ELECTRONIC-GRADE GLASS FIBER COMPOSITION, AND GLASS FIBER AND ELECTRONIC FABRIC THEREOF

Abstract

An electronic-grade glass fiber composition includes the following components with corresponding amounts by weight percentages 51.0-57.5% SiO.sub.2, 11.0-17.0% Al.sub.2O.sub.3, >4.5% and ≤6.4% B.sub.2O.sub.3, 19.5-24.8% CaO, 0.1-1.9% MgO, 0.05-1.2% R.sub.2O=Na.sub.2O+K.sub.2O+Li.sub.2O, 0.05-0.8% Fe.sub.2O.sub.3, 0.01-1.0% TiO.sub.2, and 0.01-1.0% F.sub.2. A weight percentage ratio C1=SiO.sub.2/B.sub.2O.sub.3 is 8.1-12.7, a weight percentage ratio C2=B.sub.2O.sub.3/(R.sub.2O+MgO) is 1.7-6.3, and a total weight percentage of the above components is greater than or equal to 99%.

Claims

1. An electronic-grade glass fiber composition, comprising the following components with corresponding amounts by weight percentage: TABLE-US-00020 SiO.sub.2 51.0-57.5%  Al.sub.2O.sub.3 11.0-17.0%  B.sub.2O.sub.3 >4.5% and ≤6.4% CaO 19.5-24.8%  MgO  0.1-1.9% R.sub.2O = Na.sub.2O + 0.05-1.2% K.sub.2O + Li.sub.2O Fe.sub.2O.sub.3 0.05-0.8% TiO.sub.2 0.01-1.0% F.sub.2 0.01-1.0% wherein a weight percentage ratio C1=SiO.sub.2/B.sub.2O.sub.3 is 8.1-12.7, a weight percentage ratio C2=B.sub.2O.sub.3/(R.sub.2O+MgO) is 1.7-6.3, and a total weight percentage of the above components is greater than or equal to 99%.

2. The electronic-grade glass fiber composition of claim 1, wherein a weight percentage ratio C3=(SiO.sub.2+Al.sub.2O.sub.3)/(B.sub.2O.sub.3+MgO) is 9.0-15.0.

3. The electronic-grade glass fiber composition of claim 1, wherein a weight percentage ratio C4=CaO/(CaO+MgO) is greater than or equal to 0.915.

4. The electronic-grade glass fiber composition of claim 1, wherein a weight percentage of R.sub.2O is 0.1-0.8%.

5. The electronic-grade glass fiber composition of claim 1, wherein a weight percentage of MgO is 0.45-1.9%.

6. The electronic-grade glass fiber composition of claim 1, wherein a weight percentage of B.sub.2O.sub.3 is 4.55-6.1%.

7. The electronic-grade glass fiber composition of claim 1, wherein a weight percentage of F.sub.2 is 0.3-1.0%.

8. The electronic-grade glass fiber composition of claim 1, wherein a weight percentage of Li.sub.2O is less than 0.1%.

9. The electronic-grade glass fiber composition of claim 1, wherein a combined weight percentage of B.sub.2O.sub.3+MgO is 5.0-7.6%.

10. The electronic-grade glass fiber composition of claim 1, wherein a combined weight percentage of SiO.sub.2+Al.sub.2O.sub.3 is 68.5-74.0%.

11. The electronic-grade glass fiber composition of claim 1, wherein a combined weight percentage of CaO+MgO+R.sub.2O is 20.5-25.8%.

12. The electronic-grade glass fiber composition of claim 1, wherein a weight percentage of CaO is 22.2-24.8%.

13. The electronic-grade glass fiber composition of claim 1, comprising the following components with corresponding amounts by weight percentages: TABLE-US-00021 SiO.sub.2 51.0-57.5%  Al.sub.2O.sub.3 11.0-17.0%  B.sub.2O.sub.3 >4.5% and ≤6.4% CaO 19.5-24.8%  MgO  0.1-1.9% R.sub.2O = Na.sub.2O + 0.05-1.2% K.sub.2O + Li.sub.2O Fe.sub.2O.sub.3 0.05-0.8% TiO.sub.2 0.01-1.0% F.sub.2 0.01-1.0% wherein the weight percentage ratio C1=SiO.sub.2/B.sub.2O.sub.3 is 8.1-12.7, the weight percentage ratio C2=B.sub.2O.sub.3/(R.sub.2O+MgO) is 1.7-6.3, a weight percentage ratio C3=(SiO.sub.2+Al.sub.2O.sub.3)/(B.sub.2O.sub.3+MgO) is 9.0-15.0, a weight percentage ratio C4=CaO/(CaO+MgO) is greater than or equal to 0.915, and a total weight percentage of the above components is greater than or equal to 99%.

