the present invention also relates to a method for blending a spinnable bitumen composition, the method comprising: blending a first bitumen with one or more bitumens, wherein the blending enables the spinnability or fiber properties of the bitumen composition, or both.

[0032] The present invention also relates to a method for preparing carbon fiber composite materials, the method comprising: combining at least one composite filler with at least one matrix, the composite filler comprising carbon fibers manufactured from the aforementioned spinnable pitch composition, wherein the matrix is ​​a thermosetting matrix, a thermoplastic matrix, cement, concrete, ceramic, metal, metal alloy, or a combination thereof.

[0033] All numerical values ​​in the specific embodiments and claims herein are modified with “about” or “approximately” and take into account experimental errors and biases expected by those skilled in the art. Unless otherwise stated, the ambient temperature (room temperature) is from about 18°C ​​to about 20°C.

[0034] The following abbreviations are used in this article: DSC stands for Differential Scanning Calorimetry; T g Glass transition temperature; MCRT is microcarbon residue test; Pa·s is Pascal-second; wt% is weight percentage; vol% is volume percentage; psi is pounds per square inch; psig is pounds per square inch, gauge pressure; WHSV is gravity hourly space velocity.

[0035] As used in this invention and the claims, the singular forms “a,” “an,” “the,” and “the” include the plural forms, unless the context clearly specifies otherwise.

[0036] The term “and / or” as used in phrases such as “A and / or B” in this article is intended to include “A and B”, “A or B”, and “A” and “B”.

[0037] When the term "between" is used in this document to refer to a range, the term includes the endpoints of the range. That is, "between 2% and 10%" means 2%, 10%, and all percentages between these terms.

[0038] As used herein, the term "asphalt" refers to a complex, high-boiling-point mixture primarily composed of aromatic compounds and alkyl-substituted aromatic compounds, which is glassy at ambient temperature and has a softening point above 50°C. These aromatic compounds are primarily hydrocarbons, but heteroatoms and trace metals can be present in these materials. When cooled from a melt, asphalt solidifies into a glassy state, and its high polydispersity (size and shape) inhibits crystallization even at low cooling rates. Asphalt can include petroleum asphalt, coal tar pitch, natural asphalt, asphalt contained as a byproduct in the naphtha cracking industry, high-carbon asphalt obtained from petroleum asphalt, and other substances with asphalt-like properties manufactured as products in various industrial processes. Asphalt exhibits a wide softening temperature range and is typically derived from petroleum, coal tar, plant, or small-molecule catalytic oligomerization reactions (e.g., acid-catalyzed oligomerization). Asphalt can also be called tar, bitumen, or asphalt. When asphalt is made from plants, it is also referred to as a resin. In the gas oil or naphtha cracking industry, various pitches can be obtained as products, serving as carbonaceous residues composed primarily of aromatic organic compounds. These pitches are solid at room temperature and exhibit a relatively wide softening temperature range. Therefore, pitches can be obtained from the heat treatment and distillation of petroleum fractions. "Petroleum pitch" refers to the residual carbonaceous material obtained from crude oil distillation and catalytic cracking of petroleum distillates. "Coal tar pitch" refers to the material obtained through coal distillation.

[0039] As used herein, the term "mesophase" refers to a polydisperse liquid crystal material (e.g., a disk-shaped liquid crystal) composed of planar aromatic molecules. "Mesophase pitch" consists of an "mesophase" and an optional isotropic phase. When examined using a polarizing microscope, the mesophase exhibits optical anisotropy. For example, based on the total volume of the pitch, mesophase pitch can be pitch containing more than about 10% by volume of mesophase. The mesophase content of the pitch can be measured, for example, by embedding various pitch samples in epoxy resin and then polishing the samples until they become highly reflective. A series of images can be recorded to quantify the anisotropy content.

[0040] As used herein, the term "blend" refers to a mixture of two or more types of bitumen. Blends can be produced, for example, by solution blending, melt blending in a heated mixer, physical blending of liquid bitumen and different solid bitumen, or physical blending of solid bitumen. Suitable solvents for solution blending can include benzene, toluene, naphthalene, xylene, pyridine, quinoline, and aromatic fractions derived from refining or chemical processes, such as clarified oils, reformed oils, tar distillates, etc. Solution blending, solid blending, and / or melt blending can occur at temperatures from about 20°C to about 400°C.

[0041] As used herein, a “thermosetting matrix” refers to a synthetic polymer-reinforced material that typically transforms from a liquid to a solid state through an irreversible chemical change. Thermosetting matrices can also include cement, concrete, ceramics, glass, metals, or metal alloys. Thermosetting matrices can be combined with resins such as polyesters, vinyl esters, epoxy resins, bismaleimides, cyanate esters, polyimides, or phenolic resins. When cured by heat and / or chemicals (catalysts or accelerators) or other means, thermosetting matrices become substantially infusible and insoluble. Once cured, a thermosetting matrix cannot be returned to its uncured state. Composites made from thermosetting matrices are high-strength and exhibit very good fatigue strength. Such composites can be very brittle and may have low impact toughness. For example, thermosetting matrices can be used in high-temperature applications and / or situations requiring chemical resistance.

[0042] As used herein, "thermoplastic matrix" refers to a polymer that can be molded, melted, and reshaped without altering its physical properties. In some cases, thermoplastic matrices are tougher and less brittle than thermoset matrices, exhibiting excellent impact resistance and damage tolerance. In others, thermoplastic matrices can remain below their glass transition temperature, thus becoming glassy and very brittle. Because the matrix can melt, composites are easier to repair and can be readily reshaped and recycled. The lower density of thermoplastic matrices compared to thermoset matrices makes them a viable alternative for applications where weight is critical.

[0043] As used herein, “tensile strength” refers to the amount of stress applied to a sample to break it. It can be expressed in Pascals or pounds per square inch (psi). ASTM D3379 can be used to determine the tensile strength of articles made from polymers.

[0044] Unless otherwise stated, the tensile rheological data of the bitumen compositions of the present invention were obtained using a commercial filament tensile rheometer (VADER from Rheo Filament). TM It is recorded in the 1000 series. The relationship between the tensile rheology of the pitch and the necessary parameters (e.g., spinning window) required for successful spinning of the pitch is also described in detail.

[0045] As used in this article, "Henki strain" refers to the logarithmic form of strain, which is the result of integrating a series of incremental mechanical deformations.

[0046] Radial Hengi strain ε R The following formula can be used to calculate:

[0047]

[0048] Where r(t) is the radius of the extended fiber at time t, and r0 is the initial radius of the fiber before extension. The maximum radial Hengyi strain refers to the strain measured instantaneously before the filament breaks.

[0049] “Axial Hengi strain” ε 轴向 The following formula can be used to calculate:

[0050]

[0051] Where L(t) is the length of the fiber at time t, and L0 is the initial length of the fiber before elongation. The maximum axial Hengyi strain refers to the strain measured before the filament breaks.

[0052] As used herein, "draw ratio" refers to the linear velocity of the fiber after stretching (e.g., the linear velocity of the guide roller) divided by the linear velocity of the fiber after extrusion. For example, the draw ratio during melt stretching can be calculated using the following formula:

[0053] Draw ratio = A / B

[0054] Where A is the linear velocity of the fiber after melt stretching (e.g., the speed of the guide roller); B is the linear velocity of the extruded fiber and can be calculated using the following formula:

[0055] Extruder linear fiber speed = 4C / (π*D*E²)

[0056] Where C is the production rate (g / min) through a single orifice; D is the melt density of asphalt (g / cm³). 3 ); and E is the diameter (in centimeters) of the orifice through which the fiber is extruded.

[0057]

[0058]

[0059] The numerical ranges used in this document include the values ​​listed within the range. For example, the numerical range “from 1 wt% to 10 wt%” includes 1 wt% and 10 wt% within the range, as well as all points within the range.

[0060] As used in this article, "glass transition temperature" (T) g This refers to the midpoint of the temperature during the second heating scan of a differential scanning calorimeter (DSC) experiment, where a continuous step change in heat capacity (or the peak value at the first derivative of the heat flux) is recorded at a heating and cooling rate of 10 °C / min. For the purposes disclosed herein, T... g Thermal analysis TAINSTRUMENTS Q2000 can be used TM To measure, as shown.

[0061] "Softening point" refers to the temperature or range at which a substance softens. Here, the softening point (SP) is determined using a METTLER TOLEDO dropping point apparatus, such as the METTLER TOLEDO DP70, according to a procedure similar to ASTM D3104.

[0062] The "trace carbon residue test," also known as the "MCRT," is a standard test method (trace method) for determining carbon residue. The carbon residue value of various petroleum materials serves as an approximation of the material's tendency to form carbonaceous deposits under degradation conditions similar to those used in the test method, and can be used as a guide for the manufacture of specific feedstocks. However, caution is required when interpreting the results. This test method covers the determination of the amount of carbon residue formed after evaporation and pyrolysis of petroleum materials under specific conditions, and is designed to provide some indication of the relative coke formation tendency of such materials. Here, the MCRT is measured according to the ASTM D4530-15 standard test method.

[0063] This paper uses mass spectrometry to determine the molecular composition of asphalt. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provides the high precision and high resolution required for asphalt analysis. Laser desorption / ionization (LDI) was used to generate ions in the gas phase for mass analysis of non-volatile asphalt samples. Solid asphalt samples were weighed and dissolved in tetrahydrofuran (THF) by sonication for 5 to 10 minutes, resulting in a solution with a final concentration of approximately 2,000 ppm. Small aliquots (<5 μL) of the asphalt solution were then deposited onto a MALDI target, and the target was loaded into the MALDI instrument after solvent evaporation. The MALDI instrument is equipped with dual ion sources capable of operating in electrospray and matrix-assisted laser desorption / ionization modes (ESI and MALDI, respectively). Ions were generated by irradiating the target surface with a solid-state Nd:YAG laser (λ = 355 nm). The system can irradiate asphalt samples, generating ions that are then transported via ion optics to the center of a superconducting magnet (15 Tesla) and contained in an ion trap, where they undergo circular motion due to the Lorentz force of the magnetic field. Once contained, the ions can be excited to a larger radius, and the image current can be measured. The frequency of this current is directly related to the mass-to-charge ratio (m / z) of the particles. To generate ions with minimal fragmentation, the laser can be operated at 11% of its laser power, just above the ionization threshold. The asphalt sample can be irradiated, and 200 individual scans can be acquired and averaged to generate a final average mass spectrum representative of the asphalt sample. Data can be acquired from m / z 200 to 3,000 in absorption mode. The source optics can be adjusted as follows: skimmer 1 22.0 V, funnel RF amplitude 120 Vpp, funnel 1140 V, transmission line RF 350.0 Vpp, octupole frequency 1.0 MHz, octupole RF amplitude 350 Vpp, Q1 mass 300. To detect and perform quality analysis, the ion chamber can be operated under the following conditions: 2.0V for both front and rear trap plates, 1.5V gated injection DC bias, 0.0V side pulse, -30.0V quench for the rear trap plate, and continuous ramp power supply excitation. Once completed, a peak list can be immediately exported and formula assignments performed.

