Patent Grant
11306021
Glass fibers are manufactured from various raw materials combined in specific proportions to yield a desired composition, commonly termed a “glass batch.” This glass batch may be melted in a melting apparatus and the molten glass is drawn into filaments through a bushing or orifice plate (the resultant filaments are also referred to as continuous glass fibers). A sizing composition containing lubricants, coupling agents and film-forming binder resins may then be applied to the filaments. After the sizing is applied, the fibers may be gathered into one or more strands and wound into a package or, alternatively, the fibers may be chopped while wet and collected. The collected chopped strands may then be dried and cured to form dry chopped fibers or they can be packaged in their wet condition as wet chopped fibers.
The composition of the glass batch, along with the fiberglass manufactured therefrom, is often expressed in terms of the oxides contained therein, which commonly include SiO2, Al2O3, CaO, MgO, B2O3, Na2O, K2O, Fe2O3, TiO2, Li2O, and the like. Numerous types of glasses may be produced from varying the amounts of these oxides, or eliminating some of the oxides in the glass batch. Examples of such glasses that may be produced include R-glass, E-glass, S-glass, A-glass, C-glass, and ECR-glass. The glass composition controls the forming and product properties of the glass. Other characteristics of glass compositions include the raw material cost and environmental impact.
For instance, E-glass is an aluminoborosilicate glass, generally alkali-free, and commonly used in electrical applications. One advantage of E-Glass is that its liquidus temperature allows operating temperatures for producing glass fibers to be approximately 1900° F. to 2400° F. (1038° C. to 1316° C.). The ASTM classification for E-glass fiber yarns used in printed circuit boards and aerospace applications defines the composition to be 52 to 56 weight % SiO2, 16 to 25 weight % CaO, 12 to 16 weight % Al2O3, 5 to 10 weight % B2O3, 0 to 5 weight % MgO, 0 to 2 weight % Na2O and K2O, 0 to 0.8 weight % TiO2, 0.05 to 0.4 weight % Fe2O3 and 0 to 1.0 weight % Fluorine.
Boron-free fibers are sold under the trademark ADVANTEX® (Owens Corning, Toledo, Ohio, USA). Boron-Free fibers, such as are disclosed in U.S. Pat. No. 5,789,329, incorporated herein by reference in its entirety, offer a significant improvement in operating temperatures over boron-containing E-glass. Boron-Free glass fibers fall under the ASTM definition for E-glass fibers for use in general-use applications.
R-Glass is a family of glasses that are composed primarily of the oxides of silicon, aluminum, magnesium, and calcium with a chemical composition that produces glass fibers with a higher mechanical strength than E-Glass fibers. R-Glass has a composition that contains about 58 to about 60% by weight SiO2, about 23.5 to about 25.5% by weight Al2O3, about 14 to about 17% by weight CaO plus MgO, and less than about 2% by weight of miscellaneous components. R-Glass contains more alumina and silica than E-Glass and requires higher melting and processing temperatures during fiber forming. Typically, the melting and processing temperatures for R-Glass are higher than those for E-Glass. This increase in processing temperature requires the use of a high-cost platinum-lined melter. In addition, the close proximity of the liquidus temperature to the forming temperature in R-Glass requires that the glass be fiberized at a viscosity lower than E-Glass, which is customarily fiberized at or near about 1000 poise. Fiberizing R-Glass at the customary 1000 poise viscosity would likely result in glass devitrification, which causes process interruptions and reduced productivity.
High performance glass fibers possess higher strength and stiffness, compared to traditional E-glass fibers. In particular, for some products, stiffness is crucial for modeling and performance. For example, composites, such as wind turbine blades, prepared from glass fibers with good stiffness properties would allow for longer wind turbine blades on electrical generating wind stations while keeping flexure of the blade within acceptable limits.
Additionally, high-performance glass compositions are desired that possess favorable mechanical and physical properties (e.g., elastic modulus and tensile strength), while maintaining desirable forming properties (e.g., liquidus temperature and fiberizing temperature). Elastic modulus is a measure of the fiber stiffness, defining a relationship between the stress applied to a material and the strain produced by the same material. A stiff material has a high elastic modulus and changes its shape only slightly under elastic loads. A flexible material has a low elastic modulus and changes its shape considerably.
Various exemplary embodiments of the present inventive concepts are directed to a glass composition comprising: SiO2 in an amount from 50.0 to 65.0% by weight; Al2O3 in an amount from 18.0 to 23.0% by weight; CaO in an amount from 1 to 5.0% by weight; MgO in an amount from 9.0 to 14.0% by weight; Na2O in an amount from 0.0 to 1.0% by weight; K2O in an amount from 0.0 to less than 1.0% by weight; Li2O in an amount from 1.0 to 4.0% by weight; TiO2 in an amount from 0.0 to 2.5% by weight; Y2O3 in an amount from 0 to 10.0% by weight; La2O3 in an amount from 0 to 10.0% by weight; Ce2O3 in an amount from 0 to 5.0% by weight; and Sc2O3 in an amount from 0 to 5.0% by weight. The glass composition includes a total concentration of La2O3+Y2O3 in an amount from 2.0 to 10.0% by weight.
In some exemplary embodiments, the glass fiber formed from the glass composition has an elastic modulus between 88 and 115 GPa and a tensile strength according to ASTM D2343-09 of at least 4,400 MPa.
The glass composition may further include 0 to about 7.0% by weight Ta2O5; 0 to about 7.0% by weight Ga2O3; 0 to about 2.5% by weight Nb2O5, and 0 to about 2.0% by weight V2O5.
In various exemplary embodiments, the glass composition is essentially free of B2O3.
In various exemplary embodiments, the glass composition includes 6.0 to 10 wt. % Y2O3.
In various exemplary embodiments, the glass composition includes greater than 1.5 to 10 wt. % La2O3.
In various exemplary embodiments, the glass composition comprises 1.5 to 3.5% by weight Li2O.
In various exemplary embodiments, the glass composition comprises a ratio of MgO/(CaO+SrO) of greater than 2.1.
In various exemplary embodiments, the composition includes at least 4% by weight of Y2O3, La2O3, Ce2O3, and Sc2O3.
Further exemplary aspects of the present inventive concepts are directed to a glass fiber formed from a composition comprising: SiO2 in an amount from 50.0 to 65.0% by weight; Al2O3 in an amount from 18.0 to 23.0% by weight; CaO in an amount from 1 to 8.5% by weight; MgO in an amount from 9.0 to 14.0% by weight; Na2O in an amount from 0.0 to 1.0% by weight; K2O in an amount from 0.0 to less than 1.0% by weight; Li2O in an amount from 0.0 to 4.0% by weight; TiO2 in an amount from 0.0 to 2.5% by weight, Y2O3 in an amount from 6.0 to 10.0% by weight; La2O3 in an amount from 0 to 10.0% by weight; Ce2O3 in an amount from 0 to 5.0% by weight; and Sc2O3 in an amount from 0 to 5.0% by weight. The glass fiber has an elastic modulus between 88 and 115 GPa.
In various exemplary embodiments, the composition comprises 0.5 to 3.5% by weight Li2O.
In various exemplary embodiments, the glass composition includes greater than 1.5 to 10 wt. % La2O3.
In various exemplary embodiments, the glass composition comprises a ratio of MgO/(CaO+SrO) of greater than 2.1.
In various exemplary embodiments, the composition includes at least 4% by weight of Y2O3, La2O3, Ce2O3, and Sc2O3.
Further exemplary embodiments are directed to a glass fiber that has an elastic modulus of 89 to 100 GPa.
Yet further exemplary aspects of the present inventive concepts are directed to a method of forming a continuous glass fiber comprising providing a molten glass composition; and drawing the molten composition through an orifice to form a continuous glass fiber.