14. The electronic-grade glass fiber composition of claim 1, comprising the following components with corresponding amounts by weight percentages: TABLE-US-00022 SiO.sub.2 52.0-57.0%  Al.sub.2O.sub.3 12.0-16.0%  B.sub.2O.sub.3 >4.5% and ≤6.4% CaO 20.0-24.4%  MgO  0.1-1.9% R.sub.2O = Na.sub.2O + 0.05-1.2% K.sub.2O + Li.sub.2O Fe.sub.2O.sub.3 0.05-0.8% TiO.sub.2 0.01-1.0% F.sub.2 0.01-1.0% wherein the weight percentage ratio C1=SiO.sub.2/B.sub.2O.sub.3 is 8.3-12.5, the weight percentage ratio C2=B.sub.2O.sub.3/(R.sub.2O+MgO) is 1.7-6.3, and a total weight percentage of the above components is greater than or equal to 99%.

15. The electronic-grade glass fiber composition of claim 1, comprising the following components with corresponding amounts by weight percentages: TABLE-US-00023 SiO.sub.2 52.0-57.0% Al.sub.2O.sub.3 12.0-16.0% B.sub.2O.sub.3 >4.5% and ≤6.4% CaO 20.0-24.4% MgO  0.1-1.9% R.sub.2O = Na.sub.2O + 0.05-0.95% K.sub.2O + Li.sub.2O Fe.sub.2O.sub.3  0.05-0.8% TiO.sub.2  0.05-0.8% F.sub.2  0.05-0.8% wherein the weight percentage ratio C1=SiO.sub.2/B.sub.2O.sub.3 is 8.3-12.5, the weight percentage ratio C2=B.sub.2O.sub.3/(R.sub.2O+MgO) is 1.7-6.3, a weight percentage ratio C3=(SiO.sub.2+Al.sub.2O.sub.3)/(B.sub.2O.sub.3+MgO) is 9.0-15.0, a weight percentage ratio C4=CaO/(CaO+MgO) is greater than or equal to 0.915, and a total weight percentage of the above components is greater than or equal to 99%.

16. The electronic-grade glass fiber composition of claim 1, further comprising one or more components selected form the group consisting of SO.sub.3, SrO, CeO.sub.2, La.sub.2O.sub.3, Y.sub.2O.sub.3, ZrO.sub.2 and ZnO, with a combined weight percentage of the one or more components being less than 1%.

17. An electronic-grade glass fiber, being produced using the composition of claim 1.

18. The electronic-grade glass fiber of claim 17, having a dielectric constant of 6.3-7.0 at 1 MHz at room temperature.

19. An electronic fabric, comprising the glass fiber of claim 17.

20. The electronic fabric of claim 19, being used as a base material for printed circuit boards.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0073] In order to better clarify the purposes, technical solutions and advantages of the examples of the present disclosure, the technical solutions in the examples of the present disclosure are clearly and completely described below. Obviously, the examples described herein are just part of the examples of the present disclosure and are not all the examples. All other exemplary embodiments obtained by one skilled in the art on the basis of the examples in the present disclosure without performing creative work shall all fall into the scope of the present disclosure. What needs to be made clear is that, as long as there is no conflict, the examples and the features of examples in the present application can be arbitrarily combined with each other.

