Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C13/00—Fibre or filament compositions

Definitions

• the present invention relates to glass compositions and fibers. More particularly, the present invention relates to glass compositions and fibers having a low dielectric constant and a low dissipation factor. Further, the glass fibers of the present invention are preferably suitable for use in connection with electronic related devices such as reinforcement for printed circuit board laminates and the like.
• Modern electronic devices commonly include printed circuit boards reinforced with glass fibers.
• Many modern electronic devices such as mobile or stationary wireless telephones, computers, smartphones, tablets, and the like, have electronic systems that operate at high processing speeds and high or ultra-high frequencies.
• the glass When glass is exposed to such a high or ultra-high frequency electromagnetic field, the glass absorbs at least some energy and converts the absorbed energy to heat.
• the energy that is converted by the glass into heat is called dielectric loss energy.
• E-Glass Two types of glass fibers commonly used to reinforce printed circuit boards are E-Glass and D-Glass.
• E-Glass has a relatively high dielectric constant ranging from about 6.1 and a relatively high dissipation factor ranging from about 38x10 -4 at a frequency of about 10 GHz at room temperature. Accordingly, because E-Glass can yield relatively high dielectric losses, E-Glass is a poor reinforcement material for printed circuit boards having higher densities of electronic components and higher processing speeds.
• D-Glass on the other hand, has a relatively low dielectric constant and dissipation factor. D-Glass, however, has relatively high melting temperatures, relatively poor workability, relatively poor mechanical performance, and relatively poor water resistance.
• D-Glass may inadequately adhere to epoxy resins, and commonly includes imperfections in the form of striae and bubbles. Accordingly, neither E-Glass nor D-Glass are ideally suited for use as reinforcement fibers in high speed printed circuit boards, and neither is well- suited for circuit boards that operate at high or ultra-high frequencies from about 100 MHz to about 18 GHz.
• a glass composition comprising: between 48.0 to 57.0 weight percent S1O2; between 15.0 weight percent B2O3 and 26.0 weight percent B2O3; between 12.0 weight percent AI2O3 and 18.0 weight percent AI2O3; between greater than 3.0 and 8.0 weight percent P2O5; between greater than 0.25 weight percent and 7.0 weight percent CaO; 5.0 or less weight percent MgO; and, 6.0 or less weight percent " PO2; wherein the composition has a glass viscosity of 1000 poise at a temperature greater than 1350 °C, and wherein the composition has a liquidus temperature greater than 1100 °C.
• the class composition further comprises: between 49.0 to 56.5 weight percent S1O2; between 15.5 to 25.5 weight percent B2O3; between 12.5 to 17.50 weight percent AI2O3; between greater than 3.0 and 7.5 weight percent P2O5; between greater than 0.25 weight percent and 6.5 weight percent CaO; 4.5 or less weight percent MgO; and 5.5 or less weight percent PO2.
• the glass composition further comprises: between 50.0 to 56.0 weight percent S1O2; between 16.0 to 25.0 weight percent B2O3; between 13.0 to 17.0 weight percent AI2O3; between greater than 3.0 and 7.0 weight percent P2O5; between greater than 0.25 and 6.0 weight percent CaO; 4.0 or less weight percent MgO; and 5.0 or less weight percent PO2.
• the composition further comprises one or more of: no less than 49.0 weight percent S1O2; no more than 56.5 weight percent S1O2; no less than 15.5 weight percent B2O3; no more than 25.5 weight percent B2O3; no more than 17.50 weight percent AI2O3; no more than 7.0 weight percent P2O5;
• the composition further comprises one or more of: no less than 50.0 weight percent S1O2; no more than 56.0 weight percent S1O2; no less than 16.0 weight percent B2O3; no more than 25.0 weight percent B2O3; no more than 17.0 weight percent AI2O3; no more than 7.0 weight percent P2O5; 6.0 or less weight percent CaO; 4.0 or less weight percent MgO; and/or no more than 5.0 weight percent " PO2.
• the composition has a liquidus temperature greater than 1100 °C.
• the composition has a liquidus temperature greater than 1150 °C. [0014] In an embodiment of the invention, the composition has a liquidus temperature greater than 1200 °C.
• the composition has a glass viscosity of 1000 poise at a temperature greater than 1355 °C.
