Continuous basalt fibers from hyaloclastite and method of making and using same

Abstract

The present invention comprises a method for manufacturing continuous basalt fibers. The method comprises the steps of supplying one or more natural minerals selected from basalt, intermediate basalt or hyaloclastite with an andesite chemical composition, volcanic glass, volcanic ash or lava quenched by water, melting said minerals, and extruding the molten material into continuous fibers.

Description

Technology Field

[0001] The present invention generally relates to a manufacturing process for producing basalt fibers, such as continuous basalt fibers (CBF) and short basalt fibers. The present invention relates to a manufacturing process for continuous basalt fibers that produces fibers with improved physical properties while requiring less energy and consequently resulting in lower CO2 emissions. Background Technology

[0002] Basalt fibers are produced from basalt rock by melting the rock and converting the molten material into fibers. Basalt is a rock of igneous origin. The primary energy consumption in preparing the basalt raw material for fiber production occurs under natural conditions. Basalt continuous fibers, staple fibers, and superthin fibers are produced and used. Basalt Continuous Fiber (BCF) is used to produce reinforcing materials, composite products, and woven and nonwoven materials. Basalt Staple Fiber is used to produce thermal insulation materials. Basalt SuperThin Fiber (BSTF) is used to produce high-quality thermal insulation, soundproofing, and fire-resistant materials. The technology for producing Basalt Continuous Fiber (BCF) can be a one-stage process, namely the melting, homogenization, and fiber drawing of the basalt, or a two-stage process in which the basalt is first melted at a high temperature and then cooled to a lower temperature to draw the fibers. Further processing of BCF as a material is carried out using "cold technologies" with low energy costs.

[0003] The chemical composition and mineral content of basalt vary considerably. For applications such as tiles, stone castings, or staple fibers, basalt with a wide range of properties can be used. However, for the production of continuous basalt fibers (CBF), the requirements of the prior art are much stricter, and only a narrow range of basalt chemical compositions can be used to manufacture CBF. Due to these strict composition and mineral content requirements, the list of available basalt mines worldwide is very short. Today, major CBF manufacturers are known to use raw materials from mines in western Ukraine or Georgia, consisting of andesite basalt with a SiO2 content exceeding 50% by weight.

[0004] Basalt fibers are generally manufactured from a single material, namely crushed basalt, obtained from carefully selected quarry sources. Basalt with high acidity (silica content exceeding 46%) and low iron content is considered desirable for fiber production. Unlike other composites such as glass fibers, no materials are essentially added during their production. The basalt is simply washed and then melted. The manufacture of basalt fibers requires melting 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 basalt fiber filaments. Basalt fibers typically have a filament diameter of 10 to 20 μm, which is sufficiently large beyond the 5 μm respiratory threshold, making basalt fibers a suitable substitute for asbestos. Furthermore, they possess a high modulus of elasticity, resulting in high specific strength, which is three times that of steel. Thin fibers are generally used primarily for fiber applications in woven fabric production. Thicker fibers are used, for example, in filament winding for the production of Compressed Natural Gas (CNG) cylinders or pipes. The thickest fibers are used in the form of pultrusion, geogrids, unidirectional fabrics, multiaxial fabrics, and cut strands for concrete reinforcement. One of the current applications of continuous basalt fiber is the production of basalt rebar, which replaces traditional rebar in the construction market.

[0005] The mineral feedstock can be melted in a furnace that may be a gas or other type of fuel combustion furnace or an electric arc furnace. Regardless of the type of furnace used to melt the mineral feedstock, the remaining steps of the basalt fiber manufacturing process are generally similar.

[0006] The natural minerals used in the basalt fiber manufacturing process of the prior art are essentially crystalline, such as crystalline basalt, particularly andesite basalt, and have been geologically weathered due to the age of their formation. Crystalline minerals have a higher melting point compared to amorphous or partially amorphous minerals with similar chemical compositions, and as a result, require higher temperatures and longer times in a melting furnace. Additionally, older mineral layers are weathered or altered, causing the iron contained in the crystalline basalt to become iron oxide within macrocrystalline structures, usually in the form of magnetite, hematite, or ferrite (or weathered olivine or amphibole), resulting in a relatively high melting point.

[0007] Therefore, it would be desirable to provide continuous basalt fibers and a manufacturing process thereof that use a wider range of starting materials. Additionally, it would be desirable to provide a manufacturing process for continuous basalt fibers that has higher energy efficiency and results in relatively lower CO2 emissions.

[0008] Summary of the Invention

[0009] The present invention satisfies the aforementioned requirements by providing an improved continuous basalt fiber and an improved continuous basalt fiber manufacturing process.

[0010] In one disclosed embodiment, the present invention includes a process for manufacturing basalt fibers using basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals. Preferably, the basaltic hyaloclastite or intermediate basaltic hyaloclastite useful for the present invention comprises about 30 to about 57 weight% SiO2, about 10 to about 18 weight% Al2O3, about 8 to about 18 weight% Fe2O3, and about 4 to about 25 weight% CaO, preferably the sum of Al2O3+Fe2O3 is between about 20 to about 35 weight%, preferably the ratio between Al2O3 and Fe2O3 is between about 0.75 and about 1.50 or ideally about 1, and the ratio between SiO2 and the sum of Al2O3+Fe2O3 is preferably between about 1.25 and 2.25, and ideally about 1.5.

[0011] In another disclosed embodiment, the present invention comprises a basaltic hyaloclastite or intermediate basaltic hyaloclastite mineral having an amorphous content of at least 30 weight%.

[0012] In another disclosed embodiment, the present invention comprises basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals having a basaltic or intermediate chemical composition and a mineral composition having at least 30 weight% amorphous content, lava quenched by water, volcanic ash, scoria or pumice minerals.

[0013] In another disclosed embodiment, the present invention comprises a basaltic hyaloclastite or intermediate basaltic hyaloclastite mineral from one or more of hyaloclastite, lava, volcanic ash, scoria, and pumice minerals having a basaltic or intermediate chemical composition and a mineral composition having at least 30 weight% amorphous content, wherein the hyaloclastite, lava, volcanic ash, scoria, and pumice are quenched by water.

[0014] Therefore, the objective of the present invention is to provide an improved continuous basalt fiber manufacturing process with reduced CO2 emissions.

[0015] Another objective of the present invention is to provide an improved continuous basalt fiber manufacturing process that uses less energy.

[0016] A further objective of the present invention is to provide an improved continuous basalt fiber manufacturing process that reduces wear and damage to manufacturing equipment, such as fiber extrusion dies.

[0017] Another objective of the present invention is to provide a continuous basalt fiber manufacturing process that requires a lower temperature and a shorter time in the melting furnace compared to the prior art, thereby reducing the total discharge and increasing the production capacity of the furnace.

[0018] These and other objects, features, and advantages of the present invention will become apparent from a review of the detailed description of the disclosed embodiments below and the appended claims.

[0019] Detailed description of the disclosed embodiments

[0020] Hyaloclastite is generally a tuff-like breccia rich in black volcanic glass, formed during volcanic eruptions where lava flows reach the sea or other bodies of water, underwater, beneath glaciers, or on the surface. It has the appearance of angular fragments ranging in size from about 1 millimeter to several centimeters. Larger fragments can be found up to the size of phyllo lava. Hyaloclastite masses contain various minerals, including but not limited to sideromelane, tachylite, palagonite, olivine, pyroxene, amphibole, biotite, hyperstein, feldspartoid, plagioclase, calcite, and others. Fracturing can occur through explosive eruption processes or through essentially non-explosive processes involving the spalling of the phyllobasal shell due to the rapid fracturing of molten lava or thermal shock. Basalt glass quenched by water is called sieromelan, a type of clear, pure glass that lacks the very small iron oxide crystals found in the more common, opaque type of basalt glass called tachylite. In hyaloclastite, these glassy fragments are typically surrounded by a yellow to brown palagonite matrix, a waxy substance formed from the hydration and alteration of sieromelan and other minerals. Depending on the type of lava, the cooling rate, and the degree of lava fracturing, particles of volcanic glass (sieromelan) can be mixed with other volcanic rocks or crystalline minerals such as olivine, pyroxene, magnetite, quartz, plagioclase, and calcite.

