TWI330622B - Glass compositions, glass fibers, and methods of inhibiting boron volatization from glass compositions - Google Patents

Description

1330622 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION Embodiments of the present invention generally relate to glass compositions and methods for inhibiting the volatilization of boron therefrom during melting and formation. More specifically, certain embodiments of the present invention are directed to a fiberizable glass composition comprising boron oxide and at least one rare earth oxide. Other embodiments of the invention are directed to methods of inhibiting volatilization of a fiberizable glass composition comprising boron oxide from the side. Other embodiments of the invention relate to glass fibers comprising boron oxide and at least one rare earth oxide and articles of manufacture made therefrom. [Prior Art] Oxidation rot (B2〇3) is often added to a glass composition to improve the processing characteristics of the glass composition. For example, B2?3 can be added to the fiberizable glass composition to improve the fiber forming characteristics of the glass composition. As used herein, the term "fibrable glass composition" means a glass that can be formed into substantially continuous glass fibers by any method known in the art for forming substantially continuous glass fibers. combination. More specifically, the addition of B2〇3 to the fiberizable glass composition results in a decrease in the forming temperature of the glass fibers and a wider fiber forming window. As used by this university, surgery «. The forming temperature " means the temperature at which the glass composition has a viscosity of 丨000 poise (or l〇g3 temperature "). Therefore, the addition of B2〇3 to the fiberizable glass composition can be advantageous in reducing the processing cost while improving the robustness of the fiber forming process. However, when the viable glass composition including 匕〇3 is processed at a high temperature, a part of B2〇3 in the σ is volatilized. B2〇3 during processing 95764.doc 1330622 The volatilization of the viable glass composition is undesirable because it causes the boron-containing particulate matter to be emitted from the processing equipment (hereinafter referred to as "boron emission") because it is expected to come from The boron emission of the processing equipment is controlled to some extent or below certain limits. Sometimes expensive emission control systems are installed to reduce or control the shed launch from the equipment. Therefore, the use and use of b2〇3 is improved. Processing Costs Associated with Glass Compositions One example of a commercially important bismuth-containing fiberizable glass composition that can be effectively used to make glass fibers suitable for a variety of applications, including electronic and structural reinforcement applications, is B2-containing E glass of 〇3. The E glass composition containing boron oxide usually contains up to ίο重量百分比 ("% by weight) of the intentional b2〇3 additive. As used herein, the term "standard contains 3" broken glass" or "standard E glass composition containing B2"3 means "2 to 10% by weight of B2"3; 16 to 25% by weight iCaO; 12 to 16 wt% A1203; 52 to 62 wt% 3丨02; 〇 to 5% by weight iMgO; 0 to 2 wt% iNa2C^K20; 0 to 1.5 wt% Ti02; 0.05 to 0.8 weight a glass composition of %iFe2〇3; and 0 to 1% by weight of F2.

In the American Society for Testing Materials Standard Number: D. °'〇0 » "Standard

Specification for Glass Fiber Strands" Intermediate material, an example of a standard glass composition containing 1〇3 of e-glass fiber that can be effectively used in the manufacture of 95764.doc 1330622 for electronic and aerospace applications is as follows: 5 to 10% by weight tB2〇3; 16 to 25 wt% tCaO; 12 to 16 wt% Al2〇3; 52 to 56 wt% Si〇2; 0 to 5 wt% tMgO; 0 to 2 wt%/◦ Na20 and K20; 0 to 0.8% by weight of Ti02; 〇·〇5 to 0.4% by weight of iFe203; and 〇 to 1% by weight of iF2. However, as previously discussed, boron is deficient in volatilization of the viable glass composition containing b2〇3 during processing. Although a boron-free E-glass composition (ie, an E-glass composition without B2〇3) and a low-boron glass composition (ie, an E-glass composition containing less than 2% by weight of yttrium 3) are available However, such E-glass compositions may require more temperatures than standard glass compositions containing 1 to 3 for both melting and fiber forming. Therefore, not only the energy consumption for melting and forming such compositions is higher than the energy consumption for smashing and forming standard E-glass containing B2〇3, but also due to the requirement of rising temperature, processing equipment (ie, melting furnace) The life of the bushing used to form the fiber is relatively short. In addition, for certain applications (e.g., electronic applications), low boron and boron free glass fibers do not meet the requirements of the American Society for Testing and Materials Standard No.: D578-00, - Standard Specification for Glass Fiber Strands. 95764.doc 1330622 Accordingly, it is advantageous to develop a glass composition comprising b2o3 and, in the opinion, to develop a fiberizable glass composition comprising b2〇3 for use in forming fibers for electronic and structural reinforcement applications, And the side volatilization is reduced compared to the standard B = (10) glass composition. Further, it is advantageous to develop a method for suppressing the volatilization of boron from the glass composition comprising (iv) and being usable together with a plurality of glass compositions containing B203. SUMMARY OF THE INVENTION Certain non-limiting embodiments of the present invention provide a fiberizable glass composition. For example, a non-limiting embodiment of the present invention provides a fiberizable glass composition comprising 9 to 16 weight percent A 1203, 05 to 13 weight percent B2 〇 3, 16 to 25 weight percent Ca 〇, 〇 to 6 weight percent of MgO, 48 to 62 weight percent of Si 〇 2, 〇 to 4 weight percent of Ti 〇 2 and ίο;, where 1 〇 3 and 1 〇 3 molar ratio varies from 〇〇 1 To 0.33, and R is at least one rare earth element. Another non-limiting embodiment of the present invention provides a fiberizable glass composition comprising 12 to 16 weight percent Al 2 〇 3, 5 to 1 weight percent ΙΟ 3, 16 to 25 weight percent Ca 〇, 〇 to 4% by weight of MgO, 52 to 56% by weight of Si 〇 2, 〇 to 〇 8 weight percent of TiO 2 , and R 203 ' wherein the molar ratio of 〇 2 〇 3 and b 2 〇 3 varies from 〇〇 1 to 0.33 'And R is at least one rare earth element. Another non-limiting embodiment of the present invention provides a fiberizable glass composition comprising 9 to 16 weight percent of a 12 〇 3, 〇 5 to 13 weight percent of B 2 〇 3, 16 to 25 weight percent CaO, 〇 to 6 weight percent of MgO, 48 to 62 weight percent of si 〇 2, 〇 to 4 weight percent of 95,764.doc 1330622

Ti〇2, and La203' wherein the molar ratio of La203 to B2〇3 varies from ooi to 0.33. Yet another non-limiting embodiment of the present invention provides a fiberizable glass composition comprising 12 to 16 weight percent Ai2〇3, 5 to 1 weight percent B2〇3, 16 to 25 weight percent ca 〇, 2 to 4 weight percent of MgO, 52 to 56 weight percent of si 〇 2, 〇 to 〇 8 weight percent of Τι〇2 and R2〇3 'where r2〇3 and b2〇3 are molar ratios 1 varies to 〇33, and R is at least one rare earth element. Another non-limiting embodiment of the present invention provides a fiberizable glass composition comprising 12 to 16 weight percent Al2〇3, 5 to 1 weight percent, and a B2〇3, 16 to 25 weight percent Ca 〇, 〇 to 4% by weight of MgO, 52 to 56% by weight of Si 〇 2, 〇 to 〇 8 weight percent

Ti〇2 and NdA3, wherein the molar ratio of Nd2〇3 to ΙΑ varies from 〇〇1 to 0.33. Other non-limiting embodiments of the present invention provide glass fibers formed from the fiberizable glass compositions in accordance with various non-limiting embodiments of the present invention, while other non-limiting embodiments provide for the use of various non-accurants in accordance with the present invention. Polymeric composites made from glass fibers of the limiting examples, and in detail 'printed circuit boards. Certain non-limiting embodiments of the present invention provide methods for inhibiting the volatilization of boron from a glass composition comprising ruthenium during melting and forming. For example, according to one non-limiting embodiment, a method for inhibiting volatilization of boron from a glass composition comprising ruthenium is provided, the method comprising adding R2 〇3 to the glass composition prior to processing the glass composition , such that the glass group 95764.doc 1330622 has a molar ratio of bismuth 3 to 匕〇3 from the change of 0.0 to 〇33 before processing, wherein R is at least one rare earth element; and the glass composition is processed, Where after processing, the opposite side loss of the glass composition is no more than 5 weight percent of the amount of B2 〇3 initially supplied to the composition. [Embodiment] Certain embodiments of the present invention advantageously provide a viable glass composition comprising B2〇3 and having reduced boron volatilization compared to a standard glass composition comprising 1〇3, while maintaining The log3 forming temperature and acceptable processing window required for commercial fiber forming operations. Moreover, the fiberizable glass compositions in accordance with certain embodiments of the present invention can be adapted to form glass fibers that can be used in a variety of applications, including both electronic and structural reinforcement applications. Moreover, as discussed in detail below, the inventors have discovered that a fiberizable glass composition in accordance with certain embodiments of the present invention can have advantageous dielectric properties and can be used to provide advantageous dielectric properties and may be desirable Glass fiber used in certain microelectronic packaging applications, such as printed circuit board applications. In addition, the glass fibers in accordance with embodiments of the present invention can impart improved laser drilling response to the printed circuit board when incorporated into a printed circuit board. The glass fibers made in accordance with certain embodiments of the present invention provide improved composite strength when incorporated into a polymeric polymeric matrix material. Other embodiments of the present invention advantageously provide a method for inhibiting the volatilization of boron from a glass composition comprising B2〇3 during processing of the glass composition at elevated temperatures. The method according to these non-limiting embodiments can be particularly effective for reducing boron emissions from glass refining furnaces and other refining and tempering glass processing equipment, and can be used effectively to reduce self-directed melt fiber formation. The boron emission of the device. 95764.doc 1330622 A specific, non-limiting embodiment of the invention will now be discussed. It will be appreciated that the values discussed herein, such as, but not limited to, the weight percent of the material and the length of time or temperature, are approximate and due to a variety of factors well known to those skilled in the art (such as, but not limited to, measurement standards, equipment, and Technology) and subject to change. Although the numerical values and parameters used to describe the broad scope of the invention are approximated, the numerical values set forth in the specific examples are reported as precise as possible. However, as will be appreciated by those of ordinary skill in the art, such values may contain certain errors necessarily caused by the respective measurement techniques and devices. 0 Various non-limiting embodiments in accordance with the present invention will now be described. Fibrillatable glass composition. In a first non-limiting embodiment of the fiberizable glass composition according to the present invention, a fiberizable glass composition is provided which comprises: 9 to 16 weight percent Al2?3; 0.5 to 13 weight percent B203; 16 to 25 weight percent of CaO; 0 to 6 weight percent of MgO; 48 to 62 weight percent of Si〇2; 〇 to 4 weight percent of Ti02; and R203, of which R2〇3 and B2〇3 of mole The ratio varies from ow to 〇_33' and R is at least one rare earth element.

