Continuous basalt fibers from hyaloclastite, and methods for manufacturing and using the same.

Abstract

This invention includes a method for producing continuous basalt fibers. [Solution] The method involves supplying a natural mineral from one or more of hyaloclastite, volcanic glass, volcanic ash, or lava rapidly cooled by water, having a basaltic, intermediate basaltic, or andesitic chemical composition, melting the mineral, and then extruding the molten material to form continuous fibers.

Description

[Technical Field]

[0001] Technical field of inventions The present invention relates to a manufacturing process for producing basalt fibers, such as continuous basalt fibers (CBFs) and short basalt fibers. The present invention relates to a manufacturing process for continuous basalt fibers that requires less energy to produce fibers with improved properties, thereby reducing CO2 emissions. [Background technology]

[0002] Background of the Invention Basalt fibers are produced by melting basalt and converting the molten material into fibers. Basalt is an igneous rock. The main energy consumption for preparing the basalt raw material for fiber production is carried out under natural conditions. Basalt continuous, staple, and super-thin fibers are produced and used. Basalt continuous fibers (BCF) are used to produce reinforcing materials and composites, textiles, and nonwoven materials. Basalt staple fibers are used to produce thermal insulation materials. Basalt super-thin fibers (BSTF) are used for the production of high-quality thermal insulation, soundproofing, and fireproofing materials. The technology for producing continuous basalt fibers (BCF) may involve a one-step process of melting, homogenizing, and extracting basalt fibers, or a two-step process where the basalt is first melted at a high temperature, then cooled to a lower temperature to extract the fibers. Further processing of BCF into materials is carried out using energy-efficient "cold technologies."

[0003] The chemical composition and mineral content of basalt vary considerably. Basalt with a wide range of properties can be used for applications such as tiles, stone castings, or staple fibers. However, for the production of continuous basalt fibers (CBF), the requirements of conventional technology become much stricter, and only a very narrow range of basalt chemical compositions can be used to manufacture CBF. These stringent requirements for composition and mineral content result in a very short list of possible basalt mines worldwide. Today, major CBF manufacturers are known to use raw materials from mines in western Ukraine and Georgia, which consist of andesitic basalts with an SiO2 content exceeding 50% by weight.

[0004] Basalt fibers are generally made from crushed basalt, a single material sourced from carefully selected quarries. Highly acidic (silica content exceeding 46%) and low iron content basalt is considered desirable for fiber production. Unlike other composite materials such as glass fiber, essentially no other materials are added during its production process. The basalt is simply washed and then melted. The production of basalt fibers requires melting the crushed and washed basalt rock at approximately 1,500°C (2,730°F). The molten rock is then extruded through small nozzles to produce continuous filaments of basalt fiber. Basalt fibers typically have a filament diameter of 10–20 μm, which is well above the respiratory limit of 5 μm, making basalt fibers a viable alternative to asbestos. It also possesses a high modulus of elasticity, resulting in a specific strength that is up to three times that of steel. Thinner fibers are typically used for textile applications, primarily for producing textiles. Thicker fibers are used in filament winding, for example, in the production of compressed natural gas (CNG) cylinders or pipes. The thickest fibers are used for pultrusion, geogrid, unidirectional fabric, multiaxial fabric production, and in the form of chopped strand for concrete reinforcement. One current application for continuous basalt fibers is the production of basalt rebar as a substitute for conventional steel rebar in the construction market.

[0005] The mineral raw materials can be melted in a furnace that may be a gas-fired or other fuel-fired furnace, or an electric arc furnace. Regardless of the type of furnace used to melt the mineral raw materials, the rest of the manufacturing process for basalt fibers is generally similar.

[0006] Currently, the natural minerals used in conventional basalt fiber manufacturing processes are crystalline basalt, particularly andesitic basalt, which are inherently crystalline and are further geologically weathered over time since their formation. Crystalline minerals have higher melting points compared to amorphous or partially amorphous minerals with similar chemical compositions, resulting in higher temperatures and longer melting times in the furnace. Furthermore, older mineral products are weathered or altered, and the iron contained in crystalline basalt is usually found as iron oxide in macrocrystals, typically existing as magnetite, hematite, or ferrite (or weathered olivine or common hornblende), which also have relatively high melting points.

[0007] Therefore, it would be desirable to provide continuous basalt fibers and processes for producing them that utilize a wider range of starting materials. Furthermore, it would be desirable to provide processes for producing continuous basalt fibers that are more energy-efficient and have relatively lower CO2 emissions. [Overview of the project] [Problems that the invention aims to solve]

[0008] Summary of the Invention The present invention satisfies the aforementioned requirements by providing improved continuous basalt fibers and an improved process for producing continuous basalt fibers. [Means for solving the problem]

[0009] In one disclosed embodiment, the present invention includes a process for producing basaltic fibers using basaltic hyaloclastite or an intermediate basaltic hyaloclastite mineral. Preferably, the basaltic hyaloclastite or intermediate basaltic hyaloclastite useful in the present invention contains, by weight, about 30 to about 57% SiO2, about 10 to about 18% Al2O3, about 8 to about 18% Fe2O3, and about 4 to about 25% CaO, more preferably the total value of Al2O3 + Fe2O3 is about 20 to about 35% by weight, and also preferably the ratio of Al2O3 to Fe2O3 is about 0.75 to about 1.50, ideally or about 1, and further preferably the ratio of SiO2 to the total value of Al2O3 + Fe2O3 is about 1.25 to 2.25, ideally about 1.5.

[0010] In another disclosed embodiment, the present invention comprises basaltic hyaloclastite or intermediate basaltic hyaloclastite mineral containing at least 30% amorphous content by weight.

[0011] In another disclosed embodiment, the present invention includes basaltic hyaloclastite or intermediate basaltic hyaloclastite mineral, which is derived from one or more minerals of hyaloclastite, water-quenched lava, volcanic ash, scoria, or pumice, having a basaltic or intermediate chemical composition and a mineral composition with at least 30% amorphous content by weight.

[0012] In another disclosed embodiment, the present invention comprises basaltic hyaloclastite or intermediate basaltic hyaloclastite mineral obtained from one or more of the minerals selected from the group consisting of hyaloclastite, lava, volcanic ash, scoria and pumice, which have a basaltic or intermediate chemical composition and a mineral composition with an amorphous content of at least 30% by weight, wherein said hyaloclastite, lava, volcanic ash, scoria and pumice are quenched with water.

[0013] Accordingly, it is an object of the present invention to provide an improved process for producing continuous basalt fiber with reduced CO₂ emissions.

[0014] Another object of the present invention is to provide a process for producing continuous basalt fiber that uses less energy.

[0015] A further object of the present invention is to provide an improved process for producing continuous basalt fiber that can reduce wear and tear on manufacturing equipment such as fiber extrusion dies.

[0016] Another object of the present invention is to provide a process for producing continuous basalt fiber which, compared with the prior art, requires lower temperature and shorter residence time in a melting furnace, thereby reducing overall emissions and increasing the production capacity of the melting furnace.

[0017] These and other objects, features and advantages of the present invention will become apparent upon consideration of the following detailed description of the appended claims and the disclosed embodiments. Mode for Carrying Out the Invention

[0018] Detailed description of the disclosed examples Hyaloclastite is typically a tuff-like breccia rich in black volcanic glass, formed during volcanic eruptions underwater, under ice, or where surface flows reach the sea or other bodies of water. It has the appearance of angular fragments ranging in size from about 1 millimeter to several centimeters. Larger fragments can also be found, up to the size of pillow lava. Without limitation, several minerals, including sideromelane, tachylyte, palagonite, olivine, pyroxene, hornblende, biotite, hypersthene, feldspathoids, plagioclase, and calcite, are found within hyaloclastite masses. Fragmentation can occur by explosive eruption processes or by substantially non-explosive processes associated with spalling of pillow basalt rinds due to thermal shock or chill shattering of molten lava. Water-quenched basalt glass is called sideromelane and is a transparent, pure variety of glass that lacks the extremely fine iron oxide crystals found in the more common opaque basalt glass called tachylyte.In hyaloclastite, these glassy fragments are typically surrounded by a matrix of yellow-to-brown palagonite, which is a waxy substance formed from the hydration and alteration of sideromelane and other minerals. Depending on the type of lava, the cooling rate, and the amount of lava fragmentation, volcanic glass (sideromelane) particles may be mixed with other volcanic rocks and crystalline minerals such as olivine, pyroxene, magnetite, quartz, plagioclase, and calcite.

