Glass composition and method for making fibers
阅读说明：本技术 用于制造纤维的玻璃组合物及方法 (Glass composition and method for making fibers ) 是由 P·B·麦金尼斯 D·A·霍夫曼 M·L·科尔文-爱迪生 于 2013-10-18 设计创作，主要内容包括：提供了改进的玻璃配料组合物以及纤维化该组合物以形成纤维的方法。本组合物的配料可以包括：40-60wt％SiO-2；15-50wt％Al-2O-3；0-30wt％MgO；0-25wt％CaO；0-5wt％Li-2O；0-9wt％B-2O-3以及0-5wt％Na-2O。由该组合物形成的纤维可具有大于82.7GPa(12MPSI)的杨氏模量。该纤维还可具有至少100ng/cm～2/小时的良好生物可溶性(k-(dis))。(Improved glass batch compositions and methods of fiberizing the compositions to form fibers are provided. The ingredients of the present composition may include: 40-60 wt% SiO 2 ；15‑50wt％Al 2 O 3 ；0‑30wt％MgO；0‑25wt％CaO；0‑5wt％Li 2 O；0‑9wt％B 2 O 3 And 0-5 wt% Na 2 And O. Fibers formed from the composition may have a Young's modulus of greater than 82.7GPa (12 MPSI). The fiber can also haveHas a length of at least 100ng/cm 2 Good biosolubility per hour (k) dis )。)
1. A composition for forming glass fibers comprising:
45-55wt％SiO2；
20-45wt％Al2O3；
21-25wt％MgO；
3-25wt％CaO；
0-5wt％Na2O；
0-5wt％Li2o; and
0-5wt％B2O3wherein the glass fibers are biosoluble having greater than about 200ng/cm2K per hourdis。
2. The composition of claim 1, wherein k of the compositiondisGreater than about 300ng/cm2In terms of hours.
3. The composition of any one of claims 1 to 2, wherein k of the compositiondisGreater than about 1000ng/cm2In terms of hours.
4. The composition of any one of claims 1 to 3, wherein the composition comprises, in weight percent:
5. the composition of any of claims 1 to 4, wherein the glass fiber formed from the glass composition has a Young's modulus of greater than about 82.7 GPa.
6. The composition of any of claims 1 to 5, wherein the glass fiber formed from the glass composition has a Young's modulus of greater than about 89.6 GPa.
7. The composition of any of claims 1 to 6, wherein the glass fibers formed from the glass composition have a density of from about 2.4 to 3.0 g/cc.
8. Has a density of greater than about 200ng/cm2K per hourdisFormed from a composition comprising:
45-55wt％SiO2；
20-45wt％Al2O3；
10-30wt％MgO；
3-25wt％CaO；
0-5wt％Li2o; and
0-5wt％B2O3,，
wherein the composition is Na-free2O and has a liquidus of at least 2600 ° F, the glass fibers having a density of from 2.4 to 3.0 g/cc.
9. The biosoluble glass fiber of claim 8, wherein the glass fiber is suitable for use in reinforcing composite materials.
10. The biosoluble glass fiber of claim 8, wherein the glass fiber is formed by a mineral wool process.
11. The biosoluble glass fiber of claim 8 wherein the glass fiber has a young's modulus of greater than about 82.7 GPa.
12. The biosoluble glass fiber of claim 11 wherein the glass fiber has a young's modulus of greater than about 89.6 GPa.
13. The biosoluble glass fiber of claim 8, wherein the glass fiber has greater than about 300ng/cm2K per hourdisThe value is obtained.
14. A method of forming glass fibers comprising:
providing a glass batch comprising:
40-60wt％SiO2；
31-50wt％Al2O3；
15-30wt％MgO；
0-3wt％CaO；
0-5wt％Na2O；
0-5wt％Li2o; and
0-9wt％B2O3and are and
fiberizing the glass furnish using a mineral wool process to form glass fibers, wherein the glass fibers are biosoluble having greater than about 100ng/cm2K per hourdisWherein the glass fibers have a Young's modulus of greater than about 82.7 GPa.
15. The method of claim 14, wherein the glass fibers have a length greater than about 200ng/cm2K per hourdisThe value is obtained.
16. The method of any one of claims 14 to 15, wherein the glass fibers have greater than about 300ng/cm2K per hourdisThe value is obtained.
17. The method of any of claims 14-16, wherein the glass fibers formed by the method have a density of from about 2.4 to 3.0 g/cc.