Yet further exemplary aspects of the present inventive concepts are directed to a reinforced composite product comprising a polymer matrix; and a plurality of glass fibers formed from a glass composition comprising SiO2 in an amount from 50.0 to 65.0% by weight; Al2O3 in an amount from 18.0 to 23.0% by weight; CaO in an amount from 1 to 5.0% by weight; MgO in an amount from 9.0 to 14.0% by weight; Na2O in an amount from 0.0 to 1.0% by weight; K2O in an amount from 0.0 to less than 1.0% by weight; Li2O in an amount from 1.0 to 4.0% by weight; TiO2 in an amount from 0.0 to 2.5% by weight, Y2O3 in an amount from 0 to 10.0% by weight; La2O3 in an amount from 0 to 10.0% by weight; Ce2O3 in an amount from 0 to 5.0% by weight; and Sc2O3 in an amount from 0 to 5.0% by weight. The glass composition includes a total concentration of La2O3+Y2O3 in an amount from 2.0 to 10.0% by weight.
The glass fibers have an elastic modulus between 88 and 115 GPa and a tensile strength according to ASTM D2343-09 of at least 4,400 MPa.
In some exemplary embodiments, the reinforced composite product is in the form of a wind turbine blade.
The foregoing and other objects, features, and advantages of the invention will appear more fully hereinafter from a consideration of the detailed description that follows.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which these exemplary embodiments belong. The terminology used in the description herein is for describing exemplary embodiments only and is not intended to be limiting of the exemplary embodiments. Accordingly, the general inventive concepts are not intended to be limited to the specific embodiments illustrated herein. Although other methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein.
As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Unless otherwise indicated, all numbers expressing quantities of ingredients, chemical and molecular properties, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present exemplary embodiments. At the very least each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the exemplary embodiments are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Every numerical range given throughout this specification and claims will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein. Moreover, any numerical value reported in the Examples may be used to define either an upper or lower end-point of a broader compositional range disclosed herein.
The present disclosure relates to a high-performance glass composition with improved elastic modulus. Such glass compositions are particularly interesting in the field of wind products, such as wind turbines that require longer blades in order to generate more energy. The longer blades require materials with higher elastic modulus in order to withstand forces applied to them without breaking. The subject glass compositions include lithium and optionally rare earth oxides. Additionally, the subject glass compositions include higher levels of magnesium and alumina than other glass compositions in this space.
The glass compositions disclosed herein are suitable for melting in traditional commercially available refractory-lined glass furnaces, which are widely used in the manufacture of glass reinforcement fibers.
The glass composition may be in molten form, obtainable by melting the components of the glass composition in a melter. The glass composition exhibits a low fiberizing temperature, which is defined as the temperature that corresponds to a melt viscosity of about 1000 Poise, as determined by ASTM C965-96(2007). Lowering the fiberizing temperature may reduce the production cost of the glass fibers because it allows for a longer bushing life and reduced energy usage necessary for melting the components of a glass composition. Therefore, the energy expelled is generally less than the energy necessary to melt many commercially available glass formulations. Such lower energy requirements may also lower the overall manufacturing costs associated with the glass composition.
For example, at a lower fiberizing temperature, a bushing may operate at a cooler temperature and therefore does not “sag” as quickly as is typically seen. “Sag” is a phenomenon that occurs when a bushing that is held at an elevated temperature for extended periods of time loses its determined stability. Thus, by lowering the fiberizing temperature, the sag rate of the bushing may be reduced, and the bushing life can be maximized.
In some exemplary embodiments, the glass composition has a fiberizing temperature of less than 2,650° F., including fiberizing temperatures of no greater than 2,600° F., no greater than 2,550° F., no greater than 2,510° F., no greater than 2470° F., no greater than 2420° F., no greater than 2410° F., no greater than 2405° F., no greater than 2400° F., and no greater than 2390° F., and no greater than 2385° F. In some exemplary embodiments, the glass composition has a fiberizing temperature no greater than 2,600° F., such as no greater than 2,500° F., and no greater than 2,200° F. In some exemplary embodiments, the glass composition has a fiberizing temperature of at least 2,000° F., including at least 2,050° F., at least 2,075° F., at least 2,100° F., and at least 2,150° F.
Another fiberizing property of a glass composition is the liquidus temperature. The liquidus temperature is defined as the highest temperature at which equilibrium exists between liquid glass and its primary crystalline phase. The liquidus temperature, in some instances, may be measured by exposing the glass composition to a temperature gradient in a platinum-alloy boat for 16 hours (ASTM C829-81(2005)). At all temperatures above the liquidus temperature, the glass is completely molten, i.e., it is free from crystals. At temperatures below the liquidus temperature, crystals may form.
In some exemplary embodiments, the glass composition has a liquidus temperature below 2,600° F., including liquidus temperature of no greater than 2,500° F., no greater than 2,450° F., no greater than 2,405° F., no greater than 2,350° F., no greater than 2,300° F., no greater than 2,250° F., no greater than 2,225° F., no greater than 2,200° F., no greater than 2,175° F., and no greater than 2,150° F. In some exemplary embodiments, the glass composition has a liquidus temperature between 2,050° F. and 2,550° F., including between 2,130° F., and 2,490° F., between 2,190° F. and 2,405° F., and between 2,250° F. and 2,450° F.
A third fiberizing property is “ΔT”, which is defined as the difference between the fiberizing temperature and the liquidus temperature. If the ΔT is too small, the molten glass may crystallize within the fiberizing apparatus and cause a break in the manufacturing process. Desirably, the ΔT is as large as possible for a given forming viscosity because it offers a greater degree of flexibility during fiberizing and helps to avoid devitrification both in the glass distribution system and in the fiberizing apparatus. A large ΔT additionally reduces the production cost of the glass fibers by allowing for a greater bushing life and a less sensitive forming process.
In some exemplary embodiments, the glass composition has a ΔT of at least −60° F., including at least −20° F., including at least 40° F., including at least 80° F., including at least 100° F., at least 110° F., at least 120° F., at least 135° F., at least 150° F., and at least 170° F. In various exemplary embodiments, the glass composition has a ΔT between 100° F. and 250° F., including between 120° F. and 200° F., and between 150° F. and 215° F.
The glass composition may include about 50.0 to about 65.0% by weight SiO2, about 18.0 to about 23.0% by weight Al2O3, about 9.0 to about 14.0% by weight MgO, about 1.0 to about 5.0% by weight CaO, about 0.0 to about 1.0% by weight Na2O, 0 to about 1 less than 0.0% by weight K2O, 0 to about 2.5% by weight TiO2, 0 to about 0.8% by weight Fe2O3, and about 0.0 to about 4.0% by weight Li2O. The glass composition may further include 0 to about 10.0% by weight Y2O3, 0 to about 10.0% by weight La2O3, 0 to about 5.0% by weight Ce2O3, and 0 to about 5.0% by weight Sc2O3. The glass composition may further include 0 to about 7.0% by weight Ta2O5, 0 to about 7.0% by weight Ga2O3, 0 to about 2.5% by weight Nb2O5, and 0 to about 2.0% by weight V2O5.
In some exemplary embodiments, the glass composition may include about 52.0 to about 60.0% by weight SiO2, about 18.4 to about 21.5% by weight Al2O3, about 9.3 to about 12.0% by weight MgO, about 1.5 to about 8.0% by weight CaO, about 0.01 to about 0.5% by weight Na2O, about 0.01 to about 0.5% by weight K2O, about 0.01 to about 2.0% by weight TiO2, about 0.01 to about 0.6% by weight Fe2O3, and about 0.1 to about 3.5% by weight Li2O. The glass composition may further include about 1.0 to about 7.0% by weight Y2O3, about 1.0 to about 7.0% by weight La2O3, about 0.01 to about 4.0% by weight Ce2O3, and about 0.01 to about 4.0% by weight Sc2O3. The glass composition may further include about 0.01 to about 5.5% by weight Ta2O5, about 0.1 to about 5.5% by weight Ga2O3, and about 0.01 to about 2.0% by weight Nb2O5.