[0064] FT-ICR MS, combined with molecular weight distribution, can provide heteroatom class distributions and Z-distributions that can be used to construct heavy hydrocarbon composition models. FT-ICR MS can provide petroleum composition in terms of hydrogen deficiency number (Z number), heteroatom content (SNO), and total carbon number distribution. Detailed classification helps to narrow down the Z-distribution of bitumen compositions and significantly improves the dynamic range of FT-ICR MS. Ultra-high resolution enables the resolution of overlapping peaks. Therefore, FT-ICR MS can provide three layers of chemical information for petroleum systems. The first layer is heteroatom class (or compound class), such as hydrocarbons (HC); hydrocarbons containing one sulfur atom (1S); hydrocarbons containing one nitrogen atom (1N); hydrocarbons containing two oxygen atoms (2O); hydrocarbons containing one nitrogen and one oxygen atom (1N1O), etc. The second layer is the Z-number distribution (or uniform coefficient distribution) within various compound classes. Z is defined as the hydrogen deficiency number, such as the general chemical formula CH. 2c+Z N n S s O o Where c is the number of carbon atoms, and Z is the number of hydrogen atoms required to produce (e.g., benzene C6H6 should be C6H). 2x6+(Z＝-6) Therefore, the Z number for benzene should be -6), where s is the number of sulfur atoms and o is the number of oxygen atoms. The more negative the Z number, the more unsaturated the molecule. Another commonly used term is double bond equivalent (DBE). For a typical petroleum system, DBE = Ch / 2 + n / 2 + 1, where n is the number of nitrogen atoms. Therefore, Z is closely related to the double bond equivalent and can be expressed as Z = -2x(DBE) + n + 2. The third level of information is the total carbon number distribution or molecular weight distribution of various homologues. If the core structure of the compound is known, the total alkyl side chain information can be deduced.

[0065] As used in this article, M n It is the number average molecular weight, M w It is the weight-average molecular weight, and M z This is the z-mean molecular weight. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as M... w Divide by M n Unless otherwise stated, all molecular weight units (e.g., M) are... w M n M z All are g / mol.

[0066] This invention illustrates a spinning temperature (T) capable of being maintained at approximately SP-30°C to approximately SP+80°C. sA spinnable pitch composition achieving a radial Hengyi strain of approximately 0.7 or higher is described. Carbon fiber breakage can be caused by, for example, the loss of the ability of the mesophase pitch to flow through the spinneret; structural weaknesses in the carbon fiber due to dimensional changes; the accumulation of tensile stress in the molten material sufficient to cause filament breakage; and the formation of volatiles leading to gas formation, resulting in fiber breakage and spinneret charring. Therefore, it is desirable to determine the conditions suitable for spinning fibers from a given pitch before spinning. The present invention includes a method for evaluating whether a given pitch composition is suitable for spinning fibers and what the necessary conditions are. Advantageously, the present invention provides new tools for: (a) evaluating the spinnability of a given pitch composition; (b) adjusting the key process conditions required for reliably spinning carbon fibers; and (c) reliably manufacturing pitch with rheological properties suitable for spinning into carbon fibers. The present invention also provides an evaluation of the spinnability of a pitch composition that relies on measuring the tensile rheology of the pitch and quantitative measurements to determine the properties of the pitch composition (e.g., maximum radial Hengyi strain, maximum fracture stress, maximum engineering strain), while requiring very little material to measure these properties.

[0067] This document also discusses various applications of carbon fiber composites formed from the bitumen compositions of the present invention. These carbon fiber composites can be used in many applications requiring weight reduction while simultaneously increasing strength and stiffness. The carbon fiber composites can also be used in offshore drilling (e.g., offshore drilling for oil and gas production) to improve corrosion resistance, fatigue resistance, and heat resistance, producing components including, but not limited to, platforms, risers, mooring lines, anchors, drill pipes, or related equipment and systems. Other product applications can include, for example, automotive (e.g., body parts such as body panels, trunk lids, front ends, bumpers, doors, chassis, suspension systems such as leaf springs, drive shafts), aerospace (aircraft and space systems), sports equipment (e.g., golf clubs, tennis rackets, bicycles, skateboards, skis, helmets, boating or waterskiing equipment), construction (non-structural and structural systems), military (e.g., flying drones, armor, armored vehicles, military aircraft), wind energy industry, energy storage applications, refractory materials, carbon-carbon composites, carbon fibers, and many insulation and sealing materials (e.g., concrete) used in building and road construction, turbine blades, lightweight cylinders and pressure vessels, offshore mooring lines and drilling risers, medical equipment, etc.

[0068] Asphalt composition and its manufacturing method

[0069] The bitumen composition described in this article can be spun at a temperature of approximately SP-30°C to approximately SP+80°C (T sThe pitch can achieve a radial Hengyi strain of about 0.7 or more before fracture, for example, a radial Hengyi strain of 0.7 to 10. Typically, the pitch spinning temperature can range from about 30°C below the pitch softening point to about 80°C above the pitch softening point. The pitch can achieve an axial strain of less than about 8 and / or a tensile viscosity of about 5 Pa·s or more, for example, a tensile viscosity from about 5 Pa·s to about 500,000 Pa·s. The pitch composition is further described below.

[0070] The asphalt composition of the present invention can be isotropic asphalt or mesophase asphalt.

[0071] The isotropic bitumen of the present invention can be obtained from any suitable feed selected from the following: main bottoms (MCB), hydrotreated main bottoms, steam cracker tar, hydrotreated steam cracker tar (HDT-SCT), crude oil, hydrotreated crude oil, coal tar pitch, petroleum pitch, vacuum residue (VR), atmospheric residue, bitumen, asphaltenes, bitumen, reformate, coking gas oil, heavy coking gas oil, hot tar, thermal distillate fractions, and any combination thereof.

[0072] The method for producing mesophase pitch is not limited to any particular method. Therefore, coal tar, naphtha tar, cracked tar, clarified oil, or asphaltic substances produced by distillation or heat treatment of these heavy oils can be used as starting materials for producing mesophase pitch. The percentage of mesophase in the pitch can be increased by subjecting the pitch to one or more heat treatments at temperatures well above the pitch softening point for a period of time. Without being bound by any theory, the content of mesophase can affect spinning; for example, as the percentage of mesophase increases, the viscosity increases, and the temperature dependence on viscosity also increases. The mesophase pitch of this invention exhibits non-Newtonian behavior, which can be revealed by the change in viscosity with shear rate. Furthermore, the tensile rheology of the pitch may be more sensitive. The viscosity of isotropic feed is lower than that of anisotropic feed, and spinning can be performed at lower temperatures. Carbon fibers made from isotropic pitch are more flexible than those made from mesophase pitch, which may be brittle.

[0073] Based on the total volume of the asphalt composition, the asphalt composition may have an intermediate phase content of less than about 5% by volume (or less than about 4.5% by volume, or less than about 4% by volume, or less than about 3.5% by volume, or less than about 3% by volume, or less than about 2.5% by volume, or less than about 2% by volume, or less than about 1.5% by volume, or less than about 1% by volume, or less than about 0.5% by volume).

[0074] Alternatively, based on the total volume of the asphalt composition, the asphalt composition may have an intermediate phase content of more than about 5% by volume (or more than about 10% by volume, or more than about 15% by volume, or more than about 20% by volume, or more than about 25% by volume, or more than about 30% by volume, or more than about 35% by volume, or more than about 40% by volume, or more than about 45% by volume, or more than about 50% by volume, or more than about 55% by volume, or more than about 60% by volume, or more than about 65% by volume, or more than about 70% by volume, or more than about 75% by volume, or more than about 80% by volume, or more than about 85% by volume, or more than about 90% by volume, or more than about 95% by volume or more than about 98% by volume).

[0075] Based on the total weight of the asphalt composition, the asphalt composition may have a residual carbon content of about 20% by weight to about 99% by weight, for example about 30% by weight to about 99% by weight, for example about 40% by weight to about 99% by weight, for example about 50% by weight to about 99% by weight, for example about 50% by weight to about 95% by weight, for example about 50% by weight to about 90% by weight, for example about 50% by weight to about 85% by weight, for example about 50% by weight to about 80% by weight.

[0076] Asphalt compositions can be characterized using mass spectrometry. Methods for characterizing asphalt (e.g., petroleum asphalt) using mass spectrometry include one or more of the following: transferring the asphalt to a MALDI target; generating pseudomolecular ions and molecular ions from the asphalt using laser desorption / ionization; analyzing at least one mass-to-charge ratio of the asphalt in positive mode on a high-resolution Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS); assigning at least one molecular formula to the detected pseudomolecular ions and molecular ions; and generating the molecular weight distribution and molecular composition of the asphalt. In this paper, the peak resolution at approximately 50 to approximately 1,000 (or approximately 100 to approximately 900, or approximately 200 to approximately 800, or approximately 300 to approximately 700) m / z can be approximately 100,000 to approximately 3,000,000 (or approximately 200,000 to approximately 3,000,000, or approximately 200,000 to approximately 2,500,000, or approximately 300,000 to approximately 2,500,000, or approximately 300,000 to approximately 2,500,000) m / z. The peak resolution can be approximately 1,300,000 (or about 400,000 to about 2,000,000, or about 500,000 to about 2,000,000, or about 600,000 to about 1,900,000, or about 700,000 to about 1,800,000, or about 800,000 to about 1,700,000, or about 900,000 to about 1,600,000, or about 1,000,000 to about 1,500,000). For example, the peak resolution at m / z 400 can be about 1,300,000. Pseudo-molecular ions and molecular ions can be generated by ablating the sample with an ultraviolet solid-state laser and obtaining mass spectrometry. The molecular formula of pitch can be determined by precise mass measurement, thereby enabling the measurement of the amount of double bond equivalents.

[0077] The bitumen composition may contain one or more of the following: at least 80% by weight of hydrocarbons, 0% to 20% by weight of 1-sulfur (1S), 0% to 5% by weight of 2-sulfur (2S), 0% to 15% by weight of 1-oxygen (1O), 0% to 5% by weight of 2-oxygen (2O), 0% to 5% by weight of 1S1N, 0% to 5% by weight of 1N1O, 0% to 5% by weight of 1S1O, 0% to 5% by weight of 1S2O, 0% to 1% by weight of 2S1O, and 0% to 1% by weight of 2N2O.

[0078] The bitumen composition can have an m / z value ranging from about 250 to about 1,000 and contain at least 60% bitumen ion current (e.g., at least 65%, at least 70%, at least 75%, at least 80%), as determined by FT-ICR MS.

[0079] The asphalt composition may be an isotropic asphalt with a Z number distribution (Z) in the following range: about -250 to about -10 (or about -240 to about -10, or about -230 to about -10, or about -220 to about -10, or about -210 to about -10, or about -200 to about -10, or about -200 to about -12, or about -190 to about -12, or about -180 to about -12, or about -160 to about -14, or about -150 to about -14, or about -140 to about -12, or about -130 to about -14, or about -120 to about -16, or about -110 to about -20).

[0080] The asphalt composition may be M having m / z in the following range: n Isotropic asphalt: approximately 400 to approximately 800 (or approximately 420 to approximately 780, or approximately 440 to approximately 760, or approximately 460 to approximately 740, or approximately 480 to approximately 720, or approximately 500 to approximately 700). For example, isotropic asphalt can have an M of m / z 652. n .

[0081] The asphalt composition may be M having m / z in the following range: W Isotropic asphalt: approximately 400 to approximately 1,100 (or 405 to 1,000, or 410 to 975, or 415 to 950, or 415 to 925, or 420 to 900, or 420 to 880, or 440 to 860, or 460 to 840, or 480 to 820, or 500 to 800). For example, isotropic asphalt can have an M of m / z 697. W .