Background
Glass fibers for composite applications are made from various raw materials that are combined in specific proportions to produce the desired chemical composition. Such proportions are commonly referred to as "glass batch". The composition of the glass batch materials, and the glasses made therefrom, is generally expressed as a percentage of the components, which are expressed as oxides. SiO 22、A12O3、CaO、MgO、B2O3、Na2O、K2O、Fe2O3And minor amounts of other oxides are common components of glass batch materials. Various types of glasses can be produced by varying the amount of these oxides in the glass batch or omitting some of these oxides. Examples of such glasses that can be produced include E-glass, S-glass, R-glass, A-glass, C-glass, and ECR-glass. The glass composition determines properties of the glass including properties such as viscosity, liquidus temperature, durability, density, strength, and young's modulus of the glass. Non-physical considerations for commercial glass compositions include raw material costs and environmental impacts resulting from the manufacture of glass.
E-glass compositions are the most commonly used glass compositions for making continuous glass fiber strands used in textile and reinforcement applications. One advantage of E-glass is that its liquidus temperature is about 200F below its formation temperature, which is generally defined as the temperature at which the viscosity of the glass is equal to 1000 poise. E-glass has a wide range of forming temperatures and low devitrification rates. Historically, commercial E-glass compositions have a formation temperature between 2150 ° f and 2350 ° f and a liquidus value from about 100 ° f to 250 ° f below the formation temperature.
The most common high strength glass composition used to make continuous glass fiber strands is "S-glass". S-glass is a family of glasses consisting mainly of oxides of magnesium, aluminum and silicon, with a chemical composition that produces glass fibers with higher mechanical strength than E-glass fibers. S-glass typically has a composition that was originally designed for use in high strength applications, such as ballistic armor. Some examples of S-glasses include Owens CorningAndhaving a young's modulus of about 88 GPa. Another example is S-2 of AGYIt is an S-glass that may have a Young' S modulus of about 89.6GPa (13 MPSI).
Many glasses with high mechanical strength can be very expensive to produce due to their high forming temperatures and due to other process limitations. In addition, many glasses with high mechanical strength may not be soluble in biological fluids. The lack of solubility in biological fluids may limit the formation of products that are acceptable to the user. Accordingly, there remains a need in the art for improved glass compositions and methods of making such glasses that provide high mechanical strength, with the advantage of being soluble in biological fluids.
Disclosure of Invention
In some embodiments of the present invention, high modulus glass compositions are provided that can form fibers for composites. In some embodiments, the compositions of the present invention are based on a eutectic composition: 48 wt% SiO2、35wt％A12O3And 17 wt% MgO. In other embodiments, the present compositions comprise: about 40-60 wt% SiO2；15-50wt％A12O3；0-30wt％MgO；0-25wt％CaO；0-5wt％Li2O；0-9wt％B2O3And 0-5 wt% Na2And O. In some exemplary embodiments, fibers formed from the composition have a Young's modulus of greater than about 82.7GPa (12MPSI), or about 89.6GPa (13MPSI), or about 96.5GPa (14 MPSI). In other exemplary embodiments, fibers formed from the composition have a Young's modulus of greater than 103.4GPa (15 MPSI).
In further exemplary embodiments, the fibers formed from the composition are also biosoluble. Biosolubility is a measure of the rate at which a material dissolves in a biological fluid. For example, the fibers may have a tenacity greater than about 100ng/cm2Fibre biosoluble per hour. In other examples, the chemical composition of the composition is controlled to provide greater than about 200ng/cm2Per hour or even greater than about 300ng/cm2Fibre biosolubility per hour is possible.
In still other embodiments of the present invention, methods of forming fibers having high modulus are provided. The process may comprise forming fibres from the composition of the invention, for example using a conventional mineral wool process. The method may also include using conventional glass fiber forming methods.
Detailed Description
The present invention will now be described, from time to time, with reference to specific embodiments thereof. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are, of course, provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the description of the invention 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.
All numbers expressing quantities of ingredients, properties (e.g., molecular weights), 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" unless otherwise indicated. Accordingly, the numerical properties set forth in the specification and claims are approximations that may vary depending upon the desired properties sought to be obtained in the embodiments of the present invention, unless otherwise indicated. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention 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 errors found in their respective measurements.