[0021] Hyaloclastite is typically found within or adjacent to subglacial volcanoes such as tuyas. A tuya is a unique type of volcano with flat, steep sides that forms when lava erupts beneath or through thick glaciers or ice sheets. Hyaloclastite ridges are also called tindars, while subglacial hills are referred to as tuyas or mobergs. These were formed by subglacial volcanic eruptions during the Last Ice Age. Subglacial hills are a type of subglacial volcano. This type of volcano is formed when lava erupts beneath thick glaciers or ice sheets. Because the magma forming these volcanoes was not hot enough to melt vertical passages penetrating the overlying glacial ice, it instead formed hyaloclastite and phyllo lava deep within the ice layer. As the glaciers retreated, the subglacial volcanoes were exposed with their unique shapes, formed as a result of being trapped within the glacial ice. Subglacial volcanoes are somewhat rare globally because they are confined to regions that were formerly covered by continental ice sheets and experienced active volcanic activity during the same period. Even today, volcanic eruptions beneath existing glaciers can produce hyaloclastite. Hyaloclastite tuff-like breccia is a pyroclastic rock in which glassy juvenile clasts are embedded within a fine-grained matrix dominated by glassy fragments. Hyaloclastite breccia is generally a product of phreatomagmatic eruptions, particularly those involving magma eruptions into bodies of water, and is formed by the fracturing of rapidly cooled magma. They often form from basaltic magma and are associated with phyllolava and sheet flows. Additionally, other types of lava, such as intermediate or andic lava, can also form hyaloclastite under similar rapid cooling or quenching conditions.

[0022] Occasionally, subglacial or underwater eruptions can generate volcanic ash released into the atmosphere, which can then fall back to the ground. Sometimes, due to the fine size of the volcanic particles, this may be referred to as "volcanic ash" by different experts in the field of geology, even though the definition of volcanic ash can be controversial. Additionally, subglacial or underwater eruptions may have been caused by magma in which large amounts of gas were trapped within the lava. The exsolution of large amounts of gas can produce minerals with a very high porous or frothy structure and bulk density similar to scoria or pumice.

[0023] Volcanic basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals, such as hyaloclastite quenched by water, volcanic ash, scoria, or pumice, can be classified as follows according to their silica content: basaltic (less than 53 wt% SiO2), intermediate (about 53%–57 wt% SiO2), or silicic (about 57%–63 wt% SiO2), such as andicin. However, for the purposes of the present invention, the basaltic range starts at about 40% SiO2 and the andicin range ends at 63% to 65% SiO2.

[0024] Basaltic hyaloclastite, volcanic ash, or pumice generally contains 40 to 53 wt% silica (SiO2) in amorphous, crystalline, or a combination thereof, essentially calcic plagioclase feldspar, and pyroxene (typically augite), regardless of the presence of olivine. In addition to silica, basaltic hyaloclastite, volcanic ash, or pumice generally contains about 10 to 18 wt% Fe2O3, about 6 to 18 wt% CaO, about 5 to 15 wt% MgO, and various proportions of other elements. Intermediate basaltic hyaloclastite, volcanic ash, or pumice generally contains about 53 to 57 wt% silica (SiO2). In addition to silica, intermediate basaltic hyaloclastite, volcanic ash, or pumice generally contains about 5 wt% to about 12 wt% Fe2O3, about 6 wt% to about 10 wt% CaO, about 3 wt% to about 10 wt% MgO, and various proportions of other elements. Basaltic hyaloclastite, volcanic ash, or pumice may also contain biotite, hypersthene (a type of orthopyroxene), and feldspartoids. The average specific gravity of basaltic hyaloclastite, volcanic ash, or pumice is about 2.7-3.0 gm / cm³.

[0025] Andesite is an abundant igneous rock (volcanic rock) of intermediate composition with a fine-grained to semicrystalline texture. In a general sense, it is an intermediate type between basalt and dacite. Andesite hyaloclastite, volcanic ash, or pumice contains about 57 wt% to about 63 wt% silicon dioxide (SiO2). For the purposes of the present invention, andesite is defined as having a SiO2 content of up to 65%. In addition to silica, andesite hyaloclastite, volcanic ash, or pumice generally contains about 5 wt% to about 10 wt% Fe2O3, about 5 wt% to about 10 wt% CaO, about 3 wt% to about 8 wt% MgO, and various proportions of other elements.

[0026] The most important point is that hyaloclastite or water-quenched lava deposits are geologically young in age and occur rarely, with amorphous and / or crystalline substrates being little to no alteration, whereas the crystalline basalt used in modern fiber-forming processes occurs frequently as geologically old mineral layers and contains weathered or altered crystals, which requires more energy to melt at higher temperatures compared to the hyaloclastite melting process.

[0027] The iron oxide found in crystalline basalt or crystalline andesitic basalt lava used in modern CBF production is ferric (Fe 3+It includes the oxidized form of ) or the form of ferric oxide (Fe2O3), magnetite, or hematite. Crystalline minerals containing ferric oxide, such as altered or weathered amphibole, magnetite, or hematite, may remain in the molten composition and react with the platinum-rhodium bushing used in the prior art extrusion process. This causes excessive wear of the bushing, resulting in associated repair and replacement costs. Additionally, if oxidized iron crystals or microcrystals are still present in the molten material, such crystals may cause breakage in the continuous fiber extrusion / drawing process, causing the process to stop and requiring a new process restart. Or, even if oxidized iron crystals are present in the molten material but do not cause breakage in the continuous fiber extrusion / drawing process, such oxidized iron crystals present in the continuous fiber act as "pinches," weak points, or structural fracture points within the fiber, causing failure under load and resulting in a weaker fiber overall. Current state-of-the-art processes all utilize crystalline basalt or crystalline andesitic basalt minerals, which are likely to be geologically weathered or altered and contain oxidized iron crystals; therefore, to completely melt and homogenize iron and quartz within the melt, a higher melting temperature is required compared to basaltic or intermediate hyaloclastite minerals, where iron exists in a non-oxidized state or in an amorphous state along with most elements. To address this issue, current state-of-the-art technology has utilized intermediate or andesitic basalt minerals, in which case the iron content is reduced to the minimum necessary to still achieve desired properties, less than 10% for intermediate basalt and less than 8% for andesitic basalt. However, selecting minerals with lower iron content, such as andesitic basalt, results in selecting minerals with higher silica content, which in turn contains more quartz crystals.Quartz crystals also exhibit problems similar to those of oxidized iron crystals, and must be melted at relatively high temperatures and dissolved within the molten composition to form a molten composition sufficiently amorphous for drawing or extruding fibers. Current continuous basalt fibers are all believed to be produced by melting crystalline intermediate basalt or andesite basalt containing at least one or both of oxidized iron-type crystals or quartz. Most basalt deposits have significantly high iron content, a substantial portion of which is ferric Fe. 3+ Or it is in the oxidized form of Fe2O3; on the other hand, all types of lava quenched by water, such as hyaloclastite, are Fe known as ferric iron. 3+ It contains little to no oxidized iron in the form of Fe2O3 (hematite), and almost all iron is Fe, known as ferrous iron. 2+ It is of this form. However, iron found in water-quenched lava-type minerals such as hyaloclastite exists within an amorphous matrix or a matrix that is partially amorphous and partially microcrystalline; in this case, the melting point is lower and ferrous iron or Fe 2+ It does not cause iron-related problems found in macrocrystalline minerals, such as basalt, used in current technology. Furthermore, by selecting basaltic hyaloclastite or intermediate basaltic hyaloclastite, CBF contains a larger amount of iron compared to the small amount found in andic basalt, resulting in stronger fibers; this is because, in the case of basaltic hyaloclastite, the amount of iron exceeds 10–12%, which certainly exceeds the 8% found in the latest commercially available continuous basalt fibers. Therefore, ferrous Fe derived from lava quenched by water 2+ is ferric oxide or Fe found in currently used crystalline basalt 3+Iron does not cause problems in terms of mechanical wear and potential fiber extrusion breakage or weakening of fiber strands. Furthermore, since basaltic hyaloclastite and intermediate basaltic hyaloclastite do not contain any quartz crystals, they further lower the melting point of the mineral composition for fiber extrusion.

[0028] U.S. Patent No. 9,771,294 proposes a two-step process in which basalt is first melted at a high temperature, such as 2000°C, to ensure that all crystals and microcrystals are dissolved in the melt, and then cooled to a lower temperature to draw fiber strands from it. The present invention uses a mixture of mineral raw materials having an amorphous or a combination of amorphous and microcrystalline composition, which results in a target melting temperature of a composition much lower than that required by U.S. Patent No. 9,771,294.