[0082] The bitumen composition can be an isotropic bitumen, which, based on total ionic strength, contains about 35% or more of molecules with Z = 6 to -50, about 60% or more of Z = -51 to -100 and about 2% or more of molecules with Z greater than -100.

[0083] Alternatively, the bitumen composition may be an intermediate phase bitumen having a Z number distribution (Z) in the range of about -300 to about -20 (or -250 to -10, or -252 to -12, or -254 to -14, or -256 to -16, or -258 to -18, or -260 to -20 or -270 to -20).

[0084] The asphalt composition may be M having m / z in the following range: n Mesophase bitumen: about 500 to about 1,200 (or 500 to 1,100, or 525 to 1,000, or 550 to 950, or 600 to 900 or 650 to 850).

[0085] The asphalt composition may be M having m / z in the following range: w Mesophase bitumen: about 500 to about 1,000 (or 550 to 950, or 600 to 900 or 650 to 850).

[0086] The bitumen composition may be mesophase bitumen, which, based on total ionic strength, contains less than 5% of Z=6 to -50, more than 40% of Z=-51 to -100, more than 30% of Z=-101 to -150, more than 10% of Z=-151 to -200 and more than 0.1% of molecules with Z greater than -200.

[0087] Alternatively, the bitumen composition may be an intermediate phase bitumen with a Z number distribution (Z) in the range of about -250 to about -10 (or -252 to -12, or -254 to -14, or -256 to -16, or -258 to -18 or -260 to -20).

[0088] The asphalt composition may be M having m / z in the following range: n Mesophase bitumen: about 500 to about 1,000 (or 550 to 950, or 600 to 900 or 650 to 850).

[0089] The asphalt composition may be M having m / z in the following range: w Mesophase bitumen: about 500 to about 1,000 (or 550 to 950, or 600 to 900 or 650 to 850).

[0090] The bitumen composition may be mesophase bitumen, which, based on total ionic strength, contains less than 5% of Z=6 to -50, more than 40% of Z=-51 to -100, more than 30% of Z=-101 to -150, more than 10% of Z=-151 to -200 and more than 0.1% of molecules with Z greater than -200.

[0091] The softening point of the pitch composition suitable for spinning is typically less than about 400°C (or less than about 350°C, or less than about 300°C, or less than about 250°C, or less than about 200°C, or less than about 150°C, or less than about 100°C), as determined according to a procedure similar to the test method in ASTM D 3104, wherein the procedure is performed under nitrogen at a heating rate of 2°C / min to a temperature of about 400°C.

[0092] The glass transition temperature (T) of the asphalt composition of the present invention gThe value can be less than about 315°C (or less than about 275°C, less than about 235°C, less than about 195°C, less than about 155°C, less than about 115°C, or less than about 75°C), as determined by a second heating scan of a differential scanning calorimetry (DSC) experiment conducted under an inert atmosphere (N2) at a heating and cooling rate of 10°C / min.

[0093] The bitumen composition of the present invention can be spun at temperatures ranging from about 30°C below the softening point of the bitumen composition to about 80°C above the softening point of the bitumen composition. s The asphalt composition can achieve a pre-fracture radial Henrykle strain of about 0.7 to about 10 (where the lower limit can be about 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, etc.). The asphalt composition may be able to achieve a pre-fracture radial Henrykle strain of about 0.7 to about 10, for example about 1 to about 10, for example about 1.5 to about 10, for example about 2 to about 10, for example about 2.5 to about 10, for example about 3 to about 10, for example about 3.5 to about 10, for example about 4 to about 10, or for example about 4.5 to about 10.

[0094] The asphalt composition can be spun at temperatures ranging from about 30°C below the softening point of the asphalt composition to about 80°C above the softening point of the asphalt composition. s The axial strain is in the range of about 0.1 to about 8 (where the upper limit may be less than or equal to about 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3 etc., and may be as low as about 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1 etc.).

[0095] The bitumen composition can be spun at temperatures ranging from about 30°C below the softening point of the bitumen composition to about 80°C above the softening point of the bitumen composition (T). s The tensile strain rate is within the range of approximately 0.1 s-1. -1 approximately 100s -1 (The lower limit can be greater than or equal to approximately 0.1s) -1 0.2s -1 0.3s -1 0.4s -1 0.5s -1 0.6s -1 0.7s -1 0.8s -1 0.9s -1 1.0s -1 (etc.). The asphalt composition can have a tensile strain rate in the range of approximately 0.1 s². -1 approximately 100s -1For example, about 0.1s -1 approximately 95s -1 For example, about 0.5s -1 approximately 90s -1 For example, about 0.5s -1 approximately 80s -1 For example, about 0.5s -1 approximately 70s -1 For example, about 0.5s -1 approximately 60s -1 For example, about 1 second -1 approximately 50s -1 For example, about 1 second -1 approximately 40s -1 For example, about 1 second -1 approximately 30 seconds -1 For example, about 1 second -1 approximately 20 seconds -1 For example, about 1 second -1 approximately 20 seconds -1 For example, about 1 second -1 approximately 15 seconds -1 For example, about 1 second -1 approximately 10 seconds -1 For example, about 1.5s -1 approximately 10 seconds -1 For example, about 2 seconds -1 approximately 10 seconds -1 For example, approximately 2.5 to approximately 10 seconds -1 For example, about 3 seconds -1 approximately 10 seconds -1 .

[0096] The maximum critical stress of the asphalt composition can be more than about 100 Pa (or more than about 250 Pa, or more than about 500 Pa, or more than about 750 Pa, or more than about 1,000 Pa). For example, the maximum critical stress of the asphalt composition can be from about 100 Pa to about 10,000,000 Pa, for example from about 250 Pa to about 7,500,000 Pa, for example from about 500 Pa to about 1,500,000 Pa, for example from about 1,000 Pa to about 1,000,000 Pa, for example from about 1,500 Pa to about 750,000 Pa, for example from about 2,000 Pa to about 500,000 Pa, for example from about 2,500 Pa to about 250,000 Pa. Alternatively, the maximum critical stress of the asphalt composition may be from about 1,000 Pa to about 50,000,000 Pa, for example from about 1,500 Pa to about 25,000,000 Pa, for example from about 5,000 Pa to about 20,000,000 Pa, for example from about 10,000 Pa to about 15,000,000 Pa.

[0097] Spinning temperature (T) of the bitumen composition in the range of approximately 30°C below the softening point of the bitumen composition to approximately 80°C above the softening point of the bitumen composition. s The tensile viscosity at ) can be from about 5 Pa·s to about 500,000 Pa·s (where the lower limit can be above about 5 Pa·s, for example above about 70 Pa·s, for example above about 75 Pa·s, for example above about 100 Pa·s, for example above about 125 Pa·s, for example above about 150 Pa·s, for example above about 200 Pa·s, for example above about 250 Pa·s, for example above about 300 Pa·s, for example above about 350 Pa·s, for example above about 400 Pa·s, for example above about 450 Pa·s, for example above about 500 Pa·s).

[0098] In at least one embodiment, the pitch composition suitable for spinning as described herein comprises: an intermediate phase content of less than 5% by volume based on the total volume of the pitch, and a softening point (SP) of less than about 400°C; and wherein the spinning temperature (T) is in the range of SP-30°C to SP+80°C. s Under these conditions, the asphalt is capable of achieving a radial Hengyi strain greater than about 0.7 before fracture, and wherein the asphalt has one or more of the following: an axial strain less than about 8; a tensile viscosity greater than about 5 Pa·s; a maximum critical stress greater than about 10,000,000 Pa; and a stress greater than 0.1 s⁻¹. -1 The tensile strain rate.

[0099] In an alternative embodiment, the pitch composition suitable for spinning as described herein comprises: a mesophase content of greater than about 5% by volume based on the total volume of the pitch and a softening point of less than about 400°C; and wherein the spinning temperature (T) is in the range of about SP-30°C to about SP+80°C. s Under these conditions, the asphalt is capable of achieving a radial Hengyi strain before fracture of about 0.7 to about 10, and wherein the asphalt has one or more of the following: an axial strain of about 0.1 to about 8; a tensile viscosity of about 5 Pa·s to about 500,000 Pa·s; a maximum critical stress of about 100 Pa to about 10,000,000 Pa; and a tensile viscosity of about 0.1 s⁻¹. -1 approximately 100s -1 The tensile strain rate.

[0100] The hydrocarbon feed can be a bitumen feed consisting of various heavy oils and / or heavy hydrocarbon fractions comprising a majority of aromatic compounds. The aromatic carbon content can vary depending on the feed. For example, when the feed contains vacuum residue, the aromatic carbon content can be from about 20% to about 40%, or when the feed contains isotropic bitumen, the aromatic carbon content is from about 50% to 70%, or when the feed contains main bottoms (MCB), the aromatic carbon content is from about 45% to about 55%. Some heavy oil fractions are usable without further processing (e.g., fractions that can be produced into mesophase bitumen by solvent extraction), while other fractions can be at least partially converted into mesophase bitumen feed through heat treatment and / or limited polymerization. Suitable fractions for use as bitumen and / or for forming mesophase bitumen can include, but are not limited to, heavy oil; coal tar fractions formed during coal-to-coke conversion; bottom fractions derived from fluid catalytic cracking; steam cracker tar; bitumen formed by acid-catalyzed oligomerization reactions; bitumen formed by blown gas reactions; bitumen formed during slurry hydroconversion and / or fixed-bed hydroconversion (e.g., hydroconversion of heavy oil); and / or “rock” fractions generated during solvent deasphalting of heavy oil. More generally, bitumen fractions for forming carbon fibers can be formed from any of the above-mentioned sources.

[0101] The reaction zone can be a catalytic conversion zone, a thermal conversion zone, or a combination thereof. In at least one embodiment, the reaction zone is a hydrogenation processing zone. The temperature of the reaction zone can be above about 200°C, for example, from about 200°C to about 500°C, for example, from about 250°C to about 450°C, for example, from about 300°C to about 400°C. The pressure of the reaction zone can be above about 10 psig (or above about 12 psig, or above about 14 psig, or above about 16 psig, or above about 18 psig, or above about 20 psig, or above about 25 psig, or above about 50 psig). The reaction zone can have a pressure in the range of from about 200 psig to about 3,000 psig, for example, from about 300 psig to about 2,500 psig, for example, from about 400 psig to about 2,000 psig, for example, from about 500 psig to about 1,500 psig and / or at about 0.1 hr. -1 approximately 4 hours -1 (or approximately 0.2hr) -1 Approximately 3.8 hours -1 or approximately 0.4hr -1 Approximately 3.6 hours -1 or approximately 0.6hr -1 From approximately 3.4 hours -1 or approximately 0.8hr -1 From approximately 3.2 hours -1 or about 1 hour -1 approximately 3 hours -1The weight hourly space velocity (WHSV) is within the range of ). The reaction zone may contain hydrogen, nitrogen, air, steam or other inert gases or any combination of these gases.

[0102] The reaction zone may contain a catalyst comprising one or more transition metal catalysts. The one or more transition metal catalysts may be selected from: Pt, Pd, W, V, Co, Ni, or Mo. Catalyst systems suitable for the invention herein may include catalysts comprising one or more transition metal catalysts and one or more solid supports. Solid supports enable catalytic reactions such as pitch feed hydrotreating under multiphase conditions. In a more specific embodiment, the solid support may be silica. Other suitable solid supports may include, but are not limited to, alumina, silica-alumina, porous carbon, zeolites, zirconium oxide, titanium dioxide, and refractory oxides.

