CN113698105B - High-strength glass fiber composition and preparation method thereof - Google Patents
High-strength glass fiber composition and preparation method thereof Download PDFInfo
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- CN113698105B CN113698105B CN202110775334.6A CN202110775334A CN113698105B CN 113698105 B CN113698105 B CN 113698105B CN 202110775334 A CN202110775334 A CN 202110775334A CN 113698105 B CN113698105 B CN 113698105B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
Abstract
The invention discloses a high-strength glass fiber composition and a preparation method thereof, belonging to the technical field of inorganic nonmetallic materials. The high-strength glass fiber composition consists of the following components: siO 2 2 60‑70wt％；Al 2 O 3 12‑16wt％；CaO 8‑12wt％；MgO 2‑5wt％；Yb 2 O 3 1‑3wt％；PbO 0.5‑1wt％；SrO2‑4w％；BaO 0.1‑1wt％；B 2 O 3 1‑1.5wt％；R 2 3-3 wt% of O2; the R is 2 O is Na 2 O、K 2 O and Li 2 A mixture of O; wherein K is 2 O stands for R 2 5-10% of total weight of O and Na 2 O and Li 2 The weight ratio of O is 1. In the invention, siO 2 And Al 2 O 3 In the formed network, various ions are introduced, and the synergistic effect among the ions is utilized, so that the network is tighter, and the tensile strength is improved.
Description
Technical Field
The invention relates to the technical field of inorganic nonmetallic materials, in particular to a high-strength glass fiber composition and a preparation method thereof.
Background
Glass fiber (Fiberglass) is an inorganic non-metallic material with excellent performance, has good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but is brittle and has poor wear resistance. The hair-care fiber is made of six kinds of ores of pyrophyllite, quartz sand, limestone, dolomite, borocalcite and boromagnesite through the processes of high-temperature melting, wire drawing, winding, weaving and the like, wherein the diameter of each monofilament ranges from several micrometers to twenty micrometers, the diameter of each monofilament is equivalent to 1/20-1/5 of that of one hair, and each bundle of fiber precursor consists of hundreds of even thousands of monofilaments. Glass fibers are commonly used in various fields of national economy, such as reinforcing materials, electrical insulating materials, thermal insulating materials, and circuit substrates in composite materials. In the application process of the glass fiber, along with the continuous increase of the size of a composite material product, people put forward higher and higher requirements on the mechanical property of the glass fiber.
In the prior art, the high-strength glass fiber composition has higher forming temperature, and the components added in the formula and the mixture ratio thereof are unreasonable, thus easily causing performance reduction or pollution. For example, the addition of antimony oxide as a fining agent can affect human health; fe 2 O 3 Due to the introduction of the components, phase separation of glass is easily caused, so that the stability is poor and the mechanical strength is poor; too high a magnesium oxide content increases the tendency of the glass to devitrify.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a high-strength glass fiber composition and a preparation method thereof; the glass fiber composition can effectively reduce the glass fiber forming temperature, and has higher tensile strength on the basis of ensuring better stability.
In order to solve the technical problems, the invention provides the following technical scheme:
on one hand, the invention provides a high-strength glass fiber composition which comprises the following components in percentage by weight:
said R is 2 O is Na 2 O、K 2 O and Li 2 A mixture of O; wherein K is 2 O stands for R 2 5-10% of total weight of O and Na 2 O and Li 2 The weight ratio of O is 1.
Preferably, the high-strength glass fiber composition consists of the following components in percentage by weight:
further, the CaO is mixed with Al 2 O 3 The weight ratio of (1); the weight ratio of SrO to PbO is 2-8.
Preferably, the CaO is in combination with Al 2 O 3 The weight ratio of (1); the weight ratio of SrO to PbO is 2-5.
On the other hand, the invention also provides a preparation method of the high-strength glass fiber composition, which comprises the following steps: weighing raw materials according to a proportion, putting the raw materials into a glass melting furnace, carrying out vitrification and melting treatment, and then carrying out spinning forming to obtain the glass fiber.
Further, the fiber forming temperature of the high-strength glass fiber composition is 1320-1400 ℃.
Furthermore, the liquidus temperature of the high-strength glass fiber composition is 1270-1310 ℃, and the temperature difference delta T between the fiber forming temperature and the liquidus temperature is 41-91 ℃.
Compared with the prior art, the invention has the following beneficial effects:
SiO in the invention 2 The skeleton body forming the glass is a network forming substance, and SiO is limited for improving the strength of the glass fiber and ensuring the chemical stability 2 The content is high.
Al 2 O 3 The addition of (2) has influence on the crystallization tendency, stability and mechanical strength of the glass fiber, and the stability and mechanical strength of the glass fiber can be improved as the addition amount is higher, but the crystallization rate is increased, the melting difficulty is improved, the viscosity is increased, and the difficulty in the glass melting process is increased.