As discussed in more detail below, 'because the fiberizable glass composition according to this non-limiting embodiment of the invention includes at least one rare earth oxide, the fiberizable glass compositions comprise a similar amount of B2〇3 The B 95764.doc (iv) glass composition may have reduced butterfly volatilization compared to the glass composition. Moreover, although not limiting herein, it is believed that the fibrillable glass compositions according to this non-limiting embodiment are suitable for use in most of the standard B2〇3-containing E glass fibers. A second non-limiting embodiment of the fiberizable glass composition according to the present invention provides a fiberizable glass composition comprising: 12 to 16 weight percent Al 2 〇 3 ; 5 to 10 weight percent β 2 〇 3 ;

16 to 25 weight percent of ca 〇; 〇 to 4 weight percent of MgO; 52 to 56 weight percent of Si 〇 2; 0 to 0.8 weight percent of TiO 2 ; and R 2 〇 3 ' of which R 2 〇 3 and B 2 〇 3 The ear ratio varies from 0.01 to 0.33 ' and R is at least one rare earth element.

As discussed above with respect to the first non-limiting embodiment, the fibrillatable glass composition according to this non-limiting embodiment of the invention includes at least one rare earth oxide, so the fiberizable glass composition according to this embodiment There may be reduced boron volatilization compared to a standard E glass composition comprising a similar amount of B2〇3. Further, although not limiting herein, since the fiberizable glass composition according to this non-limiting embodiment includes 5 to 1% by weight of B2〇3, the fiberizable glass compositions are particularly suitable. For the formation of glass fibers for electronic applications. Although not required, according to a non-limiting embodiment of the above-described fiberizable glass composition, the at least one rare earth element 'R' may be selected from the group 3 element of the periodic table 95764.doc 12-1330622, and it is desirable A group consisting of 铳 (sc), 钇 (γ), and lanthanoid elements (that is, elements having an atomic number of 57 (镧La) to 71 (Lu)) is selected. Although not intended to be limiting herein, it is believed that rare earth elements selected from the group consisting of Sc, Y and lanthanides are the preferred rare earth elements for such fiberizable glass compositions because such elements are generally stable. 3+ valence or oxidation state and ionic potential in glass higher than alkali or alkaline earth elements. As used herein, the term "ion potential" means the charge or oxidation state of a cation ("z") divided by the ionic radius of a cation ("r") or z/r in angstroms (in or

Meter). Further, the term "ion potential in glass" means the charge or oxidation state of a cation divided by the ionic radius of a cation in the glass.

More specifically, it is believed that the stable 3 + oxidation state of these elements and the ionic potential of the glass 1 direction promote the above non-limiting examples according to the invention: certain rare earths in the fiberizable glass composition Excellent formation of borate complexes. As discussed in detail below, such rare earth-methane complexes can be used to volatilize (4) from the viable glass composition and provide a glass composition that is comparable to or under the standard 32. Dielectric properties. However, any rare earth element having a stable 3 + oxidation state and a suitably high ionized carbide in the glass can be effectively classified into the above-mentioned fibrillating (four) composition I according to the present invention. More specifically, Rather, there is no limitation in this context, but a rare earth element symplectic having a 3 + oxidation state and a glass ion potential of at least 25 is used for h, and 10 is used for the above non-limiting according to the present invention. A particularly desirable rare earth element in the actual glass composition. =1. A non-limiting example of a right dry rare earth element suitable for use in the non-limiting embodiment of the invention described above, and a position in the glass from 95764.doc -13-133252. For comparison, Table 1 also shows the ion potentials in several glass and metal elements. The ionic radii for other rare earth members can be found in RD Shannon and CT Prewitt "Effective Ionic Radii in Oxides and Fluorides" (Acta Cryst. B25 (1969) 925-946) (can be used to calculate the corresponding glass Additional information on the ionic potentials is specifically incorporated herein by reference. Table 1 Ionic potential in the oxidation state of the group element 1 Rare earth 1 Sc 3+ 3.448-4.110 Y 3+ 2.956-3.363 La 3+ 2.542-2.828 Ce 3+ 2.632-2.901 Nd 3+ 2.752-3.015 Sm 3+ 2.752-3.112 Eu 3+ 2.804-3.158 Gd 3+ 2.830-3.198 Er 3+ 3.000-3.405 Lu 3+ 3.093-3.538 Metal Li 1+ 1.351 Na 1+ 0.885-0.980 K 1+ 0.662-0.725 Rb 1+ 0.625-0.671 Cs 1 + 0.588 Soil test Mg 2+ 2.778, 4.082 Ca 2+ 1.786-2.00 Sr 2+ 1.250-1.160 Ba 2+ 1.360-1.420 95764.doc • 14- 1 Based on the coordination number of 6 to 8 with oxygen. In a third non-limiting embodiment of the fiberizable glass composition according to the present invention, the rare earth element R is cerium. More specifically, according to this non-limiting embodiment, the fiberizable glass composition comprises: 9 to 16 weight percent Al2〇3; 1330622 0.5 to 13 weight percent b2〇3; 16 to 25 weight percent Ca 〇; 〇 to 6 weight percent of MgO; 48 to 62 weight percent of Si 〇 2; 〇 to 4 weight percent of Ti 〇 2 ;

La203 ’ among them! The molar ratio of ^2〇3 and ]32〇3 varies from 〇1 to 0.33. Although not intended to be limiting herein, since the fibrillatable glass composition according to this non-limiting embodiment of the invention comprises La2〇3, the viable glass compositions have a similar amount of b2 The standard E glass composition of 〇3 has a low boron volatilization. Moreover, the fiberizable glass composition according to this non-limiting embodiment is a desirable composition for a low cost, high capacity fiber forming operation to form glass fibers to be incorporated into the polymeric composite. More specifically, although not limiting herein, it is used in a fiberizable glass composition according to this non-limiting embodiment.

La^3 is what we want because "2〇3 will not contribute to the color or redox state of the glass composition, and La2〇3 is the lowest cost rare earth oxide currently available. As mentioned earlier, The addition of at least one rare earth oxide to the fiberizable glass composition according to non-limiting embodiments of the present invention can advantageously inhibit boron during processing of the glass at elevated temperatures, such as during melting and/or fiber formation. The glass compositions are volatilized. Further, as described below, the presence of at least one rare earth oxide in the glass composition according to the non-limiting embodiment of the present invention promotes enhanced dielectric in the glass fibers thus formed. 95764.doc -15· 1330622 Characteristics and Laser Drilling Responses Although not intended to be bound by any particular theory, generally the glass formed from the bismuth citrate composition includes an amorphous Si 〇 2 mesh. And amorphous B2〇3 mesh. See s Wang and JF Stebbins Multiple-Quantum Magic-Angle Spinning 17〇 NMR Studies of Borate, Borosilicate, and Boroaluminate Glas Ses, " (J. Am. Ceram. Soc., 82 (1999) 1519). Amorphous B2〇3 mesh usually comprises a polygonal B〇3 structural unit. However, when an alkali metal oxide is introduced into the shed In a stellate glass composition (such as a standard B2〇3 E glass composition), the metal oxide tends to preferentially diffuse or split into the amorphous b2〇3 network. When the material is introduced into the amorphous Βζ03 network, a tetrahedral B〇4 structural unit is formed, and the alkali metal cation acts to compensate the local charge by forming an alkali metal borate complex. See j. Zh〇 Ng and pj

Bray's "Change in Boron Coordination in Alkali Borate

Glasses, and Mixed Alkali Effects, as Elucidated by NMR, " (J. Non-Cryst. Solids, 111 (1989) 67-76). However, such alkali metal borate complexes have a high vapor phase pressure and are easily volatilized at high temperatures. Thus, when a borophosphonate glass composition comprising one or more metal oxides is melted, a portion of the rot in the glass composition will volatilize due to the high vapor phase pressure of the alkali metal borate complex. Lost. The soil oxides have similar behavior to metal oxides in forming borate complexes in AO3 glass compositions. However, although the soil cation has a higher ionic potential in the glass than the metal cation (see Table 1) and the alkaline borate complex is less prone than the alkali metal borate complex, 95764.doc • 16· 1330622 hair 'but adding a high concentration of CaO plus a small amount of MgO (ie, about 0.5% by weight or less of MgO additive) to a standard b2〇3 containing E glass composition sometimes cannot be as desired Effectively inhibits the volatilization of boron from the molten glass. The rare earth oxide added to the alkali tellurite glass composition will also tend to split into the amorphous B2〇3 network. However, in contrast to the metal oxides, when rare earth oxides are introduced into the amorphous B2〇3 network, the rare earth cations form a mismatch with two BO3 structural units and one b〇4 structural unit. Things. See H. Li, L. Li, J.D. Vienna, M. Qian, Z. Wang, J.G. Darab, D.K. Peeler "Neodymium (III) in