[0103] The method of the present invention may further include separating the bituminous composition in one or more separation processes. Suitable examples of separation processes may include, but are not limited to, distillation, deasphalting, chromatographic separation, membrane filtration, or combinations thereof. The bituminous composition may be characterized as being relatively free of impurities and ash.

[0104] Suitable diluents / solvents for separation may include noncoordinate inert liquids. Examples include: straight-chain and branched hydrocarbons and aromatic solvents such as isobutane, ethane, propane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, benzene, toluene, pyridine, quinoline, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; and perhalogenated hydrocarbons such as perfluorinated C424. 4-10 Alkanes, chlorobenzenes, and aromatic and alkyl-substituted aromatic compounds such as benzene (e.g., xylene), toluene, mesitylene, and xylene; and polar solvents (e.g., acetone, N,N-dimethylformamide, acetonitrile, pyridine, quinoline, dimethyl sulfoxide, N-methylpyrrolidone, and mixtures thereof). In some embodiments, the solvent is substantially an aromatic compound, wherein the aromatic compound may be present in the solvent at an amount of more than about 50% by weight, for example, more than about 75% by weight, for example, more than about 90% by weight, based on the total weight of the solvent.

[0105] Spinning pitch into fibers

[0106] After separation, the asphalt composition can be directly spun into fibers.

[0107] As mentioned above, in some cases, the first pitch can be combined with the second pitch for spinning, wherein the first pitch is spun at a spinning temperature (T). s The viscosity of the second pitch at the spinning temperature (T) is similar to that of the first pitch at the spinning temperature (T). sThe viscosity of the first bitumen differs from that of the second bitumen. In some cases, the viscosity of the first bitumen is greater than that of the second bitumen. In other cases, the viscosity of the first bitumen is lower than that of the second bitumen. It is desirable and advantageous to blend two or more bitumen to control the properties (e.g., tensile strength) of the melt spinning or the corresponding carbon fibers formed therefrom. More specifically, the first bitumen can be combined with the second bitumen for spinning, wherein the first bitumen can form a first layer (e.g., an inner / center layer) and the second bitumen can thereby form a second layer (e.g., an outer layer) on the surface of the first layer. Other non-limiting examples may include: 1) having a second bitumen formed on the surface of the first bitumen, wherein the second bitumen reacts with air at a greater rate than the first bitumen to produce an oxide layer, thereby preventing the fibers from sticking during winding; 2) having a bitumen that is harder on the outside than on the inside; 3) having a bitumen that is more resistant to surface defects on the outside than on the inside; 4) having a second bitumen that is primarily used to produce narrower fibers in the center / inner layer to increase the strength of the center / inner layer fibers; 5) having a second bitumen that forms a better interface with the matrix. For example, the filaments described herein can be manufactured using two different pitches in a bicomponent spinning machine to produce fibers having different materials (pitches) geometrically arranged along the long axis of the filament (fiber). For example, “side-by-side” fibers can be produced, in which the two pitches are arranged along the long axis of the fiber. In other instances, other geometric arrangements are possible, such as “sheath-core” fibers. Other arrangements, including but not limited to “tilted trefoil,” “island in the sea,” or other geometric shapes, are also possible.

[0108] The method of the present invention may include: at a spinning temperature (T) s Carbon fibers are manufactured from the above-mentioned pitch composition (an isotropic and / or anisotropic pitch composition with a mesophase content of less than about 5% by volume or more than about 5% by volume, based on the total volume of the pitch composition) at temperatures within the range of ), wherein the spinning temperature (T) s The range is determined by the following operation: at a series of different temperatures (°C) and strain rates (s). -1 The maximum radial Hengyi strain (ε) before fracture was measured. R，C ); and determined that the continuous range includes approximately 0.5 (ε) R，max) Approximately 2(ε) R，max The corresponding highest measured maximum radial Hengyi strain (ε) within the range R，max The temperature of the carbon fiber product. Alternatively, the carbon fiber product requirements and process spinning design may necessitate achieving a minimum radial Hengyi strain. In this case, the spinning window, i.e., the range of conditions under which filaments can be manufactured, can be determined by selecting the corresponding maximum radial Hengyi strain (ε). R The temperature range should be determined to be at least as large as the minimum process radial Hengi strain.

[0109] Therefore, the method of the present invention may include: at a spinning temperature (T)s Carbon fibers are manufactured from pitch compositions within a temperature range of ) where the spinning temperature (T) s The range is determined by the following: over a range of different temperatures (°C) and strain rates (s). -1 The maximum radial Hengyi strain (ε) before fracture was measured. R，C ); and determine the corresponding maximum radial Hengyi strain (ε) R，C ) located at the minimum process radial Hengyi strain (ε R，工艺 The temperature range above ) and where the minimum process radial Hengyi strain (ε) R，工艺 The minimum process radial Hengyi strain (ε) is in the range of approximately 0.7 to approximately 10. R，工艺 The value will be determined based on the product requirements and spinning process design of the product to be manufactured from the fiber. For example, if a fiber with a diameter of 10 μm is desired and the capillary size of the process spinneret is 300 μm, a minimum process radial Hengyi strain of 6.8 can be indicated.

[0110] The method of the present invention may further include: using a capillary size r0 and a final fiber radius r f The spinneret, where the ratio r f / r0=exp(-ε R / 2), where r f In the range of about 1 μm to about 1,000 μm, r0 is in the range of about 100 μm to about 10,000 μm, and wherein at the spinning temperature (T s The maximum radial Hengi strain within the range is at least

[0111]

[0112] In at least one embodiment, the capillary size r0 is r f / [exp(-ε R / 2)], wherein the spinning temperature (T) is between 30°C below the softening point of the bitumen composition and 80°C above the softening point of the bitumen composition. s ) below, ε R The value is 0.7 or higher. The capillary size r0 can be in the range of about 50 μm to about 5,000 μm, or about 75 μm to about 4,000 μm, or about 100 μm to about 3,000 μm, or about 150 μm to about 1,500 μm, or about 200 μm to about 1,000 μm. For example, the capillary size r0 can be about 300 μm.

[0113] Spinning pitch-based carbon fibers can be performed using a melt spinning process. This process can use a pitch composition with a softening point of about 50°C to about 400°C (or greater than about 110°C, or greater than about 120°C, or greater than about 130°C, or greater than about 140°C, or greater than about 150°C, or greater than about 160°C, or greater than about 170°C, or greater than about 180°C, or greater than about 190°C, or greater than about 200°C, or greater than about 250°C, or greater than about 300°C, or greater than about 320°C). The pitch composition of the present invention can be introduced into an extruder, wherein the pitch composition can be heated, sheared, and extruded through a capillary to form carbon fibers.

[0114] The rheological properties of bitumen, due to the manufacturing process, can significantly affect its spinnability. Shear rheology of bitumen—important in extruder operation—is commonly used to characterize bitumen. However, once the bitumen leaves the spinneret, the tensile flow properties become the primary parameter controlling spinnability. Measurements of the stress evolution of the bitumen composition and its radial Henryk strain can indicate the maximum stress the fiber can withstand before fracture. During these measurements, changes in radius and axial position can be recorded, and the radial Henryk strain (Equation 1) and axial strain (Equation 2) can be determined, providing the maximum fracture strain. Measurements of radial Henryk strain, axial Henryk strain, and stress at various temperatures and strain rates, as described above, require only a minimal amount of bitumen composition. Tensile rheological properties can be measured on a wide range of bitumen compositions to determine suitable bitumen compositions for spinning and to quantify the effect of processing conditions on spinnability. The performance of these measurements can be further used as indicators of fiber structure and / or fiber properties.

[0115] Spinability is also affected by the presence of volatile components, which can form bubbles during spinning, causing fibers to break during the spinning process. Importantly, at the spinning temperature (T... s At a certain temperature, the amount of volatile substances in asphalt should be minimized. The amount of volatile substances present can be controlled by adjusting the spinning temperature (T). s The volatile matter content of the asphalt in this invention can be evaluated by thermogravimetric analysis (TGA). The volatile matter content of the asphalt in this invention can range from 0% by weight to about 1% by weight, preferably from 0% by weight to about 0.5% by weight.

[0116] Furthermore, optimizing spinning conditions based on the rheological properties of pitch can affect the draw ratio (DDR). A higher DDR indicates a higher orientation of the mesophase and a higher tensile modulus along the fiber axis. The DDR is determined by the speed ratio under spinning conditions.

[0117] Isotropic pitch-based fibers near spinning temperature (T sThe processing temperature of DDR can be in the range of about 100 to about 5000 (or about 200 to about 4000, or about 300 to about 3000, or about 400 to about 2000 or about 500 to about 1000).

[0118] Mesophase pitch-based fibers near spinning temperature (T s The processing temperature of DDR can be in the range of about 1.5 to about 2,000 (or about 10 to about 1,500, or about 50 to about 1,250 or about 100 to about 1,000).

[0119] Once the fiber is spun, it can be oxidized, carbonized, and / or graphitized, thereby transforming the fiber (commonly referred to as raw fiber) into stabilized fiber, carbon fiber, and / or graphite fiber.

[0120] Various methods for stabilizing pitch-based carbon fibers have been proposed in the prior art, and the most common practice is oxidation treatment in an oxygen-containing atmosphere, such as air. The stabilization of pitch fibers is a solid-phase oxidation reaction that transforms pitch into a form that is not easily fusible or infusible. In some cases, the air may contain NO2 as an oxidizing gas. This stabilization improves the handling of the carbon fibers and allows them to be carbonized without melting. Oxidation of the fiber surface is generally faster than that of the fiber center, thus stabilizing fibers with different degrees of oxidation in the surface and center can be formed. In some cases, it has been found that adding water to the oxidizing atmosphere, such as air, can optimize the oxidation of the surface and center.

[0121] The stable bitumen can then undergo carbonization by prolonged heating in an inert or mostly inert atmosphere at temperatures ranging from 500°C to 2,000°C. If graphitization is desired, the carbonized fibers can be graphitized by further prolonged heating in an inert or mostly inert atmosphere at temperatures ranging from approximately 1,600°C to 3,000°C.

[0122] Carbon fiber composite materials and their manufacturing methods.

[0123] Furthermore, the method of the present invention provides a carbon fiber composite material comprising: carbon fibers manufactured from a pitch composition, wherein the pitch composition is spun at a temperature (T0) ranging from about 30°C below the softening point of the pitch composition to about 80°C above the softening point of the pitch composition. s Under these conditions, a radial Hengi strain of approximately 0.7 or more before fracture can be achieved.

[0124] The present invention also provides a method for forming a composite material, wherein carbon fibers are formed from a single bitumen or a mixture of two or more bitumens and a matrix. The matrix may be a thermosetting matrix, a thermoplastic matrix, or a combination thereof.

[0125] Carbon fiber composites may comprise carbon fibers made from pitch, wherein the pitch is spun at a temperature (T0) ranging from about 30°C below the softening point of the pitch composition to about 80°C above the softening point of the pitch composition. s Under these conditions, radial Hengyi strain above 0.7 before fracture can be achieved. Based on the total volume of the carbon fiber composite, the carbon fiber composite can contain approximately 1 vol% to approximately 70 vol% carbon fiber and approximately 99 vol% to approximately 30 vol% matrix.

