HIGH-MAGNESIUM GLASS FIBER COMPOSITION WITH HIGH SPECIFIC MODULUS AND GLASS FIBER

Abstract

A high-magnesium glass fiber composition with high specific modulus and a glass fiber is provided. The glass fiber composition includes the following contents of components in percentage by mass: 58.5-63.0% of SiO2, 15.0-20.0% of Al2O3, 0.3-2.5% of CaO, 16.0-19.5% of MgO, 0.2-0.6% of Fe2O3, 1.0-3.5% of Y2O3 and B2O3, 0.1-1.0% of B2O3, and 0.3-0.8% of K2O and Na2O. The glass fiber composition has a density of less than 2.610 g/cm3, and the glass fiber has an elasticity modulus of equal to or greater than 94.0 GPa and a specific modulus of equal to or greater than 3.67*106 m.

Claims

1. A high-magnesium glass fiber composition with high specific modulus, comprising the following contents of components in percentage by mass: 58.5-63.0% of SiO.sub.2, 15.0-20.0% of Al.sub.2O.sub.3, 0.3-2.5% of CaO, 16.0-19.5% of MgO, 0.2-0.6% of Fe.sub.2O.sub.3, 1.0-3.5% of Y.sub.2O.sub.3 and B.sub.2O.sub.3, 0.1-1.0% of B.sub.2O.sub.3, and 0.3-0.8% of K.sub.2O and Na.sub.2O.

2. The high-magnesium glass fiber composition with high specific modulus according to claim 1, wherein the content of Y.sub.2O.sub.3 and B.sub.2O.sub.3 in percentage by mass satisfies that a B.sub.2O.sub.3/Y.sub.2O.sub.3 ratio is 0.2-0.5.

3. The high-magnesium glass fiber composition with high specific modulus according to claim 1, wherein the contents of Al.sub.2O.sub.3 and MgO in percentage by mass satisfy that a MgO/Al.sub.2O.sub.3 ratio is 0.8-1.2.

4. The high-magnesium glass fiber composition with high specific modulus according to claim 1, wherein the following contents of components in percentage by mass comprise: 59.0-62.5% of the SiO.sub.2, 16.5-19.0% of the Al.sub.2O.sub.3, 0.5-2.5% of the CaO, 16.0-19.0% of the MgO, 0.2-0.5% of the Fe.sub.2O.sub.3, 1.0-3.0% of the Y.sub.2O.sub.3 and the B.sub.2O.sub.3, 0.2-0.9% of the B.sub.2O.sub.3, and 0.3-0.6% of the K.sub.2O and the Na.sub.2O.

5. The high-magnesium glass fiber composition with high specific modulus according to claim 1, wherein the high-magnesium glass fiber composition with high specific modulus has a density of equal to or less than 2.61 g/cm.sup.3.

6. A glass fiber made from the high-magnesium glass fiber composition with high specific modulus according to claim 1, wherein the glass fiber has a specific modulus of equal to or greater than 3.67*10.sup.6 m.

7. The glass fiber made from the high-magnesium glass fiber composition with high specific modulus according to claim 6, wherein the glass fiber has an elastic modulus of equal to or greater than 94.0 GPa.

8. The glass fiber made from the high-magnesium glass fiber composition with high specific modulus according to claim 6, wherein the glass fiber has a forming temperature of 1,290 C.-1,320 C.

9. The glass fiber made from the high-magnesium glass fiber composition with high specific modulus according to claim 6, wherein the glass fiber has a liquidus temperature of 1,260 C.-1,280 C.

10. The high-magnesium glass fiber composition with high specific modulus according to claim 1, wherein the content of Y.sub.2O.sub.3 and B.sub.2O.sub.3 in percentage by mass satisfies that the content of Y.sub.2O.sub.3 and B.sub.2O.sub.3 is 1.0-3.2% and a B.sub.2O.sub.3/Y.sub.2O.sub.3 ratio is 0.2-0.5.

11. The high-magnesium glass fiber composition with high specific modulus according to claim 1, wherein the contents of Al.sub.2O.sub.3 and MgO in percentage by mass satisfy that a MgO/Al.sub.2O.sub.3 ratio is 0.85-1.15.