[0019] Hyaloclastites are typically found within or around subglacial volcanoes such as tuyas, which are a unique type of volcano characterized by flat-topped and steep-sided peaks, formed when lava erupts beneath or through thick glaciers or ice sheets. Ridges of hyaloclastites are also called tindars, and subglacial mounds are called tuyas or mobergs. They were formed by subglacial volcanic eruptions during the last glacial period. Subglacial mounds are a type of subglacial volcano. This type of volcano forms when lava erupts beneath a thick glacier or ice sheet. The magma that formed these volcanoes was not hot enough to completely melt the glacial ice covering the upper layers into a vertical tube. Instead, it formed hyaloclastite and pillow lava deep within the glacial ice field. As the glacier retreated, subglacial volcanoes with unique shapes, resulting from being trapped within the glacial ice, became visible. Subglacial volcanoes are relatively rare globally and are limited to areas that were once covered by continental ice sheets and where active volcanism existed during the same period. Volcanic eruptions currently occurring beneath glaciers may similarly form hyaloclastite.Hyaloclastite tuff-like breccias are pyroclastic rocks containing glassy juvenile clasts within a fine-grained matrix primarily composed of glassy shards. Hyaloclastite breccias are typically products of phreatomagmatic eruptions, particularly those associated with the eruption of magma into a water body, but they are also formed by the fracturing of rapidly cooled magma. They are often formed from basaltic magma and are associated with pillow lavas and sheet flows. Furthermore, any other type of lava, such as intermediate or andesitic lava, can form hyaloclastite under similar rapid cooling or quenching conditions.

[0020] Occasionally, subglacial and underwater eruptions may produce releases of volcanic ash that are ejected into the atmosphere and can subsequently fall and re-land on the Earth's surface. While the definition of volcanic ash may be debatable, different experts in the field of geology may sometimes refer to fine volcanic particles as "volcanic ash." It is also possible that subglacial or underwater eruptions were caused by magma containing large amounts of gas trapped within the lava. Large amounts of gas elution may create minerals with a bulk density similar to scoria or pumice, and with very high porosity or vesicular structure.

[0021] Intermediate basaltic hyaloclastite minerals or volcanic basaltic hyaloclastites, such as pumice, scoria, volcanic ash, and hyaloclastites rapidly cooled by water, can be classified based on their silica content, such as andesitic (approximately 57–63 wt% SiO2), intermediate (approximately 53–57 wt% SiO2), and basaltic (less than 53 wt% SiO2). However, for the purposes of this invention, the basaltic range begins at approximately 40% SiO2 and the andesitic range ends at 63%–65% SiO2.

[0022] Basaltic hyaloclastite, volcanic ash, or pumice generally contains 40% to 53% by weight of silica (SiO2), which is present in amorphous or crystalline form, or a combination thereof, essentially in calcium-rich calcic plagioclase and pyroxene (usually augite), with or without olivine. In addition to silica, basaltic hyaloclastite, volcanic ash, or pumice generally contains about 10% to 18% by weight of Fe2O3, about 6% to 18% by weight of CaO, about 5% to 15% by weight of MgO, and other elements in varying proportions. Intermediate basaltic hyaloclastite, volcanic ash, or pumice generally contains about 53% to 57% by weight of silica (SiO2). Intermediate basaltic hyaloclastite, volcanic ash, or pumice generally contain, in addition to silica, about 5% to 12% by weight of Fe₂O₃, about 6% to 10% by weight of CaO, about 3% to 10% by weight of MgO, and other elements in varying proportions. Basaltic hyaloclastite, volcanic ash, or pumice may also contain biotite, rhodochrosite (a type of orthorhombic pyroxene), and feldspar. The average specific density (specific gravity) of basaltic hyaloclastite, volcanic ash, or pumice is about 2.7–3.0 g / cm³. 3 That is the case.

[0023] Andesite is an abundant igneous (volcanic) rock with an intermediate composition, exhibiting aphanitic to porphyritic textures. In a general sense, it is an intermediate type between basalt and dacite. Andesitic hyaloclastite, volcanic ash, or pumice contains silicon dioxide (SiO2) in the range of about 57% to about 63% by weight. For the purposes of this invention, andesite is defined as having an SiO2 content of up to 65%. In addition to silica, andesitic hyaloclastite, volcanic ash, or pumice generally contain about 5% to about 10% by weight of Fe2O3, about 5% to about 10% by weight of CaO, about 3% to about 8% by weight of MgO, and other elements in varying proportions.

[0024] Most importantly, hyaloclastite or lava deposits rapidly cooled by water are rare in that, despite their young geological age, they show little to no alteration of the amorphous and / or crystalline matrix. In contrast, crystalline basalt used in state-of-the-art fiber forming processes, while geologically older mineral formations, results in weathered or altered crystals that require more energy to melt at higher temperatures compared to the hyaloclastite dissolution process.

[0025] Iron oxide found in crystalline basalt or crystalline andesitic basalt lava used in state-of-the-art CBF (Continuous Basalt Fiber) production is trivalent iron (Fe). 3+), or iron(III)(Fe2O3), magnetite, or hematite. Iron oxide containing altered or weathered amphibole, magnetite, or hematite may remain in the melt composition when reacting with platinum-rhodium bushings used in conventional extrusion processes. This can cause excessive wear of the bushings, resulting in associated repair and replacement costs. Furthermore, if crystalline or microcrystalline iron remains in the melt, such crystals may cause fracture in the continuous fiber extrusion / tensile process, resulting in process shutdown and the need to restart the process. Alternatively, if the iron oxide crystals present in the melt do not cause fracture during the extrusion / tensile process of the continuous fibers, then the iron oxide crystals present within the continuous fibers act as "pinches," weak points, or structural fracture points within the fibers, causing breakage under load, resulting in weaker fibers overall. Current state-of-the-art processes using crystalline basalt or crystalline andesitic basalt minerals, which contain oxidized iron crystals and are likely to be geologically weathered or altered, require higher melting temperatures to completely dissolve and homogenize the iron and quartz in the melt compared to basaltic or intermediate hyaloclastite minerals where iron exists in an unoxidized state or is contained in an amorphous state, like most elements. Current cutting-edge technologies have attempted to solve this problem by using intermediate or andesitic basaltic minerals with reduced iron content to the minimum still necessary to achieve the desired properties, such as less than 10% iron content in intermediate basalt and less than 8% iron content in andesitic basalt. However, selecting minerals with lower iron content, such as andesitic basalt, results in minerals with higher silica content, which in turn means that the silica content contains more quartz crystals.Quartz crystals also present similar challenges to oxidized iron crystals, requiring relatively high temperatures to melt and dissolve them into a melt composition in order to produce a sufficiently amorphous melt composition for pulling or extruding fibers. It is believed that all current continuous basalt fibers are made by melting crystalline intermediate basalt or andesitic basalt containing at least one of oxidized iron type crystals or quartz or both. Most basalt deposits have a fairly high iron content, the majority of which is trivalent iron (Fe₂). 3+ ) or an oxidized form of iron(III) oxide (Fe2O3). On the other hand, any type of lava rapidly cooled with water, such as hyaloclastite, contains iron ions or Fe2O3 (Hematite). 3+ It contains little to no iron oxidized to this form, and almost all of the iron is Fe, known as ferrous iron (divalent iron). 2+ It exists in this form. However, iron found in minerals of the lava type that have been rapidly cooled by water, such as hyaloclastite, exists in an amorphous or partially amorphous and partially microcrystalline matrix, where the melting point is lower, and it is also present as ferrous iron (divalent iron) or Fe 2+ This avoids the iron-related challenges found in macrocrystalline minerals such as basalt, which are currently used in practice. Furthermore, compared to the lower iron content found in andesitic basalt, selecting basaltic hyaloclastite or intermediate basaltic hyaloclastite CBF results in stronger fibers, as the iron content in basaltic hyaloclastite exceeds 10 to 12%, significantly higher than the 8% iron content of currently available, state-of-the-art continuous basalt fibers. Therefore, ferrous iron (divalent iron) Fe derived from lava rapidly cooled by water is also important. 2+ In terms of mechanical wear, potential fiber extrusion fracture, or reduction in fiber strand strength, the iron(III) oxide or Fe currently used in crystalline basalt is problematic. 3+Does not cause various problems such as those induced by ions. Furthermore, basaltic hyaloclastite and intermediate basaltic hyaloclastite do not contain any quartz crystals, which can further lower the melting point of the mineral composition for extruding fibers.