[0126] The matrix used in this article can be manufactured from the following materials: thermosetting polymers (e.g., cyclopentadiene, dicyclopentadiene, epoxy resin, bitumen, phenolic resin, vinyl ester, polyimide, and polyester), thermoplastic polymers (e.g., including one or more of the following: polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyamide, polyvinyl chloride, polyetheretherketone, polyetherketoneketone, polyaryletherketone, polyetherimide, and polyphenylene sulfide), cement, concrete, ceramics, metals, metal alloys, or combinations thereof. For example, bitumen itself can be used as a matrix and / or binder for carbon fiber composites by impregnating numerous oxidized fibers, carbon fibers, or graphite fibers, or oxidized, carbonized, or graphitized fiber webs with bitumen and then carbonizing the assembly, thereby enabling the manufacture of carbon-carbon composites. In this case, carbon fibers can be laid in the desired shape and then impregnated. The resulting material can then be carbonized at high temperatures to form solid carbon blocks. Typically, the bitumen impregnation is repeated multiple times before forming the final carbon product. This method is commonly used when manufacturing carbon brakes.

[0127] The present invention also relates to a method for manufacturing carbon fiber composite materials, the method comprising: combining at least one composite filler with at least one matrix, the composite filler comprising carbon fibers manufactured from the aforementioned spinnable pitch composition, wherein the matrix can be a thermosetting matrix, a thermoplastic matrix, cement, concrete, ceramic, metal, metal alloy, or a combination thereof. The composite filler can be used in the carbon fiber composite material after stabilization, carbonization, or graphitization processes. The composite filler can be short or continuous, pad-like, bundle-like, unidirectional or multidirectional, woven or nonwoven. For example, the composite filler can be a nonwoven fabric and / or continuous filament yarn. The continuous filament can be wound on a spool or wound on a nonwoven fabric such as meltblown or spunbond fabric, wherein the fibers are laid on a fiber web or pad. Carbon fiber composite components can be manufactured using conventional molding, roving, autoclaving, or pultrusion processes.

[0128] In at least one embodiment, the described carbon fiber composite exhibits superior stiffness, strength, corrosion resistance, density, thermal conductivity, and / or electrical conductivity compared to similar composites without incorporated carbon fibers. Furthermore, carbon fiber-reinforced composites tend to be lighter in weight and exhibit higher specific strength (relative to mass-normalized strength) compared to other reinforcing agents. Additionally, such carbon fiber composites can exhibit a low coefficient of thermal expansion, particularly when using fibers with high graphite content. These properties can be customized by controlling the orientation / texture of the carbon fiber pitch.

[0129] End use

[0130] Carbon products can include the carbon fiber composite materials described herein, which comprise a pitch composition suitable for spinning containing pitch having a softening point (SP) below 400°C and a spinning temperature (T) in the range of about SP-30°C to about SP+80°C. s The radial Henki strain before fracture can be achieved at a range of approximately 0.7 to approximately 10, and the bitumen may have: an intermediate phase content of less than approximately 5% by volume based on the total volume of the bitumen; an axial Henki strain in the range of approximately 0.1 to approximately 8; and a fracture elongation of approximately 0.1 s. -1 approximately 100s -1 The tensile strain rate is within the range of about 1,000 Pa to about 10,000,000 Pa; the maximum critical stress is within the range of about 5 Pa·s to about 500,000 Pa·s; and / or the tensile viscosity is within the range of about 5 Pa·s to about 500,000 Pa·s. Alternatively, the asphalt may have: an intermediate phase content based on the total volume of the asphalt, ranging from about 5 vol% to about 100 vol%; an axial Hengyi strain ranging from about 0.1 to about 8; and a tensile viscosity within the range of about 0.1 s. -1 approximately 100s -1 The tensile strain rate in the range of about 1,000 Pa to about 10,000,000 Pa; and / or the tensile viscosity in the range of about 5 Pa·s to about 500,000 Pa·s.

[0131] Non-limiting examples of carbon products may include automotive body parts (e.g., trunk lids, roofs, front ends, bumpers, doors, chassis, suspension systems such as leaf springs, drive shafts), marine moorings and drilling risers, wind turbine blades, insulation and sealing materials (e.g., concrete) for building and road construction, aircraft and aerospace systems, high-performance seagoing vessels, aircraft, sports equipment, unmanned aerial vehicles, armor, armored vehicles, military aircraft, energy storage systems, refractory materials, lightweight cylinders and pressure vessels, and medical devices. Furthermore, the fibers of this invention (e.g., filaments or webs) can be used as insulation materials (e.g., thermal insulation or sound insulation materials), or as shielding materials (e.g., electromagnetic shielding or radio frequency shielding materials), or as friction control surfaces (e.g., brake pads, such as aircraft brake pads). Carbon fibers can be contained in graphite foam, and pitch compositions having the aforementioned properties can be used to manufacture graphite foam to prevent explosions, etc.

[0132] According to at least one embodiment of the present invention, in order to form an asphalt composition and further form a carbon fiber composite material, the asphalt composition can be mixed according to any suitable mixing method to produce the aforementioned spinnable asphalt composition and spun into carbon fibers (e.g., raw carbon fibers). The spun carbon fibers (e.g., raw carbon fibers) can then be oxidized to form stable carbon fibers and can further undergo carbonization and graphitization processes under inert conditions to produce carbon fiber fillers. Stabilization, carbonization, and graphitization conditions can be used according to methods obvious to those skilled in the art. The carbon fiber fillers can comprise stabilized, carbonized, or graphitized carbon fibers. The carbon fiber fillers can then be used to form carbon articles and / or additionally incorporated into the associated asphalt composition.

[0133] The implementation methods disclosed herein include:

[0134] A. A pitch composition suitable for spinning. The pitch composition suitable for spinning comprises pitch having a softening point (SP) below 400°C and a spinning temperature (T) in the range of about SP-30°C to about SP+80°C. s It can achieve radial Hengi strain of about 0.7 to about 10 before fracture.

[0135] B. A method for manufacturing carbon fiber. The method includes: at a spinning temperature (T...) s Carbon fibers are manufactured from a pitch composition at temperatures within the range of ) , wherein the spinning temperature (T) s The range is determined by varying the temperature (°C) and strain rate (s). -1 The maximum radial Hengyi strain (ε) before fracture was measured. R To determine; and to determine the temperature range in which the maximum radial Hengyi strain (ε) is found. RIt is located above the minimum process radial Hengi strain, and the minimum process radial Hengi strain is in the range of about 0.7 to about 10.

[0136] C. Carbon fiber composite material. The carbon fiber composite material comprises carbon fibers manufactured from a pitch composition, wherein the pitch composition comprises a pitch having a softening point (SP) below 400°C and a spinning temperature (T) in the range of about SP-30°C to about SP+80°C. s It can achieve radial Hengi strain of about 0.7 to about 10 before fracture.

[0137] Implementation methods A, B, and C may each have any combination of one or more of the following additional elements:

[0138] Element 1: Based on the total volume of asphalt, the asphalt contains less than 5% by volume of intermediate phase.

[0139] Element 2: Wherein, based on the total volume of asphalt, the asphalt contains approximately 0.1% to approximately 2% by volume of intermediate phase content.

[0140] Element 3: Wherein, based on the total volume of asphalt, the asphalt contains approximately 0.1% to 100% by volume of intermediate phase content.

[0141] Element 4: Based on the total volume of bitumen, bitumen contains approximately 5% to 100% of intermediate phase.

[0142] Element 5: The spinning temperature (T) of the bitumen in the range of approximately SP-30°C to approximately SP+80°C. s It can achieve radial Hengi strain of about 0.1 to about 8 before fracture.

[0143] Element 6: wherein the axial or radial Henry's strain of the asphalt is located at approximately 0.1 s. -1 approximately 100s -1 Within the range of tensile strain rates.

[0144] Element 7: The spinning temperature (T) of the bitumen in the range of approximately SP-30°C to approximately SP+80°C. s Under these conditions, axial Hengyi strains of approximately 0.1 to approximately 8 can be achieved, and the bitumen has a strain of approximately 0.1 s-1. -1 approximately 100s -1 Range of tensile strain rates.

[0145] Element 8: Wherein the asphalt has a maximum critical stress in the range of about 100 Pa to about 10,000,000 Pa.

[0146] Element 9: The maximum critical stress is approximately 1,000 Pa to approximately 10,000,000 Pa.

[0147] Element 10: The bitumen composition comprises a mixture of two or more types of bitumen.

[0148] Element 11: The asphalt has a tensile viscosity in the range of about 5 Pa·s to about 500,000 Pa·s.

[0149] Element 12: Wherein the softening point (SP) is in the range of about 100°C to about 350°C.

[0150] Element 13: The bitumen has a glass transition temperature (T0) of about 65°C to about 275°C. g ).

[0151] Element 14: wherein, based on the total weight of the bitumen composition, the bitumen has a residual carbon content of about 20% to about 99% by weight.

[0152] Element 15: The asphalt composition is combined with the matrix material.

[0153] Element 16: Wherein the bitumen composition is used as a matrix in the manufacture of composite materials.

[0154] Element 17: The matrix material is a thermosetting matrix, a thermoplastic matrix, cement, concrete, ceramics, metal, metal alloy or a combination thereof.

[0155] Element 18: The thermoplastic matrix is ​​selected from: polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyamide, polyvinyl chloride, polyetheretherketone, polyetherketoneketone, polyaryletherketone, polyetherimide and polyphenylene sulfide and any combination thereof.

[0156] Element 19: wherein the asphalt composition is used to prepare fibers, oxidized fibers, carbonized fibers, graphitized fibers, fiber webs, oxidized fiber webs, carbonized fiber webs or graphitized fiber webs.

[0157] Element 20: Carbon fiber is manufactured by spinning two or more pitches together.

[0158] Element 21: Two or more types of asphalt each have different viscosities.

[0159] Element 22: Two or more types of asphalt each have different softening points (SP).

[0160] Element 23: Wherein, based on the total volume of asphalt, the asphalt contains less than 5% by volume of intermediate phase.

[0161] Element 24: Wherein, based on the total volume of bitumen, bitumen contains approximately 0.1 vol% to approximately 100 vol% of an intermediate phase content.

[0162] Element 25: wherein the bitumen is capable of achieving an axial Hengi strain of about 0.1 to about 8 and a tensile viscosity of about 5 Pa·s to about 500,000 Pa·s.

[0163] Element 26: which is used during spinning at approximately 0.1s -1 approximately 100s -1 The tensile strain rate within the range is used to spin the pitch.

[0164] Element 27: The bitumen has a glass transition temperature (T0) of about 65°C to about 275°C. g ).

[0165] Element 28: wherein, based on the total weight of the bitumen composition, the bitumen has a residual carbon content of about 20% to about 99% by weight.

[0166] Element 29: The bitumen thereon is spun from two or more types of bitumen.

[0167] Element 30: Carbon product, wherein the carbon product comprises the carbon fiber.

[0168] Element 31: The method described therein includes using a capillary size (r0) and a final fiber radius (r). f The spinneret of ) where r f In the range of about 1 μm to about 1,000 μm, r0 is in the range of about 100 μm to about 10,000 μm, and wherein at the spinning temperature (T s The maximum radial Hengi strain within the range is at least

[0169]

[0170] Element 32: where r0 is in the range of about 100 μm to about 5,000 μm.

[0171] Element 33: The bitumen composition comprises: bitumen, wherein the bitumen has a spinning temperature (T) in the range of about SP-30°C to about SP+80°C. s It has a softening point (SP) below 400°C.

[0172] Element 34: Wherein, based on the total volume of asphalt, the asphalt has an intermediate phase content of less than 5% by volume.