[0029] In conventional basalt fiber manufacturing, basalt is Fe such as Fe2O3 3+ It is important to determine whether it contains containing crystals and whether iron-rich basalt particles should be separated from iron-poor basalt particles. In the case of basaltic hyaloclastite or intermediate basaltic hyaloclastite, iron is mostly or entirely ferrous Fe 2+ It is in the form of ferric Fe such as Fe2O3 (hematite). 3+Iron in this form is contained within amorphous or microcrystalline matrices that are very small or non-existent. In the basalt fiber extrusion equipment of the prior art, wear of platinum-rhodium bushings is a significant cost factor in the basalt fiber manufacturing process, and reducing such wear and damage is essential to improving the manufacturing process and reducing overall costs. Therefore, using minerals containing reduced or no Fe2O3 (ferric oxide / hematite) is a significant improvement in the ability to extrude continuous basalt fibers. Water-quenched lavas, such as basaltic hyaloclastite and intermediate basaltic hyaloclastite, contain most of the iron in the form of Fe2O3. 2+ This problem is resolved because it exists within an amorphous or microcrystalline matrix, or a combination thereof, in which iron is not directly bonded to oxygen. Furthermore, although basaltic hyaloclastite and intermediate basaltic hyaloclastite are rare, they are more common and abundant in certain regions of the world than the extremely rare crystalline basalt of Ukraine, Russia, and Georgia currently used in the manufacture of continuous basalt fibers.

[0030] Another aspect of the mineral selection process discovered by the present invention is that not all iron-containing crystals melt at the same temperature. The melting temperature of iron as a metal and the melting temperature of oxidized iron crystals, such as ferrite, hematite, or magnetite, are approximately 1,500°C. Olivine crystals contain iron largely Fe 2+ It is included in this state, but is sometimes oxidized Fe depending on ore deposit weathering and other factors. 3+ It is also included in the state. Weathered or altered olivine containing ferrite will have a ferrite-like melting point higher than that of unaltered olivine. Basaltic hyaloclastite or intermediate basaltic hyaloclastite may contain small amounts of olivine, but this exists within a microcrystalline matrix. Non-oxidized Fe 2+While iron-containing olivine has a melting point of 1,200°C, Fe 3+ Olivine containing iron oxide has a higher melting point exceeding 1,400°C. Pyroxene crystals are generally Fe 2+ It contains iron in the form of... Microcrystalline pyroxene crystals found in lava quenched by water do not contain oxidized iron. Crystalline amphibole minerals are similar to the aforementioned olivine, so altered or weathered amphibole will contain oxidized iron, which must melt at a higher temperature than unaltered amphibole. The melting points of pyroxene and amphibole are lower than those of olivine, ranging from about 1,000°C to 1,100°C. In other words, current state-of-the-art technology selects the mineral with the lowest iron content (less than 10%, and in most cases less than 8%) and melts it at temperatures exceeding 1,450°C, typically up to 1,600°C or higher, thereby [removing] Fe 3+ While mitigating the presence of iron oxide-containing crystals, the present invention Fe 2+ A mineral having the maximum amount of iron content in the state (which may be indicated as either FeO or Fe2O3 in XRF analysis), the iron is present in an amorphous matrix or a combination of amorphous and microcrystalline matrix, and iron-containing crystals such as unaltered olivine or unaltered amphibole have substantially lower melting points than iron oxide-containing macrocrystalline crystals such as ferrite, hematite, magnetite, altered olivine or altered amphibole.

[0031] An additional concern regarding current state-of-the-art technology processes is the crystallization of fibers that occurs as the extruded fiber strands are cooled while being extruded through a die or bushing, or thereafter. The cooling process from the melting temperature to a suitable temperature for winding onto a spool has the potential to cause crystal formation within the fiber strands. Therefore, it is important or desirable that the melt does not contain any crystals or microcrystals, as such crystals or microcrystals induce further crystal growth during the fiber strand cooling process. In other words, it is important that the melt composition at the point of fiber drawing be mostly or completely amorphous; that is, there should be no macrocrystals or microcrystals (containing less than 20 weight percent of crystalline or microcrystals). The chemical composition of the mineral to be melted and the melting process are optimized to minimize and eliminate the possibility of crystal formation during the cooling process, because any crystal formation within the fiber strands can cause the continuous fiber to break or weaken the fiber strands. Current state-of-the-art technology has attempted to address this problem by selecting minerals with an andesic basaltic chemical composition having a limited amount of iron content to prevent crystal formation, as iron oxide crystals are the primary cause of harmful crystal formation when extruded fiber strands are cooled and such crystal formation is typically in the form of olivine. The present invention solves this problem associated with the prior art by using minerals having an amorphous or a combination of amorphous and microcrystalline content with a lower melting point. Ideally, the melting point of the mineral composition used to produce continuous fibers in the present invention is lower than the olivine crystal formation temperature, which can start at 1,400°C and, in some cases, even higher.The present invention comprises selecting a mineral in an amorphous state, such as lava quenched by water, having a basaltic, intermediate, or andic chemical composition having a relatively lower melting point than the prior art, or in a combined state of amorphous and microcrystalline, thereby reducing energy consumption, wherein the mineral is ferric Fe. 3+ Alternatively, it does not contain iron oxide and / or quartz. By selecting amorphous or combination of amorphous and microcrystalline minerals, the molten composition achieves an amorphous state at lower temperatures and in shorter periods, thereby using less energy. 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, resulting in fiber strands with a higher amorphous content, more consistent and higher tensile strength, and improved physical properties.

[0032] As used herein, the term "un-oxidized iron" refers to Fe that may appear as FeO or Fe2O3 in XRF analysis. 2+ Iron or ferrous iron, or iron is Fe 2+ Other more complex compounds in the state, or iron is Fe 2+ It refers to any crystalline, microcrystalline, or amorphous mineral or matrix that exists in a disordered / amorphous state or is combined with other elements, such as in the chemical formulas of pyroxene, olivine, and amphibole. In these minerals, Fe 2+ is not directly bonded to the oxygen atom. Therefore, in this sense, Fe 2+ It is in a non-oxidized state as implied in the present invention. Examples of minerals containing non-oxidized iron include all water-quenched lava having a basaltic, intermediate basaltic, or andic chemical composition. Non-oxidized ferrous iron Fe 2+Examples of iron-containing crystals or microcrystals include pyroxene, unaltered olivine, and unaltered amphibole.

[0033] As used herein, the term "oxidized iron" refers to Fe 3+ Or iron is Fe 3+ It refers to any crystal, mineral, or substrate that exists in a specific form, is directly bonded to oxygen as in Fe2O3, or has reacted with oxygen. Examples of minerals containing iron oxide include ferrite, hematite, magnetite, weathered or altered olivine, and weathered or altered amphibole.

[0034] As used herein, the terms “basaltic hyaloclastite,” “intermediate basaltic hyaloclastite,” or “andic hyaloclastite” refer to hyaloclastite, lava, volcanic ash, or pumice of any source, regardless of the mineral source of origin, provided that it is quenched by water unless otherwise specified, having an amorphous content of about 30% to 100% by weight and a crystalline content of 0% to about 70% by weight, wherein the crystalline matrix consists of microcrystals and the iron contained therein is Fe 2+ It exists in the form of an amorphous or microcrystalline matrix; that is, iron found in microcrystals is in a disordered / amorphous state or is bonded to other elements and is not directly bonded to oxygen. The aforementioned range includes all intermediate values ​​in between.

[0035] As used herein, the term “substantially free” means containing less than about 2 weight percent. For example, basal hyaloclastite that is substantially free of ferrite, hematite, magnetite, altered or weathered olivine or altered or weathered amphibole means that basal hyaloclastite contains less than 2 weight percent of ferrite, hematite, magnetite, altered or weathered olivine or altered or weathered amphibole.

[0036] Basaltic or mafic hyaloclastite, volcanic ash, or pumice generally contains about 6% to about 18% by weight of calcium noncarbonate found in an amorphous matrix or a combination of amorphous and microcrystalline matrix. As the amount of SiO2 increases from the low 40% by weight SiO2 of basaltic hyaloclastite, volcanic ash, scoria, or pumice to the andic and daisite silica range, calcium noncarbonate, magnesium, and iron decrease, so that virtually no calcium noncarbonate is available in the rhyolitic range.

[0037] In the prior art, the chemical composition and mineralogical characteristics (petrology) of the basalt define its fiber-forming ability, and therefore these characteristics must conform to specific criteria. General limits for oxide content are presented in Table 1 below. Different literature suggests different oxide equivalent ranges based on limitations or prior experience.