Alumino-Borosilicate Glasses,"(Journal of Non-Crystalline Solids, 278 (2000) 35_57) and H. Li, γ Su, LL^DM Strachan "Raman Spectr〇sc〇pic Study 〇f Gad〇linium (ni ) in Sodium-aluminoborosilicate Glass, " (Journal of Non-Qyst· Solids, 292 (2001)^7-176). Since these rare earth borate complexes have a lower vapor phase pressure than the above alkali metal borate complexes, such rare earth borate complexes will not readily volatize when the field glass melts. Therefore, the ratio of boron volatilization from the glass composition including the rare earth oxide should be lower than that of a similar glass composition not containing the rare earth oxide. Further, since the rare earth cation (and, in particular, the element selected from the group consisting of ～, γ, and the cation of the lanthanoid element) has a higher ion potential than both the alkali metal cation and most of the alkaline earth cation (see Table 1) Therefore, when rare earth oxides and alkaline earth oxides and/or alkali metal oxides are added to the borosilicate glass group α, the soil complex salt complex will be compared with the metal (tetra) acid salt and most of the base 95764. Doc 1330622 The borate complex is preferentially formed. Referring now to Figures la and lb (which are described in more detail below in Example 1), a "B MAS NMR (Magic Angle Spin Nuclear Magnetic Resonance) curve is shown, &quot ;b MAS NMR is derived from a series of non-limiting examples of a fibrillatable glass composition according to a non-limiting embodiment of the invention identified as composition 丨_4 in Example 1 (by Figures 1a and 1b) The number 1 _4 indicates) and the formation of boron in the standard E 3 glass composition of Βζ〇 3 (indicated as "A in Figure 1 & and ratio) as set forth in Example 1. More specifically, Figure la shows the use of the invention according to the previously discussed A non-limiting example of a non-limiting example of a viable glass composition of a non-limiting embodiment and a percentage of moles of B〇3 structural units as a function of mole % La2〇3 of a standard B203-containing E glass composition ("Mo*%") curve of B203; and Figure lb shows the curve of Molar% B2〇3 in the form of BO4 structural unit as a function of moir/〇La2〇3 for the same glass composition As can be seen from the graph of ia & lb, as the content of La2〇3 increases in the glass composition, the percentage of b2〇3 in the form of B〇4 structural unit decreases, and B〇3 structure The percentage of 匕〇3 in the form of a unit increases. As mentioned above, this is attributable to the rare earth borate complex in the glass structure and the alkali metal borate complex with increasing LkO3 addition. The ratio may be preferentially shaped. Furthermore, as previously discussed, since the rare earth borate complex has a lower vapor phase pressure than the alkali metal borate complex, boron is contemplated from the previously discussed non-limiting according to the present invention. A series of non-limiting example glass compositions of the examples The rate of volatilization will be lower than the ratio of boron volatilized from the standard E glass composition containing B2〇3. Referring now to Figures 2 and 3, as discussed in more detail below in Example 2, Figure 2 95764.doc -18-II shows Boron emissivity vs. time curve for a non-limiting example of a viable glass composition according to non-limiting embodiment 2 of the composition 4 (indicated as 4" in Figure 2) Privately defined B glass 3 E glass group 5 = (indicated as "A") butterfly emissivity versus time curve, line. In addition, as discussed in more detail in Example 3 below, Figure 3 shows the thousand ^ 圆 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁 宁, ], , , ) The curve of the emissivity versus time and the standard Β2〇<ε glass composition (indicated as "Α"). The curves of both Figures 2 and 3 are obtained using the thermogravimetric analysis (or "TGA" which is well known in the art. As can be seen from Figure (1), an example of a fiberizable glass composition 4 The bismuth has a lower emissivity than the standard E-glass composition containing ία. Although not limiting herein, the fiberizable glass compositions according to various non-limiting embodiments of the invention discussed herein are contemplated. The relative boron loss may be less than 5% during processing (eg, during melting and fiber formation). As used herein, the term "relative boron loss" means the amount of bismuth in the glass batch composition ( "Wb") (ie, before processing) minus the amount of B2〇3 ("WG") determined in the processed glass divided by the amount of B2〇3 in the glass batch composition Amount (ie, (Wb_Wg) / Wb), and it may refer to boron volatilization during no processing. However, those skilled in the art will appreciate that it is generally desirable to have the lowest possible relative boron loss. Thus, the relative boron loss from the fiberizable glass composition in accordance with non-limiting embodiments of the present invention can be less than 2%. Moreover, the fiberizable glass compositions of various non-limiting embodiments in accordance with the present invention as discussed herein may have no relative loss of boron during processing of 95764.doc • 19-1330622. In addition to the desired low boron volatilization, as previously discussed, the fiberizable glass compositions according to the non-limiting examples of this disclosure may have desirable "electrical characteristics (and in particular, These commercially available B2〇3 containing E glass compositions typically have an intercalation of about 73 at 丨MHz, as compared to or below the dielectric constant and low dissipation factor of commercially available b2〇aE glass compositions. Electrical constant and dissipation factor of about 0.01 at ^ MHz. For example, although not limited herein, the fiberizable glass composition according to a non-limiting embodiment of the present invention may have 1 MHz. The dielectric constant of no more than about 7.5 and the dissipation factor of no more than about 1 at 1 MHz. It is more desirable that the fiberizable glass composition according to a non-limiting embodiment of the invention may have a frequency of 1 MHz. A dielectric constant of less than about 7.3 and a dissipation factor of no more than about 〇〇〇5 at i MHz. As previously discussed, the alkali metal borate is present due to the presence of an alkali metal cation in the standard B2〇32E glass composition. Complex compounds will be formed. These complexes are accompanied by tetrahedral complexes. Boron (meaning, tetrahedral 3〇4 structural unit). However, such tetrahedral B〇4 structural units contain non-bridged oxygen, the polarity of which is substantially greater than bridging oxygen. Conversely, trihedral B〇3 The structural unit only includes bridging oxygen and thus is less polar than the B〇4 structural unit. As a result, only the borate glass having the B〇3 structural unit has a dielectric constant close to 3 at 1 MHz, and has a BO3 unit and a B〇4 unit. The borate glass of the mixture has a dielectric constant of up to 8 at 1 MHz. See η · Scholze's Glass Nature. Structure, and Properties (Springer_) translated by MJ Larkin