12. The high-magnesium glass fiber composition with high specific modulus according to claim 1, wherein the high-magnesium glass fiber composition with high specific modulus of the present disclosure is made from the following raw materials: quartz powder, calcined kaolin, quicklime, talc powder, yttrium oxide, magnesium oxide, and calcium boride, the quartz powder has a particle size of 40 m-50 m, the calcined kaolin has a particle size of 50 m-100 m, the quicklime has a particle size of 100 m-200 m, the talc powder has a particle size of 50 m-100 m, the yttrium oxide has a particle size of 30 m-75 m, the magnesium oxide has a particle size of 50 m-80 m, and the calcium boride has a particle size of 40 m-75 m.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0034] FIG. 1 shows SN curves of pultruded plates made from glass fibers in Embodiment 1, Embodiment 2 and Comparative Embodiment 3 of the present disclosure in a fatigue property test.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0035] The present disclosure is further described below in conjunction with embodiments.

[0036] A method for manufacturing a high-magnesium glass fiber with high specific modulus of the present disclosure includes the following steps: [0037] (1) Calculating the mass of various raw materials required according to contents of various components, weighing the various raw materials, evenly mixing the raw materials by a pneumatic force, conveying the raw materials to a feed bin at a furnace head to obtain a mixed batch and then putting the mixed batch into a large tank furnace by a feeding material at a constant speed; [0038] (2) Subjecting the mixed batch to melting at 1,450 C.-1,550 C. in the tank furnace, followed by clarification to obtain homogeneous glass melt; [0039] (3) Subjecting the molten glass to drawing at 1,290 C.-1,320 C. through a discharge spout on a platinum-rhodium discharge plate to form a glass fiber; and [0040] (4) Coating the glass fiber with an infiltrating agent through an oiling device, and pulling the glass fiber to a drawing machine for high-speed drawing to form a raw filament product.

[0041] Ingredients and specifications of the various raw materials used are shown in Table 1.

TABLE-US-00001 TABLE 1 Ingredients and specifications of various raw materials used Raw material name Oxide name and content Particle size Quartz SiO.sub.2 99.0% 40-50 m powder Calcined Al.sub.2O.sub.3 40.0%, SiO.sub.2 53.0% 50 m-100 m kaolin Quicklime CaO 93.0% 100 m-200 m Talc powder SiO.sub.2 60.0%, MgO 30.0% 50 m-100 m Magnesium MgO 93% 50 m-80 m oxide Yttrium oxide Y.sub.2O.sub.3 97.0% 30 m-75 m Colemanite B.sub.2O.sub.3 40.0%, CaO 26.0%, 40 m-75 m SiO.sub.2 7.0%

[0042] The raw materials with different particle size distributions are adopted in the present disclosure. On the one hand, the mixing uniformity of the raw materials is ensured. On the other hand, the introduction of ultrafine powder is reduced, which is conducive to the discharge of bubbles in the molten glass. The present disclosure is applicable to a large tank furnace and is conducive to improving the production efficiency.

[0043] Method for manufacturing a pultruded plate: Glass fiber yarns are neatly and evenly arranged by a yarn guide arrangement device, evenly impregnated in a resin tank, preliminarily shaped by a preforming device to extrude excess resin, then sent into a mold for heating and curing, and pulled out of the mold by a pulling device to obtain a composite plate.

[0044] Fatigue life SN curve: When a glass fiber reinforced composite material is subjected to a fatigue load, partial work will form defects in the material. With increase of the number of loading, the defects are accumulated continuously. When the number of loading reaches a life value of the material, cracks will expand to a critical point, causing damage to the material. A load-fatigue life curve (SN curve) of a material is a monotone decreasing curve, and that is to say, the fatigue life of the material is decreased monotonically with increase of an externally applied load.