[0038] Table 1 - Range of oxide equivalent values ​​for minerals suitable for basalt fibers:

[0039]

[0040] Acidity modulus (M a ) is an important parameter calculated from the oxide content and is defined as follows:

[0041]

[0042] The oxide symbol indicates the weight percentage of the oxide. M a represents the ratio of acidic oxides to basic oxides.

[0043] The optimal chemical composition for the production of continuous basalt fibers is considered to be a composition in which the acidity rate is in the range of 3 to 6.

[0044] The acidity can be modified by adding various oxides depending on the chemical composition of the starting mineral and the target chemical composition. For example, the addition of CaO and / or MgO decreases the acidity. The addition of Al2O3 and / or SiO2 increases the acidity. For example, in the case of lava with a low acidity, the acidity of the melt can be increased by adding high-silica content lava such as pumice or perlite. In particular, silica fume can be used to increase the acidity. In the case of basaltic hyaloclastite with a low acidity that may not be optimal for CBF production, it is preferable to use amorphous silica or aluminosilicate to increase acidity without adding new crystalline components.

[0045] Viscosity modulus (M v ) is another important factor in determining the optimal mineral and its adjustment for producing suitable basalt fibers. Viscosity (M v ) is defined by the following formula:

[0046]

[0047] Here, x is the mole fraction of the oxide. M presented by the latest technology for CBF production v The limit of is generally between 2 and 3.

[0048] The viscosity of the basalt melt is another key factor in basalt fiber production. Basalt minerals or mixtures are heated and melted during the fiber production process. One of the most important characteristics of basalt determining its suitability for continuous fiber manufacturing is its viscosity η (in Pa·s units). Viscosity must remain within a certain range to enable optimal fiber production. The viscosity η (T) of the basalt melt can be calculated using a simple equation determined empirically. The variables in the equation are the weight percent composition, temperature T, and acidity M. a am:

[0049]

[0050] Here, T is the temperature in ℃. This equation is established for a specific type of basalt and a specific temperature range. Therefore, this equation is applicable only to basalt with the same or similar composition and in the temperature range of 1200 to 1450℃.

[0051] Other methods for calculating the viscosity of basalt melts are also available from the available data. Oxides such as silica SiO2, alumina Al2O3, magnesium oxide MgO, and trivalent iron Fe2O3 increase viscosity, but ferric oxide has a detrimental effect on the mechanical parts of extrusion equipment. Alkali metal oxides such as K2O and Na2O and divalent iron FeO lower viscosity.

[0052] To begin selecting a mineral suitable for producing continuous basalt fibers in the prior art, the chemical composition must first satisfy the elemental range presented in Table 1 above. Next, the acidity (M a ) and viscosity (M v ) should be determined and adjusted as needed to meet the range suitable for manufacturing basalt fibers. The acidity rate should be in the range of 3 to 6, and the viscosity rate should be in the range of 2 to 3.

[0053] Tables 2 and 3 below show the chemical oxide analysis of basaltic hyaloclastite or intermediate basaltic hyaloclastite according to the present invention, e.g., hyaloclastite from various sources, volcanic ash or pumice-based minerals, and show CaO levels and FeO, MgO correlated with SiO2 content. The oxide values ​​for Ca, Mg, Fe, Na, and K presented in Table 3 below are examples of preferred oxide levels for the production of basalt fibers according to the present invention.

[0054] Table 2 - Desirable Chemical Composition of Minerals Suitable for Basalt Fiber Production

[0055]

[0056] Table 3 - Preferred chemical composition of basaltic hyaloclastite, intermediate basaltic hyaloclastite, and andesic hyaloclastite minerals, showing the preferred ratios between various elements and the sum of various elements

[0057]

[0058] All of the above examples, excluding the PTR example, exhibit characteristics desirable for use as basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals to be mixed with limestone for the manufacture of basalt fibers according to the present invention.

[0059] All of the above examples are minerals collected, processed, and analyzed by the inventor in various regions of the world. The three-letter notation indicates the source of the mineral.

[0060] In addition, it is important that the ratio of Si to the sum of Fe and Al (SiO2 / (Fe2O3+Al2O3)) is low, preferably about 1.5, more preferably about 1.25 to about 2.25, as this improves the properties of the melt.

[0061] The sodium equivalent (Na2O + 0.658 K2O) of the mineral according to the present invention may be relatively high, but this may be a desirable characteristic for manufacturing alkali-resistant fibers.

[0062] Mineralogical XRD data confirms some of the above, namely the substantial absence of quartz. The absence of quartz has additional positive effects when compared to the quartz found in currently used basalt. Quartz is a hard mineral that requires high specific energy and a higher melting temperature to melt. It is very important that the basaltic hyaloclastite or intermediate basaltic hyaloclastite according to the present invention contains substantially no quartz, which provides specific advantages to the basalt fiber manufacturing process, whereas conventional basalt from Ukraine and Georgia currently used for basalt fiber manufacturing contains varying amounts of quartz. The basaltic hyaloclastite or intermediate basaltic hyaloclastite contains CaO distributed between amorphous and feldspars, with little to no CaO derived from carbonates, which contributes to reducing CO2 emissions during the melting process; that is, it not only improves melting but also enhances the uniformity and efficiency of the melt, thereby lowering the melting temperature and reducing energy consumption.

[0063] The first three samples in Tables 2 and 3 above, LS36-10, TDR, and SND, exhibit a basaltic chemical composition 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 low range of chemical compositions required for the manufacture of basalt fibers. To increase the acidity, amorphous alumina and silica, which are preferably present in a mainly amorphous or a combination of amorphous and microcrystalline forms, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic or rhyolitic hyaloclastite, may be added. To further adjust melting properties such as viscosity, viscosity ratio, and surface tension, other minerals or elements such as one or more of boron, boron 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, fluorides, and chlorites may be added in an amount of less than 1 weight% each. Additionally, one or more of lanthanum oxide, lanthanide, boron, borax, etc. may be added in an amount of less than 3 weight% each to adjust viscosity properties.

[0064] The following three samples, AB, BKP, and PVT, have similar basaltic chemical compositions, with total silica and alumina of 59.69–63.9% and total amounts of non-carbonate calcium, magnesium, and iron oxides of 28.94–34.61%. The oxide values ​​of these samples fall within the chemical composition range required for the manufacture of basalt fibers. To increase the acidity, amorphous alumina and silica, which exist primarily in amorphous or a combination of amorphous and microcrystalline forms, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic or rhyolitic hyaloclastite, may be added. To decrease the acidity, amorphous calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide, which exist in amorphous forms such as quicklime and calcined dolomite lime, may be added to these samples. To further adjust melting properties such as viscosity, viscosity ratio, and surface tension, other minerals or elements such as one or more of boron, boron 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, fluorides, and chlorites may be added in an amount of less than 1 weight percent each. Additionally, one or more of lanthanum oxide, lanthanide, boron, and borax may be added in an amount of less than 3 weight percent each to adjust viscosity properties. If desired, zirconium oxide (ZrO2) may be added up to about 12 weight percent to improve alkali resistance and other properties.

[0065] The following two samples, RDF and THR, have similar basaltic chemical compositions with a slightly higher total silica and alumina content of 65.6–67.38% and a total amount of non-carbonate calcium, magnesium, and iron oxides of 25.91–27.14%. The oxide values ​​of these samples fall within the chemical composition range required for the manufacture of basalt fibers. To increase the acidity, amorphous alumina and silica containing elements that exist mainly in amorphous or a combination of amorphous and microcrystalline forms, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic or rhyolitic hyaloclastite, may be added. To decrease the acidity, amorphous calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide, such as quicklime and calcined dolomite lime, may be added to these samples. To further adjust melting properties such as viscosity, viscosity ratio, and surface tension, one or more of boron, boron 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, fluorides, and chlorites may be added in an amount of less than 1 weight% each. Additionally, one or more of lanthanum oxide, lanthanide, boron, and borax may be added in an amount of less than 3 weight% each to adjust viscosity properties. If desired, up to about 12 weight% of zirconium oxide (ZrO2) may be added to improve alkali resistance and other properties.