[0026] U.S. Patent No. 9,771,294 proposes a method that uses a two-stage process, in which basalt is first melted at a high temperature such as 2000°C to ensure that all crystals and microcrystals are completely melted in the melt, and then cooled to a lower temperature for drawing fiber strands therefrom. The present invention uses a mineral raw material mix having a composition consisting of amorphous material, or a combination of amorphous material and microcrystals, which results in a target melt temperature far lower than the temperature required in U.S. Patent No. 9,771,294.

[0027] In the conventional production of basalt fibers, basalt contains Fe such as Fe2O3 3+ It is important to determine whether the iron-containing crystals are contained, and to separate iron-rich basalt particles from iron-poor basalt particles. In the case of basaltic hyaloclastite or intermediate basaltic hyaloclastite, iron is contained in an amorphous or microcrystalline matrix, where most or all of the iron is divalent iron (Fe 2+ ) form, and there is little or no iron in the form of trivalent iron (Fe 3+ ) such as Fe2O3 (hematite). In prior art basalt fiber extrusion equipment, wear of platinum-rhodium bushings is a significant cost factor in the basalt fiber production process, and reducing such wear and damage is essential to improving the production process and reducing overall cost. Therefore, the use of minerals with reduced or no content of Fe2O3 (iron(III) oxide / hematite) represents a significant improvement in the ability to extrude continuous basalt fibers. Water-quenched lavas, such as basaltic hyaloclastite and intermediate basaltic hyaloclastite, solve this problem, because most of the iron contained therein is Fe2+ This is because it is of a certain type and exists in an amorphous or microcrystalline matrix, or a combination thereof, in which iron is not directly bonded to oxygen. Furthermore, while basaltic hyaloclastite and intermediate basaltic hyaloclastite are rare, they are more common and abundant in certain parts of the world than the extremely rare crystalline basalt from Ukraine, Russia, and Georgia, which is currently used to produce continuous basalt fibers.

[0028] Another aspect of the mineral sorting process discovered by this invention is that not all iron-containing crystals melt at the same temperature. The melting point of iron as a metal, and the melting point of iron oxide crystals such as ferrite, hematite, or magnetite, is approximately 1,500°C. Olivine crystals are primarily composed of iron. 2+ Although it tends to be present in this state, depending on the weathering state of the deposit and other factors, oxidized Fe may be present. 3+ It is contained in this state. Weathered or altered olivine containing ferrite has a melting point closer to that of ferrite, higher than that of unaltered olivine. Basaltic hyaloclastite or intermediate basaltic hyaloclastite may contain small amounts of olivine, but in a microcrystalline matrix. Unoxidized Fe 2+ Olivine containing iron oxide has a melting point of 1,200°C, while iron oxide Fe 3+ Olivine containing Fe has a higher melting point than 1,400°C. Pyroxene crystals are Fe 2+It contains iron in this form. Microcrystalline pyroxene found in lava rapidly cooled by water does not contain oxidized iron. Hornblende crystalline minerals are similar to olivine described above, and altered or weathered hornblende will contain oxidized iron, requiring a higher temperature to melt than unaltered hornblende. The melting points of pyroxene and hornblende are lower than those of olivine, approximately 1,000°C to 1,100°C. In other words, current state-of-the-art technology involves selecting minerals with the lowest iron content (less than 10%, generally less than 8%) and melting them at temperatures above 1,450°C, typically reaching or exceeding 1,600°C, thereby extracting Fe 3+ To reduce the presence of crystals containing oxidized iron, the present invention provides an amorphous matrix or a combination matrix of amorphous and microcrystalline materials containing Fe 2+ While minerals with the highest iron content in their respective states (which may be shown by XRF analysis as either FeO or Fe2O3) are used, iron-containing crystals such as unaltered olivine or unaltered common hornblende have considerably lower melting points than iron oxide-containing macrocrystals such as ferrite, hematite, magnetite, altered olivine, or altered common hornblende.

[0029] A current concern with state-of-the-art processes is the crystallization of fibers that occurs while the extruded fiber strand is being pushed through dies or bushings, or as it cools afterward. The cooling process from the melting temperature to a temperature suitable for winding onto a spool can induce crystal formation within the fiber strand. Therefore, it is important or desirable that the melt contains no crystals or microcrystals, as this sows the seeds for higher crystal growth during the cooling process of the fiber strand. In other words, it is important that the melt composition when drawing fibers is largely amorphous, i.e., completely free of macrocrystals and microcrystals (crystal or microcrystal content less than 20% by weight). The chemical composition of the minerals to be melted and the melting process are optimized to minimize or eliminate the potential for crystal formation during the cooling process, because crystal formation within fiber strands may cause fracture within the continuous fibers or reduce the strength of the fiber strands. Current state-of-the-art technology has primarily attempted to solve this problem by selecting minerals with a chemical composition of andesitic basalt with a limited amount of iron content to prevent crystal formation, as iron oxide crystals are a major factor in harmful crystal formation during the cooling of extruded fiber strands, although crystal formation usually occurs in the form of olivine. This invention solves this problem related to the prior art by using minerals that have a lower melting point and contain amorphous or amorphous and microcrystalline combinations. Ideally, the melting point of the mineral composition used to produce continuous fibers in this invention is lower than the crystal formation temperature of olivine, which can begin at 1,400°C and possibly higher.The present invention involves selecting minerals in an amorphous or amorphous-microcrystalline state, having a basaltic, intermediate or andesitic chemical composition, and possessing a relatively lower melting point than conventional technologies, such as lava rapidly cooled by water, thereby reducing energy consumption, and the minerals being Fe. 3+ It does not contain iron ions or iron oxide and / or quartz. By selecting minerals consisting of amorphous or amorphous and microcrystalline materials, the melt composition reaches an amorphous state at lower temperatures and in shorter times, thereby reducing energy consumption. Furthermore, at lower temperatures, the formation of iron crystals or other types of crystals within the extruded and cooled fiber strands is reduced or eliminated, thereby creating fiber strands with a higher amorphous content, greater uniformity and tensile strength, and improved physical properties.

[0030] As used herein, the term "un-oxidized iron" refers to Fe 2+ This refers to the ion or ferrous iron, and is detected as FeO or Fe2O3 in XRF analysis (X-ray fluorescence analysis), or the ion is Fe 2+ As other more complex compounds, or as ions of Fe 2 It may be in the form of any crystal, microcrystalline or amorphous mineral or matrix that is compounded with other elements or in an irregular / amorphous state, such as pyroxene, olivine, and common hornblende. In these minerals, Fe 2+ It is not directly bonded to an oxygen atom. Therefore, in this sense, Fe 2+ It is in an unoxidized state as defined in this invention. Examples of minerals containing unoxidized iron include lava rapidly cooled with any water, and having a basaltic, intermediate basaltic, or andesitic chemical composition. Unoxidized ferrous iron (Fe) 2+ Examples of ion-containing crystals or microcrystals include pyroxene group, unaltered olivine, unaltered common hornblende, and similar materials.

[0031] As used herein, the term "oxidized iron" refers to Fe 3+ Or the ion is Fe 3+ This refers to any crystal, mineral, or matrix that is in the form of iron oxide or that is directly bonded to or reacted with oxygen, such as Fe2O3. Examples of minerals containing iron oxide include ferrite, hematite, magnetite, weathered or altered olivine, weathered or altered common hornblende, and similar materials.

[0032] The terms “basaltic hyaloclastite,” “intermediate basaltic hyaloclastite,” or “andesitic hyaloclastite” as used herein refer to hyaloclastite, lava, volcanic ash, and pumice of any origin, as long as they have been rapidly cooled by water. That is, unless otherwise specified, regardless of the mineral source from which they originate, they have an amorphous content of approximately 30% to 100% by weight and a crystalline content of 0% to approximately 70% by weight, where the crystalline matrix consists of microcrystals and contains Fe 2+ Iron in its morphology refers to iron present in an amorphous or microcrystalline matrix. That is, iron found in microcrystals is in an irregular / amorphous state, or bonded to other elements but not directly to oxygen. The above range also includes all intermediate values.

[0033] As used herein, the term “substantially free” means that the content is less than approximately 2% by weight. For example, a basaltic hyaloclastite that is substantially free of ferrite, hematite, magnetite, altered or weathered olivine, or altered or weathered common amphibole means that the basaltic hyaloclastite contains less than 2% by weight of ferrite, hematite, magnetite, altered or weathered olivine, or altered or weathered amphibole.

[0034] Basaltic or mafic hyaloclastites, volcanic ash, or pumice generally contain about 6% to 18% by weight of uncarbonated calcium, found with amorphous or a combination of amorphous and microcrystalline matrices. As the amount of SiO2 increases from the lower limit of 40% by weight in basaltic hyaloclastites, volcanic ash, scoria, or pumice to the andesitic and dacitic silica range, uncarbonated calcium, magnesium, and iron decrease to the rhyolitic range where uncarbonated calcium is substantially unavailable.