The glass composition includes at least 50% by weight and no greater than 75% by weight SiO2. In some exemplary embodiments, the glass composition includes at least 52% by weight SiO2, including at least 55% by weight, at least 57% by weight, at least 58.5% by weight, and at least 59% by weight. In some exemplary embodiments, the glass composition includes no greater than 70% by weight SiO2, including no greater than 68% by weight, no greater than 65.5% by weight, no greater than 64.5% by weight, no greater than 62.5% by weight, and no greater than 60.5% by weight. In some exemplary embodiments, the glass composition includes about 50% by weight to about 65% by weight, or about 52% by weight to about 60% by weight SiO2.
To achieve both the desired mechanical and fiberizing properties, one important aspect of the glass composition is having an Al2O3 concentration of at least 15.0% by weight and no greater than 25% by weight. Including greater than 25% by weight Al2O3 causes the glass liquidus to increase to a level above the fiberizing temperature, which results in a negative ΔT. Including less than 15% by weight Al2O3 forms a glass fiber with an unfavorably low modulus. In some exemplary embodiments, the glass composition includes at least 18.0% by weight Al2O3, including at least 18.4% by weight, at least 19.0% by weight, at least 19.5% by weight, and at least 20.0% by weight. In some exemplary embodiments, the glass composition includes about 18.4 to about 23 wt. % Al2O3, including about 18.8 to about 21.5 wt. % Al2O3.
The glass composition further advantageously includes at least 8.0% by weight and no greater than 15% by weight MgO. Including greater than 15% by weight MgO will cause the liquidus temperature to increase, which also increases the glass's crystallization tendency. Including less than 8.0% by weight forms a glass fiber with an unfavorably low modulus if substituted by CaO and an unfavorable increase in viscosity if substituted with SiO2. In some exemplary embodiments, the glass composition includes at least 9.0% by weight MgO, including at least 9.2% by weight, at least 9.3% by weight, at least 9.8% by weight, at least 10% by weight, at least 10.5% by weight, at least 11.0% by weight, at least 11.5 wt. %, at least 12.0 wt. %, and at least 13% by weight MgO. In some exemplary embodiments, the glass composition comprises an MgO concentration between about 9.0 and about 14% by weight, or between about 9.3 and about 12% by weight.
The glass composition may optionally include CaO at concentrations up to about 10.0 wt. %. Including greater than 10% by weight CaO forms a glass with a low elastic modulus. In some exemplary embodiments, the glass composition includes between 0 and 9% by weight CaO, including between 0.5 and 8.8% by weight, between 1.0 and 8.5% by weight, between 1.5 and 8.0% by weight, and between 2.0 and 7.5% by weight. In some exemplary embodiments, the glass composition includes between 1.0 and 5.0 wt. % CaO, or between 1.2 and 4.7 wt. % CaO, or between 1.3 and 4.55 wt. % CaO.
In some exemplary embodiments, the total concentration of MgO and CaO is at least 10% by weight and no greater than 22% by weight, including between 12.5% by weight and 20% by weight, and between 14% by weight and 18.5% by weight.
The glass composition may include up to about 3.0% by weight TiO2. In some exemplary embodiments, the glass composition includes about 0% by weight to about 2.5% by weight TiO2, including about 0.01% by weight to about 2.0% by weight and about 0.1 to about 0.75% by weight.
The glass composition may include up to about 1.0% by weight Fe2O3. In some exemplary embodiments, the glass composition includes 0% by weight to about 0.8% by weight Fe2O3, including about 0.01% by weight to about 0.6% by weight and about 0.1 to about 0.35% by weight.
The glass composition may include up to about 5.0% by weight Li2O. In some exemplary embodiments, the glass composition includes about 0.0% by weight to about 4.0% by weight Li2O, including about 0.1% by weight to about 3.5% by weight and about 0.5 to about 3.0% by weight. In some exemplary embodiments, the glass composition includes about 1.0 to about 4.0 wt. % Li2O, or about 1.5 to about 3.8 wt. % Li2O.
In some exemplary embodiments, the glass composition includes less than 2.0% by weight of the alkali metal oxides Na2O and K2O, including between 0 and 1.5% by weight, between 0.05 and 0.75% by weight, and between 0.1 and 0.25% by weight. The glass composition may include both Na2O and K2O in an amount greater than 0.01% by weight of each oxide. In some exemplary embodiments, the glass composition includes about 0 to about 1% by weight Na2O, including about 0.01 to about 0.5% by weight, about 0.03 to about 0.3% by weight, and 0.04 to about 0.15% by weight. In some exemplary embodiments, the glass composition includes about 0 to about 1% by weight K2O, including about 0.01 to about 0.5% by weight, about 0.03 to about 0.3% by weight, and 0.04 to about 0.15% by weight. In some exemplary embodiments, the glass composition includes less than 1.0% by weight K2O, such as less than 0.75% by weight, or less than 0.50% by weight.
The glass composition may include up to about 1.5% by weight ZrO2. In some exemplary embodiments, the glass composition includes about 0.01% by weight to about 1.0% by weight ZrO2, including about 0.05% by weight to about 0.8% by weight and about 0.1 to about 0.5% by weight.
In some exemplary embodiments, the glass composition includes up to 15.0% by weight of the rare earth oxides Y2O3, La2O3, Ce2O3, and Sc2O3 (“R2O3”), including between 0 and 12.0% by weight, or between 1.0 and 10.0% by weight. The glass composition may include any of the R2O3 oxides in an amount greater than 0.01% by weight. In some exemplary embodiments, the glass composition includes about 0 to about 10% by weight Y2O3, including about 1.0 to about 9.9% by weight, about 3.0 to about 9.5% by weight, and 6.0 to about 9.0% by weight. In some exemplary embodiments, the glass composition includes about 0 to about 10% by weight La2O3, including about 0.01 to about 7.5% by weight, about 0.05 to about 4.0% by weight, and 0.1 to about 3.0% by weight. In some exemplary embodiments, the glass composition includes about 0 to about 5.0% by weight Ce2O3, including about 0.01 to about 4.0% by weight, about 0.05 to about 2.0% by weight, and 0.1 to about 1.5% by weight. In some exemplary embodiments, the glass composition includes about 0 to about 5% by weight Sc2O3, including about 0.01 to about 4.0% by weight, about 0.05 to about 3.2% by weight, and 0.1 to about 3.0% by weight.
In some exemplary embodiments, the glass composition includes a total concentration of CeO2+Sc2O3 that is at least 1.0% by weight, including at least 1.5% by weight, at least 1.75% by weight, at least 2.0% by weight, at least 2.1% by weight, at least 2.2% by weight, and at least 2.5% by weight.
The glass composition may include up to about 7.0% by weight Ta2O5. In some exemplary embodiments, the glass composition includes about 0.01% by weight to about 5.5% by weight Ta2O5, including about 0.05% by weight to about 3.5% by weight and about 0.1 to about 3.0% by weight.
The glass composition may include up to about 7.0% by weight Ga2O3. In some exemplary embodiments, the glass composition includes about 0.01% by weight to about 5.5% by weight Ga2O3, including about 0.05% by weight to about 5.0% by weight and about 0.1 to about 4.5% by weight.
The glass composition may include up to about 2.5% by weight Nb2O5. In some exemplary embodiments, the glass composition includes about 0.01% by weight to about 2.0% by weight Nb2O5, including about 0.05% by weight to about 1.5% by weight and about 0.1 to about 0.7% by weight.
The glass composition may include up to about 2.0% by weight V2O5. In some exemplary embodiments, the glass composition includes about 0.01% by weight to about 1.5% by weight V2O5, including about 0.05% by weight to about 1.2% by weight and about 0.1 to about 1.0% by weight.
The glass compositions may include up to about 1.0% by weight of Sm2O3 and/or Gd2O3. However, various exemplary embodiments limit the total concentration of Sm2O3 and Gd2O3 to less than 0.5% by weight, including less than 0.1% by weight, and less than 0.05% by weight.