[0074] In the present disclosure, the components of the electronic-grade glass fiber composition expressed as percentage amounts by weight are: 51.0-57.5% SiO.sub.2, 11.0-17.0% Al.sub.2O.sub.3, greater than 4.5% and less than or equal to 6.4% B.sub.2O.sub.3, 19.5-24.8% CaO, 0.1-1.9% MgO, 0.05-1.2% R.sub.2O=Na.sub.2O+K.sub.2O+Li.sub.2O, 0.05-0.8% Fe.sub.2O.sub.3, 0.01-1.0% TiO.sub.2, and 0.01-1.0% F.sub.2; wherein the range of the weight percentage ratio C1=SiO.sub.2/B.sub.2O.sub.3 is 8.1-12.7, the range of the weight percentage ratio C2=B.sub.2O.sub.3/(R.sub.2O+MgO) is 1.7-6.3, and the total weight percentage of the above components is greater than or equal to 99%. The composition has the advantage of high cost performance. It can reduce the cost and volatilization of raw materials, improve dielectric properties of the glass, increase mechanical properties and water resistance, and improve temperature range for fiber formation. The composition is suitable for large-scale tank furnace production.

[0075] The specific content values of SiO.sub.2, Al.sub.2O.sub.3, B.sub.2O.sub.3, CaO, MgO, Na.sub.2O, K.sub.2O, Li.sub.2O, TiO.sub.2, Fe.sub.2O.sub.3 and F.sub.2 in the electronic-grade glass fiber composition according to the present disclosure are selected to be used in the examples, which are compared with the properties of five comparative examples (numbered B1-B5) in terms of the following eight property parameters, with B1 being a conventional E-glass fiber composition for electronic applications, B2 being a conventional D-glass fiber composition and B3-B5 being general-purpose E-glass fiber compositions for reinforcement.

[0076] (1) Forming temperature, the temperature at which the glass melt has a viscosity of 10.sup.3 poise.

[0077] (2) Liquidus temperature, the temperature at which the crystal nucleuses begin to form when the glass melt cools off—i.e., the upper limit temperature for glass crystallization.

[0078] (3) ΔT value, which is the difference between the forming temperature and the liquidus temperature and indicates the temperature range at which fiber drawing can be performed.

[0079] (4) Tensile strength, the maximum tensile stress that the glass fiber can withstand, which can be measured on impregnated glass roving according to ASTM D2343.

[0080] (5) Dielectric constant, to be determined in a procedure as follows: Mix the glass-making raw materials well and then add them to a platinum crucible; hold the crucible in a high-temperature electric furnace and at 1550±30° C. for 6 hours to obtain a well refined and homogenized glass liquid; pour the glass liquid into a preheated stainless steel mold to make glass blocks, hold these glass blocks in a muffle furnace for annealing, and then cut, sand and polish the annealed glass blocks to make rectangular glass pieces with a thickness of about 1.5 mm and a length and width each of about 30 mm; and coat the glass pieces with silver to form electrodes and then test these pieces to obtain dielectric constant values. A smaller dielectric constant means a weaker polarization of the glass medium and a better insulation of the glass, and vice versa.

[0081] (6) Amount of bubbles, to be determined in a procedure as follows: Use special molds to compress the glass batch materials in each example into samples of same dimension, which will then be placed on the sample platform of a high temperature microscope. Heat the samples according to standard procedures up to the pre-set spatial temperature 1500° C., and then the glass samples is directly cooled off with the cooling hearth of the microscope to the ambient temperature without heat preservation. Finally, each of the glass samples is examined under a polarizing microscope to determine the amount of bubbles in the samples. Wherein, the amount of bubbles is identified according to a specific amplification of the microscope.

[0082] (7) Water resistance, to be characterized in terms of weight loss rate. The test procedure is as follows: Put the glass powder with a particle size of 40-80 mesh into water at 95° C. for 24 hours, stir the mixture at regular intervals, and measure and determine the weight loss rate of the glass powder. A smaller weight loss rate means a better water resistance of the glass, and vice versa.

[0083] (8) Raw material cost coefficient. Set the cost of the conventional E-glass fiber composition B1 as the benchmark, its cost coefficient being 1.0. The costs of other compositions are calculated in comparison with the benchmark. A smaller cost coefficient of raw materials means a lower cost of the composition, and vice versa

[0084] The aforementioned eight parameters and the methods of measuring them are well-known to one skilled in the art. Therefore, these parameters can be effectively used to explain the technical features and advantages of the electronic-grade glass fiber composition according to the present disclosure.