[0066] The next sample, VCR, has an intermediate to andicin chemical composition with a slightly higher total silica and alumina content of 69.81%. The oxide value of this sample falls within the range of chemical composition required for the manufacture of basalt fibers. To increase the acidity, amorphous alumina and silica containing elements that exist mainly in amorphous or a combination of amorphous and microcrystalline forms, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic or rhyolitic hyaloclastite, may be added. To decrease the acidity, amorphous calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide, such as quicklime and calcined dolomite lime, may be added to this sample. To further adjust melting properties such as viscosity, viscosity ratio, and surface tension, one or more of boron, boron 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, fluorides, and chlorites may be added in an amount of less than 1 weight% each. Additionally, one or more of lanthanum oxide, lanthanide, boron, and borax may be added in an amount of less than 3 weight% each to adjust viscosity properties. If desired, up to about 12 weight% of zirconium oxide (ZrO2) may be added to improve alkali resistance and other properties.

[0067] The last sample, PTR, has an andesite chemical composition with a slightly higher total silica and alumina content of 73.44%. The oxide value of this sample falls within the upper limit range of the chemical composition required for the manufacture of basalt fibers, although it may fall outside this range in some applications. To reduce the acidity, amorphous calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide, such as quicklime and calcined dolomite lime, may be added to this sample. To further adjust melting properties such as viscosity, viscosity, and surface tension, one or more of boron, boron 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, fluorides, and chlorites may each be added in an amount of less than 1 weight%. Additionally, one or more of lanthanum oxide, lanthanide, boron, borax, etc., may be added in amounts of less than 3 weight percent each to control viscosity properties. If desired, up to about 12 weight percent of zirconium oxide (ZrO2) may be added to improve alkali resistance and other properties.

[0068] The chemical composition described herein is measured by the XRF (X-ray fluorescence) method. This is a non-destructive analytical technique used to determine the elemental composition of materials. An XRF analyzer determines the chemical composition of a sample by measuring the fluorescent (or secondary) X-rays emitted from the sample when excited by a primary X-ray source. Since each element present in a sample generates a series of characteristic fluorescent X-rays ("fingerprints") unique to that specific element, XRF spectroscopy is an excellent technique for the qualitative and quantitative analysis of material composition. However, it should be noted that since XRF analysis quantifies major elements in oxide equivalents, the oxide designation does not necessarily accurately reflect the chemical form in which the element actually exists. In particular, iron is designated as FeO or sometimes Fe2O3, but it may actually exist in other chemical forms within the mineral, such as in a disordered / amorphous state, or bonded to other metals or elements but not to oxygen. The chemical analysis described herein is a total oxide equivalent XRF scan known and used in the art to determine the chemical composition of minerals.

[0069] Sample preparation for XRF can be performed using two different methods: the pressed powder method and the fused glass disk method. Pressed powder specimens are typically ground in a tungsten carbide ring and puck mill using a binder to reduce particle size and provide a dense powder mount that remains intact during transport and analysis. The advantages of this preparation method include simplicity and a superior detection limit, but the disadvantage is the so-called "mineralogical effect," which requires a similar matrix between the sample used in the calibration curve and the unknown specimen for the calibration to be effective.

[0070] Basaltic hyaloclastite, intermediate basaltic hyaloclastite, or andesic hyaloclastite minerals quenched by water, lava, volcanic ash, and pumice, etc., may contain microcrystals of calcium, iron, alumina, silicates, and other minerals, for example, clinopyroxene Ca(Mg,Fe,Al,Ti)(Si,Al)2O6, calcium plagioclase feldspars (Na,Ca)Al(Si,Al)3O8, olivine (Fe,Mg)2SiO4, and hornblende (Ca,Na). 2-3 (Mg,Fe,AI)5(AI,Si)8O 22 Examples include (OH,F)2, etc., which are examples of microcrystalline materials containing non-carbonate elements that can be melted at a lower temperature in the basalt fiber manufacturing process according to the present invention, such as calcium, magnesium, potassium, sodium, and ferrous iron, thereby achieving reduced emissions and reduced energy consumption according to the present invention. Iron may be present in an amorphous matrix, or in microcrystalline monoclinic pyroxene Ca(Mg,Fe,Al,Ti)(Si,Al)2O6 and / or olivine (Fe,Mg)2SiO4 microcrystals.

[0071] Table 4 below shows examples of hyaloclastite, lava, volcanic ash, or pumice containing varying amounts of amorphous and crystalline content. Samples 14 and 15 are rhyolitic glasses such as perlite, with a CaO content of less than 1%, which contrasts with the basaltic hyaloclastite of samples 1 to 13, where the CaO ranges from 9 to 16%.

[0072] Table 4

[0073]

[0074] Samples 1 to 13 of Table 4 above have a composition that is desirable for use in forming continuous basalt fibers according to the present invention.

[0075] When using basaltic hyaloclastite or intermediate basaltic hyaloclastite, most or all of the elements are contained within the amorphous matrix. Therefore, mineral-related concerns in conventional manufacturing processes are absent or significantly reduced. At most, the crystals found in hyaloclastite will be microcrystalline, not the large crystals found in conventional basalt. Furthermore, since some or most of the matrix of basaltic hyaloclastite or intermediate basaltic hyaloclastite will be in an amorphous form, the amount of crystalline material is reduced in terms of range and proportion. Consequently, these can be reduced to plagioclase, pyroxene, and amphibole. Depending on the amorphous content and the consequent crystalline composition, the chemical composition of the raw material mixture determines the most desirable product type for manufacturing. In particular, hyaloclastite with an amorphous content of 40–80 wt% is desirable for the manufacture of continuous basalt fibers. As another example, a raw material mixture having an amorphous content of 30% may be most suitable for manufacturing staple fibers. A factor to consider here is that the amorphous and microcrystalline content of the raw material mixture found in hyaloclastite makes the melting phase more uniform, as the amorphous material melts more uniformly with the microcrystals at a specific temperature to form a molten composition that is ideally completely or 100% amorphous, with an amorphous content of more than about 80%, preferably more than about 88%, more preferably more than about 90%, and most preferably more than about 95%. In the case of conventional basalt, it is difficult to obtain a suitable melting state due to the numerous crystals present within it and the fact that, as shown in the table above, these crystals are relatively large and each has a unique melting temperature. This is precisely why many types of basalt around the world have been attempted for manufacturing basalt fibers but have failed.Regarding the hyaloclastite according to the present invention, it is desirable that a relatively large amount of amorphous content exists and the crystalline portion is microcrystalline, which reduces the total number of crystals present in the hyaloclastite and thereby reduces variability in melt optimization. In other words, instead of using basalt containing 5 to 12 types of crystalline minerals and having a relatively large crystal structure, using lava quenched by water that is 100% amorphous and does not contain crystals, or contains a combination of amorphous and 1 to 4 types of microcrystals, significantly simplifies melt optimization, which ultimately improves the basalt fiber manufacturing process. Therefore, the use of the hyaloclastite according to the present invention improves the uniformity and efficiency of the melt, lowers the melting temperature, reduces energy consumption, and consequently reduces emissions such as CO2.

[0076] To increase the acidity, amorphous alumina and silica containing elements that exist primarily in amorphous or a combination of amorphous and microcrystalline forms, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic or rhyolitic hyaloclastite, may preferably be added. The amounts of these elements or oxides are calculated to satisfy the target mixture chemical composition up to about 20 weight percent of the hyaloclastite main component. To decrease the acidity, amorphous calcium oxide, limestone, magnesium oxide, dolomite, sodium oxide, and potassium oxide, such as quicklime and calcined dolomite lime, may preferably be added to these samples. The amounts of these elements or oxides are calculated to satisfy the target mixture chemical composition up to about 20 weight percent of the hyaloclastite main component. To further adjust melting properties such as viscosity, viscosity ratio, and surface tension, one or more of boron, boron 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, fluorides, and chlorites may be added in an amount of less than 1 wt% each. Additionally, one or more of lanthanum oxide, lanthanide, boron, and borax may be added in an amount of less than 3 wt% each to control viscosity properties. If desired, up to 12 wt% of zirconium oxide (ZrO2) may be added to improve alkali resistance and other properties. The aforementioned ranges include all intermediate values ​​in between.

[0077] These compounds can also adjust and improve the temperature reduction characteristics of the extruded melt, thereby influencing the physical crystallization or solidification properties of the fibers. This leads to the optimization of the physical and chemical properties of basalt fiber products.