[0035] In conventional techniques, the chemical composition and mineralogical characteristics (petrology) of basalt determine its ability to form fibers; therefore, these properties must conform to specific criteria. General limitations (ranges) of oxide content are shown in Table 1 below. Depending on limited or conventional experience, different sources yield different ranges of equivalent oxide content.

[0036] [Table 1]

[0037]

number

[0038] The optimal chemical composition for the production of continuous basalt fibers is thought to be one in which the acidity is in the range of 3 to 6.

[0039] Acidity can be adjusted (changed) by adding various oxides, depending on the chemical composition of the starting minerals and the target chemical composition. For example, the addition of CaO and / or MgO decreases acidity. For example, the addition of Al2O3 and / or SiO2 increases acidity. For example, for lava with low acidity, lava with high silica content, such as pumice and perlite, can be added to increase the acidity of the melt. Silica fume can be used in particular to increase acidity. In the case of basaltic hyaloclastite with low acidity, which may not be optimal for CBF production, it is desirable to use amorphous silica or aluminosilicate to increase acidity without adding any new crystalline components.

[0040] Viscosity modulus is another important factor in determining the optimal minerals and their preparations for producing suitable basalt fibers. Viscosity modulus M v It is defined by the following formula:

number

[0041] The viscosity of basalt melt is another crucial factor in the production of basalt fibers. One of the most important properties of basalt that determines its suitability for producing continuous fibers is its viscosity η (Pascal-second Pas). Viscosity must be within a certain range to allow for optimal fiber production. The viscosity η(T) of basalt melt can be calculated using a simple equation that has been empirically derived. The variables in this equation are the weight % composition, temperature T, and acidity M. a That is the case.

number

[0042] Other methods for calculating the viscosity of basalt melt are available from open sources. Oxides such as silica (SiO2), alumina (Al2O3), magnesium oxide (MgO), and trivalent iron (Fe2O3) increase viscosity, but their iron oxides have detrimental effects on the mechanical components of extruders. Alkali metal oxides such as K2O and Na2O, and divalent iron (FeO) decrease viscosity.

[0043] In prior art, in order to begin selecting suitable minerals for producing continuous basalt fibers, their chemical composition must meet the elemental range shown in Table 1 above. Secondly, the acidity (M a ) and viscosity coefficient (M v The following must be determined and adjusted as necessary to meet a reasonable range for the production of basalt fibers: the acidity should be in the range of 3 to 6, and the viscosity coefficient should be in the range of 2 to 3.

[0044] Tables 2 and 3 below show the chemical oxide analysis of basaltic hyaloclastite or intermediate basaltic hyaloclastite according to the present invention, such as pumice-based minerals, volcanic ash, or hyaloclastite from various sources, and also show the levels of CaO as well as MgO and FeO, associated with the SiO2 content. The oxide values ​​of Ca, Mg, Fe, Na, and K shown in Table 3 below are examples of desirable oxide levels for the production of basaltic fibers according to the present invention.

[0045] [Table 2]

[0046] [Table 3]

[0047] In the examples above, all except the PTR example exhibit desirable properties for use as a basaltic hyaloclastite or intermediate basaltic hyaloclastite mineral to be mixed with limestone for the production of basaltic fibers according to the present invention.

[0048] All of the examples above are minerals that the inventor collected, processed, and analyzed from various locations around the world. The three-letter abbreviations represent the source of the minerals.

[0049] Furthermore, it is important that the ratio of Si to the sum of Fe and Al (SiO2 / (Fe2O3+Al2O3)) is preferably about 1.5, or more preferably about 1.25 to about 2.25, which will improve the melt properties.

[0050] The sodium equivalent (Na2O + 0.658K2O) of the mineral according to the present invention may be relatively high, which can be a desirable property for the manufacture of alkali-resistant fibers.

[0051] Mineralogy XRD data confirms some of the above points, namely the substantial absence of quartz. The absence of quartz offers further advantages compared to the quartz found in basalt currently used in practice. Quartz is a hard mineral that requires high specific energy and a higher melting temperature to melt. It is extremely important to note that the basaltic hyaloclastite or intermediate basaltic hyaloclastite according to the present invention is substantially free of quartz, which brings specific advantages to the basalt fiber manufacturing process, whereas conventional Ukrainian and Georgian basalt currently used in the production of basalt fibers contains varying amounts of quartz. Basaltic hyaloclastite or intermediate basaltic hyaloclastite would not only improve the uniformity and efficiency of the melt, but would also contribute to reducing CO2 emissions during the melting process, although it contains CaO distributed between feldspar and amorphous materials, even if only a small amount, which would be derived from carbonates, thereby lowering the melt temperature and reducing energy consumption.

[0052] The first three samples in Tables 2 and 3 above, LS36-10, TDR, and SND, exhibit a basaltic chemistry with approximately 45-47% SiO2 and 14-17.6% Al2O3, resulting in a total silica and alumina content of 59.29-63.03%. The oxide values ​​of these samples fall within the lower range of the chemical composition required for basalt fiber production. To increase acidity, alumina and silica may be added, preferably in an amorphous state, such as aluminum oxide, silica fume, perlite, pumice, obsidian, dacitic hyaloclastite or rhyolitic hyaloclastite, and similar materials, with the elements present in a predominantly amorphous or a combination of amorphous and microcrystalline forms. To further adjust melt properties such as viscosity, viscosity coefficient, and surface tension, one or more other minerals or elements such as boron, boro salts, boron oxide, chromium oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, gallium oxide, rubidium oxide, strontium oxide, zirconium oxide, rubidium oxide, niobium oxide, vanadium oxide, fluoride, and chlorite may be added in amounts of less than 1% by weight each. Furthermore, to adjust viscosity properties, one or more elements such as lanthanum oxide, lanthanides, boron, and borax may be added in amounts of less than 3% by weight each.

[0053] The following three samples, AB, BKP, and PVT, have similar basaltic chemical compositions, with a total of 59.69–63.9% total silica and alumina, and 28.94–34.61% total noncarbonate calcium, magnesium, and iron oxides. The oxide values ​​of these samples are within the range of chemical composition required for basalt fiber production. To increase acidity, alumina and silica may be added, preferably in an amorphous state, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic hyaloclastite or rhyolitic hyaloclastite, and similar materials, in which the elements are mostly amorphous or in a combination of amorphous and microcrystalline forms. To reduce acidity, calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide, preferably in an amorphous state, such as burnt lime and burnt dolomitic lime, may be added to these samples. To further adjust melt properties such as viscosity, viscosity coefficient, and surface tension, other minerals or elements, such as boron, boro salts, boron oxide, chromium oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, gallium oxide, rubidium oxide, strontium oxide, zirconium oxide, rubidium oxide, niobium oxide, vanadium oxide, fluoride, and chlorite, may be added in amounts of less than 1% by weight each. Furthermore, to adjust viscosity properties, one or more of lanthanum oxide, lanthanides, boron, borax, etc., may be added in amounts of less than 3% by weight each. If desired, zirconium oxide (ZrO2) can be added in an amount of up to approximately 12% by weight to improve alkali resistance and other properties.

[0054] The following two samples, RDF and THR, exhibit similar basaltic chemical compositions, with slightly higher total amounts of silica and alumina (65.6–67.38%) and total amounts of non-carbonate calcium, magnesium, and iron oxides (25.91–27.14%). The oxide values ​​of these samples are within the range of chemical composition required for the production of basaltic fibers. To increase acidity, alumina and silica may be added, preferably in an amorphous state, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic hyaloclastite or rhyolitic hyaloclastite, and similar materials, where the elements are mostly in amorphous or a combination of amorphous and microcrystalline forms. To reduce acidity, calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide, preferably in an amorphous state, such as burnt lime and burnt dolomitic lime, may be added to these samples. To further adjust melt properties such as viscosity, viscosity coefficient, and surface tension, other minerals or elements, such as boron, boro salts, boron oxide, chromium oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, gallium oxide, rubidium oxide, strontium oxide, zirconium oxide, rubidium oxide, niobium oxide, vanadium oxide, fluoride, and chlorite, may be added in amounts of less than 1% by weight each. Furthermore, to adjust viscosity properties, one or more of lanthanum oxide, lanthanides, boron, borax, etc., may be added in amounts of less than 3% by weight each. If desired, zirconium oxide (ZrO2) can be added in an amount of up to approximately 12% by weight to improve alkali resistance and other properties.