The glass composition may include up to about 5.0% by weight ZnO. In some exemplary embodiments, the glass composition includes 0% by weight to about 2.5% by weight ZnO, including about 0.01% by weight to about 2.0% by weight and about 0.1 to about 1.0% by weight.
The inventive glass compositions may be free or substantially free of B2O3 and fluorine, although any may be added in small amounts to adjust the fiberizing and finished glass properties and will not adversely impact the properties if maintained below several percent. As used herein, substantially free of B2O3 and fluorine means that the sum of the amounts of B2O3 and fluorine present is less than 1.0% by weight of the composition. The sum of the amounts of B2O3 and fluorine present may be less than about 0.5% by weight of the composition, including less than about 0.2% by weight, less than about 0.1% by weight, and less than about 0.05% by weight.
The glass compositions may further include impurities and/or trace materials without adversely affecting the glasses or the fibers. These impurities may enter the glass as raw material impurities or may be products formed by the chemical reaction of the molten glass with furnace components. Non-limiting examples of trace materials include strontium, barium, and combinations thereof. The trace materials may be present in their oxide forms and may further include fluorine and/or chlorine. In some exemplary embodiments, the inventive glass compositions contain no more than 1.0% by weight, including less than 0.5% by weight, less than 0.2% by weight, and less than 0.1% by weight of each of BaO, SrO, P2O5, and SO3. Particularly, the glass composition may include less than about 5.0% by weight of BaO, SrO, P2O5, and/or SO3 combined, wherein each of BaO, SrO, P2O5, and SO3 if present at all, is present in an amount of less than 1.0% by weight.
In some exemplary embodiments, the glass composition comprises a ratio of MgO/(CaO+SrO) that is at least 1.5, including at least 1.7, at least 2.0, at least 2.1, at least 2.2, and at least 2.3.
As used herein, the terms “weight percent,” “% by weight,” “wt. %,” and “percent by weight” may be used interchangeably and are meant to denote the weight percent (or percent by weight) based on the total composition.
As indicated above, the inventive glass compositions unexpectedly demonstrate an optimized elastic modulus, while maintaining desirable forming properties.
The fiber tensile strength is also referred herein simply as “strength.” In some exemplary embodiments, the tensile strength is measured on pristine fibers (i.e., unsized and untouched laboratory produced fibers) using an Instron tensile testing apparatus according to ASTM D2343-09. Exemplary glass fibers formed form the above described inventive glass composition may have a fiber tensile strength of at least 4,000 MPa, including at least 4,250 MPa, at least 4,400 MPa, at least 4,500 MPa, at least 4,800 MPa, at least 4,900 MPa, at least 4,950 MPa, at least 5,000 MPa, at least 5,100 MPa, at least 5,150 MPa, and at least 5,200 MPa. In some exemplary embodiments, the glass fibers formed from the above described composition have a fiber tensile strength of from about 4200 to about 5500 MPa, including about 4300 MPa to about 5,350 MPa, about 4,600 to about 5,315 MPa. Advantageously, the combination of compositional parameters disclosed herein makes it possible to produce glass fibers having tensile strengths of at least 4,800 MPa, including at least 4,900 MPa, and at least 5,000, which has not yet been achieved by the prior art with a glass composition having desirable fiberizing properties.
The elastic modulus of a glass fiber may be determined by taking the average measurements on five single glass fibers measured in accordance with the sonic measurement procedure outlined in the report “Glass Fiber Drawing and Measuring Facilities at the U.S. Naval Ordnance Laboratory”, Report Number NOLTR 65-87, Jun. 23, 1965.
The exemplary glass fibers formed from the inventive glass composition may have an elastic modulus of at least about 88 GPa, including at least about 89.5 GPa, at least about 90.5 GPa, at least about 91 GPa, at least about 93 GPa, at least about 95 GPa, or at least about 96 GPa. In some exemplary embodiments, the exemplary glass fibers formed from the inventive glass composition have an elastic modulus of between about 88 GPa and about 115 GPa, including between about 89 GPa and about 100 GPa, and between about 93.1 GPa and about 98 GPa.
The elastic modulus may then be used to determine the specific modulus. It is desirable to have a specific modulus as high as possible to achieve a lightweight composite material that adds stiffness to the final article. Specific modulus is important in applications where stiffness of the product is an important parameter, such as in wind energy and aerospace applications. As used herein, the specific modulus is calculated by the following equation:
Specific Modulus (MJ/kg)=Modulus (GPa)/Density(kg/cubic meter)
The exemplary glass fibers formed from the inventive glass composition has a specific modulus of about 33.0 MJ/kg to about 40.0 MJ/kg, including about 34.1 MJ/kg to about 37 MJ/kg, and about 34.5 MJ/kg to about 36.5 MJ/kg.
The density may be measured by any method known and commonly accepted in the art, such as the Archimedes method (ASTM C693-93(2008)) on unannealed bulk glass. The glass fibers have a density of from about 2.0 to about 3.0 g/cc. In other exemplary embodiments, the glass fibers have a density of from about 2.3 to about 2.8 g/cc, including from about 2.4 to about 2.78 g/cc, and about 2.50 to about 2.75 g/cc.
According to some exemplary embodiments, a method is provided for preparing glass fibers from the glass composition described above. The glass fibers may be formed by any means known and traditionally used in the art. In some exemplary embodiments, the glass fibers are formed by obtaining raw ingredients and mixing the ingredients in the appropriate quantities to give the desired weight percentages of the final composition. The method may further include providing the inventive glass composition in molten form and drawing the molten composition through orifices in a bushing to form a glass fiber.
The components of the glass composition may be obtained from suitable ingredients or raw materials including, but not limited to, sand or pyrophyllite for SiO2, limestone, burnt lime, wollastonite, or dolomite for CaO, kaolin, alumina or pyrophyllite for Al2O3, dolomite, dolomitic quicklime, brucite, enstatite, talc, burnt magnesite, or magnesite for MgO, and sodium carbonate, sodium feldspar or sodium sulfate for the Na2O. In some exemplary embodiments, glass cullet may be used to supply one or more of the needed oxides.
The mixed batch may then be melted in a furnace or melter and the resulting molten glass is passed along a forehearth and drawn through the orifices of a bushing located at the bottom of the forehearth to form individual glass filaments. In some exemplary embodiments, the furnace or melter is a traditional refractory melter. By utilizing a refractory tank formed of refractory blocks, manufacturing costs associated with the production of glass fibers produced by the inventive composition may be reduced. In some exemplary embodiments, the bushing is a platinum alloy-based bushing. Strands of glass fibers may then be formed by gathering the individual filaments together. The fiber strands may be wound and further processed in a conventional manner suitable for the intended application.
The operating temperatures of the glass in the melter, forehearth, and bushing may be selected to appropriately adjust the viscosity of the glass, and may be maintained using suitable methods, such as control devices. The temperature at the front end of the melter may be automatically controlled to reduce or eliminate devitrification. The molten glass may then be pulled (drawn) through holes or orifices in the bottom or tip plate of the bushing to form glass fibers. In accordance with some exemplary embodiments, the streams of molten glass flowing through the bushing orifices are attenuated to filaments by winding a strand formed of a plurality of individual filaments on a forming tube mounted on a rotatable collet of a winding machine or chopped at an adaptive speed. The glass fibers of the invention are obtainable by any of the methods described herein, or any known method for forming glass fibers.
The fibers may be further processed in a conventional manner suitable for the intended application. For instance, in some exemplary embodiments, the glass fibers are sized with a sizing composition known to those of skill in the art. The sizing composition is in no way restricted, and may be any sizing composition suitable for application to glass fibers. The sized fibers may be used for reinforcing substrates such as a variety of plastics where the product's end use requires high strength and stiffness and low weight. Such applications include, but are not limited to, woven fabrics for use in forming wind turbine blades; infrastructure, such as reinforcing concrete, bridges, etc.; and aerospace structures.