[0045] In verifying comprehensive performance of glass fibers in embodiments and comparative embodiments, the following several parameters are selected: [0046] (1) Forming temperature, namely a temperature of glass with a viscosity of 1,000 Poise, which can be used for characterizing the forming temperature for fiber formation, where the high-temperature viscosity of the glass is obtained by using a high-temperature viscometer; [0047] (2) Liquidus temperature, namely a critical temperature at which the glass begins to devitrify, which is generally an upper limit of a crystallization temperature of the glass, where the upper limit of the crystallization temperature of the glass is obtained by using a crystallization furnace; [0048] (3) T, which is a difference value between the forming temperature and the liquidus temperature; [0049] (4) Crystallization type, where a polarizing microscope or an X-ray diffractometer is used; [0050] (5) Glass density, which is tested by a standard test method for measuring the glass density according to an ASTM C693 buoyancy method; [0051] (6) Elastic modulus, which is tested according to an ASTM D2343 standard; [0052] (7) Specific modulus, which is a ratio of the elastic modulus of a material to the density (specific modulus=elastic modulus/(density*9.8)) at a unit of 106 m; [0053] (8) Crystallization activation energy, which is calculated and obtained by reading temperature parameters on a DSC curve at a heating rate of 5 C./min, 10 C./min, 15 C./min, or 20 C./min according to a non-isothermal DSC method; and [0054] (9) Fatigue property, where a dynamic fatigue property test of a continuous fiber reinforced plastic pultruded plate is carried out using an Instron8802-250/100KN fatigue testing machine with reference to an ISO13003 (2003) standard test.

Embodiments 1-8

[0055] Composition of high-magnesium glass fiber compositions with high specific modulus and property data of glass fibers in Embodiments 1-8 are shown in Table 2.

Comparative Embodiments 1-8

[0056] Composition of glass fiber compositions and property data of glass fibers in Comparative Embodiments 1-8 are shown in Table 3.

TABLE-US-00002 TABLE 2 Data table for Embodiments 1-8 Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 1 2 3 4 5 6 7 8 Component SiO.sub.2 (%) 60.6 62.6 62.2 61.2 59.9 61.1 59.5 60.6 Al.sub.2O.sub.3 (%) 17.1 16.8 16.5 18.2 19.5 16 18.6 17.1 CaO (%) 1.5 2.5 1.1 0.5 0.7 0.8 1.4 1.5 MgO (%) 17.7 16.3 17.3 16.7 18 18.4 19 17.7 K.sub.2O + Na.sub.2O (%) 0.7 0.3 0.7 0.8 0.4 0.5 0.3 0.7 Fe.sub.2O.sub.3 (%) 0.2 0.4 0.6 0.5 0.3 0.2 0.2 0.2 B.sub.2O.sub.3 (%) 0.5 0.3 0.5 0.6 0.3 0.8 0.2 0.5 Y.sub.2O.sub.3 (%) 1.7 0.8 1.1 1.5 0.9 2.2 0.8 1.7 Ratio B.sub.2O.sub.3/Y.sub.2O.sub.3 0.29 0.38 0.45 0.40 0.33 0.36 0.25 0.29 MgO/Al.sub.2O.sub.3 1.04 0.97 1.05 0.92 0.92 1.15 1.02 1.04 Properties Forming 1320 1315 1316 1315 1311 1313 1308 1320 temperature ( C.) Liquidus 1265 1263 1273 1275 1270 1276 1273 1265 temperature ( C.) Crystallization 436 450 442 456 440 467 456 436 activation energy (kJ/mol) Crystallization Enstatite Enstatite Enstatite Enstatite Enstatite Enstatite Enstatite Enstatite type T ( C.) 55 52 43 40 41 37 35 55 Density (g/cm.sup.3) 2.61 2.605 2.598 2.597 2.599 2.591 2.596 2.61 Elastic modulus 95 96 95.8 98.5 97.1 95.4 96.5 95 (GPa) Specific 3.71 3.76 3.76 3.87 3.81 3.76 3.79 3.71 modulus (*10.sup.6 m)