According to an exemplary embodiment of the present invention, a glass batch composition useful for forming fibers is provided. Additionally, fibers formed from the glass batch composition are provided. Fibers formed using the compositions of the present invention can have significantly higher than S-glass fibers, for exampleAndand S-2The modulus of (a). Fibers formed using the compositions of the present invention may also have high strength.
In addition, as will be discussed further herein, the glass batch composition of the present invention can be used to produce fibers having high modulus without the use of conventional furnaces that can employ platinum/rhodium alloys. In other embodiments, the glass batch composition of the present invention can be formed in a conventional furnace, as will be discussed further herein.
According to an exemplary embodiment of the invention, the composition of the invention may be based on a eutectic composition: 48 wt% SiO2、35wt％Al2O3And 17 wt% MgO. For example, in some exemplary embodimentsIn one embodiment, the glass batch composition of the present invention comprises about 40 to about 60 wt% SiO2；15-50wt％Al2O3；0-30wt％MgO；0-25wt％CaO；0-5wt％Li2O；0-9wt％B2O3And 0-5 wt% Na2And O. In other exemplary embodiments, the glass composition includes about 45-55 wt% SiO2；20-45wt％Al2O3；5-25wt％MgO；3-25wt％CaO；0-5wt％Li2O；0-5wt％B2O3And 0-5 wt% Na2And O. In further exemplary embodiments, the glass composition includes about 45-55 wt% SiO2；20-35wt％Al2O3；10-20wt％MgO；5-25wt％CaO；0-5wt％Li2O；0-5wt％B2O3(ii) a And 0-5 wt% Na2O。
Other ingredients may be added to improve the properties of the resulting fiber and/or to improve the processing or biosolubility of the glass. For example, the composition may include about 5.0 wt% or less of additional compounds, such as oxides. Exemplary oxides that may be included in the composition include K as a deliberate additive or impurity2O、P2O5、ZnO、ZrO2、SrO、BaO、SO3、F2、Ce2O3、BeO、SeO2、Y2O3、La2O3、TiO2And Fe2O3And combinations thereof, each present at up to 5.0 wt%.
Additionally, for example, components can be added to the batch composition to facilitate processing, and subsequently removed, thereby forming a glass composition that is substantially free of such components. Thus, for example, very small amounts of components such as "flow" oxides may be present as trace impurities in the raw materials that provide the silica, calcia, alumina and magnesia components in the commercial practice of the present invention, or they may be processing aids that are substantially removed during manufacture. In some exemplary embodiments, such a flow oxide is present at less than about 5.0 wt%, or less than about 1.0 wt%.
In some embodiments, fibers formed from the compositions described herein have a young's modulus of greater than about 82.7GPa (12 MPSI). In other embodiments, fibers formed from the compositions described herein may have a young's modulus of greater than about 89.6GPa (13 MPSI). In still other examples, fibers formed from the composition may have a Young's modulus greater than about 96.5GPa (14MPSI), and even greater than 103.4GPa (15.0 MPSI).
In certain exemplary embodiments, such as by a biosoluble indicator (k)dis) The glass fibers formed from the furnish composition may be biosoluble, as measured. The biosoluble can be evaluated using published models for high alumina fibers. In thathttp://fiberscience.owenscorning.com/kdisapp.htmlThis model is disclosed above in the form of an online calculator. For example, the fibers can have a tenacity greater than about 100ng/cm2Fibre biosoluble per hour. In some exemplary embodiments, the fibers have a tenacity greater than about 200ng/cm2Per hour or even greater than about 300ng/cm2Fibre biosoluble per hour. In further exemplary embodiments, the fibers have a tenacity greater than about 1000ng/cm2Per hour, greater than about 2000ng/cm2Per hour, or even greater than about 10000ng/cm2Fibre biosoluble per hour. The biosolubility of the composition allows the glass to be safely fiberized using a rotating wheel of the mineral wool process or using other processes that are not conventional for forming high modulus fibers. In addition, the biosolubility of the fibers allows for the production of fibers having small diameters using traditional reinforcing fiber forming methods.
In some exemplary embodiments, the glass fibers formed from the inventive furnish compositions disclosed herein have a density from about 2.4g/cc to about 3.0 g/cc. In other exemplary embodiments, the glass fibers formed from the inventive furnish composition have a density from about 2.57g/cc to about 2.97 g/cc.