[0173] Element 35: Wherein, based on the total volume of bitumen, bitumen has an intermediate phase content of approximately 5% to 100% by volume.

[0174] Element 36: The tensile viscosity of the asphalt is in the range of about 5 Pa·s to about 500,000 Pa·s.

[0175] Element 37: wherein the bitumen has an axial Hengi strain in the range of about 0.1 to about 8.

[0176] Element 38: The pitch undergoes a process of approximately 0.1 seconds under spinning conditions. -1 approximately 100s -1 Tensile strain rate within the range.

[0177] Element 39: wherein, based on the total weight of the bitumen composition, the bitumen has a residual carbon content of about 20% to about 99% by weight.

[0178] Element 40: The method further includes: spinning pitch using two or more types of pitch.

[0179] Element 41: Two or more types of asphalt each have different viscosities.

[0180] Element 42: Two or more types of asphalt each have different softening points (SP).

[0181] Element 43: The method further includes: manufacturing carbon articles containing carbon fibers.

[0182] Element 44: In which carbon fibers are combined with matrix materials to manufacture composite materials.

[0183] Element 45: The matrix material is a thermosetting matrix, a thermoplastic matrix, cement, concrete, ceramics, metal, metal alloy or a combination thereof.

[0184] Element 46: The thermoplastic polymer thereon is selected from: polyethylene, polypropylene, high-density polyethylene, linear low-density polyethylene, low-density polyethylene, polyamide, polyvinyl chloride, polyetheretherketone, polyetherketoneketone, polyaryletherketone, polyetherimide and polyphenylene sulfide and any combination thereof.

[0185] Element 47: The carbon fiber composite material further includes fillers, wherein the fillers are selected from: carbon fiber, glass fiber, metal fiber, boron fiber, pitch, carbon black and combinations thereof.

[0186] As a non-limiting example, exemplary combinations applicable to A include, but are not limited to: 1 and 2; 1 or 2 and 3; 1 or 2 and 4; 1 or 2 and 5; 1 or 2 and 6; 1 or 2 and 6 and 7; 1 or 2 and 7; 1 or 2 and 8; 1 or 2 and 6 to 8; 1 or 2 and 7 and 8; 1 or 2 and 9; 1 or 2 and 6 to 9; 1 or 2 and 10; 1 or 2 and 11; 1 or 2 and 12; 1 or 2 and 13; 1 or 2 and 12 and 13; 1 or 2 and 13 and 14; 1 or 2 and 15; 1 or 2 and 15 to 18; 1 or 2 and 17; 15 and 16; 15 and 17; 15 and 18; and 1 or 2 and 19.

[0187] As a non-limiting example, exemplary combinations applicable to B include, but are not limited to: 20 and 21; 20 or 21 and 22; 20 or 21 and 23; 20 or 21 and 24; 20 or 21 and 25; 20 or 21 and 26 and 27; 20 or 21 and 28; 20 or 21 and 29; 20 or 21 and 30; 20 or 21 and 30 to 33; 20 or 21 and 34 and 35; 20 or 21 and 36 to 38; 20 or 21 and 41; and 20 or 21 and 42.

[0188] As a non-limiting example, exemplary combinations applicable to C include, but are not limited to: elements 44 to 47; 44 and 45; 44 or 45 and 46; 44 or 45 and 47; and 44 or 45 and 46 and 47.

[0189] To facilitate a better understanding of the embodiments of the present invention, the following preferred or representative embodiments are provided. These embodiments should not be construed as limiting or restricting the scope of the present invention.

[0190] Example

[0191] Isotropic pitch (Sample 1) was prepared as follows: A blend of 80:20 main column bottom product and steam cracking tar was hydrogenated. The resulting liquid product was vacuum distilled, and the non-distilled fraction was deasphalted in pentane and cooled to -78.5°C with dry ice. The insoluble material was filtered, collected, and washed. The separated insoluble fraction was isotropic pitch (Sample 1) with the following properties: softening point of 158.3°C, MCRT of 53.1% by weight, and T0.05 of 98°C. g .

[0192] Anisotropic asphalt, Sample 2 with a mesophase of 0.5 vol% (based on the total volume of the anisotropic asphalt), and Sample 3 with a mesophase of 14 vol% (based on the total volume of the anisotropic asphalt) were prepared as follows: Isotropic asphalt (Sample 1) was converted into corresponding anisotropic asphalts (e.g., Samples 2 and 3) by heat treatment at 400°C for 3 hours and 4 hours, respectively, at 400°C. Sample 1 was heat-treated at 400°C for 3 hours under continuous nitrogen atmosphere pressure to obtain 73% of Sample 2 (0.5 vol% mesophase, based on the total volume of the anisotropic asphalt) with the following properties: 76.7 wt% MCRT and T at 104°C. g Sample 1 was heat-treated at 400℃ for 4 hours to obtain Sample 3 (14 vol% mesophase, based on the total volume of anisotropic bitumen) with 68% of the following properties: 80 wt% MCRT and T at 114℃. g The mesophase content was measured by embedding the asphalt sample in epoxy resin, curing the sample, and then polishing the sample until its surface had high reflectivity. A series of images were then acquired to quantify the anisotropy content. Therefore, 11 images were acquired for sample 2 and 15 images were acquired for sample 3.

[0193] Rheological measurements were performed using a commercial filament tensile rheometer (VADER from Rheo Filament). TM The process was carried out using a 1000-type (e.g., type 1000). Therefore, the tensile rheological properties of various bitumens were measured to determine the bitumens suitable for spinning and the conditions for appropriately spinning these materials. The evaluation of the bitumen rheological properties and spinning windows is also described.

[0194] Figure 1A and 1B Examples are shown at 150°C under different strain rates (e.g., strain rate: 0.3 s⁻¹). -1 0.5s -1 0.7s -1 1s -1 and 1.5s -1 Tensile rheological measurements were performed on isotropic asphalt (sample 1) under the following conditions. Figure 1A The LVE in the figure shows the viscosity expected without strain hardening.

[0195] The obtained data shows that the tensile viscosity η + As time increases. For example, at 1.5 seconds -1 Under strain rate, tensile viscosity η + In 5.2 seconds, from approximately 1×10 4 Pa·s increases to approximately 4 × 10⁻⁶ 5 Pa·s, while in 0.3s -1 Under strain rate, tensile viscosity η +From approximately 1×10 in 11.1 seconds 4 Pa·s increased to approximately 9.5 × 10⁻⁶. 4 Pa·s. Therefore, this rheological measurement can determine the ability to accumulate stress in asphalt, which is required for fiber formation.

[0196] Figure 1A It describes the conditions at 150℃ under different strain rates (e.g., strain rate: 0.3s). -1 0.5s -1 0.7s -1 1s -1 and 1.5s -1 The tensile viscosity η of isotropic asphalt (sample 1) + (Pa·s) Plot of radial Hengi strain.

[0197] Figure 1B It describes the conditions at 150℃ under different strain rates (e.g., strain rate: 0.3s). -1 0.5s -1 0.7s -1 1s -1 and 1.5s -1 A graph showing the stress (Pa) versus radial Hengi strain in isotropic asphalt (sample 1) under [condition]. The results indicate that the stress depends on the strain rate and the recommended conditions that enable the formation of filaments without fracture.

[0198] Additional measurements were performed at many different temperatures to determine the temperature dependence of the maximum radial Henki fracture strain, maximum axial Henki fracture strain, and maximum fracture stress, as shown in [the original text]. Figures 2 to 4 Example in [the text]. Figures 2 to 4 In this study, Sample 1 was used as feedstock to prepare various asphalts (e.g., Samples 2 and 3) with different mesophase contents. Sample 2 (0.5 vol% mesophase, based on total volume of asphalt) and Sample 3 (14 vol% mesophase, based on total volume of asphalt) were prepared by heat treatment at 400 °C for a series of different times. The temperature difference along the x-axis (TT) g This refers to the temperature measurement value and the glass transition temperature T of asphalt as measured by DSC. g The difference lies in the optimal spinning temperature (T0) of the asphalt when it has a low mesophase content (e.g., less than 70% by volume, based on the total volume of the asphalt). s The window can be accessed via TT g It can be evaluated as a parameter or by the softening point (SP). However, when the asphalt contains a high amount of mesophase, for example, when the total volume of the asphalt contains more than 70% mesophase, it is preferable to use the temperature difference between the actual temperature T and the softening point of the asphalt (not shown), because T gIt may not be easily measured by DSC. The softening point is a simple indicator used to measure the temperature of a material flowing through a specified orifice. When the glass transition temperature and / or the solid-liquid phase transition in the intermediate phase region are unclear by DSC, the T measured by DSC... g This can produce ambiguous sample results. As the mesophase content increases, T measured using DSC becomes increasingly difficult. g It becomes more difficult because the change in heat capacity becomes less noticeable due to the widening of the band. g It is usually related to the softening point.

[0199] Figure 2 The maximum radial Hengyi fracture strain of samples 1 to 3 at different temperatures was depicted. It was observed that for sample 2, the radial Hengyi strain ε... R，C TT in the temperature range of approximately 55°C to approximately 70°C g The temperature stabilized at approximately 7, indicating that the optimal spinning temperature (T) for Sample 2 was based on the total volume of the bitumen. s The window is in the middle of 0.5% by volume. To prevent minor temperature deviations from disrupting the fiber spinning process, the spinning temperature (T) is... s ) should be in ε R，C The process should be conducted near the platform so that temperature changes result in the same material properties. If it is above TT... g Spinning at a temperature of approximately 77°C results in a severe dependence of temperature on strain, leading to potential fiber breakage or changes in fiber diameter, as the strain changes significantly with even small temperature variations.

[0200] Figure 3 This is a graph depicting the maximum axial Hengyi fracture strain of samples 1 to 3 at different temperatures. For example, the evaluation of sample 2 shows that the peak of the maximum axial strain occurs in the temperature range of approximately 50°C to approximately 65°C. g The results indicate that the optimal temperature window for this particular bitumen with 0.5 vol% mesophase still corresponds to the optimal spinning temperature (T) obtained during the measurement of maximum radial Hengyi fracture strain. s The window indicates whether and when bitumen should be spun. For example, Sample 1 should be spun at approximately 33°C to approximately 50°C. g The spinning process was carried out under these conditions, which should not be applied to spinning sample 2. It was observed that the processing window decreased with increasing heat treatment time.

[0201] Figure 4 The characteristics of sample 3 at different temperatures (TT) were described. g Critical fracture stress (Pa) and samples 1 and 2 at different temperatures TT g The maximum fracture stress (Pa) under the condition, wherein sample 2 is mesophase asphalt with a mesophase content of 0.5 vol% based on the total volume of asphalt. Figure 4The maximum stress and critical stress that the fiber can withstand before fracture are shown. The critical fracture stress of sample 3 (14 vol% mesophase, based on the total weight of pitch) demonstrates the optimal spinning temperature (T0) from approximately 50°C to approximately 70°C. s ) Window TT g This is consistent with the measurement results obtained above. The results indicate that for a material to be suitable for fiber manufacturing, it needs to be able to develop and withstand tensile stress; otherwise, fibers cannot be manufactured. The maximum value of the critical stress is the measured material limit and is only visible in sample 3. The maximum stresses obtained in samples 1 and 2 are reliably measured maximum stresses, but not material limits. It is necessary to distinguish between the measured maximum fracture stress and the critical fracture stress because the instrument's force sensitivity drops into the noise range and cannot be measured reliably. Therefore, stress values ​​obtained after this threshold are not reported. The maximum stress value is not a material limit, but an instrumental limit. If these measurements are repeated using larger diameter asphalt samples, the material limit can be obtained.