In this regard, some exemplary embodiments of the present invention include a composite material incorporating the inventive glass fibers, as described above, in combination with a hardenable matrix material. This may also be referred to herein as a reinforced composite product. The matrix material may be any suitable thermoplastic or thermoset resin known to those of skill in the art, such as, but not limited to, thermoplastics such as polyesters, polypropylene, polyamide, polyethylene terephthalate, and polybutylene, and thermoset resins such as epoxy resins, unsaturated polyesters, phenolics, vinylesters, and elastomers. These resins may be used alone or in combination. The reinforced composite product may be used for wind turbine blade, rebar, pipe, filament winding, muffler filling, sound absorption, and the like.
In accordance with further exemplary embodiments, the invention provides a method of preparing a composite product as described above. The method may include combining at least one polymer matrix material with a plurality of glass fibers. Both the polymer matrix material and the glass fibers may be as described above.
Exemplary glass compositions according to the present invention were prepared by mixing batch components in proportioned amounts to achieve a final glass composition with the oxide weight percentages set forth in Tables 1-9, below.
The raw materials were melted in a platinum crucible in an electrically heated furnace at a temperature of 1,650° C. for 3 hours.
The fiberizing temperature was measured using a rotating cylinder method as described in ASTM C965-96(2007), entitled “Standard Practice for Measuring Viscosity of Glass Above the Softening Point,” the contents of which are incorporated by reference herein. The liquidus temperature was measured by exposing glass to a temperature gradient in a platinum-alloy boat for 16 hours, as defined in ASTM C829-81(2005), entitled “Standard Practices for Measurement of Liquidus Temperature of Glass,” the contents of which are incorporated by reference herein. Density was measured by the Archimedes method, as detailed in ASTM C693-93(2008), entitled “Standard Test Method for Density of Glass Buoyancy,” the contents of which are incorporated by reference herein.
The specific modulus was calculated by dividing the measured modulus in units of GPa by the density in units of kg/m3.
The strength was measured on pristine fibers using an Instron tensile testing apparatus according to ASTM D2343-09 entitled, “Standard Test Method for Tensile Properties of Glass Fiber Strands, Yarns, and Rovings Used in Reinforced Plastics,” the contents of which are incorporated by reference herein.
Tables 1-10 illustrate the improvement in elastic modulus that the inventive glass compositions have over commercial high-performance glass (Comparative Example). The Comparative Example demonstrates an elastic modulus of 87.5 GPa, which is below the minimum elastic modulus seen from any of the inventive compositions. Instructively, each of the inventive compositions demonstrate an elastic modulus of at least 88 GPa, and more specifically at least 90 GPa.
The invention of this application has been described above both generically and with regard to specific embodiments. Although the invention has been set forth in what is believed to be the preferred embodiments, a wide variety of alternatives known to those of skill in the art can be selected within the generic disclosure. The invention is not otherwise limited, except for the recitation of the claims set forth below.
This application claims priority to U.S. Provisional Application No. 62/771,250, filed on Nov. 26, 2018, titled HIGH PERFORMANCE FIBERGLASS COMPOSITION WITH IMPROVED ELASTIC MODULUS, the entire disclosure of which is incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 5281562 | Araujo et al. | Jan 1994 | A |
| 5320986 | Taniguchi et al. | Jun 1994 | A |
| 5334558 | Dietz et al. | Aug 1994 | A |
| 5336644 | Akhtar et al. | Aug 1994 | A |
| 5340778 | Kloss et al. | Aug 1994 | A |
| 5350972 | Bucher et al. | Sep 1994 | A |
| 5372977 | Mazon-Ramos et al. | Dec 1994 | A |
| 5422755 | Morgan | Jun 1995 | A |
| 5424255 | Kassner | Jun 1995 | A |
| 5472471 | Baba et al. | Dec 1995 | A |
| 5491767 | McPherson et al. | Feb 1996 | A |
| 5548353 | Kassner | Aug 1996 | A |
| 5569630 | Landa et al. | Oct 1996 | A |
| 5641347 | Grabowski et al. | Jun 1997 | A |
| 5648302 | Brow et al. | Jul 1997 | A |
| 5665660 | Yamawaki et al. | Sep 1997 | A |
| 5674789 | Anquetil | Oct 1997 | A |
| 5698019 | Frank et al. | Dec 1997 | A |
| 5698482 | Frank et al. | Dec 1997 | A |
| 5747395 | Smith et al. | May 1998 | A |
| 5830812 | Shelestak et al. | Nov 1998 | A |
| 5837629 | Combes et al. | Nov 1998 | A |
| 5849649 | Poole | Dec 1998 | A |
| 5902665 | Kuroda | May 1999 | A |
| 5919718 | Hirota et al. | Jul 1999 | A |
| 5968857 | Pinckney | Oct 1999 | A |
| 5998037 | Sridharan et al. | Dec 1999 | A |
| 6010787 | Yamaguchi et al. | Jan 2000 | A |
| 6043171 | Siebers et al. | Mar 2000 | A |
| 6066273 | Yamaguchi et al. | May 2000 | A |
| 6074969 | Naumann et al. | Jun 2000 | A |
| 6114264 | Krumwiede et al. | Sep 2000 | A |
| 6118216 | Marlor | Sep 2000 | A |
| 6132843 | Kuroda et al. | Oct 2000 | A |
| 6133179 | Berthereau | Oct 2000 | A |
| 6147019 | Donohue | Nov 2000 | A |
| 6162749 | Brocheton et al. | Dec 2000 | A |
| 6235667 | Paloschi et al. | May 2001 | B1 |
| 6255239 | Sakoske | Jul 2001 | B1 |
| 6287993 | Fu et al. | Sep 2001 | B1 |