[0055] The following sample VCR has a slightly high total silica and alumina content of 69.81%, giving it an intermediate to andesitic chemical composition. The oxide values ​​of this sample fall within the range of chemical composition required for basalt fiber production. To increase acidity, alumina and silica may be added, preferably in an amorphous state, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic hyaloclastite or rhyolitic hyaloclastite, and similar materials, where the elements are mostly amorphous or a combination of amorphous and microcrystalline forms. To decrease acidity, calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide, preferably in an amorphous state, such as burnt lime and burnt dolomitic lime, may be added to these samples. To further adjust melt properties such as viscosity, viscosity coefficient, and surface tension, other minerals or elements, such as boron, borodic salts, boron oxide, chromium oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, gallium oxide, rubidium oxide, strontium oxide, zirconium oxide, rubidium oxide, niobium oxide, vanadium oxide, fluoride, and chlorite, may be added in amounts of less than 1% by weight each. Furthermore, to adjust viscosity properties, one or more of lanthanum oxide, lanthanides, boron, borax, etc., may be added in amounts of less than 3% by weight each. If desired, zirconium oxide (ZrO2) may be added in amounts up to about 12% by weight to improve alkali resistance and other properties.

[0056] The final sample PTR has a slightly higher andesitic chemical composition with a total silica and alumina content of 73.44%. The oxide values ​​of this sample fall within the upper range of the chemical composition required for basalt fiber production, but within the range required for some applications outside that range. To reduce acidity, calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide, preferably in an amorphous state, such as burnt lime and burnt dolomitic lime, can be added to these samples. To further adjust melt properties such as viscosity, viscosity coefficient, and surface tension, other minerals or elements, such as boron, borodic salts, boron oxide, chromium oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, gallium oxide, rubidium oxide, strontium oxide, zirconium oxide, rubidium oxide, niobium oxide, vanadium oxide, fluoride, and chlorite, may be added in amounts of less than 1% by weight each. Furthermore, to adjust viscosity properties, one or more of lanthanum oxide, lanthanides, boron, borax, etc., may be added in amounts of less than 3% by weight each. If desired, zirconium oxide (ZrO2) may be added in amounts up to about 12% by weight to improve alkali resistance and other properties.

[0057] As reported here, the chemical composition was measured by XRF (X-ray fluorescence) spectroscopy, a non-destructive analytical technique used to determine the elemental composition of a material. XRF analyzers determine the chemical properties of a sample by measuring the fluorescent (or secondary) X-rays emitted from the sample when it is excited by a primary X-ray source. Each element present in the sample produces a set of characteristic fluorescent X-rays ("fingerprints") unique to that particular element, which is why XRF spectroscopy is an excellent technique for the qualitative and quantitative analysis of material composition. It should be noted that XRF analysis quantifies major elements in terms of oxides, and the oxide representation does not necessarily accurately reflect the chemical form in which those elements actually exist. Specifically, iron is shown as FeO or sometimes Fe2O3, while it may exist in different chemical forms within minerals, such as being in an unorganized / amorphous state, or bonded to other metals or elements but not to oxygen. The chemical analysis reported here is a total oxide-based XRF scan, which is known and used in the art to determine the chemical composition of minerals.

[0058] Sample preparation for XRF can be achieved using one of two different methods: powder pressing and fused glass disks. Pressed powder samples are typically ground in a tungsten carbide ring and puck mill with a binder to provide a packed powder mount that reduces particle size and remains intact for transport and analysis. Advantages of this preparation method include simplicity and better detection limits, while disadvantages include what is known as the "mineralogical effect," which requires a similar matrix between the unknown sample and the calibration standard sample (bracketing method) to enable a calibration curve.

[0059] In the case of basaltic hyaloclastite, intermediate basaltic hyaloclastite, or andesitic hyaloclastite minerals, pumice, volcanic ash, and lava rapidly cooled by water may contain microcrystals of calcium, iron, alumina, and silicates, as well as clinopyroxene (Ca(Mg,Fe,Al,Ti)(Si,Al)2O6), calcium plagioclase feldspars (Na,Ca)Al(Si,Al)3O8), olivine (Fe,Mg)2SiO4, and common hornblende (Ca,Na). 2-3 (Mg,Fe,Al)5(Al,Si)8O 22 Other minerals such as (OH,F)2 are examples of microcrystalline minerals containing uncarbonated elements such as calcium, magnesium, potassium, sodium, and ferrous iron, which can be used to melt at lower temperatures in the basalt fiber manufacturing process of the present invention, resulting in reduced emissions and reduced energy consumption. Iron may be present in either the amorphous matrix or in the microcrystals of microcrystalline clinopyroxene Ca(Mg,Fe,Al,Ti)(Si,Al)2O6 and / or olivine (Fe,Mg)2SiO4.

[0060] Table 4 below shows examples of hyaloclastite, lava, volcanic ash, or pumice containing varying amounts of amorphous and crystalline components. Samples 14 and 15 are rhyolitic glasses such as perlite, with a CaO content of less than 1%, while the basaltic hyaloclastites of samples 1-13 have CaO content ranging from 9% to 16%.

[0061] [Table 4]

[0062] Samples 1 to 13 in Table 4 above have compositions that are desirable for use in accordance with the present invention to form continuous basalt fibers.

[0063] When using basaltic hyaloclastite or intermediate basaltic hyaloclastite, most, if not all, of the elements are contained within the amorphous matrix. Therefore, concerns from minerals in conventional manufacturing processes are absent or significantly reduced. The crystals found in hyaloclastite are at best microcrystalline, not the large crystal types found in conventional basalt. Furthermore, because some or most of the matrix in basaltic hyaloclastite or intermediate basaltic hyaloclastite is in amorphous form, the amount of crystalline material is reduced in both range and percentage. Thus, these are reduced to plagioclase, pyroxene, and amphibole. Depending on the amorphous content and the resulting crystalline composition, the chemical composition of the raw materials will determine the most preferable type of product to manufacture. In particular, hyaloclastite with an amorphous content of 40-80% by weight is preferred for the production of continuous basalt fibers. As another example, a formulation with a 30% amorphous content may be best suited for the production of staple fibers. The factor to consider here is that the amorphous and microcrystalline content of the formulation found in hyaloclastite makes the melt phase more uniform, where the amorphous material melts more uniformly with the microcrystals at a certain temperature, producing a molten composition with an amorphous content of about 80%, preferably about 88%, more preferably about 90%, most preferably about 95%, and ideally completely or 100% amorphous. In the case of conventional basalt, the numerous crystals found within it, and the fact that these crystals, as shown in the table above, are relatively large and each has its own melt temperature, creates a challenge in achieving a suitable melt. It is precisely for this reason that so many types of basalt around the world have been tried and failed in the production of basalt fibers.With respect to the hyaloclastite according to the present invention, the presence of a relatively large amorphous content is desirable, and the crystalline portion being microcrystalline reduces the total number of crystals present in the hyaloclastite, thereby reducing variability in the optimization of the melt. In other words, instead of using basalt containing 5 to 12 types of crystalline minerals and having relatively large crystal types, using 100% amorphous lava quenched with crystal-free water, or a combination of amorphous and 1 to 4 types of microcrystalline, greatly simplifies the optimization of the melt and, as a result, improves the manufacturing process of basalt fibers. The use of hyaloclastite according to the present invention therefore improves the uniformity and efficiency of the melt, thereby lowering the melting temperature, reducing energy consumption, and consequently reducing emissions such as CO2.

[0064] To increase acidity, alumina and silica, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic or rhyolitic hyaloclastite and similar materials, which contain elements mostly in amorphous or combinations of amorphous and microcrystalline forms, may be added, preferably in an amorphous state. The amount of these elements or oxides is calculated to reach up to about 20% by weight of the main components of the hyaloclastite, in order to satisfy the target formulation chemical composition. To decrease acidity, calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide may be added to these samples, preferably in an amorphous state, such as quicklime and calcined dolomite lime. The amount of these elements or oxides is calculated to range up to about 20% by weight of the main components of the hyaloclastite, in order to satisfy the target formulation chemical composition. To further adjust melt properties such as viscosity, viscosity coefficient, and surface tension, other minerals or elements, such as boron, borodes, boron oxide, chromium oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, gallium oxide, rubidium oxide, strontium oxide, zirconium oxide, rubidium oxide, niobium oxide, vanadium oxide, fluorides, and chlorite, one or more of these may be added in amounts of less than 1% by weight. Furthermore, to adjust viscosity properties, one or more of lanthanum oxide, lanthanides, boron, borax, and similar materials may be added in amounts of less than 3% by weight. If desired, zirconium oxide (ZrO2) may be added in amounts up to about 12% by weight to improve alkali resistance and other properties. The above ranges include all intermediate quantities.