• the composition has a glass viscosity of 1000 poise at a temperature greater than 1360 °C.
• a glass fiber is formed from the glass compositions described above.
• the glass fiber has a dielectric constant less than or equal to 6 and/or a dissipation factor less than or equal to 38x10 -4 at a frequency of 10 GHz at room temperature.
• the glass fiber has a dielectric constant less than or equal to 4.60 and/or a dissipation factor less than or equal to
• the glass fiber has a dielectric constant less than or equal to 4.55 and/or a dissipation factor less than or equal to
• the glass composition has an inherent network structure that is predisposed to crystalize into and form Alumino- Borate Mullite crystals.
• a process for providing continuous, manufacturable low dielectric glass fibers comprising the steps of: providing any of the glass compositions described herein to a melting zone of a glass melter; heating the composition to a forming temperature in excess of the liquidus temperature; and continuously fiberizing said molten glass whereby a low dielectric constant and low dissipation factor glass fiber is produced.
• a low dielectric glass fiber formed from a glass composition
• a glass composition comprising: between 48.0 to 57.0 weight percent S1O2; between 15.0 to 26.0 weight percent B2O3; between 12.0 to 18.0 weight percent AI2O3; between greater than 3.0 and 8.0 weight percent P2O5; between greater than 0.25 and 7.00 weight percent CaO; 5.0 or less weight percent MgO; and, 6.0 or less weight percent PO2; wherein the composition has a glass viscosity of 1000 poise at a temperature greater than 1350 °C, and wherein the glass composition has a liquidus temperature greater than 1100 °C.
• the glass composition further comprises: between 49.0 to 56.5 weight percent S1O2; between 15.5 to 25.5 weight percent B2O3; between 12.5 to 17.50 weight percent AI2O3; between greater than 3.0 and 7.5 weight percent P2O5; between greater than 0.25 and 6.5 weight percent CaO; 4.5 or less weight percent MgO; and 5.5 or less weight percent PO2.
• the glass composition further comprises: between 50.0 to 56.0 weight percent S1O2; between 16.0 to 25.0 weight percent B2O3; between 13.0 to 17.0 weight percent AI2O3; between greater than 3.0 and 7.0 weight percent P2O5; between greater than 0.25 and 6.0 weight percent CaO; 4.0 or less weight percent MgO; and, 5.0 or less weight percent PO2 .
• the glass composition further comprises one or more of: no less than 49.0 weight percent S1O2; no more than 56.5 weight percent S1O2; no less than 15.5 weight percent B2O3; no more than 25.5 weight percent B2O3; no more than 17.50 weight percent AI2O3; no more than 7.0 weight percent P2O5; 6.5 or less weight percent CaO; 4.5 or less weight percent MgO; and/or, no more than 5.5 weight percent PO2 .
• the glass composition further comprises one or more of: no less than 50.0 weight percent S1O2; no more than 56.0 weight percent S1O2; no less than 16.0 weight percent B2O3; no more than 25.0 weight percent B2O3; no more than 17.0 weight percent AI2O3; no more than 7.0 weight percent P2O5; 6.0 or less weight percent CaO; 4.0 or less weight percent MgO; and/or, no more than 5.0 weight percent " PO2.
• the glass composition has a liquidus temperature greater than 1100 °C.
• the glass composition has a liquidus temperature greater than 1150 °C.
• the glass composition has a liquidus temperature greater than 1200 °C.
• the glass composition has a glass viscosity of 1000 poise at a temperature greater than 1355 °C. [0032] In an embodiment of the invention, the glass composition has a glass viscosity of 1000 poise at a temperature greater than 1360 °C.
• the glass fiber has a dielectric constant less than or equal to 6 and/or a dissipation factor less than or equal to 38x10 -4 at a frequency of 10 GHz at room temperature.
• the glass fiber has a dielectric constant less than or equal to 4.60 and/or a dissipation factor less than or equal to
• the glass fiber has a dielectric constant less than or equal to 4.55 and/or a dissipation factor less than or equal to
• the glass fiber is formed from a glass composition which has an inherent network structure that is predisposed to crystalize into and form Alumino-Borate Mullite crystals.