In order to adjust the viscosity of the glass and the crystallization of the glass, certain content of CaO and MgO is added, and CaO and Al are subjected to crystallization 2 O 3 The weight ratio of (a) to (b), reducing the viscosity of the glass; meanwhile, the weight ratio of SrO to PbO is limited in the invention, so that the melting temperature of the glass can be reduced, and the strength can be improved to a certain extent. Further, yb 2 O 3 BaO and the like are good fluxes, and can reduce the difficulty in melting to some extent.
In the invention, siO 2 And Al 2 O 3 In the formed network, various ions are introduced, and the addition amount of each substance is limited, especially CaO and Al 2 O 3 The weight ratio of SrO to PbO, and the synergistic effect among ions are utilized to make the network more compact, and the ions are difficult to move in the network, thereby improving the tensile strength.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
In the present invention, the materials and reagents used are not specifically described, and are commercially available.
The invention provides a high-strength glass fiber composition and a preparation method thereof, and specific examples are as follows.
Example 1
The raw materials are weighed according to the formula of example 1 in the table 1, put into a glass melting furnace, vitrified and melted, and then spun and formed to obtain the glass fiber. The fiber forming temperature of the high-strength glass fiber composition is 1320-1400 ℃; the high strength glass fiber composition has a liquidus temperature of 1270-1310 ℃. And the performance of the prepared glass fiber was measured, and the results are shown in table 3.
Examples 2 to 7
The raw materials were weighed in accordance with the formulations of examples 2 to 7 in Table 1, and the other conditions were the same as in example 1. And the performance of the prepared glass fiber was measured, and the results are shown in table 3.
To further illustrate the beneficial effects of the present application, a comparative example was constructed as follows, using example 7 as an example only, for reasons of space.
Comparative example 1
The other conditions were the same as in example 7 except that PbO was replaced with the same amount of ZnO.
Comparative example 2
The same conditions as in example 7 were followed except that SrO was replaced with the same amount of ZnO.
Comparative example 3
Yb of 2 O 3 Replaced by the same amount of La 2 O 3 The other conditions were the same as in example 7.
Comparative example 4
Yb of 2 O 3 Is replaced by equal amount of Y 2 O 3 The other conditions were the same as in example 7.
Comparative example 5
Yb of 2 O 3 Replacement by equal amounts of Fe 2 O 3 The other conditions were the same as in example 7.
Comparative examples 6 to 9
The raw materials were weighed in accordance with the formulations of comparative examples 6 to 9 in Table 2, and the other conditions were the same as in example 7.
The glass fibers prepared in comparative examples 1 to 9 were subjected to property tests, and the results are shown in Table 4.
TABLE 1
TABLE 2
| Serial number | SiO 2 | Al 2 O 3 | CaO | MgO | Yb 2 O 3 | PbO | SrO | BaO | B 2 O 3 | Na 2 O | Li 2 O | K 2 O |
| Comparative example 1 | 66 | 12 | 10 | 2 | 2 | -- | 3.2 | 0.8 | 1.2 | 0.47 | 1.41 | 0.12 |
| Comparative example 2 | 66 | 12 | 10 | 2 | 2 | 0.8 | -- | 0.8 | 1.2 | 0.47 | 1.41 | 0.12 |
| Comparative example 3 | 66 | 12 | 10 | 2 | -- | 0.8 | 3.2 | 0.8 | 1.2 | 0.47 | 1.41 | 0.12 |
| Comparative example 4 | 66 | 12 | 10 | 2 | -- | 0.8 | 3.2 | 0.8 | 1.2 | 0.47 | 1.41 | 0.12 |
| Comparative example 5 | 66 | 12 | 10 | 2 | -- | 0.8 | 3.2 | 0.8 | 1.2 | 0.47 | 1.41 | 0.12 |
| Comparative example 6 | 66 | 10 | 12 | 2 | 2 | 0.8 | 3.2 | 0.8 | 1.2 | 0.47 | 1.41 | 0.12 |
| Comparative example 7 | 66 | 12 | 10 | 2 | 2 | 2 | 2 | 0.8 | 1.2 | 0.47 | 1.41 | 0.12 |
| Comparative example 8 | 66 | 12 | 10 | 2 | 2 | 0.8 | 3.2 | 0.8 | 1.2 | 0.40 | 1.20 | 0.4 |
| Comparative example 9 | 66 | 12 | 10 | 2 | 2 | 0.8 | 3.2 | 0.8 | 1.2 | 1.41 | 0.47 | 0.12 |
The components of the above examples and comparative examples were melted, spun to form glass fibers, and then formed into strands by a drawing machine. The properties were measured and the results are shown in tables 3 and 4, respectively, in which the glass fiber forming temperature (lg 3.0): the temperature at which the viscosity of the glass is 1000 Poise; liquidus temperature of glass: the critical temperature at which the glass starts to crystallize is generally the upper limit of the glass crystallization temperature; Δ T: difference between forming temperature and liquidus temperature; tensile strength of the dipped yarn: the determination is carried out by adopting a tensile testing machine according to GB/T20310-2006 determination of manufacture of glass fiber twistless roving impregnating yarn samples and tensile strength; modulus of elasticity: the test was carried out in a universal electronic tester according to ASTM D2343 standard.