[0078] In the disclosed embodiments of the present invention, basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals may be used together with limestone, dolomite, burnt lime, quick lime, aluminosilicate calcined clay, volcanic ash having properties different from the main mineral, andanic pumice, daisic pumice, rhyolitic pumice, perlite, silica fume, etc. to adjust and modify acidity, viscosity, viscosity, melt surface tension, and other necessary properties for the manufacture of basalt fibers. Basaltic hyaloclastite or intermediate basaltic hyaloclastite according to the present invention preferably originates from hyaloclastite, lava, volcanic ash or pumice, or other igneous rocks. Such basaltic hyaloclastite or intermediate basaltic hyaloclastite preferably has a chemical composition comprising about 30 wt% to about 57 wt% SiO2, about 6 wt% to about 18 wt% Al2O3, about 6 wt% to about 18 wt% Fe2O3, and about 4 wt% to about 25 wt% CaO, preferably the sum of Al2O3+Fe2O3 is between about 20 wt% and about 35 wt%, preferably the ratio between Al2O3 and Fe2O3 is between about 0.75 and about 1.50 or ideally about 1, and the ratio between SiO2 and the sum of Al2O3+Fe2O3 is preferably between about 1.25 and 2.25, and ideally about 1.5.

[0079] In addition to the above, other compounds such as K2O, TiO2, P2O5, MnO, various metals, rare earth trace elements, and other unidentified elements may be present in small amounts. These other compounds together account for less than 10 weight percent of the total chemical composition of basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals, such as hyaloclastite, lava, scoria, volcanic ash, or pumice minerals.

[0080] In another disclosed embodiment of the present invention, 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.

[0081] The basaltic hyaloclastite or intermediate basaltic hyaloclastite mineral according to the present invention may be in a microcrystalline or amorphous (vitreous) form and is typically found in combinations of both in various proportions. Preferably, the hyaloclastite, volcanic ash, or pumice according to the present invention comprises about 30% by weight to 100% by weight of an amorphous form, more preferably about 40% by weight to about 80% by weight of an amorphous form, most preferably about 50% by weight to about 70% by weight of an amorphous form, and particularly about 80% by weight to about 95% by weight of an amorphous form. The crystalline portion of the hyaloclastite preferably comprises 0 wt% to about 20 wt% olivine, 0 wt% to about 40 wt% clinopyroxene, 0 wt% to about 60 wt% plagioclase, and 0 wt% to about 40 wt% (or less than 40 wt%) of other minerals, such as calcite, amphibole, biotite, potassium feldspars (K-feldspars), mordenite, clinoamphibole, hyperstein (a type of orthorhombic pyroxene), feldspathoid sulfides, metals, rare earth minerals, other unidentified minerals, and combinations thereof. The aforementioned ranges include all intermediate values ​​in between.

[0082] In the disclosed embodiments, the hyaloclastite or water-quenched lava mineral selected for the raw material mixture used in the molten composition may be reduced to an appropriate particle size to facilitate the efficient melting of the composition. Size reduction may be performed using appropriate crushing, grinding, or crushing equipment. Examples of such equipment include roller mills, hammer mills, High Pressure Grinding Roll (HPGR) mills, disc mills, jet mills, etc. Hyaloclastite particles may be produced by grinding using a hammer, disc, ball mill, and vibratory grinder, 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 equipment. The target particle size may be sand or gravel size, or may be a fine sand-like particle size ranging from 1 mm or less to 20 mm or more. The size of the raw material feed composition may be any appropriate size depending on the requirements of the type of melting furnace used in the melting process, which is not the subject of the present invention.

[0083] In another embodiment of the present invention, while the hyaloclastite mineral is reduced to a desired size required for the molten composition, it may be exposed to a microwave energy field so that the microwaves can assist the melting process by transforming or converting the crystalline or microcrystalline portions of the mineral into amorphous or microcrystalline portions, because more amorphous portions melt and homogenize more easily and at lower temperatures than macrocrystalline portions. For example, a mineral having 20% ​​amorphous content and 80% microcrystalline content exposed to a microwave energy field during or after the size reduction process described above may be converted to 50% amorphous content and 50% microcrystalline content. In another example, a mineral having 50% amorphous content and 50% microcrystalline content exposed to a microwave energy field during or after the size reduction process described above may be converted to 80% amorphous content and 20% microcrystalline content. The resulting mineral maintains its chemical composition, while the amorphous portion is increased by the modified amorphous-to-crystalline composition, which significantly improves the efficiency of the melting process. Consequently, the melting point is lowered, and thus the melting temperature of the molten composition is also lowered. Therefore, the term "hyaloclastite" can be applied not only to amorphous / microcrystalline compositions in their natural state, but also to compositions in which a portion of the crystalline content is modified into an amorphous state by microwave treatment during or after the mineral grinding or size reduction process to increase the amorphous content. Both the amorphous and microcrystalline materials of hyaloclastite will melt at lower temperatures and / or faster than minerals that are mostly macrocrystalline. Therefore, the use of minerals with the highest amount of amorphous composition, such as highly amorphous hyaloclastite, is preferred in the present invention. These features allow the process to operate faster at lower temperatures and with less energy consumption, and reduce the risk of crystallization of the fiber strands.Accordingly, the present invention provides a more efficient process and produces continuous fibers with improved properties at a lower cost when using hyaloclastite as specified in the present invention.

[0084] In a further embodiment of the present invention, hyaloclastite is tested to measure the content of iron oxide, which may be contained in small amounts in the form of magnetite, ferrite, or hematite within basaltic, intermediate, or andic hyaloclastite. If iron oxide crystals are found, the size reduction process may include an optional process for removing the iron oxide through magnetic separation. This process may be applied during or after the size reduction process. Since the iron oxide contained in magnetite has ferromagnetic properties, it can be separated by a magnetic field. Since the iron oxide contained in ferrite also has ferromagnetic properties, it can likewise be separated by a magnetic field. As the hyaloclastite particles move from the grinding mill to the storage silo, the hematite crystals can be removed using a magnet suitable for generating a magnetic field of sufficient strength, in a suitable batch necessary for removing and separating hematite crystals from the hyaloclastite to be used in the molten composition for drawing fibers. Since the iron oxide contained in hematite has weak magnetism, it can be separated using a strong magnet, such as a rare-earth magnet. Alternatively, as described above, hyaloclastite containing a small amount of hematite can be treated with a microwave field to increase the magnetic properties of the hematite and then separated by a magnetic field. Any suitable type of magnet, such as a conventional magnet, an electromagnet, or a rare-earth magnet, can be positioned to form a magnetic field as the hyaloclastite is moved by a conveyor belt, duct, or similar device while being reduced in size. Any suitable type or arrangement of magnet to form a magnetic field strong enough to separate the ferromagnetic iron oxide crystal portion of the molten composition may be used in the present invention.

[0085] In the disclosed embodiments of the present invention, a mixture of hyaloclastite or water-quenched lava raw materials according to the present invention is introduced into a melting furnace suitable for producing a molten composition. Any melting furnace capable of forming a molten composition in a temperature range of 1,200°C to 1,500°C may be used. The type of melting furnace used is not the subject of the present invention. The bottom or side of the melting furnace is provided with an outlet of sufficient diameter to allow the molten material to pass through and fall onto an extrusion die below, e.g., a platinum-rhodium die or bushing. Any type of extrusion die suitable for the manufacture of continuous basalt fibers may be used. A rotary drum for winding the fibers into roving may be used below the extrusion die at a distance suitable for the manufacture of continuous basalt fibers. Between the extrusion bushing or die, the fibers may be coated with a lubricant, binder, curing agent, or resin to improve fiber properties. Any type of organic or inorganic material known in the art may be used to improve the properties of the plastic or fiber. An example of such a material is an amine curing agent. Any coating agent known in the relevant technical field may be used, and the type and method thereof are not the subject of this invention.

[0086] In the disclosed embodiments of the present invention, hyaloclastite, hyaloclastite quenched by water, volcanic glass, volcanic ash, or lava substantially does not contain ferrite, hematite, or magnetite.

[0087] In another disclosed embodiment of the present invention, hyaloclastite, hyaloclastite quenched by water, volcanic glass, volcanic ash, or lava does not substantially contain Fe2O3.

[0088] In the disclosed embodiments of the present invention, the melt preferably has a temperature of about 1250°C to about 1900°C, more preferably about 1300°C to about 1800°C, most preferably about 1300°C to about 1500°C, particularly about 1500°C to about 1700°C, even more particularly about 1500°C to about 1800°C, most particularly about 1500°C to about 1900°C, preferably about 1300°C to about 2000°C, more preferably about 1300°C to about 1700°C. The aforementioned ranges include all intermediate values ​​in between.