[0202] Figure 2 , 3 The measurements shown in Figure 4 indicate that the maximum strain and maximum fracture stress that the fibers can withstand before breakage are highly temperature-dependent and unique to each sample. The results from these measurements reveal the optimal temperature window for successfully spinning these pitches. Therefore, for a specific pitch with a defined volume percentage of mesophase and at a desired final radius, it is possible to measure the maximum values ​​of strain and stress, providing insight into suitable spinning conditions for producing the desired fibers. Using these findings in conjunction with the relevant mathematical relationships described herein, it is possible to provide an indication of the maximum capillary radius in the die used to manufacture carbon fibers.

[0203] Figure 5 and 6 The temperature dependence of axial and radial Henryk's strains for samples 2 (0.5 vol% mesophase) and 3 (14 vol% mesophase) is illustrated separately. Furthermore, these measurements reveal the dependence of axial Henryk's strain on radial Henryk's strain and how much the material must be stretched to achieve a given radial strain. The measurements obtained here clearly and quantitatively describe the appropriate spinning temperature (T0). s The range of the fiber's maximum radial and axial Hengyi strains, the maximum stress the fiber can withstand, the maximum achievable draw ratio (DDR), and the maximum capillary size suitable for a given pitch are determined to achieve the desired carbon fiber diameter.

[0204] Figure 5 Examples of sample 2 undergoing tensile flow at various temperatures in 1s are shown. -1 Axial Hengyi strain versus radial Hengyi strain (ε) at strain rateR The dependence of strain on strain. Each temperature represents an experiment conducted from strain value 0 to maximum strain value. Figure 5 A strong temperature dependence on the maximum axial and radial Henrykyi strains is shown, and the dependence of the axial Henrykyi strain on the radial Henrykyi strain is also illustrated. The maximum axial Henrykyi strain ranges from 0.5 to about 3.5, and the maximum radial Henrykyi strain ranges from about 0 to about 7. The effect of temperature on the axial Henrykyi strain on the radial Henrykyi strain is illustrated at 160 °C and 175 °C. At these temperatures, the maximum axial Henrykyi strain varies between 3.6 and 2.6, while the maximum radial Henrykyi strain remains constant at around 7. For sample 2, the axial Henrykyi strain is strongly temperature-dependent, while the maximum radial Henrykyi strain is relatively independent of temperature.

[0205] Figure 6 Example of sample 3 in 1s -1 Axial Henki strain (ε) at strain rate 轴向 ) for radial Hengi strain (ε R The relationship between the axial Henry strain ε of asphalt and the axial strain ε of the asphalt. 轴向 and radial Hengi strain ε R Continuous measurements were taken during the experiment. Figure 6 This indicates that both axial and radial Henryklein strain decrease with increasing temperature. The maximum axial Henryklein strain value of approximately 4 and the maximum radial Henryklein strain value of approximately 6.6 occur at temperatures between 165°C and 175°C, while at temperatures between 183°C and 185°C, the maximum axial Henryklein strain value is approximately 1.44 and the maximum radial Henryklein strain value is approximately 3.5 to approximately 4. Furthermore, Figure 6 The significant change in the dependence of axial Hengyi strain on radial Hengyi strain as the temperature increases at 183 °C and 185 °C is illustrated. A linear response to fiber breakage is obtained. However, when the temperature drops to 178 °C, a linear response with a radial Hengyi strain as high as approximately 5 is obtained. Above this radial Hengyi strain value, the axial Hengyi strain increases rapidly. As the temperature further decreases to 165 °C, an initial linear response with a radial Hengyi strain as high as approximately 1 is obtained. Above this value, the axial Hengyi strain increases rapidly to a radial Hengyi strain of approximately 2.5. As the radial Hengyi strain increases above 2.5, a linear response is observed. These results highlight the extreme temperature dependence of the rheological properties and underscore the importance of understanding these properties to generate stable spinning conditions. The results show that the Hengyi strain properties are strongly temperature-dependent and indicate that even a temperature change of 5 °C (from 178 °C to 183 °C) can have a significant impact on the minimum achievable fiber diameter. For example, for a capillary diameter of 1 mm, at ε R The smallest fiber achievable at ε = 6.6 is approximately 40 μm, while ε RA ratio of 3.5 will produce a fiber diameter of approximately 170 μm. Optimizing spinning conditions based on the rheological properties of a given pitch affects the draw ratio (DDR) and is crucial for obtaining maximum fiber performance and achieving a stable state of pitch spinning (e.g., continuous spinning). A higher DDR indicates a higher orientation of the mesophase and a higher tensile modulus along the fiber axis.

[0206] Figure 7 This is a graph depicting the average molecular weight distribution of Sample 1 (0 vol% mesophase), Sample 2 (0.5 vol% mesophase), and Sample 3 (14 vol% mesophase), where the m / z range of the detected ions is approximately from m / z 250 to 1550. With increasing mesophase content, M... W The curves remained relatively unchanged. The increase in the content of the mesophase did indeed lead to the production of low Z-type substances, but no increase in high molecular weight was observed in the mass spectrometry data generated using laser desorption / ionization.

[0207] Figure 8 This is a graph showing the Z-number distribution of the most abundant substances (hydrocarbons (HC), hydrocarbons containing one nitrogen atom (1N), hydrocarbons containing one oxygen atom (1O), and hydrocarbons containing two oxygen atoms (2O)) and samples 1 (0 vol% mesophase), 2 (0.5 vol% mesophase), and 3 (14 vol% mesophase). For clarity, molecular categories less than 0.05 wt% are not described in this paper. Hydrocarbons and oxygen-containing substances are dominant. The wide range of Z-number distributions indicates the presence of polycyclic aromatic hydrocarbons and polycyclic aromatic oxides. Figure 8 Samples 1 through 3 are low-nitrogen asphalt samples. Therefore, HC and 1O compounds dominate the class distribution, followed by 2O compounds. Sample 1 contains approximately 91.5 wt% hydrocarbons, approximately 0.2 wt% N, approximately 6.5 wt% O, and approximately 1.5 wt% 2O. Sample 2 contains approximately 94 wt% hydrocarbons, approximately 0.35 wt% N, approximately 4.5 wt% O, and approximately 0.7 wt% 2O. Sample 3 contains approximately 95 wt% hydrocarbons, approximately 0.2 wt% N, approximately 3.5 wt% O, and approximately 0.5 wt% 2O. These values ​​represent only the major molecular categories; the remaining molecular substances are a compromise between various combinations of 1 and 2, with the total percentage of N / S / O compound categories (e.g., 1N / 1S / 1O) less than 1%.

[0208] Figure 9This is a graph showing the mass-to-charge ratio (m / z) of hydrocarbon (HC), 1-oxygen (1O), and 2-oxygen (2O) substances present in Sample 1 (0 vol% mesophase), Sample 2 (0.5 vol% mesophase), and Sample 3 (14 vol% mesophase). Table 1 summarizes the details of the number of molecules determined for a given Z number range. The determined molecular strengths for the given Z number ranges of Samples 1 to 3 are summed. Untreated bitumen compositions (e.g., Sample 1) contain Z values ​​ranging from -130 to -24, while heat-treated bitumen compositions (e.g., Samples 2 and 3) contain Z values ​​ranging from -260 to -24. As exemplified in Table 1, Sample 1 contains 37.26% of Z = 6 to -50, 60.49% of Z = -51 to -100, and 2.25% of Z = -101 to -150 molecules based on total ionic strength. Sample 2, based on total ionic strength, contains 3.63% of molecules with Z = 6 to -50, 44.94% of molecules with Z = -51 to -100, 36.75% of molecules with Z = -101 to -150, 13.59% of molecules with Z = -151 to -200, and 1.09% of molecules with Z greater than -200. Sample 3, based on total ionic strength, contains 4.28% of molecules with Z = 6 to -50, 47.91% of molecules with Z = -51 to -100, 36.30% of molecules with Z = -101 to -150, 11.25% of molecules with Z = -151 to -200, and 0.26% of molecules with Z greater than -200.

[0209] Figure 9 Images of asphalt samples (samples 1 to 3) (HC, 1O, and 2O) are shown. The X-axis represents the mass-to-charge ratio (m / z). The Y-axis represents the Z-number. Molecular abundance is represented by shading of a gray pattern. Similarly, the number of molecules increases from sample 1 (0% mesophase) to sample 3 (14% mesophase). The molecular weight increase in samples 2 and 3 is driven by an increase in core size and aromatic content, which is visible in the broad Z-class distribution present after heat treatment (e.g., the treated sample has Z-class molecules exceeding -200).

[0210] Table 1

[0211]

[0212] A direct correlation between the tensile rheological behavior of three different asphalt samples and the melt spinning process was established. Figures 10A to 10C Isotropic pitch (sample 4), mesophase pitch with 3% by volume of mesophase (sample 5), and mesophase pitch with 17% by volume of mesophase (sample 6) were prepared from hydrotreated steam cracking tar.

[0213] Isotropic pitch (sample 4) was prepared as follows: steam cracking tar was hydrogenated and all liquid products (TLP) were separated by vacuum distillation to produce a distillate fraction with a temperature of 524°C to 559°C and a softening point of 74.9°C. This distillate fraction was used to manufacture anisotropic pitch (samples 5 and 6).

[0214] Anisotropic asphalt samples 5 and 6 were prepared as follows: approximately 2g of feed (i.e., the distillate fraction at 524°C to 559°C) was placed in a glass bottle and placed in a PAC. TM In a miniature carbon residue analyzer, the sample (i.e., the distillate from 524°C to 559°C) was heated to 100°C over 10 minutes under a nitrogen flow (600 mL / min). Immediately afterwards, the sample was heated to 400°C using a heating rate of 30°C / min and a nitrogen flow rate of 600 mL / min. After reaching 400°C, the flow rate was reduced to 150 mL / min, and the sample was held at 400°C for a specified time (6 hours for sample 5; 5 hours for sample 6). Following this hot soaking, the sample was cooled to ambient temperature over several hours under nitrogen at a flow rate of 600 mL / min. Sample 5 was prepared by heat treatment for 6 hours, yielding 25 wt% of the product (75 wt% volatiles), and sample 6, the mesophase sample, was prepared by heat treatment at 400°C for 5 hours, yielding 28 wt% mesophase pitch (72 wt% volatiles). For these specific samples, a five-hour run produced 17% mesophase, while a six-hour run produced 3% mesophase. These values ​​were checked twice using two different batches of material and found to be identical. The expected difference in mesophase values ​​is likely due to the variability of each run, as no mixing occurred. Although the absolute softening points of these bitumens were measured according to ASTM D3104, it was noted that the inhomogeneity of softening in these samples was observed using a hot-stage microscope. Therefore, not all bitumen softened at the measured bitumen softening point, and fragments existed that behaved as solid material at specific temperatures. This complexity affected spinning experiments by clogging the spinnerets, introducing heterogeneity into the samples and complicating the results.