| 6297181 | Kunert et al. | Oct 2001 | B1 |
| 6323585 | Crane et al. | Nov 2001 | B1 |
| 6329310 | Peuchert et al. | Dec 2001 | B1 |
| 6333287 | Seto | Dec 2001 | B1 |
| 6333288 | Clement et al. | Dec 2001 | B1 |
| 6335299 | Foguenne et al. | Jan 2002 | B1 |
| 6399527 | Kishimoto et al. | Jun 2002 | B1 |
| 6451720 | Kishimoto et al. | Sep 2002 | B1 |
| 6458730 | Nagata et al. | Oct 2002 | B1 |
| 6461734 | Carre | Oct 2002 | B1 |
| 6461736 | Nagashima et al. | Oct 2002 | B1 |
| 6476975 | Yoshii et al. | Nov 2002 | B1 |
| 6511932 | Yamaguchi et al. | Jan 2003 | B2 |
| 6518211 | Bradshaw et al. | Feb 2003 | B1 |
| 6524685 | Torr et al. | Feb 2003 | B1 |
| 6524982 | Nagata et al. | Feb 2003 | B1 |
| 6548434 | Nagashima | Apr 2003 | B2 |
| 6596659 | Nagata et al. | Jul 2003 | B1 |
| 6610620 | Nagata et al. | Aug 2003 | B1 |
| 6610621 | Masuko | Aug 2003 | B2 |
| 6611372 | Peyghambarian et al. | Aug 2003 | B1 |
| 6623845 | Katsumura et al. | Sep 2003 | B1 |
| 6627569 | Naumann et al. | Sep 2003 | B1 |
| 6630420 | Naumann et al. | Oct 2003 | B1 |
| 6632758 | Beall et al. | Oct 2003 | B2 |
| 6635591 | Nagata et al. | Oct 2003 | B2 |
| 6642161 | Nagata et al. | Nov 2003 | B2 |
| 6642162 | Nagata et al. | Nov 2003 | B2 |
| 6645888 | Nagata et al. | Nov 2003 | B2 |
| 6645889 | Nagata et al. | Nov 2003 | B2 |
| 6645890 | Nagata et al. | Nov 2003 | B2 |
| 6645891 | Nagata et al. | Nov 2003 | B2 |
| 6645892 | Nagata et al. | Nov 2003 | B2 |
| 6645894 | Endo | Nov 2003 | B2 |
| 6649549 | Nagata et al. | Nov 2003 | B2 |
| 6667259 | Clasen et al. | Dec 2003 | B2 |
| 6677046 | Hachitani et al. | Jan 2004 | B2 |
| 6713419 | Onozawa et al. | Mar 2004 | B1 |
| 6716780 | Landa et al. | Apr 2004 | B2 |
| 6753279 | Kohli | Jun 2004 | B2 |
| 6753280 | Seto et al. | Jun 2004 | B2 |
| 6764972 | Yoshii et al. | Jul 2004 | B2 |
| 6764973 | Berthereau et al. | Jul 2004 | B2 |
| 6777358 | Snowdon et al. | Aug 2004 | B2 |
| 6816235 | Kido et al. | Nov 2004 | B2 |
| 6831030 | Koyama et al. | Dec 2004 | B2 |
| 6841493 | Cho et al. | Jan 2005 | B2 |
| 6844278 | Wang et al. | Jan 2005 | B2 |
| 6859606 | Jiang et al. | Feb 2005 | B2 |
| 6912093 | Endo | Jun 2005 | B2 |
| 6924245 | Sakamoto | Aug 2005 | B2 |
| 6936556 | Sridharan et al. | Aug 2005 | B2 |
| 6939820 | Numaguchi et al. | Sep 2005 | B2 |
| 6992030 | Paulson | Jan 2006 | B2 |
| 6992031 | Naumann et al. | Jan 2006 | B2 |
| 6995101 | Zou et al. | Feb 2006 | B2 |
| 7008892 | Bourova et al. | Mar 2006 | B2 |
| 7115536 | Hayden et al. | Oct 2006 | B2 |
| 7141524 | Wolff et al. | Nov 2006 | B2 |
| 7144834 | Clasen et al. | Dec 2006 | B2 |
| 7189672 | Aitken et al. | Mar 2007 | B2 |
| 7192898 | Mori et al. | Mar 2007 | B2 |
| 7211957 | Bergmann et al. | May 2007 | B2 |
| 7250383 | Inoue et al. | Jul 2007 | B2 |
| 7291571 | Sprenger et al. | Nov 2007 | B2 |
| 7323426 | Aitken | Jan 2008 | B2 |
| 7323427 | Wolff et al. | Jan 2008 | B2 |
| 7341964 | Emlemdi | Mar 2008 | B2 |
| 7341966 | Marques | Mar 2008 | B2 |
| 7371703 | Masumura et al. | May 2008 | B2 |
| 7375043 | Fechner et al. | May 2008 | B2 |
| 7396785 | Takada et al. | Jul 2008 | B2 |
| 7396788 | Kawai et al. | Jul 2008 | B2 |
| 7407902 | Hasegawa et al. | Aug 2008 | B2 |
| 7425518 | Yoshida et al. | Sep 2008 | B2 |
| 7435695 | Hormadaly | Oct 2008 | B2 |
| 7435696 | Scheffler-Hudlet et al. | Oct 2008 | B2 |
| 7449419 | Li | Nov 2008 | B2 |
| 7456121 | Comte | Nov 2008 | B2 |
| 7465686 | Comte | Dec 2008 | B2 |
| 7470640 | Badding et al. | Dec 2008 | B2 |
| 7473660 | Comte | Jan 2009 | B2 |
| 7476633 | Comte et al. | Jan 2009 | B2 |
| 7493008 | Barbosa et al. | Feb 2009 | B2 |
| 7497093 | Rosenflanz | Mar 2009 | B2 |
| 7498731 | Fechner et al. | Mar 2009 | B2 |
| 7501366 | Wolff et al. | Mar 2009 | B2 |
| 7501369 | Tachiwana | Mar 2009 | B2 |
| 7504350 | Coster et al. | Mar 2009 | B2 |
| 7507681 | Aitken et al. | Mar 2009 | B2 |
| 7515332 | Tsuda | Apr 2009 | B2 |
| 7515802 | Peuchert et al. | Apr 2009 | B2 |
| 7517822 | Fechner et al. | Apr 2009 | B2 |
| 7521387 | Xue et al. | Apr 2009 | B2 |
| 7528083 | Shimizu et al. | May 2009 | B2 |
| 7528084 | Emlemdi | May 2009 | B2 |
| 7531474 | Shiraishi | May 2009 | B2 |
| 7531475 | Kishimoto et al. | May 2009 | B2 |
| 7553785 | Ritter et al. | Jun 2009 | B2 |
| 7560404 | Shelestak et al. | Jul 2009 | B2 |
| 7576021 | Miyauchi et al. | Aug 2009 | B2 |
| 7585798 | Yoshida et al. | Sep 2009 | B2 |
| 7598192 | Wolff et al. | Oct 2009 | B2 |
| 7605099 | Wolff et al. | Oct 2009 | B2 |
| 7618909 | Fujiwara et al. | Nov 2009 | B2 |
| 7629279 | Tanaka et al. | Dec 2009 | B2 |
| 7632767 | Nagashima et al. | Dec 2009 | B2 |
| 7635521 | Aitken et al. | Dec 2009 | B2 |
| 7638448 | Wolff et al. | Dec 2009 | B2 |
| 7659222 | Shimizu | Feb 2010 | B2 |
| 7670973 | Ritter et al. | Mar 2010 | B2 |
| 7670977 | Teyssedre et al. | Mar 2010 | B2 |
| 7677059 | Mori et al. | Mar 2010 | B2 |
| 7682999 | Teyssedre | Mar 2010 | B2 |
| 7687417 | Hang et al. | Mar 2010 | B2 |
| 7687418 | Peuchert et al. | Mar 2010 | B2 |
| 7687419 | Kawai | Mar 2010 | B2 |
| 7691763 | Arbab et al. | Apr 2010 | B2 |
| 7700869 | Thomsen et al. | Apr 2010 | B2 |
| 7700870 | Thomsen et al. | Apr 2010 | B2 |
| 7709406 | Cornelius et al. | May 2010 | B2 |
| 7745361 | Kasuga et al. | Jun 2010 | B2 |
| 7820575 | Nagashima et al. | Oct 2010 | B2 |
| 7825051 | Smith et al. | Nov 2010 | B2 |
| 7858546 | Miyauchi et al. | Dec 2010 | B2 |
| 7863207 | Son et al. | Jan 2011 | B2 |
| 7884041 | Uehara | Feb 2011 | B2 |
| 7892995 | Castillo | Feb 2011 | B2 |
| 7897531 | Ishioka | Mar 2011 | B2 |