[0089] In one disclosed embodiment, the molten phase at the fiber drawing temperature forms a molten composition that is amorphous or amorphous and microcrystalline, wherein the amorphous content is greater than about 80%, preferably greater than about 88%, more preferably greater than about 90%, most preferably greater than about 95%, particularly completely or 100% amorphous. The aforementioned ranges include all intermediate values ​​in between.

[0090] In another disclosed embodiment of the present invention, the fiber strand preferably has a diameter of about 1 micron to about 18 microns, more preferably about 4 microns to about 15 microns, and most preferably about 6 microns to about 12 microns. The fiber may also be 8 microns to about 10 microns, and particularly about 7 microns. The aforementioned ranges include all intermediate values ​​in between.

[0091] In a further disclosed embodiment of the present invention, the continuous fiber strand comprises an amorphous or amorphous and microcrystalline content, wherein the amorphous content is greater than about 80%, preferably greater than about 88%, more preferably greater than about 90%, most preferably greater than about 95%, and ideally completely or 100% amorphous. The aforementioned ranges include all intermediate values ​​in between.

[0092] In one embodiment, the fiber forming unit produces a continuous fiber or a plurality of fibers, i.e., roving. The present invention may use any type of melting furnace and fiber forming unit, such as a gas or electric melting furnace, a single-stage or multi-stage temperature unit, or a single or multiple fiber taphole, which are not the subject of the present invention. Specific details for implementing the invention

[0093] The following examples are intended to illustrate selected embodiments of the present invention and are not intended to limit the scope of the invention. All percentages used herein are weight percent unless otherwise specifically stated.

[0094] Example 1

[0095] Hyaloclastite, basaltic hyaloclastite, or intermediate basaltic hyaloclastite minerals are mined from quarries and transported to basalt fiber manufacturing plants, where they are crushed into fine particle sizes suitable for the basalt fiber manufacturing process. Hyaloclastite or basaltic hyaloclastite or intermediate basaltic hyaloclastite minerals preferably have a chemical composition comprising about 30 wt% to about 57 wt% SiO2, about 10 wt% to about 18 wt% Al2O3, about 8 wt% to about 18 wt% Fe2O3, and about 4 wt% to about 25 wt% CaO, preferably the sum of Al2O3 + FeO is between about 20 wt% and about 35 wt%, preferably the ratio between Al2O3 and FeO is between about 0.75 and about 1.50, or ideally about 1, and the ratio between SiO2 and the sum of Al2O3 + Fe2O3 is preferably between about 1.25 and 2.25, and ideally about 1.5. Hyaloclastite does not contain any iron oxide-containing crystals. Minor components, such as limestone, are ground to a particle size similar to that of crushed hyaloclastite. The crushed limestone and basaltic or intermediate basaltic hyaloclastite minerals are mixed together in an approximate ratio suitable for the basalt fiber manufacturing process, namely, a ratio of about 75% to about 98% by weight of basaltic hyaloclastite or intermediate basaltic hyaloclastite and about 2% to about 25% by weight of limestone minerals. The mixed mineral feed composition is preheated and then fed into a melting furnace typically used for basalt fiber manufacturing. The melting furnace is heated to a temperature of about 1250°C to 1650°C, and the mixed composition is maintained in the melting furnace for a sufficient amount of time to melt. After the composition is melted, basalt fibers are produced following a standard fiber extrusion or fiberization process.

[0096] Example 2

[0097] The Hyaloclastite AB1 minerals of Tables 2 and 3 above are mined from a quarry and transported to a basalt fiber manufacturing plant, where they are crushed into fine particle sizes suitable for the basalt fiber manufacturing process. The Hyaloclastite has the chemical composition shown in Tables 2 and 3. The Hyaloclastite does not contain iron oxide-containing crystals. To increase the acidity, amorphous alumina and silica containing elements that exist mainly in amorphous or a combination of amorphous and microcrystalline forms, such as alumina oxide, silica fume, perlite, pumice, obsidian, dacitic or rhyolitic Hyaloclastite, may be added. The amount of these elements or oxides is calculated to satisfy the target mixture chemical composition up to about 15 weight percent of the main component of the Hyaloclastite. To further adjust melting properties such as viscosity, viscosity ratio, and surface tension, other minerals or elements such as one or more of boron, boron 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, fluorides, and chlorites may be added in an amount of less than 1 weight percent each. Additionally, one or more of lanthanum oxide, lanthanide, boron, and borax may be added in an amount of less than 3 weight percent each to adjust viscosity properties. If desired, up to about 12 weight percent of zirconium oxide (ZrO2) may be added to improve alkali resistance and other properties. One or more of the above materials are added to the hyaloclastite up to a maximum of 3 weight percent. Silica fume and hyaloclastite minerals are mixed together in an approximate ratio suitable for the basalt fiber manufacturing process, namely, a ratio of about 85% to about 98% by weight of basaltic hyaloclastite or intermediate basaltic hyaloclastite and about 2% to about 15% by weight of silica fume.The mixed mineral feed composition is preheated and then fed into a melting furnace typically used for manufacturing basalt fibers. The melting furnace is heated to a temperature of approximately 1250°C to 1650°C, and the mixed composition is maintained in the melting furnace for a sufficient amount of time for the composition to melt. After the composition is melted, basalt fibers are produced following a standard fiber extrusion or fiberization process.

[0098] Example 3

[0099] The intermediate basaltic hyaloclastite mineral PTR of Tables 2 and 3 above is mined from a quarry and transported to a basalt fiber manufacturing plant, where it is crushed to a fine particle size suitable for the basalt fiber manufacturing process. The chemical composition of the PTR intermediate basaltic hyaloclastite mineral is presented in Tables 2 and 3. This mineral has a composition of 60% amorphous and 40% microcrystalline. To reduce acidity, small amounts of components such as dolomite or calcined lime are crushed to a particle size similar to that of hyaloclastite. The crushed dolomite and intermediate hyaloclastite minerals are mixed together in an approximate ratio suitable for the basalt fiber manufacturing process, namely, a ratio of about 75% to about 98% by weight of intermediate basaltic hyaloclastite and about 2% to about 15% by weight of dolomite mineral. To further adjust melting properties such as viscosity, viscosity ratio, and surface tension, other minerals or elements, such as one or more of boron, boron 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, fluorides, and chlorites, may be added in an amount of less than 1 weight percent each. Additionally, one or more of lanthanum oxide, lanthanide, boron, and borax may be added in an amount of less than 3 weight percent each to adjust viscosity properties. If desired, up to about 12 weight percent of zirconium oxide (ZrO2) may be added to improve alkali resistance and other properties. One or more of the above materials are added to the hyaloclastite in an amount of up to 3 weight percent. The mixed mineral feed composition is preheated and then fed into a melting furnace typically used for manufacturing basalt fibers. The melting furnace is heated to a temperature of approximately 1450°C, and the mixed composition is maintained in the melting furnace for a sufficient amount of time for the composition to melt. After the composition is melted, basalt fibers are produced following a standard fiber extrusion or fiberization process.

[0100] Example 4

[0101] Hyaloclastite having the chemical composition and properties described in Example 2 above is crushed and sieved to a particle size of 2 mm to form a raw mineral feed. The mineral feed composition is fed into a melting furnace typically used for the manufacture of continuous basalt fibers. The melting furnace is heated to a temperature of approximately 1350°C, and the composition is maintained within the furnace for a sufficient amount of time to melt. After the composition is melted, continuous basalt fibers are produced following a standard fiber extrusion or fiberization process. The continuous basalt fibers are coated with a warm-curable amine curing agent. Fiber strands are collected from the bottom and wound into roving. The individual fibers are then bonded together, impregnated with resin, and bonded and cured together through a full-trusion process to form reinforcing rods.

[0102] Example 5

[0103] An andic hyaloclastite mineral having the chemical composition of Example 3 above is mined from a quarry and transported to a basalt fiber manufacturing plant, where it is crushed and sieved to a fine particle size suitable for a continuous basalt fiber manufacturing process. The fine particle size mineral is exposed to a microwave field, and the crystalline composition is adjusted to 80% amorphous and 20% microcrystalline. Additionally, one or more of lanthanum oxide, lanthanide, boron, and borax may be added in amounts of less than 3 weight percent each to control viscosity properties. If desired, up to about 12 weight percent of zirconium oxide (ZrO2) may be added to improve alkali resistance and other properties. One or more of these materials are added to the hyaloclastite up to a maximum of 3 weight percent. The mixed mineral feed composition is then fed into a melting furnace typically used for basalt fiber manufacturing. The melting furnace is heated to a temperature of approximately 1350°C, and the mixed composition is maintained in the melting furnace for a sufficient amount of time for the composition to melt. After the composition is melted, continuous basalt fibers are produced following a standard fiber extrusion or fiberization process.