• the present invention also includes a fiberglass reinforced article, such as a printed circuit board, incorporating glass fibers of the present invention. Further, the present invention includes a product incorporating a glass fiber, such as disclosed above, and wherein the product may be a printed circuit board, a woven fabric, a non- woven fabric, a unidirectional fabric, a chopped strand, a chopped strand mat, a composite material, and a communication signal transport medium.
• the present invention includes a process for providing continuous, manufacturable low dielectric glass fibers.
• the process may include the steps of providing a glass composition, such as disclosed herein, to a melting zone of a glass melter; heating the composition to a forming temperature in excess of the liquidus temperature; and continuously fiberizing the molten glass whereby a low dielectric constant and low dissipation factor glass fiber is produced.
• FIG. 1 is a graph showing the relationship between liquidus temperature (Tnq) and dissipation factor (Df), in accordance with some embodiments of the invention.
• the present invention is directed to glass compositions and fibers preferably having low dielectric constant values and low dissipation factors, also referred to herein as tan d.
• the glass fibers of the present invention are preferably suitable for use in connection electronic devices and systems that operate at high processing speeds and/or high frequencies, such as mobile or stationary wireless telephones, computers, smartphones, tablets, and the like.
• the glass fibers of the present invention preferably yield a lower dielectric constant and dissipation factor than that of E-Glass but with better workability properties than D-Glass.
• the present invention also discloses fiberglass reinforced articles, products incorporating glass fibers, such as printed circuit boards, woven fabrics, non-woven fabrics, unidirectional fabrics, chopped strands, chopped strand mats, composite material, and communication signal transport mediums, and a process for providing continuous and manufacturable low dielectric glass fibers.
• the composition of the present invention is generally composed of one or more of the following oxides including silicon oxide (S1O2), boron oxide (B2O3), aluminum oxide (AI2O3), calcium oxide (CaO), phosphorous oxide (P2O5), magnesium oxide (MgO), and titanium oxide (T1O2). Additional oxides may be present as discussed below without departing from the spirit and scope of the present invention.
• the composition of the present invention in some embodiments, has a liquidus temperature greater than 1100 °C and a glass viscosity of 1000 poise at a temperature (T log 3) greater than 1350 °C.
• the glass fibers of the present invention preferably have a dielectric constant less than or equal to 6, and/or a dissipation factor less than or equal to 38x10 -4 at a frequency of 10 GHz at room temperature.
• the composition of the present glass preferably has the ability to fiberize continuously because of its positive difference (DT 3 ) between the T log 3 viscosity temperature and liquidus temperature.
• liquidus is given its ordinary and customary meaning, generally inclusive of the temperature, (Tiiq) at which equilibrium exists between liquid glass and its primary crystalline phase, whereas at all temperatures above the liquidus, the glass melt is free from crystals in its primary phase and at temperatures below the liquidus, crystals may form in the melt.
• the liquidus temperature therefore provides a useful lower temperature limit above which it is possible to continuously fiberize the glass.
• T log 3 viscosity temperature is understood to mean the temperature at which the glass has a viscosity equal to 1000 poise (denoted by T log 3).
• delta-T also referred to as “DT 3 ”
• DT 3 is given its ordinary and customary meaning in the art, generally inclusive of the difference between the fiberizing temperature and the liquidus, and thus, is a fiberizing property of the glass composition.
• the larger the delta-T the more process flexibility exists during the formation of glass fibers and the less likely devitrification (crystallization) of the glass melt will occur during melting and fiberizing.
• the greater the delta-T the lower the production cost of the glass fibers, in part by extending bushing life and by providing a wider fiber-forming process window.
• fiber refers to an elongated body, the length dimension of which is greater than the transverse dimensions of width and thickness. Accordingly, the term fiber includes monofilament, multifilament, ribbon, strip, staple and other forms of chopped, cut or discontinuous fiber and the like having regular or irregular cross- sections. Fiber and filament are used interchangeably herein.
• E-Glass is used according to its meaning as described in ASTM D-578.
• D-Glass refers to a glass composition having the properties as set forth herein.
• low dielectric constant is meant a glass fiber having a dielectric constant lower than E-Glass.
• E-Glass has a dielectric constant of about 6.1 at a frequency of 10 GHz at room temperature.
• low dissipation factor is meant a glass fiber having a dissipation factor lower than E-Glass.