Typically, continuous glass fibers are formed by passing molten glass material through a bushing. As the glass exits the bushing through very fine orifices, the glass is cooled, such as by water jets, and mechanically drawn onto a high speed winder. As the fiber is wound, the tension causes the molten glass stream to be drawn into a thin, fibrous element known as a filament. However, in some exemplary embodiments, the inventive glass fibers are discontinuous and may be formed using any known fiber forming process, such as mineral wool processes, steam jet processes, rotary processes, flame attenuation (flame attenuation), and the like.
In some exemplary embodiments, the mineral wool process includes any suitable furnace, such as a dome furnace or a tank furnace (not shown), into which the batch components may be introduced and melted to form a molten material. The molten glass from the furnace flows into a cylindrical vessel that includes small holes. As the cylindrical vessel rotates, a horizontal stream of glass begins to flow out of the orifice. The stream of molten glass can be attenuated by a downward stream of air, hot gases, or both. In some exemplary embodiments, the fibers fall against one or more fiberizing rollers. The first fiberizing roll operates to disperse the molten material to form fibers, which can then be advanced to an optional second fiberizing roll. In some exemplary embodiments, the second fiberizing roll rotates in an opposite direction to the first roll and further disperses the material to form finished fibers. In some exemplary embodiments, high pressure air jets may again be used between the first and second rolls to further attenuate the fibers.
In some exemplary embodiments, the fibers may have the sizing composition applied as they exit the roll (sizing composition), or the fibers may be collected and the sizing composition applied in a post-manufacturing process. It will be appreciated that any suitable sizing composition may be used to size the fibers, and that the sizing composition may be selected to be compatible with the particular resin system of the composite article made using the fibers. One skilled in the art will appreciate that any suitable method of forming discontinuous fibers may be used to form the fibers. When a discontinuous process is used to form the fibers, the fibers produced by the discontinuous process can have dimensions that allow the fibers to be respirable. In particular, in the airDuring attenuation, the discontinuous fibers can risk being released into the air and become respirable. An advantage of the present invention is that any respirable fiber produced by the discontinuous process exhibits kdisGreater than 100ng/cm2Biosoluble/hour, such that the fiber is soluble in biological fluids.
It will be appreciated that other fiberizing methods may be useful for forming fibers from the glass batch composition. For example, the glass compositions of some embodiments may be formed using conventional glass forming processes for producing continuous fibers. For example, a conventional direct melt process may be used, and the fibers may be formed by any suitable bushing (e.g., platinum or platinum/rhodium bushings) and wound on a winder. In other embodiments, the fibers may be formed using conventional batch processes. For example, the fibers may be formed using a platinum-lined furnace and produced using any suitable bushing. When a ferrule is used to form the fibers, the fiber diameter can be controlled to produce continuous fibers having a desired diameter. One advantage of the present invention is that continuous fibers can be formed having very small diameters while exhibiting biosoluble properties, strength, and modulus.
The fibers of the present invention may be used as reinforcement in composite articles formed using any suitable resin, to form fabrics useful in forming composite articles, or for any other purpose.
Examples
The invention will be better understood by reference to the following examples, which are provided by way of illustration and not limitation. Fibers having the compositions listed in tables I-A-I-I include the listed ingredients in weight percent. (note that indicates the expected value).
TABLE I-A
Tables I-B
Tables I-C
Tables I-D
Tables I-E
Tables I-F
Tables I-G
Tables I-H
Tables I-I
The fibers of the above examples were formed in a laboratory grade furnace using a single hole bushing. Young's modulus was measured using a well-demonstrated sonic technique, in which the speed of sound was measured in a single fiber. The raw fiber strength was measured by pulling the raw fiber (pristine fiber) from a single hole thimble and measuring the failure stress over a two inch gauge length. Biosolubility was assessed using the published model for high alumina fibers. In thathttp://fiberscience.owenscorning.com/ kdisapp.htmlThis model is disclosed above in the form of an online calculator.
It should be understood that where minor amounts of components are specified in the composition (e.g., amounts of about 2.0 weight percent or less), these components may be present as trace impurities present in the starting materials, rather than intentionally added.
The present invention should not be considered limited to the particular embodiments described herein, but rather should be understood to cover all aspects of the invention. Various modifications, equivalent processes, as well as numerous structures and devices to which the present invention may be applicable will be readily apparent to those of skill in the art to which the present invention is directed. It will be understood by those skilled in the art that various changes may be made without departing from the scope of the invention and it is not intended to limit the scope to that described in the specification.