[0104] Example 6

[0105] The characteristics of basaltic hyaloclastite with an average particle size of 200 microns are analyzed. The chemical composition is analyzed using XRF, and the results are presented in Table 5 below.

[0106] Table 5 - XRF Chemical Composition

[0107]

[0108] The crystalline composition is analyzed using XRD, and the results are presented in Table 6 below.

[0109] Table 6 - Crystalline composition of minerals:

[0110]

[0111] Before melting the raw mineral composition in a melting furnace to draw continuous basalt fibers, basaltic hyaloclastite is analyzed to determine the wetting angle of the melt. The wetting angle correlates with the melting temperature and viscosity and is a critical factor in the continuous basalt fiber draw / extrusion process where the melt comes into contact with a bushing or extrusion die. According to current technology, the wetting angle must be less than 20° and greater than 0. Basaltic hyaloclastite samples are placed under a Linseis heated optical microscope, and while heating and melting, the equipment captures images of the sample's melting and deformation, from which the wetting angle is calculated. The wetting angles in relation to the melting temperature are presented in Table 7 below. From this test protocol, it is determined that the target temperature of the melt composition should be approximately 1300°C and the wetting angle should be approximately 10-12°.

[0112] Table 7 - Melting Temperature and Wetting Angle

[0113]

[0114] After evaluating the wetting angle, the basaltic hyaloclastite raw material mixture is fed into an electric induction melting furnace, and at a temperature of 1309°C, it is determined that the composition is sufficiently melted to begin fiber drawing. No additional additives are used in the raw material mixture to form the molten composition, nor are any resins or additives used in the drawn fiber strands themselves. The continuous basalt fiber is drawn using a spindle motor equipped in a spooling cylinder at a speed of 550 m / min (meters / min). The fiber is wound onto a spool. After drawing is complete, the fiber strands are randomly removed from the bundle. A total of 17 specimens are cut to short lengths and mounted on mounting tabs, with both ends bonded to the mounting tabs using Locktite SuperGlue resin. The fibers mounted on the tabs are left to cure for 24 hours. The total length of the fibers mounted on the tabs is measured to be 63 mm, resulting in a test section length of approximately 12.7 mm to 15 mm. Subsequently, the diameter of each fiber specimen is measured using a digital microscope equipped with an RZ x1500 magnification polarizing objective lens. The fiber diameter is measured before each fiber specimen undergoes tensile strength testing using an Instron 68SC-2 instrument. Fiber diameters are measured at randomly selected locations within the test area and at the fracture location after each test. The fiber strand diameters produced in this run are ±15 microns, as shown in the table below. The diameter at the fracture location is used to determine the results according to standard C1557-14. If the fiber fractures along its entire length, the fiber diameter measured before the test is used for the result. The Instron testing machine is equipped with 50 N pneumatic grips at each end of the fiber mounting tab. The pulling speed of both ends of the fiber (crosshead speed) is 50 mm / m (mm per minute). The tensile strength test results are presented in Table 8 below. This demonstrates that the fiber strands exhibit suitable tensile strength characteristics despite not being treated with any resin or curing agent.

[0115] Table 8 - Instron ASTM C1557-14 Tensile Strength Results:

[0116]

[0117] Example 5

[0118] A basaltic hyaloclastite raw material mixture having the chemical and crystalline mineral compositions shown in Example 4 above is introduced into an electric induction melting furnace and melted at a temperature of 1335°C. It is confirmed that the molten composition is sufficiently melted to begin fiber drawing. No additional additives are used in the raw material mixture to form the molten composition. As the fiber strand passes through the bushing and is drawn out, Huntsman Chemical Company's amine curing agent Aradur ® 3475 (1,3-cyclohexanedimethaneamine) is coated. The continuous basalt fibers are drawn out at a speed of 550 m / min using a spindle motor equipped in a spooling cylinder. The fibers are wound onto a spool. After the run is complete, fiber strands are randomly removed from the bundle. A total of 19 specimens are selected and prepared, and tested using the same equipment described in Example 4 above. The diameter of the fiber strands produced in this experiment is ±15 microns, as shown in Table 9 below. The results of the tensile strength test are presented in Table 9 below. Fiber production in this manner exhibits improved tensile strength characteristics because the fiber strands are treated with an amine curing agent.

[0119] Table 9 - Instron ASTM C1557-14 Tensile Strength Results:

[0120]

[0121] Example 6

[0122] A basaltic hyaloclastite raw material mixture having the chemical and crystalline mineral compositions shown in Example 4 above is introduced into an electric induction melting furnace and melted at a temperature of 1335°C. It is confirmed that the composition is sufficiently melted to begin fiber drawing. No additional additives are used in the raw material mixture to form the molten composition. As the fiber strand passes through the bushing and is drawn out, Huntsman Chemical Company's amine curing agent Aradur ® 3475 (1,3-cyclohexanedimethaneamine) is coated. The continuous basalt fiber is drawn out at a speed of 1650 m / min using a spindle motor equipped in a spooling cylinder. The fiber is wound onto a spool. After the run is complete, the fiber strands are randomly removed from the bundle. A total of 20 specimens are selected and prepared, and tested using the same equipment described in Example 4 above. The fiber strand diameters produced in this experiment are ±9 microns, as shown in Table 10 below. The tensile strength test results are presented in Table 10 below. Fiber production in this manner exhibits improved tensile strength characteristics because the fiber strands are treated with an amine curing agent, despite the significantly increased speed rate and greatly reduced fiber strand diameter.

[0123] Table 10 - Instron ASTM C1557-14 Tensile Strength Results:

[0124]

[0125] Of course, it should be understood that the foregoing relates only to specific disclosed embodiments of the present invention, and that numerous modifications or changes may be made without departing from the spirit and scope of the invention as described in the appended claims.

Claims

Claim 1 A method comprising the following steps: a step of melting basaltic hyaloclastite or intermediate basaltic hyaloclastite, wherein the basaltic hyaloclastite or intermediate basaltic hyaloclastite has an amorphous content of at least 20 weight%; and a step of extruding the molten material into a continuous fiber. Claim 2 A method according to claim 1, wherein the basaltic hyaloclastite or intermediate basaltic hyaloclastite comprises about 30 to about 57 weight% SiO2, about 10 to about 18 weight% Al2O3, about 8 to about 18 weight% Fe2O3, and about 4 to about 25 weight% CaO. Claim 3 A method according to claim 2, wherein the sum of Al2O3 + Fe2O3 is about 20 wt% to about 35 wt%, the ratio between Al2O3 and Fe2O3 is between about 0.75 and about 1.50, and the ratio between SiO2 and the sum of Al2O3 + Fe2O3 is between about 1.25 and about 2.

25. Claim 4 A method according to claim 1, wherein the basaltic hyaloclastite or intermediate basaltic hyaloclastite has an amorphous content of about 30% by weight to 100% by weight. Claim 5 A method according to claim 1, wherein the basaltic hyaloclastite or intermediate basaltic hyaloclastite has an amorphous content of about 50% by weight to 100% by weight. Claim 6 A method according to claim 1, wherein the basaltic hyaloclastite or intermediate basaltic hyaloclastite has an amorphous content of about 80% to 100% by weight. Claim 7 A method according to claim 1, wherein a portion of basaltic hyaloclastite or intermediate basaltic hyaloclastite that is not in an amorphous form is mainly in a microcrystalline form. Claim 8 A method according to claim 1, wherein the basaltic hyaloclastite or intermediate basaltic hyaloclastite substantially does not contain ferrite, hematite, magnetite, altered or weathered olivine or altered or weathered amphibole. Claim 9 A method according to claim 1, wherein basaltic hyaloclastite or intermediate basaltic hyaloclastite substantially does not contain Fe2O3. Claim 10 In claim 1, the method wherein the molten material is at a temperature of about 1250°C to 1450°C. Claim 11 A method according to claim 1, wherein the molten material has an amorphous content exceeding about 80%. Claim 12 In paragraph 1, a method in which continuous fibers are treated with a binder during the extrusion process. Claim 13 A method according to claim 1, wherein the diameter of the continuous fiber is about 4 microns to about 20 microns. Claim 14 A method according to claim 1, wherein the continuous fiber strand has an amorphous content exceeding about 80 weight%.

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