[0085] The specific procedures for the experiments are as follows: Each component can be acquired from the appropriate raw materials. Mix the raw materials in the appropriate proportions so that each component reaches the final expected weight percentage. The mixed batch melts and the molten glass refines. Then the molten glass is drawn out through the tips of the bushings, thereby forming the glass fiber. The glass fiber is attenuated onto the rotary collet of a winder to form cakes or packages. Of course, conventional methods can be used to further process these glass fibers to meet the expected requirement.

[0086] Comparisons of the property parameters of the examples of the electronic-grade glass fiber composition according to the present disclosure with those of the comparative examples are further made below by way of tables, where the component contents of the compositions for producing glass fiber are expressed as weight percentage. What needs to be made clear is that the total amount of the components in an example is slightly less than 100%, and it should be understood that the remaining amount is trace impurities or a small amount of components which cannot be analyzed.

TABLE-US-00015 TABLE 1A A1 A2 A3 A4 A5 Component SiO.sub.2 54.70 54.70 54.20 54.70 55.50 Al.sub.2O.sub.3 14.50 14.50 14.50 14.50 14.50 CaO 23.35 23.00 23.00 23.00 22.35 MgO 0.50 0.50 0.50 0.50 1.00 B.sub.2O.sub.3 5.30 5.65 5.65 5.65 4.55 TiO.sub.2 0.30 0.30 0.30 0.30 0.30 Fe.sub.2O.sub.3 0.30 0.30 0.30 0.30 0.30 K.sub.2O 0.30 0.30 0.30 0.30 0.30 Na.sub.2O 0.30 0.15 0.30 0.25 0.20 F.sub.2 0.35 0.50 0.35 0.35 0.80 Li.sub.2O — — — 0.05 — ZrO.sub.2 — — 0.50 — — Ratio C1 10.32 9.68 9.59 9.68 12.20 C2 4.82 5.95 5.14 5.14 3.03 C3 11.93 11.25 11.17 11.25 12.61 C4 0.979 0.979 0.979 0.979 0.957 Parameter Forming 1193 1192 1196 1187 1198 temperature/° C. Liquidus 1082 1080 1082 1076 1084 temperature/° C. ΔT/° C. 111 112 114 111 114 Tensile strength/ 2130 2110 2160 2200 2150 MPa Dielectric constant 6.70 6.65 6.60 6.75 6.75 Amount of 6 7 10 6 8 bubbles/pcs Water resistance, 0.50 0.45 0.45 0.55 0.50 in weight loss rate/% Raw materials 0.79 0.80 0.84 0.83 0.78 cost coefficient

TABLE-US-00016 TABLE 1B A6 A7 A8 A9 A10 Component SiO.sub.2 54.20 56.50 53.00 54.00 54.60 Al.sub.2O.sub.3 15.00 12.70 17.00 16.00 14.60 CaO 22.80 21.50 22.20 22.20 23.00 MgO 0.50 1.50 0.65 0.65 0.65 B.sub.2O.sub.3 6.10 6.10 5.45 5.45 5.45 TiO.sub.2 0.40 0.25 0.25 0.25 0.25 Fe.sub.2O.sub.3 0.25 0.25 0.40 0.40 0.40 K.sub.2O 0.30 0.40 0.30 0.30 0.30 Na.sub.2O 0.30 0.40 0.25 0.25 0.25 F.sub.2 0.05 0.30 0.40 0.40 0.40 Ratio C1 8.89 9.26 9.72 9.91 10.02 C2 5.55 2.65 4.54 4.54 4.54 C3 10.48 9.11 11.48 11.48 11.34 C4 0.979 0.935 0.972 0.972 0.973 Parameter Forming 1195 1192 1197 1198 1192 temperature/° C. Liquidus 1083 1079 1086 1083 1081 temperature/° C. ΔT/° C. 112 113 111 115 111 Tensile strength/ 2150 2120 2130 2160 2130 MPa Dielectric constant 6.60 6.70 6.75 6.70 6.75 Amount of 6 6 9 7 6 bubbles/pcs Water resistance, 0.50 0.55 0.45 0.45 0.50 in weight loss rate/% Raw materials 0.80 0.81 0.80 0.79 0.79 cost coefficient