Verlag, New York, 1991), p. 3, 18, and references cited therein. As a result of the increase in the number of B〇4 structural units in the glass composition, the dielectric constant and dissipation factor of the glass composition should also increase. However, when a rare earth gasification is added to the glass composition' as discussed above, the rare earth cation will preferentially form a rare earth borate complex, thereby reducing or preventing the formation of a metal test acid salt complex. As shown in Figures la and lb, for a given b2 〇 3 content, as the amount of rare earth oxide additive increases, the number of B 〇 4 structural units decreases and the number of B 〇 3 structural units increases. Accordingly, it is contemplated that a fiberizable glass composition in accordance with a non-limiting embodiment of the present invention will have a lower dielectric constant and dissipation factor than a standard glass composition containing 1 in 3 having a similar B2?3 content. This effect is further demonstrated in Figure 4 for a series of fibrillatable glass compositions discussed above with respect to Figures 1a and 1b. As shown in Figure 4, as the molar ratio of La2〇3 to B2〇3 increases, the molar ratio of the normalized BO3 structural unit to the sum of the B〇3+B〇4 structural units in the glass composition increases. Big. Increasing the number of B〇3 building blocks as previously discussed is advantageous for providing the desired dielectric constant to the fiberizable glass composition. Thus, although not required, the above-described non-limiting embodiment of the fiberizable glass composition according to the present invention may comprise a molar ratio of BCV (B〇3+B〇4) of at least 0.775, and desirably has greater than 0.775 The molar ratio of B03/(B〇3+B〇4). Because the fiberizable glass composition according to various non-limiting embodiments of the present invention may have a lower dielectric constant and dissipation factor than a standard B2〇3 containing E glass composition, a non-limiting implementation in accordance with the present invention Example fiberizable compositions are particularly desirable for use in microelectronic packaging applications, such as printed circuit board ("PCB") applications. For example, although there is no limitation in the text 95764, doc -21 - 1330622, it is generally understood in the art that the propagation speed of one of the signal lines is affected by the dielectric constant of the surrounding material. For example, the dielectric constant of the board will affect the propagation of the signal in the PCB signal line. More specifically, the higher the dielectric constant of the PCB, the longer the signal propagation time (ie, the slower the propagation speed) ^ In addition, those skilled in the art will appreciate that PCBs are typically made of glass fiber reinforced polymers. A material or composite is formed comprising a polymeric matrix material (such as an epoxy resin) reinforced with a woven or non-woven glass fabric. Therefore, the dielectric constant of such composite PCBs is affected by the dielectric constant of the polymeric matrix material and the dielectric constant of the reinforced glass fibers. Thus, for a given polymeric matrix material, reducing the dielectric constant of the glass fiber will result in a reduction in the dielectric constant of the PCB and a relatively short signal propagation time in the PCB. Similarly, the degradation of the signal as it propagates through the signal line is affected by the dissipation factor of the surrounding material. For example, the dissipation factor of the PCB will affect the degradation of the signal in the pcB signal line. In general, the higher the dissipation factor of the PCB, the more the signal is degraded as it propagates through the signal line. Since the dissipation factor of the PCB is related to the dissipation factor of the polymeric matrix material and the reinforced glass fiber, reducing the dissipation factor of the glass fiber for a given polymeric matrix material can result in a reduction in the dissipation factor of the PCB. And thus cause the signal to be downgraded relatively less. Surprisingly, the inventors have observed that when at least 2 weight percent of MgO is added to the fiberizable glass composition according to a non-limiting embodiment of the invention, it is comparable to a commercially available E glass composition. Further improvements were made in terms of dielectric constant and dissipation factor. Thus, a fourth non-limiting embodiment of the fiber 96564.doc 1330622 glass composition according to the present invention provides a fiberizable glass composition comprising: 12 to 16 weight percent Al2?3; 5 to 10 Weight percent b2〇3; 16 to 25 weight percent ca〇; 2 to 4 weight percent Mg〇; 52 to 56 weight percent si〇2; 0 to 0.8 weight percent Ti〇2; and R2〇3, Wherein the molar ratio of R203 to B2〇3 varies from 〇〇1 to 0.33, and R is at least one rare earth element. According to this non-limiting embodiment, the at least one rare earth element R can be selected as described above. Although not intended to be limiting herein (and as described below in Example 6) 'but for non-limiting examples of fibrillatable glass compositions in accordance with this non-limiting embodiment of the invention, it has been observed It has a dielectric constant of not more than 7.2 at 1 MHz and a dissipation factor of not more than 0.003 at 1 ΜΗζτ. Furthermore, the inventors have observed that the above-described non-limiting embodiments of the fiberizable glass compositions according to the present invention impart a good laser drilling response to the PCB in which the glass fibers thus formed are incorporated. That is, in general, laser drilling of glass fiber reinforced PCBs is difficult because of the high energy required to cut glass fibers. However, although not intended to be limiting herein, rare earth oxides in such viable glass compositions are enhanced by increasing the UV absorption of the fiberizable glass compositions in accordance with non-limiting embodiments of the present invention. The laser drill made of the glass fiber can be improved 95764.doc • 23-1330622 hole response. Accordingly, a PCB containing glass fibers made from a fiberizable glass composition according to a non-limiting embodiment of the present invention should also have a good laser drilling response. To illustrate the uv absorption rate of the fiberizable glass composition according to the present invention, the uv absorption rate of a commercially available B2〇3-containing E glass composition for electronic applications, which is represented as composition "a" in Table 2, is shown. It is compared with the absorption rate of the composition i in Table 2. Composition 1 always exhibited a higher UV energy absorption than the composition "A" in the range of about 355 nm to about 370 nm. This further uv absorption was demonstrated by further comparison of these two compositions to improve the laser drilling response of the glass fibers formed from the fiberizable glass composition. Specifically, the penetration depth of a single pulse in the glass sample of the composition "A" and the composition 1 is measured by a range of pulse energy levels varying from about 60 mJ to about 120 mJ, It was also observed that the penetration depth of the composition was significantly greater than the penetration depth of the composition "A". The present invention is not limited to the present invention, but among the rare earth oxides, cerium oxide (i.e., Ν 〇 3) may be particularly advantageous for improving the laser of the fiberizable glass composition according to various non-limiting embodiments of the present invention. Drill holes to respond. While not intending to be bound by any particular theory, it has been observed that Nd2〇3 can contribute to the additional absorption of the glass composition at wavelengths typical of typical UV laser drilling wavelengths (e.g., about 35 5 nm). For a series of non-limiting example glass compositions (discussed below) in accordance with a fifth non-limiting embodiment of the present invention, the weight percentage of Nd2〇3 in the glass composition is increased from about 1% by weight to about 8 weights. At the same time, at the same time, the content of ίο; was kept at about 6% by weight (corresponding to Nd2〇3 and ΙΟ, which were changed from 0.03 to 0.26, respectively; the molar ratio) was observed, 95764.doc • 24-1330622. The absorption rate at 355 nm increases. Therefore, an advance improvement of the laser drilling efficiency of the fibrillatable glass composition according to the fifth non-limiting embodiment of the present invention is achieved by selecting the rare earth element H. More specifically, the fiberizable glass A fifth non-limiting embodiment of the composition provides a viable glass composition comprising: '12 to 16 weight percent Al2〇3; 5 to 10 weight percent β2〇3; 16 to 25 weight percent CaO; 0 to 4% by weight of MgO; 52 to 56% by weight of Si〇2; 0 to 0.8% by weight of Ti〇2;

Nd2〇3 'where the molar ratio of Nd^ to BA varies from 〇〇1 to 0.33. As discussed above, although not intended to be limiting herein, the fibrillable glass composition according to the fifth non-limiting embodiment of the present invention may be due to the presence of a rare earth halide in the glass composition (as above) Said) and have the desired low boron emission. Moreover, as discussed above, the fiberizable glass composition according to this non-limiting embodiment may be particularly suitable for use in printed circuit board applications requiring laser drilling due to the presence of Nd2〇3 in the fiberizable glass composition. in. As indicated above, the above-described various non-limiting embodiments of the fiberizable glass composition according to the present invention may comprise a molar ratio of 仏3 to Βζ〇3, wherein R is at least one rare earth element. Although not intended 95764.doc -25- 1330622

There is a restriction in this context, but R2〇 greater than 0·33 (or 1/3) from the point of view that the fibrillable glass composition volatilizes at a high temperature and thus reduces the emission from the processing equipment. 3_Morby is not necessary. As previously discussed, although (4) is intended to be bound by any particular theory, each rare earth cation in the Xianxin glass complex is single-read with two B03 and one B04 structures to form the desired rare earth complex. A complex, so when the ratio of (10) to (10) is greater than 1/3, more rare earth cations are produced than the rare earth cations which form the desired borate complex. In addition, those skilled in the art will appreciate that rare earth oxides are expensive. Therefore, in cost sensitive applications, it is generally desirable to utilize the lowest possible molar ratio of h〇3 to B2〇3. However, the molar ratio of 112〇3 to B2〇3, which is less than 〇〇1, is less effective or ineffective in significantly reducing boron emission, since only a small number of rare earth cations will be available to form the desired rare earth boric acid. Salt complex. Thus, for example, when the cost is a factor,

The molar ratios of the scales 2〇3 and 8〇3 from 0.01 to 〇15 can be used in accordance with various non-limiting examples of the fiberizable glass compositions discussed herein. Further, 'because the previously described fiberizable glass compositions according to various non-limiting embodiments of the present invention include B2〇3, the log3 forming temperatures and processing windows of such glass compositions are similar to b2〇3 including similar amounts. The standard contains 1〇3 E glass l〇g3 forming temperature and processing window. For example, the above-described fiberizable glass composition according to various non-limiting embodiments of the present invention may have a l〇g3 forming temperature of not more than 1200 ° C, a liquidus temperature of not more than 114 及, and at least 55 ° C. AT value. As used herein, "Δ丁" or "deltaΤ" means the numerical difference between the log3 forming temperature of the glass composition and the liquidus temperature of 95764.doc -26- and which is robust to the fiber forming process. Sexual indication. For example, when the ΔΤ value is less than about 551, the fiber forming window is generally considered to be unacceptably narrow for commercial, direct melt fiber forming operations. That is, the difference between the fiber forming temperature (i.e., 1 〇 g 3 forming temperature) and the temperature at which the glass will start to crystallize or devitrify (i.e., the liquidus temperature) is relatively small. Conversely, when ΔΤ is about 55 ° C or greater, it is generally believed that the fiber forming window of the glass composition is acceptable for commercial, direct melt fiber forming operations because the fiber forming temperature and the glass will be devitrified. The difference between the temperatures is relatively large. Although not required 'but in order to adjust the processing characteristics and redox state of the glass composition', the above-described fiberizable glass composition according to various non-limiting examples of the present invention may further comprise 0 to 1% by weight of 2〇3, Not more than 1 part by weight of F2 and 〇 to 2% by weight of at least one alkali metal oxide selected from the group consisting of Na2〇, κ20 and Li20. If desired, smaller amounts (i.e., less than about 0,5% by weight) of other glass refining agents (such as sb2〇3, Mn〇2, AS2〇3) may also be combined with the fiberizable glass of the present invention. Use in combination. Moreover, those skilled in the art will appreciate that fiberizable glass compositions generally also contain minor amounts of impurities which can be attributed to, for example, impurities in the material compounding agent and/or corrosion of the furnace refractory material. For example, although not limiting herein, oxide impurities such as Na20, K20, Cr203, SrO, BaO, and Zr〇2, as well as sulfates and sulfides, may also be present in various embodiments in accordance with the present invention. Fibrillable glass compositions. Further, other impurities such as Pb, Ni, Cu, and Zn may be present in the glass composition. Non-limiting examples of glass fibers in accordance with the present invention will now be described. 95764.doc • 27· 1330622 A non-limiting embodiment of a glass fiber according to the present invention provides a glass fiber comprising: 9 to 16 weight percent of ai2〇3; 0.5 to 13 weight percent of b2〇3; 16 to 25 weight percent of ca 〇; 0 to 6 weight percent of Mg 〇; 48 to 62 weight percent of si 〇 2; 0 to 4 weight percent of Ti 〇 2; and R 2 〇 3 ' of which 1 〇 3 and 1 〇 The molar ratio of 3 varies from 〇01 to 0.33, and R is at least one rare earth element. Although not limiting herein, due to the reasons discussed above with respect to the first non-limiting embodiment of the fiberizable glass composition of the present invention, it is believed that the glass fibers according to this non-limiting embodiment Suitable for a variety of applications, including both electronic and structural reinforcement applications. A second non-limiting embodiment of the glass fiber according to the present invention provides a glass fiber comprising: 12 to 16 weight percent Α12〇3; 5 to 10 weight percent Β2〇3; 16 to 25 weight percent CaO 0 to 4 weight percent of MgO; 52 to 56 weight percent of SiO 2 ; 0 to 0.8 weight percent of Ti02; and R2〇3, wherein the molar ratio of R203 to B2〇3 varies from 〇1 to 0.33, and R is at least one rare earth element. 95764.doc • 28-1330622, although not limiting herein, due to the reasons discussed above with respect to the second non-limiting embodiment of the fiberizable glass composition of the present invention, The glass fibers of the limiting embodiments are particularly suitable for use in electronic applications. A third non-limiting embodiment of the glass fiber according to the present invention provides a glass fiber comprising: 9 to 16 weight percent of A1203; 〇·5 to 13 weight percent of b2〇3; 16 to 25 weight percent of CaO 〇 to 6 weight percent of MgO; 48 to 62 weight percent of si 〇 2; 0 to 4 weight percent of Ti 〇 2;