[0065] These compounds can also be added to adjust and improve the temperature cooling properties of the extruded melt, which in turn results in the physical crystallization or solidification properties of the fibers. This, in turn, leads to the optimization of the physical and chemical properties of basalt fiber products.

[0066] In the disclosed embodiments of the present invention, basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals may be used in combination with limestone, dolomite, quicklime, quick lime, aluminosilicate calcined clays, volcanic ash having properties different from the main mineral, andesitic pumice, dacitic pumice, rhyolitic pumice, perlite, silica fume, and similar materials, thereby adjusting and modifying acidity, viscosity, viscosity coefficient, surface tension of the melt, and other properties necessary for the production of basaltic fibers. The basaltic hyaloclastite or intermediate basaltic hyaloclastite according to the present invention is preferably obtained from hyaloclastite, lava, volcanic ash or pumice, or any other igneous rock. Such basaltic hyaloclastite or intermediate basaltic hyaloclastite preferably has a chemical composition comprising about 30% to about 57% by weight of SiO2, about 6% to about 18% by weight of Al2O3, about 6% to about 18% by weight of Fe2O3, and about 4% to about 25% by weight of CaO, preferably the total of Al2O3 + Fe2O3 is between about 20% to about 35% by weight, preferably the ratio of Al2O3 to Fe2O3 is ideally between about 0.75 and about 1.50, or about 1, and the ratio of SiO2 to the total of Al2O3 + Fe2O3 is preferably between about 1.25 and 2.25, ideally about 1.5.

[0067] In addition to the aforementioned components, small amounts of other compounds may be present, such as K2O, TiO2, P2O5, MnO, various metals, rare earth trace elements, and other unidentified elements. Combined, these other compounds constitute less than 10% by weight of the total chemical composition of basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals, such as hyaloclastite, lava, scoria, volcanic ash, or pumice minerals.

[0068] In another disclosed embodiment, the hyaloclastite, volcanic ash, or pumice according to the present invention preferably has a density or specific gravity of about 2.4 to about 3.1.

[0069] The basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals according to the present invention can be in microcrystalline or amorphous (vitreous) form, and are usually found in combination of both in various proportions. Preferably, the hyaloclastite, volcanic ash, or pumice according to the present invention contains about 30% to 100% by weight of amorphous form, more preferably about 40% to 80% by weight of amorphous form, most preferably about 50% to 70% by weight of amorphous form, and particularly about 80% to 95% by weight of amorphous form. The crystalline portion of hyaloclastite preferably includes 0% to about 20% by weight of olivine, 0% to about 40% by weight of clinopyroxene, 0% to about 60% by weight of plagioclase, and 0% to about 40% (or less than 40% by weight) of other minerals, without limitation, including calcite, hornblende, biotite, K-feldspars, mordenite, clinoamphibole, hypersthene (a type of orthorhombic pyroxene), feldspathoids, sulfides, metals, rare earth minerals, other unidentified minerals, and combinations thereof, one or more of these. The above range includes all intermediate values.

[0070] In one disclosed embodiment, in order to facilitate the efficient melting of the composition, the hyaloclastite or water-quenched lava mineral selected for use as a formulation material for the molten composition may need to be reduced in size to suitable particles. This size reduction can be carried out using any suitable crushing, grinding, or grinding equipment. Examples of such equipment include roller mills, hammer mills, high-pressure grinding roll (HPGR) mills, disc mills, and jet mills. Hyaloclastite particles can be prepared by grinding using a hammer, disc, ball mill, and vibratory pulverizer, respectively. Alternatively, the hyaloclastite or water-quenched lava according to the present invention may be processed in multiple stages using one or more of the above. The target particle size can be the size of sand or gravel, or potentially fine sand particles ranging from 1 mm or less to 20 mm or more. The size of the raw material composition can be any suitable size depending on the requirements of the type of furnace used in the melting process, but this is not the subject of the present invention.

[0071] In another embodiment of the present invention, the hyaloclastite mineral is crushed to a desired size as needed for a melt composition, and microwaves may be exposed to a microwave energy field to assist the melting process by changing or transforming the crystalline or microcrystalline portions of the mineral into amorphous or microcrystalline portions, because larger amorphous portions melt and homogenize more easily at lower temperatures than macrocrystalline portions. As an example, a mineral with a composition of 20% amorphous and 80% microcrystalline can be transformed to a composition of 50% amorphous and 50% microcrystalline by exposure to a microwave energy field during or after the size reduction process described above. In another example, a mineral with a composition of 50% amorphous and 50% microcrystalline components, exposed to a microwave energy field during or after the size reduction process described above, may be converted to 80% amorphous and 20% microcrystalline components. The converted amorphous-to-crystalline composition increases the amorphous portion, thereby significantly improving the efficiency of the melting process, lowering the melting point, and consequently lowering the melting temperature of the melted composition, while the resulting mineral maintains its chemical composition. Thus, the term hyaloclastite applies to both the naturally occurring amorphous / microcrystalline composition or the composition in which a portion of the crystalline content is converted to an amorphous state, thereby increasing the amorphous content by microwave treatment during or after the crushing or size reduction process of the mineral. Both the microcrystalline and amorphous materials of hyaloclastite will melt more rapidly and / or at lower temperatures than minerals that are predominantly macrocrystalline. Therefore, the use of minerals with a maximum amount of amorphous composition, such as highly amorphous hyaloclastite, is desirable in this invention. This characteristic allows the process to be carried out more quickly, at lower temperatures, with less energy consumption, and with a lower risk of crystallization of the fiber strands.Therefore, when using the hyaloclastite specified by the present invention, the present invention provides a more efficient process and enables the production of continuous fibers with improved properties at a lower cost.

[0072] In further embodiments of the present invention, basaltic, intermediate, or andesitic hyaloclastite is examined to measure the content of iron oxide, which may be present in trace amounts in the form of magnetite, ferrite, or hematite. If iron oxide crystals are detected, the size reduction process may include an option to remove the iron oxide by magnetic separation. This process can be applied either during or after size reduction. Iron oxide in magnetite has ferromagnetic properties and can be separated by a magnetic field. Iron oxide in ferrite also has ferromagnetic properties and can be separated by a magnetic field. As the hyaloclastite particles are moved from the pulverizer to the storage silo, magnets suitable for generating a magnetic field of sufficient strength are used in the molten composition from which the fibers are drawn, and can therefore be used in any suitable configuration necessary to remove and separate such crystals from the hyaloclastite and can be used to remove hematite crystals. Iron oxide in hematite has weak magnetic properties and may be separated by using a strong magnet, such as a rare-earth magnet. Alternatively, hyaloclastite containing trace amounts of hematite may be treated in a microwave field as described above to increase the hematite magnetic properties and then separated by a magnetic field. When the hyaloclastite is reduced in size and moved by a conveyor belt or duct, any suitable magnet of any type, such as a conventional magnet, electromagnet or rare-earth magnet, can be configured to create a magnetic field. Any suitable type or configuration of magnet that generates a magnetic field of sufficient strength to separate the ferromagnetic iron oxide crystal portion of the molten composition can be used in this invention.

[0073] In the disclosed embodiments of the present invention, the hyaloclastite according to the present invention, or lava quenched with water, the formulation raw material composition, is placed in a furnace suitable for producing a molten composition. Any furnace suitable for producing a molten composition in a temperature range of 1,200°C to 1,500°C may be used. The type of furnace used is not the subject of the present invention. The bottom or side of the furnace will have an outlet of sufficient diameter to allow the flow of molten material to pass through and fall onto an extrusion die below, such as a platinum-rhodium die or bushing. Any type of extrusion die suitable for the production of continuous basalt fibers may be used. A spinning drum may be used to wind the fibers into rovings at a distance below the extrusion die suitable for the production of continuous basalt fibers. Between the extrusion bushing or die, lubricants, binders, curing agents, or resins may be coated onto the fibers to improve fiber properties. Any organic or inorganic agent known in the art can be used to improve the properties of plastics or fibers. One example of such agent is an amine-based curing agent. Any coating agent known in the art can be used, and the type and method thereof are not the subject of this invention.

[0074] In the disclosed embodiments of the present invention, hyaloclastite, volcanic glass, volcanic ash, or lava quenched with water substantially does not contain ferrite, hematite, or magnetite.

[0075] In another disclosed embodiment of the present invention, hyaloclastite, hyaloclastite, volcanic glass, volcanic ash, or lava quenched with water is substantially Fe2O3-free.