| 7897532 | Onoda et al. | Mar 2011 | B2 |
| 7897533 | Onoda et al. | Mar 2011 | B2 |
| 7927705 | Bayya et al. | Apr 2011 | B2 |
| 7964523 | Mayumi et al. | Jun 2011 | B2 |
| 8004196 | Fechner et al. | Aug 2011 | B2 |
| 8017537 | Seto et al. | Sep 2011 | B2 |
| 8096147 | Flemming et al. | Jan 2012 | B2 |
| 8097077 | Steidl | Jan 2012 | B2 |
| 8110513 | Ueda et al. | Feb 2012 | B2 |
| 8133828 | Denry et al. | Mar 2012 | B2 |
| 8143179 | Aitken et al. | Mar 2012 | B2 |
| 8156763 | Nagashima et al. | Apr 2012 | B2 |
| 8168551 | Iizawa et al. | May 2012 | B2 |
| 8168553 | Wolff et al. | May 2012 | B2 |
| 8168693 | Ritter et al. | May 2012 | B2 |
| 8178454 | Morisada | May 2012 | B2 |
| 8178595 | Ritter et al. | May 2012 | B2 |
| 8187715 | Danielson et al. | May 2012 | B2 |
| 8193108 | Inoue et al. | Jun 2012 | B2 |
| 8198201 | Comte et al. | Jun 2012 | B2 |
| 8203169 | Matsumoto et al. | Jun 2012 | B2 |
| 8247336 | Onoda | Aug 2012 | B2 |
| 8268065 | Ritter et al. | Sep 2012 | B2 |
| 8268739 | Ritter et al. | Sep 2012 | B2 |
| 8288298 | Mayumi et al. | Oct 2012 | B2 |
| 8298972 | Fulton et al. | Oct 2012 | B2 |
| 8304358 | Shelestak et al. | Nov 2012 | B2 |
| 8309481 | Morisada | Nov 2012 | B2 |
| 8318054 | Cid-Aguilar et al. | Nov 2012 | B2 |
| 8318619 | Comte et al. | Nov 2012 | B2 |
| 8336332 | Hayashi et al. | Dec 2012 | B2 |
| 8338321 | Morisada | Dec 2012 | B2 |
| 8346029 | Jiang | Jan 2013 | B2 |
| 8349751 | Nagai et al. | Jan 2013 | B2 |
| 8361915 | Cid-Aguilar et al. | Jan 2013 | B2 |
| 8361917 | Li et al. | Jan 2013 | B2 |
| 8367573 | Naito et al. | Feb 2013 | B2 |
| 8372768 | Morisada | Feb 2013 | B2 |
| 8389428 | Wada et al. | Mar 2013 | B2 |
| 8404606 | Wolff et al. | Mar 2013 | B2 |
| 8424344 | Zou et al. | Apr 2013 | B2 |
| 8431502 | Dejneka et al. | Apr 2013 | B2 |
| 8445394 | Aitken et al. | May 2013 | B2 |
| 8470723 | Naito et al. | Jun 2013 | B2 |
| 8476178 | Zou et al. | Jul 2013 | B2 |
| 8486850 | Li et al. | Jul 2013 | B2 |
| 8507394 | Shimizu | Aug 2013 | B2 |
| 8526475 | Li et al. | Sep 2013 | B2 |
| 8536078 | Ritzberger et al. | Sep 2013 | B2 |
| 8541327 | Lu et al. | Sep 2013 | B1 |
| 8557150 | Ritzberger et al. | Oct 2013 | B2 |
| 8598056 | Ellison et al. | Dec 2013 | B2 |
| 8670182 | Tanida et al. | Mar 2014 | B2 |
| 8697589 | Matano et al. | Apr 2014 | B2 |
| 8759237 | Ritzberger et al. | Jun 2014 | B2 |
| 8759239 | Comte et al. | Jun 2014 | B2 |
| 8763429 | Danielson et al. | Jul 2014 | B2 |
| 8765619 | Brunet et al. | Jul 2014 | B2 |
| 8766524 | Kohara et al. | Jul 2014 | B2 |
| 8778075 | Ritzberger et al. | Jul 2014 | B2 |
| 8805133 | Rhonehouse et al. | Aug 2014 | B1 |
| 8828897 | Fechner et al. | Sep 2014 | B2 |
| 8835334 | Matano et al. | Sep 2014 | B2 |
| 8858745 | Sun et al. | Oct 2014 | B2 |
| 8895460 | Tachizono et al. | Nov 2014 | B2 |
| 8906506 | Shibata et al. | Dec 2014 | B2 |
| 8951925 | George et al. | Feb 2015 | B2 |
| 8956987 | Durschang et al. | Feb 2015 | B2 |
| 8999871 | Mushiake et al. | Apr 2015 | B2 |
| 9006120 | George et al. | Apr 2015 | B2 |
| 9048056 | Yoshimura et al. | Jun 2015 | B2 |
| 9051207 | Han et al. | Jun 2015 | B2 |
| 9051209 | Melscoët-Chauvel et al. | Jun 2015 | B2 |
| 9051210 | Melscoët-Chauvel et al. | Jun 2015 | B2 |
| 9079794 | Horsley | Jul 2015 | B2 |
| 9096460 | Brix et al. | Aug 2015 | B2 |
| 9118166 | George et al. | Aug 2015 | B2 |
| 9120695 | Lee et al. | Sep 2015 | B2 |
| 9120699 | Nakane et al. | Sep 2015 | B2 |
| 9145331 | Takayama | Sep 2015 | B2 |
| 9156725 | Dejneka et al. | Oct 2015 | B2 |
| 9156729 | McGinnis et al. | Oct 2015 | B2 |
| 9206074 | Yanase et al. | Dec 2015 | B2 |
| 9230872 | Hashimoto | Jan 2016 | B2 |
| 9249048 | Ritzberger et al. | Feb 2016 | B2 |
| 9255028 | Negishi et al. | Feb 2016 | B2 |
| 9260342 | Borczuch-Laczka et al. | Feb 2016 | B2 |
| 9278883 | Li et al. | Mar 2016 | B2 |
| 9290413 | Dejneka et al. | Mar 2016 | B2 |
| 9309144 | Nonnet et al. | Apr 2016 | B2 |
| 9321674 | Ritzberger et al. | Apr 2016 | B2 |
| 9376339 | Tezuka | Jun 2016 | B2 |
| 9388069 | Schreder et al. | Jul 2016 | B2 |
| 9394194 | Negishi | Jul 2016 | B2 |
| 9399000 | Ahn et al. | Jul 2016 | B2 |
| 9409814 | Takayama | Aug 2016 | B2 |
| 9409816 | Kim et al. | Aug 2016 | B2 |
| 9428417 | Yanase et al. | Aug 2016 | B2 |
| 9434637 | Aniya | Sep 2016 | B2 |
| 9458053 | Nakane et al. | Oct 2016 | B2 |
| 9522842 | Nonnet et al. | Dec 2016 | B2 |
| 9556061 | Naito et al. | Jan 2017 | B2 |
| 9573841 | Cid-Aguilar et al. | Feb 2017 | B1 |
| 9581760 | Jiang et al. | Feb 2017 | B2 |
| 9593040 | Comte et al. | Mar 2017 | B2 |
| 9604874 | Beall et al. | Mar 2017 | B2 |
| 9617182 | Cho et al. | Apr 2017 | B2 |
| 9650286 | Comte et al. | May 2017 | B2 |
| 9658437 | Goodwin et al. | May 2017 | B2 |
| 9670089 | Yanase et al. | Jun 2017 | B2 |
| 9670090 | Naito et al. | Jun 2017 | B2 |
| 9701570 | Mauro et al. | Jul 2017 | B2 |
| 9701573 | Beall et al. | Jul 2017 | B2 |
| 9714190 | Schilm et al. | Jul 2017 | B2 |
| 9758423 | Cao et al. | Sep 2017 | B2 |
| 9809488 | Beall et al. | Nov 2017 | B2 |
| 9834472 | Gabel et al. | Dec 2017 | B2 |
| 9850163 | Beall et al. | Dec 2017 | B2 |
| 9871176 | Maloney et al. | Jan 2018 | B2 |
| 9911969 | Afyon et al. | Mar 2018 | B2 |
| 9926223 | Kim et al. | Mar 2018 | B2 |
| 9944551 | Li | Apr 2018 | B2 |
| 9957191 | Li et al. | May 2018 | B2 |
| 9963378 | Yamamoto | May 2018 | B2 |
| 9988297 | Kim et al. | Jun 2018 | B2 |
| 9991011 | Kim et al. | Jun 2018 | B2 |
| 10011519 | Himei et al. | Jul 2018 | B2 |
| 10035727 | Li et al. | Jul 2018 | B2 |