TABLE 3
As can be seen from Table 3, the high-strength glass fiber prepared by the method of the invention has the tensile strength of 3816MPa. At the same time, in SiO 2 And Al 2 O 3 In the formed network, various ions are introduced, and CaO and Al are limited 2 O 3 The weight ratio of SrO to PbO, and the synergistic effect of ions, the network is more compact, the strength is improved, and the glass fiber forming temperature and the liquidus temperature are lower, so that the preparation is convenient.
TABLE 4
As is clear from tables 1 to 4, yb in the present invention was compared with comparative examples 1 to 5 2 O 3 Respectively replaced by La 2 O 3 Or Y 2 O 3 、Ce 2 O 3 Replacing ZnO by PbO or SrO, or replacing Yb by Yb 2 O 3 Substitution of La 2 O 3 、Y 2 O 3 Or Fe 2 O 3 The resulting composition showed little difference in glass fiber forming temperature and liquidus temperature compared to the examples, but the elastic modulus and tensile strength were much lower than those of the glass fibers of the present invention. This is probably due to the good access of Pb, sr into SiO on the basis of the high-content silicon dioxide of the invention 2 And Al 2 O 3 The formed network and the large ionic radius of Yb ions act together, so that the network can be well fixed, ions are prevented from moving in the network, and the network has high elastic modulus and high tensile strength.
In comparative examples 6 to 7, caO/Al was adjusted 2 O 3 And PbO/SrO in such a range that they are outside the scope of the present invention, the resulting glass fiber has a larger difference in modulus of elasticity and tensile strength than those of example 7 of the present invention because of the specific CaO/Al ratio in the specific range 2 O 3 And PbO/SrO are cooperated, so that the viscosity of the glass in the melting process can be reduced, the crystallization tendency is effectively reduced, and the strength is improved to a certain extent.
In comparative examples 8 to 9, K was adjusted 2 The amount of O is adjusted to Na 2 O and Li 2 The ratio of O, the modulus of elasticity and the tensile strength of the obtained glass fiber are both reduced compared with those of the glass fiber obtained in example 7; this is because Li 2 O and Na 2 O can greatly accelerate the melting of the glass, improve the chemical stability, the surface tension and the crystallization capacity of the glass, ensure that all components in the glass fiber are uniformly distributed and have higher elastic modulus and higher tensile strength.
In summary, the present invention is on SiO 2 And Al 2 O 3 In the formed network, various ions are introduced, and the addition amount of each substance is limited, especially CaO and Al 2 O 3 The weight ratio of SrO to PbO, and the synergistic effect between the ions, make the network tighter and the movement of the ions in the network difficult, thereby increasing the tensile strength.
The foregoing is a preferred embodiment of the present invention and modifications and variations such as will occur to those skilled in the art are considered to be within the scope of the present invention without departing from the principles of the present invention as set forth herein.
Claims (7)
1. The high-strength glass fiber composition is characterized by comprising the following components in percentage by weight:
the R is 2 O is Na 2 O、K 2 O and Li 2 A mixture of O; wherein K 2 O stands for R 2 5-10% of total weight of O and Na 2 O and Li 2 The weight ratio of O is 1.
2. The high strength glass fiber composition of claim 1, consisting of the following components in weight percent:
3. the high strength glass fiber composition of claim 1 or 2, wherein the CaO and Al are present 2 O 3 The weight ratio of (1); the weight ratio of SrO to PbO is 2-8.
4. The high strength fiberglass composition of claim 3, wherein said CaO and Al are present 2 O 3 The weight ratio of (1); the weight ratio of SrO to PbO is 2-5.
5. The method for preparing the high-strength glass fiber composition as claimed in any one of claims 1 to 4, wherein the glass fiber is obtained by weighing raw materials in proportion, putting the raw materials into a glass melting furnace, performing vitrification and melting treatment, and then performing spinning molding.
6. The method of claim 5, wherein the high strength glass fiber composition has a fiber forming temperature of 1320 to 1400 ℃.
7. The method for preparing the high-strength glass fiber composition according to claim 6, wherein the liquidus temperature of the high-strength glass fiber composition is 1270 to 1310 ℃, and the temperature difference Δ T between the fiber forming temperature and the liquidus temperature is 41 to 91 ℃.
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| DE3026605C2 (en) * | 1980-07-14 | 1983-07-07 | Schott Glaswerke, 6500 Mainz | Acid-proof, hydrolytically stable optical and ophthalmic borosilicate glass of low density |
| MX169258B (en) * | 1986-05-28 | 1993-06-28 | Pfizer | PROCEDURE FOR THE PREPARATION OF AN ALCALIS RESISTANT GLASS FIBER |
| JP3113604B2 (en) * | 1997-03-25 | 2000-12-04 | 株式会社オハラ | Optical glass with negative anomalous dispersion |
| DE102004026433A1 (en) * | 2004-05-29 | 2005-12-22 | Schott Ag | Nanoglass powder and its use |
| JP5582381B2 (en) * | 2009-06-25 | 2014-09-03 | 日東紡績株式会社 | Oxynitride glass fiber and method for producing the same |
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