La203, in which the molar ratio of La203 to B2〇3 varies from 〇1 to 0.33. Although not limiting herein, due to the reasons discussed above with respect to the third non-limiting embodiment of the fiberizable glass composition of the present invention, it is believed that the glass fibers according to this non-limiting embodiment It is particularly suitable for applications in which the color and/or cost of glass fibers are important. A fourth non-limiting embodiment of the glass fiber according to the present invention provides a glass fiber comprising: 12 to 16 weight percent of A1203; 5 to 10 weight percent of b2〇3; 16 to 25 weight percent of CaO; .doc •29- 1330622 2 to 4 weight percent of MgO; 52 to 56 weight percent of SiO 2 ; 0 to 0.8 weight percent of Ti02; and R2O3 'where the molar ratio of R 2 〇 3 to B 2 〇 3 varies from 0.01 to 〇 · 3 3 ' and R is at least one rare earth element. It is not intended to be limiting herein, but because of the reasons discussed above with respect to the fourth non-limiting embodiment of the fiberizable glass composition of the present invention, it is particularly suitable for the glass fibers according to this embodiment. Used in PCB applications. A fifth non-limiting embodiment of the glass fiber according to the present invention provides a glass fiber comprising: 12 to 16 weight percent Al2?3; 5 to 10 weight percent b2?3; 16 to 25 weight percent Ca〇; up to 4% by weight of Mg〇; 52 to 56% by weight of si〇2; 0 to 0.8% by weight of Ti〇2;

Nd2〇3 ’, the molar ratios of 〇3 and 1〇3 vary from 〇1 to 0.33. But as a result of the above

In laser applications including laser drilling. Although not limiting, glass fiber in addition, since the 95764.doc • 30-13130622 dimension according to various non-limiting embodiments of the present invention contains B2〇3, a glass combination from which glass fibers are formed is expected The article will have similar processing characteristics to the standard E glass composition containing B2〇3. However, unlike the standard ambiguous glass fiber, since the glass fiber according to the non-limiting embodiment of the present invention is formed of a glass composition comprising cerium and at least one rare earth oxide, it is expected to be used, etc. At a volume of 32 Torr 3, the boron emission from the fiber processing equipment during melting and in the glass fibers according to the non-limiting embodiment of the present invention is lower than the boron emission from the standard glass-containing glass fiber forming operation. Furthermore, glass fibers in accordance with non-limiting embodiments of the present invention are useful for forming P C B. As previously discussed with respect to the fiberizable glass composition according to the present invention, the addition of rare earth oxides to the fiberizable glass composition comprising cerium 3 can result in ugly production in the glass composition than in the standard 32 〇 3 Feorous polar B〇4 structural units and more B〇3 structural units in the glass composition. Since the polarity of the BO3 structural unit is less than the polarity of the go* structural unit, the glass fibers formed from such fibrillatable glass compositions comprising B2〇3 and at least one rare earth oxide may have an increased number of B〇3 The advantageous dielectric properties associated with the structure unit. For example, although not limiting herein, glass fibers in accordance with various non-limiting embodiments of the present invention may have a dielectric constant of no greater than 7.5 at 丨MHz and no greater than 〇 at MHz MHz. The dissipation factor of 〇1; and it is more desirable to have a dielectric constant of less than 7.3 under the armpit and a dissipation factor of no more than 请MHzT. Moreover, as previously discussed with respect to the fiberizable glass compositions in accordance with non-limiting embodiments of the present invention, glass fibers in accordance with various non-limiting embodiments of the present invention may also have glass fibers in accordance with standard cerium-containing 3 95764.doc -31 · 1330622 Respond to improved laser drilling. Although not limiting herein, glass fibers in accordance with non-limiting embodiments of the present invention are also useful in structural reinforcement applications and impart improved strength to the resulting polymeric composites. Although not intended to be bound by any particular theory, the inventors believe that polymeric composites made using glass fibers in accordance with non-limiting embodiments of the present invention may have improved resistance due to the presence of rare earth oxides in the glass composition. Pull strength. More specifically, it has been observed that fibers having rare earth elements present on the surface thereof can have improved mechanical properties. See γ. xue, X Chengs " Effect of Rare Earth Elements* Surface Treatment on Tensile Properties and Microstructure of Glass Fiber-Reinforced Polytetrafluoroethylene Composites 5 " (j. Appl. P〇lymer Sci., 86 (2002) 1667-1672). Therefore, since the glass fiber according to the non-limiting embodiment of the present invention includes a rare earth oxide, the polymer composite prepared using the glass fibers is similar to the one containing the rare earth oxide-free additive. Polymer composites made of E glass fibers can exhibit improved mechanical properties compared to '. Any process known in the art for forming glass fibers can be used' and it is more desirable to use the process to make any of the processes known to form substantially continuous glass fibers to form a variety of non-limiting aspects in accordance with the present invention. ^& Example of fiberglass. For example, although not limiting herein, direct melting or indirect melting fiber forming methods can be used to form glass fibers in accordance with non-limiting embodiments of the present invention. These methods are well known in the art, and in view of the present disclosure, it is not necessary to further discuss it in the letter 95764.doc -32-1330622. See KLL 〇ewenstein, The Manufacturing Technology 〇f Continu〇us (1) Novgorod, 3rd edition (Elsevier, New York, 1993) pp. 47-48 and 1 17-234, which is therefore specifically cited by way of citation Break into this article ten. The invention further encompasses polymeric composites made from glass fibers in accordance with various embodiments of the present invention, and in detail PCBs. As previously discussed, embodiments of the present invention may be advantageous to provide a dielectric constant having a desired dielectric property (such as a dielectric constant and/or a dissipation factor comparable to or lower than a standard B2〇3-containing E glass fiber). glass fiber. Moreover, certain embodiments of the present invention advantageously provide glass fibers having improved laser drilling response as compared to standard B2〇3-containing e-glass fibers. Thus, glass fibers in accordance with various non-limiting embodiments of the present invention may be particularly advantageous for use in PCB applications. By way of example, 5, in one non-limiting embodiment of the polymeric composite according to the present invention, 'providing a polymeric composite' comprising a polymeric matrix material and at least one glass fiber of the polymeric matrix material, the at least one glass The fibers include: 9 to 16 weight percent of A1203; 0.5 to 13 weight percent of B203; 16 to 25 weight percent of CaO; 〇 to 6 weight percent of MgO; 48 to 62 weight percent of Si 〇 2; 〇 to 4 weight percent Ti02; and R2〇3' wherein the molar ratio of R203 and B2〇3 varies from 〇〇1 to 0.33, and R is at least one rare earth element. 95764.doc 丄330622 Although not limiting herein, it is believed that the polymeric composites according to this non-limiting embodiment of the invention are suitable for use in both electronic and structural applications. In another non-limiting embodiment of the polymeric composite according to the present invention, there is provided a polymeric composite comprising a polymeric matrix material and at least one of the polymeric matrix materials, the at least one glass The fibers include: 12 to 16 weight percent Al2〇3; 5 to 10 weight percent b2〇3; 16 to 25 weight percent CaO; 0 to 4 weight percent Mg〇; 52 to 56 weight percent Si〇2; 0 to 0.8% by weight of Ti〇2; and R2〇3' wherein the molar ratio of lanthanum and cerium varies from 〇〇1 to 0.33' and R is at least one rare earth element. Although not limiting herein, it is believed that the polymeric composites according to this non-limiting embodiment of the invention are particularly suitable for use in electronic applications. In another non-limiting embodiment of the polymeric composite according to the present invention, there is provided a polymeric composite comprising a polymeric matrix material and at least one glass fiber of the polymeric matrix material, the at least one glass fiber comprising: 9 to 16 weight percent of Al2〇3; 0_5 to 13 weight percent of b2〇3; 16 to 25 weight percent of Ca〇; 95764.doc 1330622 0 to 6 weight percent of MgO; 48 to 62 weight percent of Si〇2 0 to 4 weight percent of Ti〇2; and

La203' wherein the molar ratios of La2〇3 and b2〇3 vary from 〇1 to 0.33. Although not limiting herein, it is believed that the polymeric composites according to this non-limiting embodiment of the invention are suitable for use in both electronic and structural applications where the appearance and cost of the composite are important. In another non-limiting embodiment of the polymeric composite according to the present invention, there is provided a polymeric composite comprising a polymeric matrix material and at least one glass fiber of the polymeric matrix material, the at least one glass fiber comprising : 12 to 16 weight percent of A1203; 5 to 10 weight percent of B2〇3; 16 to 25 weight percent of CaO; 2 to 4 weight percent of MgO; 52 to 56 weight percent of SiO 2 ; 0 to 0.8 weight percent of Ti02 And R2O3, wherein the molar ratio of R2O3 to B2〇3 varies from 〇〇1 to 0.33, and R is at least one rare earth element. Although not limiting herein, it is believed that the polymeric composites according to this non-limiting embodiment of the present invention are particularly suitable for use in electronic applications, and are described in detail for use in PCB applications. In another non-limiting embodiment of the polymeric composite according to the present invention, 95764.doc -35. 1330622 2-7, a polymeric composite comprising a polymeric matrix material and the polymeric matrix material At least _ kinds of glass fibers, the at least one type of glass fiber comprises: 12 to 16 weight percent of Ai2〇3; 5 to 1 weight percent of b2〇3; 16 to 25 weight percent of CaO; 0 to 4 weight percent of MgO 48 to 62 weight percent of SiO 2 ;

Up to 1.0% by weight of Ti〇2; and

Nd2〇3, wherein N (the molar ratio of j2〇3 and b2〇3 varies from 〇〇1 to 0.33. There is no limitation herein, but the polymerization of this non-limiting twin example according to the present invention is The composite is particularly suitable for use in PCB applications including laser drilling.