TABLE-US-00017 TABLE 1C A11 A12 A13 A14 A15 Component SiO.sub.2 54.80 55.50 55.00 55.00 55.00 Al.sub.2O.sub.3 14.40 14.40 14.70 14.70 14.70 CaO 22.30 23.00 21.45 22.45 23.15 MgO 0.55 0.55 1.90 0.90 0.20 B.sub.2O.sub.3 6.10 4.70 5.10 5.10 5.10 TiO.sub.2 0.35 0.35 0.35 0.35 0.35 Fe.sub.2O.sub.3 0.35 0.35 0.30 0.30 0.30 K.sub.2O 0.30 0.30 0.30 0.30 0.30 Na.sub.2O 0.30 0.30 0.35 0.35 0.35 F.sub.2 0.45 0.45 0.45 0.45 0.45 Ratio C1 8.98 11.81 10.78 10.78 10.78 C2 5.30 4.09 2.00 3.29 6.00 C3 10.41 13.31 9.96 11.62 13.15 C4 0.976 0.977 0.919 0.961 0.991 Parameter Forming 1192 1198 1198 1195 1194 temperature/° C. Liquidus 1079 1084 1088 1080 1083 temperature/° C. ΔT/° C. 113 114 110 115 111 Tensile strength/ 2110 2180 2160 2150 2130 MPa Dielectric constant 6.65 6.80 6.75 6.70 6.70 Amount of 5 7 9 7 6 bubbles/pcs Water resistance, 0.55 0.50 0.50 0.55 0.55 in weight loss rate/% Raw materials 0.81 0.77 0.79 0.78 0.78 cost coefficient

TABLE-US-00018 TABLE 1D A16 A17 A18 A19 A20 Component SiO.sub.2 54.40 54.40 55.90 55.00 54.40 Al.sub.2O.sub.3 14.55 14.55 14.55 14.55 14.55 CaO 22.55 24.40 21.65 22.55 23.15 MgO 0.45 0.45 0.45 0.45 0.45 B.sub.2O.sub.3 6.40 4.55 5.80 5.80 5.80 TiO.sub.2 0.35 0.35 0.35 0.35 0.35 Fe.sub.2O.sub.3 0.30 0.30 0.30 0.30 0.30 K.sub.2O 0.30 0.30 0.30 0.30 0.30 Na.sub.2O 0.30 0.15 0.30 0.30 0.30 F.sub.2 0.30 0.45 0.30 0.30 0.30 Ratio C1 8.50 11.96 9.64 9.48 9.38 C2 6.10 5.06 5.52 5.52 5.52 C3 10.07 13.79 11.27 11.13 11.03 C4 0.980 0.982 0.980 0.980 0.981 Parameter Forming 1193 1194 1203 1198 1192 temperature/° C. Liquidus 1078 1083 1090 1084 1080 temperature/° C. ΔT/° C. 115 111 113 114 112 Tensile strength/ 2080 2160 2160 2130 2100 MPa Dielectric constant 6.60 6.80 6.65 6.70 6.75 Amount of 6 7 9 7 6 bubbles/pcs Water resistance, 0.60 0.50 0.50 0.55 0.55 in weight loss rate/% Raw materials 0.82 0.76 0.80 0.80 0.81 cost coefficient