• E-Glass has a dissipation factor of about 38x10 -4 at a frequency of about 10 GHz at room temperature.
• low dielectric glass fiber is meant a glass fiber with a low dielectric constant and low dissipation factor as defined herein.
• glasses that are melted at sufficiently high temperature for sufficiently long times tend to be chemically and structurally homogeneous, that is lacking in regions of different chemical makeup or atomic arrangement.
• the minimum amount of homogeneity necessary for continuous fiberization is that state of the melt where an inhomogeneity is too small to disturb the fiberization process and therefore fibers can be stably and continuously formed.
• Efficient fiberization requires a glass melt quality that is consistent with regard to a liquid's viscosity. Perturbations in viscosity disrupt flow and causes fiber breakage during forming.
• Glass melt defects either from unmelted batch materials (stones), poorly melted or homogenized glass (striae/cords) and devitrification products (crystals formed at temperatures below Tnq) are typical culprits.
• the glasses within the instant glass family are susceptible to liquid-liquid immiscibility (glass phase separation) on cooling from high temperature.
• Phase separation is the tendency for a homogeneous liquid at high temperature to thermodynamically demix into two different glasses on cooling, often with very different compositions, liquid structures and associated properties.
• phase separated glasses can exhibit discontinuous rather than continuous viscosity behavior as a function of temperature and thus phase separated regions of the melt can impede stable fiber forming.
• melt instability index a “melt instability index”
• Glass compositions for the formation of glass fibers that are preferably suitable for use in electronic applications and articles and that are preferably capable of being economically formed through continuous fiberization into glass fibers are provided.
• the glass fiber includes a composition having between 45 and 58 weight percent silicon dioxide (S1O2) (also referred to herein as silica).
• the silicon dioxide content may be between 45.5 and 57.5 weight percent.
• the silicon dioxide content may be between 46 and 57 weight percent.
• the silicon dioxide content may be less than 56.75 weight percent.
• the silicon dioxide content may be less than 56.50 weight percent.
• the viscosity of the glass may decrease to the extent that devitrification (crystallization) during fiberization results when silicon dioxide is less than 45 weight percent of the total composition of the glass fiber.
• silicon dioxide is greater than 58 weight percent of the total composition of the glass fiber, the glass may become too viscous thereby making it more difficult to melt, homogenize, and refine.
• the silica content is preferably between 45 and 58 weight percent of the total composition of the glass.
• a silica content between 45.00 and 58.00 weight percent typically yields a glass fiber having a desirable low dielectric constant as well as a low dissipation factor.
• the silica content is at least 45.50 weight percent. Alternatively, the silica content is at least 46.00 weight percent. In another embodiment of the glass fiber and/or glass composition of the present invention, the silica content is no more than 57.50 weight percent. Alternatively, the silica content is no more than 57.00 weight percent. Yet further alternatively, the silica content is no more than 56.75 weight percent. In another embodiment, the silica content is no more than 56.50 weight percent.
• the inventors have identified certain surprisingly useful and/or effective formulations wherein the glass fiber includes a composition having between 48 and 57 weight percent silicon dioxide (S1O2).
• the silicon dioxide content may be between 49 and 56.5 weight percent.
• the silicon dioxide content may be between 50 and 56 weight percent.
• the silicon dioxide content may be less than 56.0 weight percent.
• the viscosity and fiberization of the glass is typically affected. For example, the viscosity of the glass may decrease to the extent that devitrification (crystallization) during fiberization results when silicon dioxide is less than 48 weight percent of the total composition of the glass fiber.
• the silica content is preferably between 48 and 57 weight percent of the total composition of the glass. It should also be understood that S1O2 is useful for controlling stability of the formulation and that the weight percent of S1O2 is also optionally selected for such considerations in combination with the other factors described herein.
• the glass fiber in some embodiments of the invention includes a composition having greater than 18 weight percent boron oxide (B2O3) and no more than 26 weight percent boron oxide.
• B2O3 boron oxide
• the boron oxide content may be between 18.5 and 25 weight percent.
• the boron oxide content may be between 19 and 22 weight percent.
• a high percentage of boron oxide, such as above 26 weight percent may cause an excessive loss of B2O3 during melting, poor homogeneity, low strength, and poor mechanical properties.