Polymeric composites = PCBs in accordance with various embodiments of the present invention can be fabricated by any of the methods known in the art for making polymeric composites and/or. For example, although not limiting herein, a polymeric composite according to the invention is made by impregnating a woven fabric or a non-woven woven or fiberglass with a polymeric matrix material and subsequently curing the polymeric matrix material. Things. Alternatively, the chopped glass fibers can be incorporated into a polymeric matrix material and the resulting mixture extruded into the desired shape. In addition, although not limiting herein, it is possible, for example, to impregnate a woven glass fabric by using a polymeric polymeric matrix material and then partially cure the polymeric base material or "time _-ton" Immersing the sheet and forming it ^ 95764.doc -36 - 1330622 The POB of the present invention. Thereafter, the prepreg sheet (4) can be formed into a desired size and one or more layers of the prepreg sheet can be joined together to form a laminate. Copper may be coated on one or both surfaces of the laminate, and if desired 'the copper may be patterned to form - or multiple circuits and/or one or f holes may be drilled into the package Overlay to provide electrical interconnection. Thereafter, the stacks can be stacked together to form a pCB. It will be appreciated, however, that other methods for forming polymeric composites and pCBs which are not described above and which are suitable for use in forming the polymeric composites and PCBs of the present invention are well known in the art. The non-limiting examples given above are not intended to limit the invention in any way and are provided for illustrative purposes only. A method for inhibiting the volatilization of boron from a glass composition comprising 82 〇 3 according to the present invention will now be described. One non-limiting embodiment of a method for inhibiting volatilization of a glass composition comprising a b panel comprises: Adding 1〇3 to the glass composition prior to processing the glass composition such that the glass composition has a molar ratio of 1〇3 to B2〇3 from 0.01 to 0.33 before processing (where R is at least one rare earth element) And processing the glass composition, wherein after processing, the glass composition has a relative boron loss of no more than 5 percent. Moreover, in accordance with this non-limiting embodiment of the invention, the glass composition can have a relative boron loss of no more than 2 percent during processing, or more desirably no relative boron loss after processing. As previously discussed, the addition of rare earth oxides to the cerium-containing glass composition advantageously reduces the volatilization of boron from the glass composition by preferentially forming a low vapor phase pressure rare earth complex salt complex. Although not required, according to this embodiment of the invention, the glass composition may comprise from 2 to 13 weight percent of 95764.doc -37·丄330622 B2〇3. Further, although not required, when the glass composition is a fiberizable glass combination for producing glass fibers suitable for use in electronic applications, the glass composition may include 5 to 10 weight percent of B2 〇. 3. According to this embodiment of the method for inhibiting the volatilization of boron from a glass composition comprising B2〇3, the at least one rare earth element, R, may be selected from the group consisting of halogens of Group 3 of the Periodic Table of the Elements, and is desirably selected from the group consisting of Sc), lanthanum and lanthanide elements (that is, groups of elements having an atomic number of 57 (steel (La)) to 71 (Lu)). As previously discussed with respect to the fiberizable glass compositions in accordance with embodiments of the present invention, Sc, Y, and steel elements have a stable 3 + oxidation state and a relatively high ion potential in the glass (see Table 1 above). β Therefore, these elements are elements which are particularly desirable in the method for suppressing boron volatilization according to the present invention. In general, however, any rare earth element having a 3 + oxidation state of ruthenium and an ion potential in the glass of at least 2.5 can be utilized in accordance with the method of this embodiment of the invention. "External", although not limiting herein, according to this non-limiting method of the raw embodiment, processing the glass composition may include forming a temperature at or above the I 〇 g 3 of the glass composition. The glass composition is processed below. For example, processing can include melting the glass composition composition to form fibers. In a special, non-limiting example of the method of this non-limiting embodiment of the invention, 'the rare earth element is 镧', wherein the example can be effectively used. The standard for reducing boron from the use of high volume commercial processes Contains B2〇M glass. The glass composition volatilizes. Further, 'although there is no limitation herein', 95764.doc -38- ΟΔΔ according to the present invention, the method for suppressing boron volatilization, and the glass composition comprising β2ο3 and at least one metal oxide _ ° material combination can be particularly useful. By way of example, &''''''''''''''''''' Various non-limiting embodiments of the invention will now be described in the following non-limiting examples. EXAMPLES Example 1 : Four glass batches each having an example glass composition Bu 4 (given in Table 2 below) and a glass batch having a comparative example glass composition "Α" (illustrated in Table 2) were prepared as follows The reagent grade oxide powder was blended to form the desired composition as indicated in Table 2. After blending, each glass batch composition was heated to about 145 in #1〇% chain hangings. The glass composition was melted for about 4 hours. Thereafter, the "button" of each glass composition was prepared by pouring the molten glass from the crucible into a stainless steel mold, and then placed at 750 ° C. The oven was passed for 3 hours. The oven was then turned off and the glass was allowed to cool in the oven to room temperature overnight to allow the glass to anneal. In addition to the enthalpy loss during melting, the glass button was expected, and a and glass ingredients were The combination of compositions is similar. As discussed below, bismuth from the example glass composition 1 _4 is expected; the loss is less than the Β2〇3 loss of the glass composition of the comparative example. Although ν & 2〇 and Κ2〇 and fluoride ( If present, it is volatile in glass refining, but because of the low concentration of these materials in the glass composition tested, it is believed that all of the glass 95764.doc •39-13325622 glass composition is caused by the volatilization of these materials. Any change was irrelevant. After cooling to room temperature, the buttons were analyzed using 11B MAS NMR* to determine the species formation of boron in each glass composition. Based on NMR data, a molar % in the form of B〇3 was produced. B2〇3 and the curve of Mohr% in the form of B〇4 versus Molar% La2〇3. This specific curve has been discussed above with respect to Figures 1 & and ^. As previously discussed, as can be seen by la&lb It is seen that as the molar %1^2〇3 in the glass composition increases, the molar %b2〇3 in the form of the B〇3 structural unit increases, while the molar % in the form of the B〇4 structural unit 82 〇 3 was reduced. Therefore, it was found that the comparative glass composition A had a molar % B2 〇p in the form of BO* structural unit higher than any of the example glass compositions 丨_4, and the comparative glass was found. Composition A has a lower than any of the example glass compositions 14 Molar % b2 〇 3 in the form of a BO3 structural unit. As previously discussed, the formation of the B 〇 4 structural unit is associated with the formation of an alkali metal borate complex of high vapor phase pressure, while the B 〇 3 structural unit Formation of a rare earth borate complex formed with a low vapor phase pressure. Thus, since the example glass compositions 1-4 have a higher percentage of B〇3 structural units and a lower percentage than the comparative glass composition The B 〇 4 structural unit is therefore expected to have a lower boron emission during processing at elevated temperatures than at the comparative glass composition A. Furthermore, since the polarity of the B 〇 3 structural unit is less than the polarity of the b 〇 4 structural unit, It is therefore contemplated that the example glass composition 14 has a lower dielectric constant and dissipation factor than the comparative glass composition A. Further, as indicated in Table 2, the liquidus temperature (Ί, 丨 og3 forming temperature (,, Tf ") and Δτ value of each glass composition was determined. According to Α§τΜ 95764.doc -40· 1330622 C829&quot "Standard Practices for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method." to determine the liquidus temperature (TL). According to ASTM C965 " Standard Practice for Measuring Viscosity of Glass Above the Softening Point. Log3 forming temperature (TF) at melt viscosity. As can be seen from Table 2, Example Glass Compositions 2-4 have similar TL, TF, and ΔΤ values as Comparative Example Composition A. Although Example Glass Composition 1 has a comparative ratio Example Composition A has a low ΔΤ value, but Example Composition 1 is still considered suitable for use in commercial fiber forming operations. Table 2 Glass Composition Number A 1 2 3 4 La203/B203 (Morby) 0.00 0.03 0.05 0.08 0.15 Weight % Mo % % by weight Mo % % by weight Mo % % by weight Mo % % by weight Mo % % ai2o3 13.04 8.03 12.92 8.01 12.85 8.01 12.73 7.99 12.48 7.96 B2〇3 6.42 5.7 9 6.36 5.78 6.32 5.77 6.27 5.76 6.14 5.74 CaO 24.47 27.39 24.25 27.34 24.11 27.31 23.89 27.27 23.41 27.16 Fe2〇3 0.38 0.15 0.38 0.15 0.38 0.15 0.37 0.15 0.37 0.15 κ2〇0.11 0.07 0.10 0.07 0.10 0.07 0.10 0.07 0.10 0.07 La2〇3 0.00 0.00 0.89 0.17 1.48 0.29 2.35 0.46 4.31 0.86 MgO 1.30 2.02 1.29 2.02 1.28 2.02 1.27 2.01 1.24 2.00 Na20 0.40 0.41 0.40 0.41 0.40 0.41 0.39 0.41 0.39 0.41 Si02 53.27 55.66 52.80 55.56 52.48 55.50 52.02 55.40 50.98 55.18 T1O2 0.61 0.48 0.60 0.48 0.60 0.48 0.59 0.48 0.58 0.47 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 TL (°C) 1070 1074 1065 1065 1060 TF (°C) 1169 1128 1167 1159 1157 △T(0C) 99 54 102 94 97 Example 2: As above As discussed in Example 1, a glass batch having the example glass composition 4 set forth in Table 2 and a glass batch having the glass composition A of Comparative Example were prepared. The weight loss of each glass composition as a function of time was then determined using TGA. Three 50.0 grams of 95764.doc • 41 - 1330622 samples were individually tested for each glass composition. The TGA unit consists of a platinum-20% niobium alloy hanging rod and a suspension rod suspended in a furnace. The suspension rod is connected to a digital balance located outside the furnace and having an accuracy of 0.001 gram, and the measurement of the weight change as a function of time is automatically recorded every 30 seconds. The samples were heated to a temperature sufficient to achieve a melt viscosity of about 25 poise which corresponds to a temperature of about 1470 ° C for the two glass compositions. After reaching the desired viscosity, the samples were held at the temperature for 60 minutes. The data collected for each glass composition produced a graph of average boron weight loss versus melting time (i.e., fixed time). From this data, a plot of the average boron emissivity versus melting time for each glass composition (shown above in Figure 2) was generated. As indicated in the graph of Figure 2, the boron emissivity from the example glass composition 4 was lower than the boron emissivity from the comparative composition A. Danji, although not limiting herein and as previously discussed, is believed to be attributable to the formation of a high vapor phase pressure alkali metal borate complex in Comparative Example Glass Composition A, The low vapor phase pressure rare earth borate complex during the melting of the example glass composition 4 is preferentially formed. Example 3: A glass batch having the example glass composition 4 set forth in Table 2 and a glass batch having the glass composition of Comparative Example A were prepared as discussed above in the Examples. The sample per glass composition was then tested using tga as described above in Example 2, however, using a refining viscosity of (10) poise (corresponding to the temperature of the example glass composition i of about 1447 and its comparative example glass combination) A temperature of about 1488 ° C of the object A. h1 blade, the degree of presence). As shown in Fig. 3, the glass composition according to the present invention (i.e., the example glassy fines of the beer composition 1) has a lower boron emission than the glass composition of the comparative example glass 95764.doc - 42-13325622. Rate β Example 4: Button samples for each of the example glass compositions 5-22 set forth in Table 3 were made as discussed above in Example 1. The example glass compositions 5-22 are based on a designed test in which the weight percentages of Aha, B2〇3, CaO, MgO and 1^2〇3 are optionally varied to simulate commercial fiberglass production while maintaining other trace oxidations. The additive is constant. The amount of Si 〇 2 in each glass composition was adjusted to achieve 100 weight percent total oxide. After forming the button sample for each composition, the Monarch Analytical Laboratory of Maumee, 〇hi〇 used a volumetric titration, wet analysis method to measure the weight percent plume of each sample. The relative boron loss is then calculated as the difference between the amount of rhodium in the furnish composition and the amount of B2〇3 determined to be in the button sample divided by the amount of b2〇3 in the glass furnish composition. As indicated in Table 3, the relative boron loss from the example glass composition is typically less than 15 〇 during refining. (Comparatively, the inventors have found bismuth from a similar amount to the example glass composition 5-22. The relative boron loss of the Commercial E glass composition of 〇3 is about 5% (using the same wet analysis method). Further, as shown in Table 3, the example glass compositions 5-22 all have a temperature of not more than 1200 °C. 〇g3 forming temperature, and the at value is greater than 55 ° C. 95764.doc •43- 1330622 Table 3 Glass composition number 5 6 7 8 9 10 11 12 13 La2〇3/B2〇3 (Morby) 0.030 0.028 0.030 0.030 0.028 0.030 0.030 0.032 0.032 Composition (weight °/〇) A1203 13.04 13.00 12.96 12.72 12.77 12.90 12.89 13.10 12.76 B2O3 6.52 6.50 6.15 6.49 6.52 6.35 6.25 6.21 6.18 CaO 23.84 24.49 24.43 24.49 23.87 24.21 24.08 23.95 24.54 Fe203 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 K20 0.10 0.10 0.10 0.10 0.10 0.10 0.11 0.11 0.10 La2〇3 0.92 0.86 0.86 0.92 0.86 0.89 0.87 0.93 0.92 MgO 1.17 1.16 1.39 1.40 1.40 1.28 1.18 1.41 1.17 Na20 0.40 0.4 0 0.40 0.40 0.40 0.40 0.40 0.40 0.40 Si02 52.87 52.36 52.57 52.35 52.93 52.71 53.07 52.76 52.81 SrO 0.13 0.13 0.13 0.13 0.13 0.13 0.14 0.13 0.13 Ti02 0.60 0.60 0.60 0.60 0.60 0.60 0.61 0.61 0.60 Zr02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Characteristic B2〇3 (% by weight) 6.47 6.42 6.11 6.43 6.34 6.26 6.22 6.23 6.19 Relative boron loss (%) 0.77 1.23 0.65 0.92 2.76 1.42 0.48 氺 TL (°C) 1059 1066 1069 1068 1064 1066 1068 1064 1085 Tf(°C) 1172 1160 1168 1156 1161 1162 1163 1164 1163 △T(〇C) 113 94 99 88 97 96 95 100 78 Glass composition number 14 15 16 17 18 19 20 21 22 La2〇3 /B2〇3 (Morby) 0.030 0.028 0.030 0.030 0.028 0.030 0.030 0.032 0.032 Composition (% by weight) Al2〇3 13.09 12.81 13.03 12.90 12.84 13.06 12.77 12.71 12.91 B203 6.21 6.21 6.18 6.35 6.56 6.53 6.19 6.49 6.45 CaO 23.94 23.93 24.56 24.21 23.99 23.88 24.58 24.48 24.34 Fe2〇3 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.38 0.37 Κ20 0.11 0.10 0.10 0.10 0.11 0.10 0.10 0.10 0.10 La2〇3 0.87 0.93 0.92 0.89 0.93 0.86 0.86 0.86 0.91 MgO 1.17 1.41 1.17 1.28 1.18 1.40 1.40 1.16 1.39 Na2〇0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 Si02 53.08 53.07 52.50 52.71 52.86 52.62 52.56 52.67 52.37 95764.doc • 44· 1330622