| 10071933 | Wang et al. | Sep 2018 | B2 |
| 10155686 | Cao et al. | Dec 2018 | B2 |
| 10160685 | Comte et al. | Dec 2018 | B2 |
| 10239781 | Zhang et al. | Mar 2019 | B2 |
| 10294142 | Zhang et al. | May 2019 | B2 |
| 10351465 | Cao et al. | Jul 2019 | B2 |
| 10377662 | Zhang | Aug 2019 | B2 |
| 10399889 | Zhang et al. | Sep 2019 | B2 |
| 10414688 | Rampf et al. | Sep 2019 | B2 |
| 10479721 | Li | Nov 2019 | B2 |
| 20020197049 | Baniel et al. | Dec 2002 | A1 |
| 20030045421 | Burger et al. | Mar 2003 | A1 |
| 20040127342 | Liang et al. | Jul 2004 | A1 |
| 20040235636 | Tsai et al. | Nov 2004 | A1 |
| 20060033983 | Dai et al. | Feb 2006 | A1 |
| 20060204763 | Hartman et al. | Sep 2006 | A1 |
| 20070032365 | Varga et al. | Feb 2007 | A1 |
| 20070099787 | Hayden et al. | May 2007 | A1 |
| 20070158317 | Brix et al. | Jul 2007 | A1 |
| 20080068703 | Nakatsuka et al. | Mar 2008 | A1 |
| 20080153068 | Kessler et al. | Jun 2008 | A1 |
| 20090088309 | Niida et al. | Apr 2009 | A1 |
| 20090105061 | Fujiwara et al. | Apr 2009 | A1 |
| 20090131239 | Kotake et al. | May 2009 | A1 |
| 20090286058 | Shibata et al. | Nov 2009 | A1 |
| 20110003678 | Hofmann et al. | Jan 2011 | A1 |
| 20110133118 | Honma et al. | Jun 2011 | A1 |
| 20110236684 | Teschner et al. | Sep 2011 | A1 |
| 20120183785 | Schirrmeister et al. | Jul 2012 | A1 |
| 20130017387 | James, III et al. | Jan 2013 | A1 |
| 20130161569 | Ishihara | Jun 2013 | A1 |
| 20130288876 | Fujisawa et al. | Oct 2013 | A1 |
| 20130316162 | Murata et al. | Nov 2013 | A1 |
| 20140106168 | Ritter et al. | Apr 2014 | A1 |
| 20140145122 | Sawai et al. | May 2014 | A1 |
| 20150307389 | He et al. | Oct 2015 | A1 |
| 20150337106 | Kajihara et al. | Nov 2015 | A1 |
| 20150368151 | Kuwatani et al. | Dec 2015 | A1 |
| 20160068428 | Li et al. | Mar 2016 | A1 |
| 20160096768 | Takao et al. | Apr 2016 | A1 |
| 20160102010 | Beall et al. | Apr 2016 | A1 |
| 20160176752 | Gabel et al. | Jun 2016 | A1 |
| 20160236972 | Kiczenski et al. | Aug 2016 | A1 |
| 20160304391 | Eberhardt et al. | Oct 2016 | A1 |
| 20160326045 | Li | Nov 2016 | A1 |
| 20170057865 | Kim et al. | Mar 2017 | A1 |
| 20170183255 | Walther et al. | Jun 2017 | A1 |
| 20170217828 | George et al. | Aug 2017 | A1 |
| 20170327409 | Seto | Nov 2017 | A1 |
| 20170342383 | Deng et al. | Nov 2017 | A1 |
| 20180016183 | Bowden et al. | Jan 2018 | A1 |
| 20180029926 | Sato et al. | Feb 2018 | A1 |
| 20180037491 | Hijiya et al. | Feb 2018 | A1 |
| 20180050953 | Inaba et al. | Feb 2018 | A1 |
| 20180079679 | Kass | Mar 2018 | A1 |
| 20180086661 | Zhang et al. | Mar 2018 | A1 |
| 20180099895 | Horsley et al. | Apr 2018 | A1 |
| 20180099896 | Horsley et al. | Apr 2018 | A1 |
| 20180099897 | Horsley et al. | Apr 2018 | A1 |
| 20180099901 | Beally et al. | Apr 2018 | A1 |
| 20180118606 | Lambricht et al. | May 2018 | A1 |
| 20180118607 | Horsley et al. | May 2018 | A1 |
| 20180118608 | Zhang et al. | May 2018 | A1 |
| 20180118611 | Cao et al. | May 2018 | A1 |
| 20180127305 | Li | May 2018 | A1 |
| 20180127306 | Li et al. | May 2018 | A1 |
| 20180147114 | DeMartino et al. | May 2018 | A1 |
| 20180170798 | Aitken | Jun 2018 | A1 |
| 20180179103 | Zhang et al. | Jun 2018 | A1 |
| 20180179104 | Zhang et al. | Jun 2018 | A1 |
| 20180186685 | Murayama et al. | Jul 2018 | A1 |
| 20180186688 | Zhang et al. | Jul 2018 | A1 |
| 20180194673 | Liebald et al. | Jul 2018 | A1 |
| 20180208497 | Zhang et al. | Jul 2018 | A1 |
| 20180208498 | Li et al. | Jul 2018 | A1 |
| 20180222788 | Akada et al. | Aug 2018 | A1 |
| 20180222789 | Maeda et al. | Aug 2018 | A1 |
| 20180257973 | Kim et al. | Sep 2018 | A1 |
| 20180282204 | Rampf et al. | Oct 2018 | A1 |
| 20190077699 | Zhang et al. | Mar 2019 | A1 |
| 20190100453 | Zhang et al. | Apr 2019 | A1 |
| 20190169066 | Zhang et al. | Jun 2019 | A1 |
| 20190177210 | Beall et al. | Jun 2019 | A1 |
| 20190256407 | Beall et al. | Aug 2019 | A1 |
| 20190315650 | Fujiwara | Oct 2019 | A1 |
| 20190322571 | Aitken | Oct 2019 | A1 |
| Number | Date | Country |
|---|---|---|
| 1152836 | Jun 2004 | CN |
| 1171817 | Oct 2004 | CN |
| 101792267 | Aug 2010 | CN |
| 102557461 | Jul 2012 | CN |
| 101580344 | Oct 2012 | CN |
| 102786223 | Nov 2012 | CN |
| 101092308 | Feb 2013 | CN |
| 103086605 | May 2013 | CN |
| 103172267 | Jun 2013 | CN |
| 103492331 | Jan 2014 | CN |
| 102849958 | Apr 2015 | CN |
| 104478223 | Apr 2015 | CN |
| 104529173 | Apr 2015 | CN |
| 104556709 | Apr 2015 | CN |
| 103172265 | Oct 2015 | CN |
| 104973790 | Oct 2015 | CN |
| 104973791 | Oct 2015 | CN |
| 104973792 | Oct 2015 | CN |
| 103601371 | May 2016 | CN |
| 106007369 | Oct 2016 | CN |
| 107382052 | Nov 2017 | CN |
| 105517966 | Dec 2017 | CN |
| 104829130 | Jan 2018 | CN |
| 107935381 | Apr 2018 | CN |
| 552932 | Jul 1993 | EP |
| 560555 | Sep 1993 | EP |
| 997445 | Mar 2004 | EP |
| 1398303 | Nov 2015 | EP |
| 2942342 | Nov 2015 | EP |
| 2601148 | Apr 2018 | EP |
| 3321237 | May 2018 | EP |
| 3372568 | Sep 2018 | EP |
| 2011105554 | Jun 2011 | JP |
| 2014062715 | Apr 2014 | WO |
| 2015009686 | Jan 2015 | WO |
| 2016183133 | Nov 2016 | WO |
| 2017180811 | Oct 2017 | WO |
| 2017192794 | Nov 2017 | WO |
| 2018015740 | Jan 2018 | WO |
| Entry |
|---|
| International Search Report and Written Opinion from PCT/US2019/061917 dated Sep. 1, 2020. |
| International Search Report and Written Opinion from PCT/US2019/061923 dated Mar. 3, 2020. |
| Number | Date | Country | |
|---|---|---|---|
| 20200165159 A1 | May 2020 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62771250 | Nov 2018 | US |