TABLE-US-00019 TABLE 1E B1 B2 B3 B4 B5 Component SiO.sub.2 54.16 73.00 59.05 56.50 54.00 Al.sub.2O.sub.3 14.32 1.00 13.08 14.70 15.20 CaO 22.12 0.60 24.29 22.50 24.00 MgO 0.41 0.50 2.83 4.00 2.10 B.sub.2O.sub.3 7.26 22.00 0 0.50 2.50 TiO.sub.2 0.34 0 0.04 0.25 0.25 Fe.sub.2O.sub.3 0.39 0 0.36 0.30 0.30 K.sub.2O 0.25 2.90 0.23 0.35 0.40 Na.sub.2O 0.45 0.03 0.55 0.90 F.sub.2 0.29 0 0.04 0.25 0.25 Ratio C1 7.46 3.32 — 113.00 21.60 C2 6.54 6.47 0 0.10 0.74 C3 8.93 3.29 25.49 15.82 15.04 C4 0.982 0.545 0.896 0.849 0.920 Parameter Forming 1175 1410 1248 1240 1215 temperature/° C. Liquidus 1075 1250 1169 1190 1185 temperature/° C. ΔT/° C. 100 160 79 50 30 Tensile strength/ 1982 1870 2290 2180 2050 MPa Dielectric constant 6.80 4.20 7.25 7.30 7.40 Amount of 10 20 18 10 7 bubbles/pcs Water resistance, 0.80 1.80 0.35 0.55 0.80 in weight loss rate/% Raw materials 1.00 2.00 0.51 0.56 0.70 cost coefficient

[0087] It can be seen from the values in the above tables that, compared with the compositions of general-purpose E-glass fiber for reinforcement, the electronic-grade glass fiber composition according to the present disclosure has the following advantages: (1) lower dielectric constant; (2) lower forming temperature and lower liquidus temperature; and (3) wider temperature range for fiber formation.

[0088] Compared with the composition of the conventional E-glass fiber, the electronic-grade glass fiber composition according to the present disclosure has the following advantages: (1) lower raw material cost; (2) higher tensile strength and better water resistance; (3) wider temperature range for fiber formation; and (4) improved dielectric constant levels.

[0089] Compared with the composition of the conventional D-glass fiber, the electronic-grade glass fiber composition according to the present disclosure has the following advantages: (1) much lower raw material cost; (2) much higher tensile strength; (3) much better water resistance; and (4) smaller amount of bubbles.

[0090] Therefore, it can be seen from the above that, compared with the compositions of general-purpose E-glass fiber for reinforcement, conventional E-glass fiber and conventional D-glass fiber, the electronic-grade glass fiber composition according to the present disclosure has made a breakthrough in terms of cost performance of products, raw material cost, dielectric constant, tensile strength, liquidus temperature, temperature range for fiber formation, and water resistance. With unexpected technical effects, the composition enables an easy achievement of large-scale tank furnace production.

[0091] The electronic-grade glass fiber composition according to the present disclosure can be used for making glass fibers for electronic applications having the aforementioned properties. The glass fibers can then be used for making electronic fabrics.

[0092] The electronic-grade glass fiber composition according to the present disclosure in combination with one or more organic and/or inorganic materials can be used for preparing composite materials having excellent performance, such as glass fiber reinforced base materials.

[0093] It is to be noted that, in this text, the terms “comprise/comprising”, “contain/containing” or any other variants thereof are non-exclusive, so that any process, method, object or device containing a series of elements contains not only such factors, but also other factors not listed clearly, or further contains inherent factors of the process, method, object or device. Without further restrictions, a factor defined by the statement “comprises/comprising an/a . . . ”, “contain/containing an/a . . . ” or any other variants thereof does not exclude other identical factors in the process, method, object or device including said factors.

[0094] The foregoing embodiments are provided only for describing instead of limiting the technical solutions of the present disclosure. While particular embodiments of the disclosure have been shown and described, it will be obvious to those skilled in the art that modifications can be made to the technical solutions embodied by all the aforementioned embodiments, or that equivalent replacements can be made to some of the technical features embodied by all the aforementioned embodiments, without departing from the spirit and scope of the technical solutions of the present disclosure.

INDUSTRIAL APPLICABILITY

[0095] The electronic-grade glass fiber composition according to the present disclosure can reduce the cost and volatilization of raw materials and lower corrosion to refractories. It can also improve dielectric properties of the glass, increase mechanical properties and water resistance of the glass fiber, and improve temperature range for fiber formation. Thus, the composition is suitable for large-scale tank furnace production.

[0096] Compared with conventional glass fiber compositions, the electronic-grade glass fiber composition according to the present disclosure has made a breakthrough in terms of cost performance of products, raw material cost, dielectric constant, tensile strength, liquidus temperature, temperature range for fiber formation, and water resistance.

[0097] Therefore, the present disclosure has good industrial applicability.