• a boron oxide content greater than 18.00 weight percent and no more than 26.00 weight percent typically yields a glass fiber having a desirable low dielectric constant as well as a low dissipation factor.
• the boron oxide content is at least 18.50 weight percent. Alternatively, the boron oxide content is at least 19.00 weight percent. In another embodiment of the glass fiber and/or glass composition of the present invention, the boron oxide content is no more than 25.00 weight percent. Alternatively, the boron oxide content is no more than 24.00 weight percent.
• the inventors have identified certain surprisingly useful and/or effective formulations wherein the glass fiber includes a composition having between 15 weight percent boron oxide (B2O3) and 26 weight percent boron oxide. It is generally understood that B2O3 is favorable for lowering Df, but too much can create glass instability in the form of phase separation.
• the boron oxide content may be between 15.5 and 25.5 weight percent. Further alternatively, the boron oxide content may be between 16 and 25 weight percent.
• a high percentage of boron oxide, such as above 26 weight percent may cause an excessive loss of B2O3 during melting, poor homogeneity, poor mechanical properties, and glass instability in the form of phase separation.
• boron oxide content is preferably between15 weight percent and 26 weight percent of the total composition of the glass. Further, when combined with the other constituents as set forth herein, a boron oxide content between 15.00 and 26.00 weight percent typically yields a glass fiber having a desirable low dielectric constant as well as a low dissipation factor. In one embodiment of the glass fiber and/or glass composition of the present invention, the boron oxide content is at least 16.0 weight percent. Additionally, alternatively and/or optionally, the boron oxide content is no more than 20.00 weight percent. In another embodiment of the glass fiber and/or glass composition of the present invention, the boron oxide content is no more than 25.00 weight percent.
• the glass fiber in some embodiments of the present invention includes a composition having greater than 16 weight percent and no more than 23 weight percent aluminum oxide.
• the aluminum oxide content may be greater than 16 weight percent and no more than 22.5 weight percent. Further alternatively, the aluminum oxide content may be greater than 16 weight percent and no more than 22 weight percent.
• the percentage of aluminum oxide with respect to the total composition of the glass fiber may also affect the viscosity and fiberization process. For example, a high percentage of aluminum oxide, such as above 23 weight percent, may cause the melt viscosity to decrease so that devitrification during fiberization results. A low percentage of aluminum oxide, such as at or below 18 weight percent, may cause phase separation and poor fiber formation.
• the alumina content is preferably greater than 16 weight percent and no more than 23 weight percent of the total composition of the glass. Further, when combined with the other constituents as set forth herein, an alumina content between 16.00 and 23.00 weight percent typically yields a glass fiber having a desirable low dielectric constant as well as a low dissipation factor. In one embodiment of the glass fiber and/or glass composition of the present invention, the alumina content is no more than 22.50 weight percent. Alternatively, the alumina content is no more than 22.00 weight percent.
• Aluminum oxide is known to stabilize glasses that are prone to phase separation/melt instability. Flowever, it is also known to increase the tendency toward devitrification/crystallization at high levels, and therefore it can be bad for fiber forming stability with respect to delta-T.
• AI2O3 for example being the opposite of B2O3 in some respects, and other components of the described formulations, it is important to find the correct balance amongst all of them.
• the inventors have identified certain surprisingly useful and/or effective formulations wherein, in some embodiments of the invention, a balance of Df behavior and Tn q behavior is achieved when AI2O3 is present in the range of 12 to 18 weight percent.
• AI2O3 is present in the range of 12.5 to 17.5 weight percent.
• AI2O3 is present in the range of 13 to 17 weight percent, in some embodiments of the invention. It should be understood that these ranges are given to assist the reader with envisioning working formulations for the inventors’ compositions, however, it should also be understood that formulations using any weight percent including within any of the ranges of AI2O3 described herein, could be used to achieve acceptable formulations for the stated purposes of the invention.
• the glass fiber of the present invention typically also includes a composition having between greater than 3 and 8 weight percent phosphorus oxide (P2O5, also referred to as phosphorous pentoxide).
• P2O5 also referred to as phosphorous pentoxide
• the phosphorous oxide content may be between greater than 3 and 7.5 weight percent.
• the phosphorous oxide content may be between greater than 3 and 7 weight percent.