SrO 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 Ti02 0.60 0.60 0.60 0.60 0.61 0.60 0.60 0.60 0.60 Zr02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Characteristic 8203 (% by weight) Measure 6.04 6.22 6.06 6.26 6.51 6.46 6.12 6.25 6.35 Relative boron loss (〇/〇) 2.74 * 1.62 1.42 0.76 1.07 1.13 3.70 1.55 Tl(°C) 1064 1065 1080 1061 1057 1051 1083 1081 1071 Tf(°C) 1172 1168 1158 1161 1170 1166 1160 1164 1171 △T(0C) 108 103 78 100 113 115 77 83 100 *No boron loss can be detected in the sample because the weight percentage of the composition is as measured using the wet analysis method described above. The difference between the weight percent boron in the button sample and the test sample is within the experimental error. Example 5: As previously discussed, in addition to having reduced boron volatilization, the fiberizable glass composition according to embodiments of the present invention can have the desired dielectric properties. For example, Table 4 below shows the dielectric constants of two example glass compositions (23 and 24, respectively) and comparative glass compositions (labeled as glass composition B) in accordance with non-limiting examples of the present invention. And dissipation factor. Example Glass Compositions 23 and 24 and Comparative Glass Composition B both contained about 6% by weight BZ 〇 3 and about 0.6% by weight MgO. Comparative Example Glass Composition B also comprised about 0.01% by weight of κ20, about 0.9% by weight of Na20, about 1% by weight of Sr〇, and about 2% by weight of Zr〇2, which were simulated in commercial e-glass compositions. Impurity content. The glass button samples of each of the glass breaking compositions shown below in Table 4 were prepared as indicated above in Example 1. Dielectric constant and dissipation factor measurements were then taken for each glass button sample at 丨MHz & i GHz (by 95764.doc -45-1330622)

East of Hunt Valley, Trace Lab, Maryland. The dielectric constant and dissipation factor measurements were performed in accordance with ASTM D150-98 "Standard Test Methods for AC Loss Characteristics and Permittivity (Dielectric Constant) of Solid Electrical Insulation.". As indicated in Table 4, the dielectric constants ("Dk") of the example glass compositions 23 and 24 at 1 MHz are no greater than 7.5 and the dissipation factor of the example fiberizable glass composition is no greater than 0.01. Moreover, the example fiberizable glass compositions 23 and 24 have a Dk of less than 7.3 at 1 MHz and the example fiberizable glass compositions 23 and 24 have a Df of no greater than 0.005 at 1 MHz. Further, the Dk and Df values of the example glass compositions 23 and 24 at 1 GHz were lower than the Dk and Df values of the comparative fiberizable glass composition B. Although the simulated metal oxide impurity in Comparative Example Glass Composition B theoretically increases the dielectric constant and dissipation factor of the glass composition, it is believed that the substantially larger CaO content of the glass composition will be The dielectric properties in this glass composition have a major impact. Further, as shown in Table 4, the example fiberizable glass compositions 23 and 24 have a log 3 forming temperature of not more than 1200 ° C and a ΔΤ value of more than 55 ° C. Table 4 Glass Composition No. B 23 24 Mobi La2〇3/B2〇3 0. 00 0. D6 0.12 Weight & Mo % % by weight Mo % % by weight Mo % % _ αι20, 13.86 8.57 13.88 8.73 13.64 8.70 B203 6.03 5.46 6.03 5.56 5.93 5.54 _ CaO 22.97 25.82 23.00 26.31 22.61 26.22 F, 0.70 1.16 0 0 0 — 〇-Fe20, 0.36 0.14 0.36 0.14 0.35 0.14 K,0 0.10 0.07 0 0 0 〇La2〇' 0.00 0.00 1.69 0.33 3.33 0.67 ~ 95764.doc -46-