[0076] In the disclosed embodiments of the present invention, the molten material preferably has a temperature of about 1,250°C to about 1,900°C, more preferably about 1,300°C to about 1,800°C, most preferably about 1,300°C to about 1,500°C, particularly about 1,500°C to about 1,700°C, even more particularly about 1,500°C to about 1,800°C, most particularly about 1,500°C to about 1,900°C, preferably about 1,300°C to about 2,000°C, and more preferably about 1,300°C to about 1,700°C. The above ranges include all intermediate values.

[0077] In one disclosed embodiment, the molten phase at the fiber extraction temperature comprises an amorphous or amorphous and microcrystalline composition, with an amorphous content of more than about 80%, preferably more than about 88%, more preferably more than about 90%, most preferably more than about 95%, and particularly complete or 100% amorphous, producing a molten composition. The above range includes all intermediate values.

[0078] In another disclosed embodiment of the present invention, the fiber strands preferably have a diameter of about 1 to about 18 microns, more preferably about 4 to about 15 microns, and most preferably about 6 to about 12 microns. The fibers may also be 8 to about 10 microns, and particularly about 7 microns. The above ranges include all intermediate values.

[0079] In further disclosed embodiments of the present invention, the continuous fiber strand comprises amorphous, or amorphous and microcrystalline content, comprising more than about 80%, preferably more than about 88%, more preferably more than about 90%, most preferably more than about 95%, and ideally complete or 100% amorphous content. The above ranges include all intermediate values.

[0080] In one embodiment, the fiber forming unit produces continuous fibers or multiple fibers, i.e., roving. The present invention can use any type of furnace and fiber forming unit, including gas furnaces or electric furnaces, single-stage or multi-stage temperature control units, and those equipped with one or more fiber tap holes (outlets), but this is not the subject of the present invention.

[0081] The following examples illustrate selected embodiments of the present invention and are not intended to limit the scope of the invention. All percentages (%) used herein are weight percentages (weight%) unless otherwise specified. [Examples]

[0082] Experimental Example 1 Hyaloclastite, basaltic hyaloclastite, or intermediate basaltic hyaloclastite minerals are mined from quarries and transported to basalt fiber manufacturing plants, where they are crushed to a fine particle size suitable for the basalt fiber manufacturing process. Hyaloclastite, basaltic hyaloclastite, or intermediate basaltic hyaloclastite minerals preferably have a chemical composition containing about 30% to 57% by weight of SiO2, about 10% to 18% by weight of Al2O3, about 8% to 18% by weight of Fe2O3, and about 4% to 25% by weight of CaO, preferably with a total Al2O3 + FeO content between about 20% to 35% by weight, preferably with a ratio of Al2O3 to FeO ideally between about 0.75 and 1.50, or about 1, and with a ratio of SiO2 to the total Al2O3 + Fe2O3 content between about 1.25 and 2.25, or ideally about 1.5. Hyaloclastite does not contain any iron oxide crystals. Trace components such as limestone are ground to a particle size similar to that of the ground hyaloclastite. Crushed limestone and basaltic or intermediate hyaloclastite minerals are blended together in an approximate ratio suitable for the basalt fiber manufacturing process: approximately 75% to 98% by weight of basaltic hyaloclastite or intermediate basaltic hyaloclastite and approximately 2% to 25% by weight of limestone minerals. The blended mineral feed composition is preheated and then fed into a melting furnace typical of basalt fiber production. The furnace is heated to a temperature of approximately 1250 to 1650°C, and the blended composition is held in the furnace for a sufficient amount of time to melt. After the composition has melted, basalt fibers are produced according to a standard fiber extrusion or fiberization process.

[0083] Experimental Example 2 The hyaloclastite AB1 minerals described in Tables 2 and 3 above are mined from quarries and transported to basalt fiber manufacturing plants, where they are crushed to a fine particle size suitable for the basalt fiber manufacturing process. The hyaloclastite has the chemical composition shown in Tables 2 and 3. The hyaloclastite does not contain any iron oxide crystals. To increase the acidity, alumina and silica, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic or rhyolitic hyaloclastite and similar materials, which contain elements in mostly amorphous or a combination of amorphous and microcrystalline forms, may be added, preferably in an amorphous state. The amount of these elements or oxides is calculated to reach a maximum of approximately 15% by weight of the main components of the hyaloclastite to satisfy the target formulation chemical composition. To further adjust melt properties such as viscosity, viscosity coefficient, and surface tension, other minerals or elements, such as boron, borodes, boron oxide, chromium oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, gallium oxide, rubidium oxide, strontium oxide, zirconium oxide, rubidium oxide, niobium oxide, vanadium oxide, fluorides, and chlorite, may be added in amounts of less than 1% by weight each. Furthermore, to adjust viscosity properties, one or more lanthanum oxide, lanthanides, boron, borax, and similar materials may be added in amounts of less than 3% by weight each. If desired, zirconium oxide (ZrO2) may be added in amounts up to about 12% by weight to improve alkali resistance and other properties. One or more of the above may be added to hyaloclastite up to 3%. Silica fume and hyaloclastite minerals are blended together in a ratio suitable for the basalt fiber manufacturing process: approximately 85% to 98% by weight of basaltic hyaloclastite or intermediate basaltic hyaloclastite and approximately 2% to 15% by weight of silica fume. The mixed mineral feed composition is preheated and then placed into a melting furnace typically used in the production of basalt fibers. The furnace is heated to a temperature of approximately 1250 to 1650°C, and the mixed composition is held in the furnace for a sufficient amount of time to melt it.After the composition is dissolved, basalt fibers are produced through a standard fiber extrusion or fiberization process.

[0084] Experimental Example 3 From Tables 2 and 3 above, intermediate basaltic hyaloclastite mineral PTR is mined from quarries and transported to basalt fiber manufacturing plants, where it is ground to a fine particle size suitable for the basalt fiber manufacturing process. The chemical composition of intermediate basaltic hyaloclastite mineral PTR is shown in Tables 2 and 3 above. This mineral has an amorphous composition of 60% and a microcrystalline composition of 40%. To reduce acidity, trace components such as dolomite and quicklime (burnt lime) are ground to a particle size similar to that of hyaloclastite. The ground dolomite and intermediate hyaloclastite mineral are mixed in a ratio of approximately 75% to 98% by weight of intermediate basaltic hyaloclastite and approximately 2% to 15% of dolomite mineral, suitable for the basalt fiber manufacturing process. To further adjust melt properties such as viscosity, viscosity coefficient, and surface tension, other minerals or elements, such as boron, borodes, boron oxide, chromium oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, gallium oxide, rubidium oxide, strontium oxide, zirconium oxide, rubidium oxide, niobium oxide, vanadium oxide, fluorides, and chlorite, one or more of each may be added in amounts of less than 1% by weight. Furthermore, to adjust viscosity properties, one or more of lanthanum oxide, lanthanides, boron, borax, and similar materials may be added in amounts of less than 3% by weight each. If desired, zirconium oxide (ZrO2) can be added in amounts up to about 12% by weight to improve alkali resistance and other properties. One or more of the above are added to hyaloclastite up to 3%. The mixed mineral feed composition is preheated and then placed in a melting furnace typically used for the production of basalt fibers. The furnace is heated to a temperature of approximately 1450°C, and the mixed composition is held in the furnace for a sufficient amount of time to melt it. After the composition has melted, basalt fibers are produced through a standard fiber extrusion or fiberization process.

[0085] Experimental Example 4 To prepare the raw mineral feed, hyaloclastite having the chemical composition and properties shown in Experimental Example 2 above is crushed and sieved to a particle size of 2 mm. The mineral feed composition is placed in a typical melting furnace for the production of continuous basalt fibers. The furnace is heated to a temperature of approximately 1350°C, and the composition is held in the furnace for a sufficient amount of time to melt. After the composition has melted, continuous basalt fibers are produced through a standard fiber extrusion or fiberization process. The continuous basalt fibers are coated with a heat-curing amine-based curing agent. The fiber strands are collected at the bottom, wound up, and processed into rovings. The individual fibers are then bundled together, impregnated with resin, bonded by a pultrusion process, and then cured to be processed into reinforcing bars.