• P 2 0s was found to synergistically associate with the AI2O3 content of the glass, thereby decreasing the melt stability (increasing the instability index value) while simultaneously also improving the key metrics of Df and the Tiiq.
• Alkaline earth oxides (magnesium oxide (MgO), calcium oxide (CaO), and sometimes strontium oxide (SrO)) all help these glasses to melt and homogenize at reasonable temperatures achievable by melting furnaces known in the art.
• MgO increases the Df less than CaO
• SrO increases the Df more than CaO
• CaO is typically the preferred alkaline earth addition because compared to the alternatives it provides the best compromise between viscosity, Tii q and Df.
• too little alkaline earth oxide drives the glass melt toward instability (higher index numbers).
• the glass fiber composition of the present invention may also include CaO (also referred to herein as calcia) and/or MgO, as described below.
• the glass fiber of the present invention includes, in some embodiments of the invention, a composition having between greater than 0.25 weight percent calcium oxide and 7.0 weight percent calcium oxide.
• the calcium oxide content may be between greater than 0.25 weight percent and 6.5 weight percent.
• the calcium oxide content may be between greater than 0.25 weight percent and 6 weight percent.
• the calcium oxide content may be between greater than 2.5 weight percent and 5.0 weight percent.
• the weight percent of calcium oxide may impact the viscosity and devitrification process of the glass fiber.
• a high percentage of calcium oxide, such as above 7.0 weight percent may cause insufficient dielectric properties.
• a low percentage of calcium oxide, such as at or below 0.25 weight percent may cause poor fiber formation.
• calcia content is 4.5 or less weight percent.
• the calcia content is 4.25 or less weight percent.
• the calcia content is 4.00 or less weight percent.
• the glass fiber composition of the present invention may also include MgO (also referred to herein as magnesia).
• the glass fiber of the present invention may include a composition having less than or equal to 5.0 weight percent magnesium oxide.
• the magnesium oxide content may be less than or equal to 4.5 weight percent.
• the magnesium oxide content may be less than or equal to 4.0 weight percent.
• the magnesium oxide content may be less than or equal to 2.0 weight percent.
• the magnesium oxide content may be less than or equal to 1.5 weight percent.
• the weight percent of magnesium oxide also may harm the viscosity and devitrification process of the glass fiber. Further, a high percentage of magnesium oxide, such as above 5.0 weight percent may cause insufficient dielectric properties.
• Titanium oxide (T1O2) is optionally present, or intentionally introduced, in the glass composition and fibers of the present invention.
• the weight percent of titanium oxide is no more than 6.0.
• the weight percent of titanium oxide is no more than 5.5.
• the weight percent of titanium oxide is no more than 5.0. Flaving 6 weight percent or more titanium oxide seems to lead to an increased tendency towards phase separation in the glass composition and fibers, especially when combined with phosphorous pentoxide.
• Titanium oxide typically acts as a viscosity reducer and may be intentionally added or present as an impurity from conventional raw materials.
• titanium oxide may be present in the glass composition at a weight percent at or greater than 0.01.
• titanium oxide may be present in the glass composition at a weight percent at or greater than 0.05.
• titanium oxide may be present in the glass composition at a weight percent at or greater than 0.1.
• PO2 is known in the art as an acceptable additive to other low D k glasses in order to lower their viscosity.
• T log 3 - Tnq acceptable delta-T ranges
• oxides such as lithium oxide (U 2 O), sodium oxide (Na 2 0), potassium oxide (K 2 O), barium oxide (BaO), strontium oxide (SrO), zinc oxide (ZnO), fluorine (F or F2), tin oxide (SnC>2), zirconium oxide (ZrC ), chromium oxide (( 203), iron oxide (Fe2C>3), lanthanum oxide (l_a2C>3), manganese oxide (Mh2q3), yttrium oxide (Y2O3), and/or vanadium oxide (V2O3) may be present.
• oxides such as lithium oxide (U 2 O), sodium oxide (Na 2 0), potassium oxide (K 2 O), barium oxide (BaO), strontium oxide (SrO), zinc oxide (ZnO), fluorine (F or F2), tin oxide (SnC>2), zirconium oxide (ZrC ), chromium oxide (( 203), iron oxide (Fe
• the combined total of these additional oxides is no more than 3 weight percent of the total composition, so long as they do not alter the function of the glass.