TABLE-US-00003 TABLE 3 Data table for Comparative Embodiments 1-8 Comparative Embodiment Comparative Comparative Comparative Comparative Comparative Comparative Comparative Comparative Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 1 2 3 4 5 6 7 8 Component SiO.sub.2 (%) 66 57.5 55.5 62.8 59 61.4 60.6 60.1 Al.sub.2O.sub.3 (%) 22.5 21.5 17.9 17.1 16.6 15 17.1 17.1 CaO (%) 0.25 6.7 4.7 1.5 1.5 1.5 1.5 1.5 MgO (%) 11 12.8 14.7 15.5 19.8 19 17.7 17.7 K.sub.2O + Na.sub.2O (%) Trace 0.8 0.6 0.7 0.7 0.7 0.7 0.7 amount Fe.sub.2O.sub.3 (%) Trace 0.3 0.3 0.2 0.2 0.2 0.2 0.2 amount B.sub.2O.sub.3 (%) 0.5 0.5 0.5 0.3 1 Y.sub.2O.sub.3 (%) 6.2 1.7 1.7 1.7 1.9 1.7 Ratio B.sub.2O.sub.3/Y.sub.2O.sub.3 0.29 0.29 0.29 0.16 0.59 MgO/Al.sub.2O.sub.3 0.49 0.60 0.82 0.91 1.19 1.27 1.04 1.04 Properties Forming 1459 1336 1301 1335 1285 1308 1321 1315 temperature ( C.) Liquidus 1435 1292 1255 1270 1276 1282 1289 1275 temperature ( C.) Crystallization 375 368 388 405 392 408 376 396 activation energy (kJ/mol) Crystallization Quartz Cordierite Cordierite Cordierite Cordierite Cordierite Enstatite Enstatite type and and and and and and cordierite enstatite enstatite enstatite enstatite enstatite T ( C.) 24 44 46 65 9 26 32 40 Density (g/cm.sup.3) 2.488 2.598 2.675 2.595 2.608 2.603 2.617 2.607 Elastic modulus 90 92.3 95.6 92.3 94.6 93.2 94.1 93 (GPa) Specific 3.69 3.63 3.65 3.63 3.70 3.65 3.67 3.64 modulus (*10.sup.6 m)

[0057] Comparative Embodiments 1-2 show glass fiber components with high elastic modulus of a SiO.sub.2MgOAl.sub.2O.sub.3 ternary system well-known in the technical field, and both the two have the characteristics of a high content of aluminum and a low content of magnesium. In Comparative Embodiment 1, the earlier glass fiber components with high elastic modulus have higher glass fiber forming temperature and liquidus temperature, the production difficulty is great, and tank furnace production is difficult to realize. In Comparative Embodiment 2, the current conventional glass fiber components with high elastic modulus have relatively low forming temperature and liquidus temperature and relatively high elastic modulus, but cannot achieve the purpose of the present disclosure and cannot meet higher use requirements.

[0058] In Comparative Embodiment 3, the elastic modulus of the glass fiber is increased by increasing the use amount of a rare earth oxide. When the elastic modulus is increased, the density of the glass composition reaches 2.675 g/cm.sup.3, which is significantly increased, thus limiting the use of a composite material.

[0059] Comparing Comparative Embodiment 4 with Embodiment 1, when the content of MgO is adjusted to be lower than 16.0%, obvious crystallization of cordierite occurs, and the elastic modulus and the specific modulus are significantly reduced.

[0060] Comparing Comparative Embodiment 5 with Embodiment 1, when the content of MgO is adjusted to be higher than 19.5%, crystallization of cordierite occurs, and the forming temperature is significantly decreased, resulting in smaller LT and a greater risk of crystallization, such that tank furnace production is difficult to meet. With the maturity of a tank furnace drawing process technology for glass fibers, demands for fiber formation can be met when the T is equal to or greater than 35 C., and the production difficulty is gradually increased with decrease of the T.

[0061] Comparing Comparative Embodiment 6 with Embodiment 1, when the MgO/Al.sub.2O.sub.3 ratio is greater than 1.2, crystallization of cordierite occurs, and the elastic modulus is reduced.

[0062] Comparing Comparative Embodiment 7 with Embodiment 1, when the B.sub.2O.sub.3/Y.sub.2O.sub.3 ratio is less than 0.2, the liquidus temperature is increased, and the crystallization activation energy is decreased.

[0063] Comparing Comparative Embodiment 8 with Embodiment 1, when the B.sub.2O.sub.3/Y.sub.2O.sub.3 ratio is greater than 0.5, the liquidus temperature is increased, the crystallization activation energy is decreased, and the elastic modulus is significantly reduced.

[0064] The glass fibers made from the glass fiber compositions in Embodiment 1, Embodiment 2 and Comparative Embodiment 3 are then made into pultruded plates for a fatigue property test, and comparison of SN curves is shown in FIG. 1. As can be seen from FIG. 1, the pultruded plates in Embodiment 1 and Embodiment 2 have better fatigue data than that in Comparative Embodiment 3, indicating that the glass fiber composite material provided in the technical solution of the present disclosure has superior fatigue properties.