[0086] Experimental Example 5 Andesitic hyaloclastite minerals with the chemical composition shown in Experimental Example 3 above are mined from a quarry and transported to a basalt fiber manufacturing plant, where they are crushed and sieved to a fine particle size suitable for the continuous basalt fiber manufacturing process. When this fine-particle mineral is exposed to a microwave field, the crystalline composition changes to 80% amorphous and 20% microcrystalline. Furthermore, to adjust the viscosity properties, one or more of lanthanum oxide, lanthanides, boron, borax, and similar substances may be added in amounts of less than 3% by weight each. If desired, zirconium oxide (ZrO2) may be added up to about 12% by weight to improve alkali resistance and other properties. One or more of the above substances are added to the hyaloclastite up to 3%. The mixed mineral feed composition is placed in a melting furnace typically used in the production of basalt fibers. The furnace is heated to a temperature of about 1350°C, and the mixed composition is held in the furnace for a sufficient time to melt it. After the composition is dissolved, continuous basalt fibers are produced through a standard fiber extrusion or fiberization process.

[0087] Experimental Example 6 Basaltic hyaloclastite with an average particle size of 200 microns is analyzed due to its properties. Its chemical composition is analyzed using XRF, and the results are shown in Table 5 below.

[0088] [Table 5]

[0089] The crystal composition was analyzed using XRD, and the results are shown in Table 6 below.

[0090] [Table 6]

[0091] Before melting the raw mineral composition in the furnace to extract continuous basalt fibers, the basaltic hyaloclastite is analyzed to determine the wetting angle of the melt. The wetting angle correlates with the temperature and viscosity of the melt and is a crucial factor in the continuous basalt fiber extraction / extrusion process because the melt comes into contact with bushings and extrusion dies. Current practice dictates that the wetting angle should be less than 20° and greater than 0°. Samples from basaltic hyaloclastite are placed in a Linseis Heating Optical Microscope to heat and melt the sample. The microscope captures images of the melting sample, and the wetting angle is calculated based on these images. The relationship between the wetting angle and the melt temperature is shown in Table 7 below. From this test protocol, it is determined that the target melt composition should have a temperature of approximately 1300°C and a wetting angle of approximately 10–12°.

[0092] [Table 7]

[0093] After wetting angle evaluation, the basaltic hyaloclastite formulation material is charged into an electric induction melting furnace and determined to be sufficiently melted at a temperature of 1309°C to begin drawing fibers. No additional additives are used in the formulation material to create the molten composition, and no resins or additives are used in the fiber strands themselves when the fibers are drawn. The continuous basalt fibers are drawn onto a spooling cylinder by a spindle motor at a travel speed of 550 m / min. The fibers are wound onto a spool. Upon completion of winding, the fiber strands are randomly removed from the bundle. A total of 17 test pieces are cut into short lengths and placed on mounting tabs, and both ends are bonded to the mounting tabs using Locktite SuperGlue resin. The fibers mounted on the tabs can be cured over 24 hours. The total length of the fiber mounted on the tab was measured to be 63 mm, resulting in an effective specimen length (fragment length) of approximately 12.7 mm to 15 mm. Next, the diameter of each fiber specimen was measured using a digital microscope equipped with a polarizing objective lens at a magnification of RZx1500. The fiber diameter was measured before testing the tensile strength of each fiber specimen with the Instron 68SC-2 tester. The fiber diameter was measured at randomly selected locations within the test area and also at the fracture site after each test. The fiber strand diameter produced in this procedure was 15 microns, as shown in the table below. The diameter at the fracture site was used to determine the results according to the ASTM international standard C1557-14. If the fiber fractured along its entire length, the fiber diameter measured before the test was used for the result. The Instron testing machine is equipped with 50 N pneumatic grips at both ends of the fiber mounting tab. The speed at which the ends of the fiber are pulled apart (crosshead speed) is 50 mm / min. The results of the tensile strength test are shown in Table 8 below.This indicates that the fiber strands exhibit reasonable tensile strength properties even without being treated with resin or hardening agents.

[0094] [Table 8]

[0095] Experimental Example 5 A basaltic hyaloclastite preparation material having the chemical and crystalline mineral composition shown in Example 4 above was placed in an electric induction melting furnace and melted at 1335°C. The molten composition was determined to be in a sufficiently molten state to initiate fiber drawing. No additional additives were used in the preparation material to produce the molten composition. As the fiber strands were drawn through the bushing, they were coated with Aradur® 3475 (1,3-cyclohexanedimethanamine), an amine-based curing agent from Huntsman Corporation. The continuous basalt fibers were drawn into a spooling cylinder by a spindle motor at a speed of 550 m / min. The fibers were wound onto the spool. After the operation was complete, fiber strands were randomly removed from the fiber bundle. A total of 19 test specimens were selected and prepared and tested using the same apparatus as in Experimental Example 4 above. The diameter of the fiber strands produced by this operation was ±15 microns, as shown in Table 9 below. The results of the tensile strength test are shown in Table 9 below. This fiber manufacturing method demonstrates that the tensile strength properties are improved by treating the fiber strands with an amine-based curing agent.

[0096] [Table 9]

[0097] Experimental Example 6 A basaltic hyaloclastite preparation having the chemical and crystalline mineral composition shown in Experimental Example 4 was placed in an electric induction melting furnace and melted at a temperature of 1335°C. It was determined that the composition was sufficiently melted to allow for the initiation of fiber drawing. No additional additives were used in the raw material mixture to obtain the molten composition. As the fiber strands were drawn through the bushing, they were coated with Aradur® 3475 (1,3-cyclohexanedimethanamine), an amine-based curing agent from Huntsman Chemical Company. The continuous basalt fibers were drawn into a spooling cylinder by a spindle motor at a speed of 1650 m / min. The fibers were wound onto the spool. After the operation was complete, the fiber strands were randomly removed from the fiber bundle. A total of 20 test specimens were selected and prepared, and tested using the same apparatus as in Experimental Example 4. The diameter of the fiber strands produced in this operation was ±9 microns, as shown in Table 10 below. The results of the tensile strength test are shown in Table 10 below. Despite a significant increase in the take-up speed and a significant decrease in the fiber strand diameter, this fiber production method shows improved tensile strength characteristics due to the treatment of the fiber strands with an amine-based curing agent.

[0098] [Table 10]

[0099] Of course, the above only pertains to the disclosed embodiments of the present invention, and it should be understood that various modifications and changes can be made as long as they do not deviate from the spirit and scope of the invention as described in the attached claims.

Claims

1. Basaltic hyaloclastite or intermediate basaltic hyaloclastite is amorphous by weight, and the process involves melting the basaltic hyaloclastite or intermediate basaltic hyaloclastite, and A method comprising the step of extruding a molten material into a continuous fiber.

2. The method according to claim 1, wherein the basaltic hyaloclastite or intermediate basaltic hyaloclastite contains about 30 to about 57% SiO by weight. ２ It contains approximately 10 to 18% Al by weight. ２ O ３ It contains approximately 8 to 18% Fe by weight. ２ O ３ A method characterized by containing and containing about 4 to about 25% CaO by weight.

3. The method of claim 2, wherein Al ２ O ３ +Fe ２ O ３ has a total weight ratio of from about 20% to about 35%, and Al ２ O ３ and Fe ２ O ３ has a weight ratio of from about 0.75 to about 1.5, and a total weight ratio of SiO ２ and Al ２ O ３ +Fe ２ O ３ is from about 1.25 to about 2.25 by weight. A method characterized by the above.

4. A method according to claim 1, characterized in that the basaltic hyaloclastite or intermediate basaltic hyaloclastite is amorphous by weight, comprising approximately 30% to 100%.

5. A method according to claim 1, characterized in that the basaltic hyaloclastite or intermediate basaltic hyaloclastite is amorphous by weight, comprising about 50% to 100%.

6. A method according to claim 1, characterized in that the basaltic hyaloclastite or intermediate basaltic hyaloclastite is amorphous by weight, comprising about 80% to 100%.

7. A method according to claim 1, characterized in that the portion of basaltic hyaloclastite or intermediate basaltic hyaloclastite that is not amorphous is mostly in a microcrystalline form.

8. A method according to claim 1, characterized in that the basaltic hyaloclastite or intermediate basaltic hyaloclastite is substantially free of ferrite, hematite, magnetite, altered or weathered olivine, or altered or weathered common hornblende.

9. The method according to claim 1, wherein the basaltic hyaloclastite or intermediate basaltic hyaloclastite is Fe ２ O ３ A method characterized by the fact that it is substantially absent.

10. A method according to claim 1, characterized in that the molten material is at a temperature of about 1250°C to 1450°C.

11. A method according to claim 1, characterized in that the molten material has an amorphous content of about 80% or more.

12. A method according to claim 1, characterized in that the continuous fibers are treated with a binder during the extrusion process.

13. A method according to claim 1, characterized in that the continuous fiber diameter is about 4 microns to about 20 microns.

14. A method according to claim 1, characterized in that the continuous fiber strand contains an amorphous content of about 80% or more by weight.

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