• the combined total of these additional oxides may be no more than 2 weight percent of the total composition.
• the combined total of these additional oxides may be no more than 1.5 weight percent of the total composition.
• the combined total of these additional oxides may be no more than 3.0, 2.0 and/or 1.0 weight percent of the total composition, in some embodiments of the invention.
• the combined total of alkali metal oxides is preferably no more than 1.0 total weight percent of the composition. More preferably, the combined total is no more than 0.5 total weight percent of the composition. Even more preferably, the combined total is no more than 0.25 total weight percent of the composition.
• Example glass compositions and glass fibers of the present invention are set forth herein.
• the glass composition and/or glass fiber includes between 48.0 to 57.0 weight percent S1O2; between 15.0 and 26.0 weight percent B2O3; between 12.0 and 18.0 weight percent AI2O3; between greater than 3.0 and 8.0 weight percent P2O5; between greater than 0.25 and 7.0 weight percent CaO; 5.0 or less weight percent MgO; and 6.0 or less weight percent PO2.
• An alternative glass composition and/or glass fiber of the present invention may include between 49 to
• the following constituents may be included: between 50 to 56.0 weight percent S1O2; between 16.0 to 25.0 weight percent B2O3; between 13.0 and 17.0 weight percent AI2O3; between greater than 3.0 and 7.0 weight percent P2O5; between greater than 0.25 and 6.0 weight percent CaO; 4.0 or less weight percent MgO; and 5.0 or less weight percent " PO2.
• the glass composition of the present invention has a liquidus temperature greater than 1100°C. In an alternative embodiment, the glass composition may have a liquidus temperature greater than 1150°C. In yet a further alternative embodiment, the glass composition may have a liquidus temperature greater than 1200°C. Having a liquidus temperature greater than 1100°C, or more preferably greater than 1150°C, is favorable for fiberizing a glass composition according to the present invention. [0074] Further, the glass composition of the present invention may have a T log 3 viscosity temperature greater than 1350°C. Alternatively, the glass composition may have a T log 3 viscosity temperature greater than 1355°C. In yet a further alternative embodiment, the glass composition may have a T log 3 viscosity temperature greater than 1360°C. Having a T log 3 viscosity temperature greater than 1350°C is favorable for fiberizing a glass composition according to the present invention.
• the glass fibers of the present invention may have a dielectric constant less than or equal to 6.
• the glass fibers may have a dielectric constant less than or equal to 4.60.
• the glass fibers may have a dielectric constant less than or equal to 4.55.
• the glass fibers of the present invention may have a dissipation factor less than or equal to 38x10 -4 at a frequency of 10 GHz at room temperature.
• the glass fibers may have a dissipation factor less than or equal to 30x10 -4 at a frequency of 10 GHz at room temperature.
• the glass fibers of the present invention may have a dissipation factor less than or equal to 25x10 -4 at a frequency of 10 GHz at room temperature.
• the glass fibers of the present invention may be incorporated into a fiberglass-reinforced article, such as a printed circuit board. Further, the glass fibers of the present invention may be used in connection with products such as woven fabrics, non-woven fabrics, unidirectional fabrics, chopped strands, chopped strand mats, composite materials, and communication signal transport mediums.
• the present invention also includes a process for providing continuous, manufacturable low dielectric glass fibers.
• the process may include the steps of providing a glass composition, such as disclosed herein, to a melting zone of a glass melter; heating the composition to a forming temperature in excess of the liquidus temperature; and continuously fiberizing the molten glass whereby a low dielectric constant and low dissipation factor glass fiber is produced.
• the composition of the glass for providing low dielectric constant glass fibers is, at least in part, based on the weight percent of the oxides discussed above as well as the ratios and combined weights of silicon dioxide, aluminum oxide, boron oxide, calcium oxide, magnesium oxide, phosphorus oxide, and/or titanium oxide.
• the combination of these parameters in addition to other parameters discussed herein, such as T log 3 viscosity temperature, makes it possible to obtain glass fibers having a low dielectric constant and low dissipation factor as set forth herein.
• Creux's formulations illustrate glasses with wholly inferior Df behavior (Df ⁇ 0.0090 at 10 GHz), as shown in the two (2) examples of US2004/01755557.