[0215] Typical melt spinning process:The bitumen is spun into fibers using a custom extruder. A bitumen sample is loaded into the custom extruder and placed at the lowest test spinning temperature. After the extruder reaches the desired spinning temperature, the loaded hopper is allowed to stand for 5 to 10 minutes to ensure the bitumen sample is also at the selected spinning temperature. No filters or sieves are used on the spinning equipment to remove any particles present. Once the spinning temperature is reached, the winding spool is set to a low speed of approximately 100 to 200 mm / s, and double-sided tape is placed on the outer edge of the spool to help hold the fibers to the spool. The winding speed is gradually increased to minimize the chance of fiber breakage. The piston speed is then set (approximately 0.1 to 0.7 mm / s) and opened to extrude the bitumen from the nozzle. Once the bitumen begins to emerge from the nozzle, it is grasped with tweezers and guided onto the spinning spool. Once enough fibers have been collected, the piston is immediately closed and the spool is stopped. The fibers are then collected and the process is repeated, starting with a new temperature. The temperature is increased until all desired points have been tested.

[0216] To predict the achievable maximum draw ratio (DDR), the critical draw ratio (DDR) of samples 4 (isotropic pitch), 5 (3 vol% mesophase), and 6 (17 vol% mesophase) was evaluated at different temperatures. Therefore, the spinning conditions for samples 4, 5, and 6 were predicted by measuring the critical DDR (or strain) as a function of strain rate and temperature. The predicted spinning conditions were further tested to manufacture carbon fibers using the melt spinning technique described in the general melt spinning procedure above. Figures 10A to 10C The draw ratio (DDR) of carbon fibers produced from samples 4, 5, and 6 is shown, along with the critical DDR determined by tensile rheology. The DDR of both spinnable and non-spinnable pitch fibers is calculated from the fiber diameter (Equation 7) and the speed ratio under spinning conditions (Equation 5). Figures 10A to 10C This demonstrates that the tensile rheological results can be used as a tool to predict carbon fiber spinning conditions.

[0217] Figure 10A This is a graph depicting the critical DDR (Rapid Degree of Reduction) of sample 4 (isotropic pitch) at different strain rates and its corresponding fiber spinning data. The isotropic pitch fibers were spun near the spinning temperature (T0). s The materials were manufactured at a temperature similar to that obtained from the tensile rheological data of sample 4. The isotropic pitch-based fibers (DDR) Figure 10A (At temperatures close to spinning temperature T) sThe DDR ranges from 100 to 900 at certain temperatures, with a maximum DDR of 900 at 75°C. The critical DDR obtained from tensile rheology is in the range of 200 to 1,200. Since the critical DDR is estimated based on the failure response of a uniaxial tensile process, it can be expected that the maximum achievable DDR for isotropic pitch fibers will not exceed this value at the corresponding temperatures. The isotropic pitch fibers exhibit a DDR much lower than the critical DDR, indicating that the diameter of the isotropic pitch-based fibers can be further reduced (or the DDR can be increased) if the speed ratio (i.e., increasing the winding speed or DDR) is adjusted.

[0218] Figure 10B This is a graph depicting the critical DDR of sample 5 at different strain rates and its corresponding fiber spinning data. Figure 10C This is a graph depicting the critical DDR of sample 6 at different strain rates and its corresponding fiber spinning data. The spinning windows predicted from the tensile rheological data of samples 5 and 6 are also shown. Figure 10B and 10C The prediction window for sample 4 is ( ) Figure 10A The width is much narrower. High DDR (around 1,000 DDR) can only be produced near the softening point (e.g., at spinning temperature T). s To T s This is achievable at temperatures within the +10°C range, which is much narrower than the 30°C to 40°C spinning window observed in Sample 4. Figure 10A The fiber spinning of samples 5 and 6 was tested at three different temperatures (160°C, 180°C, and 230°C), and the calculated DDR values ​​were compared with the critical DDR values. Since 230°C was considered outside the predicted range of tensile rheology, only temperatures of 160°C and 180°C were considered. At 180°C, sample 5 could not be spun into continuous fibers. The results indicate that the viscosity of the molten bitumen was too low (approximately 224 to 292 Pas, depending on the shear rate), causing the bitumen to thin rapidly before reaching the spool. The DDR is determined by the speed ratio under spinning conditions (Equation 5). At 160°C, the DDR of the fibers spun from sample 5 was found to be close to the predicted limit. Therefore, the current winding speed is almost at the limit for manufacturing continuous fibers. Using higher winding speeds (or increasing the DDR) would lead to fiber breakage.

[0219] Table 2 summarizes the spinning conditions for sample 4.

[0220] Table 2

[0221] 1 160 71 700 Non-spinning 2 165 74 700 Spinable 3 170 76.7 700 Spinable 4 175 79.4 700 Spinable 5 175 79.4 350 Non-spinning 6 175 79.4 275 Non-spinning 7 180 82 700 Spinable

[0222] Table 2 (continued)

[0223]

[0224] Table 3 summarizes the spinning conditions for sample 5.

[0225] Table 3

[0226] 1 175 0.5 200 2 170 0.5 200 3 165 0.5 200 4 160 0.5 200 5 160 0.5 700 6 160 0.5 500 7 160 0.5 350 8 155 0.5 200 9 155 0.5 450 10 155 0.3 450 11 155 0.2 450 12 155 0.1 450 13 155 0.5 200

[0227] Table 3 (continued)

[0228]

[0229] Table 4 summarizes the spinning conditions for sample 6.

[0230] Table 4

[0231]

[0232] All documents mentioned herein are incorporated herein by reference for use in all jurisdictions where such practices are permitted, including any priority documents and / or test procedures, provided they do not contradict this document. It will be apparent from the foregoing general description and detailed description that, although the forms of the invention have been exemplified and described, many variations are possible without departing from the spirit and scope of the invention. Therefore, the invention is not intended to be limited thereto. For example, compositions described herein may not contain any components or compositions not expressly listed or disclosed herein. Any method may lack any steps not listed or disclosed herein. Similarly, the term “comprising” is considered synonymous with the term “including.” Whenever a method, composition, element, or group of elements is preceded by the transitional phrase “comprising,” it should be understood that we also contemplate the same composition or group of elements preceded by the transitional phrases “consistently constitutes,” “composes of,” “selected from,” or “is”, and vice versa.

[0233] Unless otherwise stated, all numerical values ​​used in this specification and related claims to express the amounts of components, properties such as molecular weight, reaction conditions, etc., should be understood to be modified by the term "about" in all cases. Therefore, unless explicitly stated otherwise, the numerical parameters listed in the following specification and claims are approximate values ​​that vary with the desired properties explored as embodiments of the invention are investigated. At least and without attempt to limit the application of the doctrine of equivalence to the scope of the claims, each numerical parameter should be interpreted at least based on the reported significant figures and by applying common rounding techniques.

[0234] Whenever a numerical range with a lower and upper limit is disclosed, any number falling within that range and any included range, including both the lower and upper limits, is specifically disclosed. In particular, each numerical range disclosed herein (in the form of “from about a to about b,” or equivalently “from about a to b,” or equivalently “from about a to b”) should be understood to list each numerical value and range contained within a wider numerical range. Furthermore, the terms in the claims have their simple, general meaning unless otherwise explicitly and clearly defined by the patentee. Additionally, the indefinite articles “a” or “an” used in the claims are defined herein as indicating one or more elements introduced therein.

[0235] One or more exemplary implementations are illustrated herein. For clarity, not all features of the physical implementation are described or shown in this application. It should be understood that in the development of the physical implementation of the present invention, many implementation-specific decisions must be made to achieve the developer's objectives, such as complying with system-related, business-related, governmental-related, and other constraints, which vary with implementation and time. Although the developer's efforts may be time-consuming, such efforts will be routine work for those skilled in the art and will benefit from the present invention.

[0236] Therefore, the present invention is well suited to achieving the stated objects and advantages, as well as those inherent therein. The specific embodiments disclosed above are merely exemplary, as the invention can be modified and practiced in different but equivalent ways, as will be apparent to those skilled in the art and those who have benefited from the teachings herein. Furthermore, the details of the constructions or designs shown herein are not intended to limit the scope of the invention, except as described in the following claims. Therefore, it is apparent that the specific exemplary embodiments disclosed above can be changed, combined, or modified, and all such changes are considered to be within the scope and spirit of the invention. The embodiments disclosed herein may be appropriately practiced in the absence of any elements not specifically disclosed herein and / or any optional elements disclosed herein.

Claims

1. A pitch composition suitable for spinning, said pitch composition comprising: The bitumen has a softening point SP below 400°C and is capable of achieving a radial Hengi strain of 0.7 to 10 before fracture at spinning temperatures in the range of SP-30°C to SP+80°C, wherein the bitumen has an m / z value in the range of 250 to 1,000 and contains at least 60% bitumen ion current, and wherein the bitumen contains 40% or more of Z = -51 to -100.

2. The asphalt composition according to claim 1, wherein the asphalt contains less than 4.5% by volume of mesophase based on the total volume of the asphalt.

3. The asphalt composition according to claim 1, wherein, based on the total volume of the asphalt, the asphalt contains an intermediate phase content in the range of 5% to 100% by volume.

4. The asphalt composition according to claim 1, wherein the asphalt is in 0.1 s -1 up to 100 s -1 Axial or radial Hengi strain can be achieved within a range of tensile strain rates.

5. The asphalt composition according to claim 1, wherein the asphalt composition comprises a mixture of two or more asphalts.

6. The asphalt composition according to claim 1, wherein the residual carbon content of the asphalt ranges from 20% by weight to 99% by weight, based on the total weight of the asphalt composition.

7. The asphalt composition according to claim 1, wherein the asphalt is an isotropic asphalt with a Z number distribution in the range of -250 to -10.

8. Fibers or fiber webs prepared using the bitumen composition according to any one of claims 1 to 7.

9. Oxidized fiber, carbonized fiber, graphitized fiber, oxidized fiber web, carbonized fiber web or graphitized fiber web prepared using the bitumen composition according to any one of claims 1 to 7.

10. A carbon fiber manufactured from a pitch composition, wherein the pitch composition comprises: pitch having a softening point SP below 400°C and capable of achieving a radial Hengyi strain of 0.7 to 10 before fracture at spinning temperatures in the range of SP-30°C to SP+80°C, wherein the pitch has an m / z value in the range of 250 to 1,000 and contains at least 60% pitch ion current, and wherein the pitch contains 40% or more of Z = -51 to -100.

11. A method for manufacturing carbon fiber from a pitch composition, the method comprising: Carbon fibers are manufactured from a pitch composition at temperatures within a spinning temperature range, wherein the spinning temperature range is defined by a series of different temperatures (°C) and strain rates (s). -1 The maximum radial Hengyi strain ε before fracture was measured. R To determine; and Determine the temperature range in which the maximum radial Hengyi strain ε is... R Located above the minimum process radial Hengi strain, wherein the minimum process radial Hengi strain is in the range of 0.7 to 10, wherein the bitumen has a value in the range of 250 to 1,000 m / z and contains at least 60% bitumen ion current, and wherein the bitumen contains 40% or more of Z = -51 to -100.

12. The method according to claim 11, further comprising: Using capillary size r0 and final fiber radius r f The spinneret, in which r f Within the range of 1 μm to 1,000 μm, r0 is within the range of 100 μm to 10,000 μm, and the maximum radial Hengyi strain within the spinning temperature range is at least ， Where r(t) is the radius of the extended fiber at time t.

13. The method of claim 11, wherein the bitumen composition comprises: bitumen having a softening point SP of less than 400°C at a spinning temperature in the range of SP-30°C to SP+80°C.

14. The method of claim 11, wherein the residual carbon content of the asphalt ranges from 20% by weight to 99% by weight, based on the total weight of the asphalt composition.

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