Example 6: 丄 (10) 622 Table 5 below shows two example glasses according to non-limiting examples of the invention, and zero (25 and 26, respectively) and a comparative glass composition (labeled as glass composition C) Dielectric constant and dissipation factor. The example glass compositions of the present invention comprise from about 8 to about 10% by weight of B2〇3 and from La2〇3 in a La203/B203 molar ratio of about 〇·〇2; and the comparative example glass composition contains about 1% by weight. B2〇3 and does not contain rare earth oxides. In addition, all of the fiberizable glass compositions shown in Table 5 contain between 2 and 3% by weight of MgO. The glass button samples of each of the fibrillable glass compositions shown below in Table 5 were prepared as indicated above in Example 1, and the dielectric constant and dissipation factor amount were as described above in Example 5. Measurement. The dielectric constant of the example composition 25 at 1 MHz and 1 GHz as indicated in Table 5 is slightly souther than the comparative composition C » However, the example composition 25 has a low dissipation factor at 1 MHz and 1 GHz. In Comparative Example Composition c. The example fiberizable glass composition 26 also has a slightly higher dielectric constant than the comparative composition c, however, this can be attributed in part to the lower 实例 of the example composition 26 compared to the comparative composition C. content. Nonetheless, the example composition 26 was significantly lower than the comparative composition at 95 MHz at 95764.doc • 47·1330622 and 1 GHz. The value of 3]. Although not intended to be bound by any particular theory, the inventors believe that the dielectric properties of the comparative glass composition C may be superior to those commercially available for electronic applications due to the relatively high Mg content of the group σ. The dielectric properties expected of the E glass. Further, as shown in Table 5, the fiberizable glass compositions 25 and % have a lod3 forming temperature of not more than 1200 C, and the ΔΤ value is more than 55 〇c. Glass composition number C 25 26 Mo Erbi La2〇3/B2〇3 0.00 0.02 0.02% by weight Moen% % by weight Mo % % by weight Mo % % AI2O3 13.49 8.33 13.36 8.31 13.66 8 48 B2O3 10.17 9.19 10.07 9.17 8.12 7.38 CaO 19.76 22.17 19.57 22.13 20.00 22 57 F2 0.34 0.57 0.34 0.56 0.35 〇58 Fe203 0.35 0.14 0.35 0.14 0.35 0.14 K2O 0.10 0.06 0.10 0.06 0.10 0 07 L&2〇3 0 0 0.97 0.19 0.94 0 18 MgO 2.43 3.80 2.41 3.79 2.46 3.86 Na20 0.42 0.43 0.42 0.43 0.43 0 44 Si〇2 52.39 54.87 51.88 54.77 53.04 55 86 SrO 0 0 0' 0 0 0 T1O2 0.56 0.44 0.55 0.44 0.56 0.45 Zr02 0 0 0 0 0 0 Total 100.0 100.0 100.0 100.0 100.0 100.0 TL ( °C) 1085 10 76 10 77 TF(°C) 1170 1161 1181 △t(oc) 85 85 104 Dk, 1MHz 7.01 7.03 7.11 Dk, 1GHz 6.83 6.94 6.97 Df, 1MHz 0.0038 0.0026 0.0020 Df, 1GHz 0.0440 0.0144 0.0052 It should be understood The present specification describes aspects of the invention that are related to a clear understanding of the invention. In order to simplify the present invention, some aspects of the present invention which will be apparent to those skilled in the art and which will not facilitate a better understanding of the present invention are not provided. Although the invention has been described in connection with certain embodiments of the inventions, the disclosure of the invention is not limited to the specific embodiments disclosed, but rather is intended to cover the invention as defined by the appended claims. Modifications within the spirit and scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Circle 1 & is a plot of the molar percentage of a series of fibrillable glass compositions, La2〇3, and the percentage of molar b2〇3 in the form of BO3. Figure lb is a plot of the molar percentage & La2〇3 of a series of fibrillatable glass compositions versus the molar percentage 匕〇3 of the BO4 form. Circle 2 is a graph of boron emissivity versus time for a viable glass composition according to a non-limiting embodiment of the invention and a comparative fibrillatable glass composition. Figure 3 is a graph of boron emissivity versus time for a viable glass composition and a comparative fibrillatable glass composition in accordance with a non-limiting embodiment of the present invention. Figure 4 is a graph showing the molar ratio of the molar ratio of b〇3/(b〇3+B〇4) to the molar ratio of La2〇3/B2〇3 of a series of fibrillatable glass compositions. 95764.doc 49-

Claims (1)

1330622 No. 093127071 Patent application rate ^^一.,—·——-- Chinese application patent scope replacement ^ (96 years month ^^ year 7 is yb X. Application patent scope: L. ------- -------- 1 · A fibrillable glass composition comprising 9 to 16 weight percent of Al2〇3; 〇·5 to 13 weight percent of b2〇3; 16 to 25 weight percent of CaO 0 to 6 weight percent of MgO; 48 to 62 weight percent of si〇2; 0 to 4 weight percent of Ti〇2; and R2〇3 'where R2〇3 and b203 have molar ratios from 0.〇 1 to 0.33, and R is at least one rare earth element. 2. The glass composition of claim 1, wherein the fiberizable glass composition has a log3 forming temperature of not more than 1200 ° C; The liquidus temperature of c and a Δ T of at least 55 ° C. 3. The fibrillable glass composition of claim 1, wherein the glass composition comprises 5 to 10 weight percent of b203. The fibrillable glass composition of 1, wherein the molar ratio of the ruthenium and the ruthenium ranges from 0.01 to 0.15. The rare earth element is selected from the group consisting of sharp, kiln and the steel element. 6. The fiberizable glass composition of claim 1 wherein the rare earth element has a 3 + oxidation state and at least An ion potential in the glass of 2.5. 7. The fibrillable glass composition of claim </ RTI> wherein the viable glass composition comprises at least 0.775 B 〇 3 structural unit plus b 〇 3 structural unit plus B The moiré ratio of the sum of the structural units of 〇4. 95764-960725.doc 1330622 8. The fibrillable glass composition of claim 1, wherein the glass composition has a relative boron loss of less than 5 percent. The fibrillable glass composition of claim 1, wherein the glass composition has a dielectric constant of not more than 7.5 at 1 MHz. The fiberizable glass composition of claim 1, wherein the glass composition The material has a dissipation factor of not more than 0.01 at 1 MHz. 11. The fiberizable glass composition of claim 1 further comprising 〇 to 1 〇 by weight of Fe 2 〇 3 ; not more than 1% by weight of ρ 2 ; and 〇 to 2% by weight At least one alkali metal oxide of the group consisting of free NazO, K2 and Li20. 12. The fiberizable glass composition of claim 1, comprising 12 to 16 weight percent of Al2?3; 5 to 10 weight percent B2〇3; 16 to 25 weight percent of CaO; 0 to 4 weight percent of MgO; 52 to 56 weight percent of Si〇2; 0 to 0.8 weight percent of Ti02; and R2O3 'where R2〇3 and B2〇3 The molar ratio ranges from 0.01 to 0.33, and R is at least one rare earth element. 13. The fibrillatable glass composition of claim 1, wherein R2〇3 comprises La2〇3. 14. The fibrillatable glass composition of claim 1 wherein the Mg bismuth content is from 2 to 4 weight percent. 15. The fibrillatable glass composition of claim 12, wherein r2〇3 comprises Nd203 〇95764-960725.doc 16. 16. 17. 18. 19. 20. 21. 22. 23. 24. It is made from the glass composition of claim 1. A polymeric composite comprising: a polymeric matrix material; and at least one of the polymeric matrix materials, such as the glass fibers of claim 16. A polymeric composite of the invention of claim 17, wherein the polymeric composite is a substrate of an electronic circuit. A method for inhibiting volatilization of a glass composition comprising a ruthenium', the method comprising: adding R2〇3 to the glass composition prior to processing the glass composition such that the glass composition has a range prior to processing a molar ratio of 2 〇 3 to 32 〇 3 from 0 01 to 0.33, wherein r is at least one rare earth element; and processing the glass composition, wherein after processing, the glass composition has a ratio of not more than The relative boron loss of 5. The method of claim 19 wherein R is selected from the group consisting of a line, a record, and a (four) element. The method of claim 19, wherein R is 镧. For example, the method of claim 19, wherein the molar ratio of r2〇3 to ίο] ranges from 0.01 to 0.15. The method of claim 19, 廿 + one, wherein the glass composition comprising B2 〇 3 comprises from 0.2 to 13 weight percent of b2 〇3. The method of claim 19, wherein the glass composition comprising Β2〇3 comprises 5 to 10% by weight of β2〇3. The method of claim 19, wherein processing the glass composition comprises processing the glass composition at a temperature of 10 g of the glass composition or higher. 26. The method of claim 19, wherein the glass composition has a relative boron loss of no greater than 2%. 27. The method of claim 19, wherein the glass composition does not have a relative boron loss. 95764-960725.doc 1330622 Patent Application No. 093127071 Chinese Graphic Replacement Page (July 96) XI. Schema: The factory is in the form of Β2〇3 (mole%) 4.64 4.60 4.56 4.52 4.48 4.44 0.0 0.2 0.4 0.6 0.8 La203 (mole%) Figure la 1.0 is in the form of Β〇4 Β203 (mole%) 1.16 1.36 1.32 1.28 1.24 1.20 0.0 0.2 0.4 0.6 0.8 1.0 La2〇3 <mole%) Figure lb c!E/6) ιρ/ΜΡ 1.4x10-3 1.2x10'3 1.0x10'3 8.0x10'4 6.0x1 Ο*4 4.0x10'4 2.0x1 ο-4 Ο 60 120 180 240 300 360 420 480 540 600 Melting time (minutes) Figure 3 95764-960725.doc