• the current invention achieves Df ⁇ 0.0028.
• Creux's T log 3 is ⁇ 1350°C and Tiiq is ⁇ 1000°C.
• Zhang does not describe Df behavior of its glasses at all. T log 3 of Zhang’s glasses are ⁇ 1350°C and Tiiq are all ⁇ 1000°C. Interestingly, Zhang describes that their glasses have excellent devitrification behavior because the primary crystal phases (Wollastonite / Diopside / Calcium Feldspar) all compete with one another. See para. [0014] of CN103351102.
• the inventors unexpectedly discovered that the measured dielectric loss of the invention appears to be intimately related to the crystallization behavior of the instant glasses. That is that glasses with higher Tii q values tend to have better, that is lower, Df characteristics.
• FIG. 1 shows this data relationship derived from the glasses of the present invention.
• the most desirable glass for obtaining low Df behavior is one which has an inherent network structure that is predisposed to crystalize into and form Alumino-Borate Mullite (needle) crystals.
• Example glass compositions made according to the present invention are set forth below. The particular components and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. In these examples and throughout this description, all percentages, proportions and ratios are by weight (mass) unless otherwise indicated.
• Exemplary glass compositions of the present invention are shown in Tables 1-12 below.
• the liquidus temperature of the example glass compositions is represented as “Tnq” and the temperature where the glass composition had a viscosity of 1000 poise is represented as “T3” (also referred to as “T log 3” viscosity temperature).
• T3 also referred to as “T log 3” viscosity temperature
• the liquidus temperature and T3 temperature of the example glass compositions were measured for some of the glass compositions and calculated for others.
• Glass fibers were formed using the example compositions and the dielectric constant and dissipation factor was measured for some of the glass fibers and calculated for others.
• the dielectric constant is represented as the “Dk” value and the dissipation factor is represented as the “Df” value.
• T log 3 viscosity temperature was measured using ASTM C 965- SI .
• the glass compositions in the examples have a dielectric constant less than 4.56, and a dissipation factor of less than or equal to 25x10 -4 .
• the dielectric constant is 4.22 to 4.56
• the dissipation factor is 18x10 -4 to 25x10 -4 . Accordingly, the glass compositions in the examples exhibited a low dielectric constant and low dissipation factor less than the dielectric properties of E-Glass.
• the glass compositions in the examples exhibited T log 3 viscosity temperatures between 1374°C to 1447°C, which is similar to typical T log 3 viscosity temperatures of D-Glass (around 1400°C). Having a T log 3 viscosity temperature greater than 1350°C is favorable for fiberizing a glass composition according to the present invention.
• the glass composition according to the examples, and according to embodiments of the invention is greater than 1350°C.
• the glass compositions in the examples exhibited a liquidus temperature between 1136 °C to 1374 °C. Having a liquidus temperature greater than 1100 °C, or in some embodiments greater than 1150 °C, is satisfactory for fiberizing a glass composition according to the present invention. Thus, the glass composition according to the examples and according to embodiments of the invention is greater than 1100 °C.
• the glass fibers of the present invention have low dielectric constants and low dissipation factors and are excellent as a glass fiber for printed wiring boards.
• the glass fibers are particularly well suited for reinforcing printed wiring boards for high- density circuits used in high speed routing systems.
• the glass compositions used to make fibers of the present invention have excellent workability. Therefore, a stable low dielectric glass fiber can be readily produced.
• a variety of base materials containing the glass fiber of the present invention can be produced, including, but not limited to, woven fabrics, non-woven fabrics, unidirectional fabrics, knitted products, chopped strand, roving, filament wound products, glass powder, and mats.
• Composite materials formed from at least one of these base materials and a plastic resin matrix such as thermoset plastic, compounded thermoplastic, a sheet molding compound, a bulk molding compound, or a prepeg
• a composite material that includes glass fibers according to the invention can be used in radar transparency applications at frequencies ranging from about 300 MHz to about 30 GHz.
• the disclosed and described processes relate to glass fibers, which can be obtained by mechanically attenuating streams of molten glass that flow out of orifices located in the base of a fiberizing bushing, which is powered by resistance heating or other means. These glass fibers may be intended especially for the production of meshes and fabrics used in composites having an organic and/or inorganic matrix.

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