Low dielectric constant glass fiber prepared at low temperature and preparation method thereof

Abstract

The application belongs to the technical field of electronic glass fiber materials, and discloses low dielectric constant glass fiber prepared at low temperature and a preparation method thereof.The glass fiber comprises the following components: SiO2 56-65%; Al2O3 12-17%; B2O3 7-15%; CeO2 1-4%; P2O5 0.5-2%; MgO+CaO 10-15%; Li2O+Na2O+K2O 0-1%.The application introduces CeO2 and P2O5 into aluminum-boron-silicon glass, the introduction of CeO2 can significantly reduce the high-temperature viscosity of the glass fiber, thereby reducing the melting temperature and the fiberizing temperature;the introduction of P2O5 can improve the deterioration of the dielectric property caused by the introduction of CeO2;through the synergistic effect of the two, the melting temperature and the fiberizing temperature can be further reduced, and the dielectric property of the glass fiber can be obviously improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of electronic glass fiber materials, and particularly relates to a low-temperature-preparable low-dielectric-constant glass fiber and a preparation method thereof. BACKGROUND

[0002] E-glass fiber is an aluminoborosilicate glass, which mainly contains SiO2, Al2O3, B2O3 and CaO. Research shows that the electrical properties of glass fiber and process production parameters cannot be both good, that is, while pursuing excellent electrical properties of glass fiber, the production difficulty of glass fiber is greatly increased. At present, low-dielectric glass fiber is mainly obtained by increasing the proportion of SiO2 in the glass component and reducing the content of alkali metal and alkaline earth metal oxides, which leads to high melting and forming temperature of glass fiber and great difficulty in industrial production. Therefore, on the basis of ensuring the excellent electrical properties of low-dielectric glass fiber, exploring the method for reducing the production difficulty of glass fiber and improving the process performance is a key problem in the research of electronic glass fiber.

[0003] In our previous patents CN115304282A and CN115321824A, lanthanum oxide is introduced into aluminoborosilicate glass to adjust the basic components of aluminoborosilicate glass. The obtained glass fiber has the characteristics of low dielectric constant and low dielectric loss, and has low melting temperature and fiberizing temperature, and excellent processing performance. Further, a silicon sol atomization infiltration liquid is used as cooling vapor mist for cooling, which can generate a SiO2 surface coating or composite structure on the surface of the glass fiber. It has been verified that the dielectric properties of the glass fiber can be further significantly improved without affecting the melting process of the glass fiber and the mechanical properties of the glass fiber matrix. It mainly utilizes the large field strength of rare earth element La2O3 and its small radius to link multiple non-bridge oxygen to play the role of network supplementing. In addition, due to the large field strength, the bridge oxygen bond near it and the bridge oxygen bond connected to it will be offset, so that the bridge oxygen bond strength is weakened, thereby achieving the effect of reducing the melting temperature and fiberizing temperature. However, the addition of rare earth oxides will still deteriorate the dielectric properties of the glass fiber to some extent.

[0004] Considering the two factors, developing a new reasonable glass component is an important task in the research and development of electronic glass fiber at present. SUMMARY

[0005] In view of the above-mentioned defects and shortcomings of the prior art, the primary object of the present application is to provide a low dielectric constant glass fiber prepared at a low temperature. The present application introduces CeO2 and P2O5 into aluminum-boron-silicon glass, the introduction of CeO2 can significantly reduce the high-temperature viscosity of the glass fiber, thereby reducing the melting temperature and the fiberizing temperature; the introduction of P2O5 can improve the deterioration of the dielectric properties caused by the introduction of CeO2, and through the synergistic effect of the two, the melting temperature and the fiberizing temperature can be further reduced while the dielectric properties of the glass fiber are significantly improved.

[0006] Another object of the present application is to provide a preparation method of the above-mentioned low dielectric constant glass fiber.

[0007] The object of the present application is achieved by the following technical solutions.

[0008] A low dielectric constant glass fiber prepared at a low temperature, comprising the following components in terms of weight percentage:

[0009] SiO2 56~65%;

[0010] Al2O3 12~17%;

[0011] B2O3 7~15%;

[0012] CeO2 1~4%;

[0013] P2O5 0.5~2%;

[0014] MgO+CaO 10~15%;

[0015] Li2O+Na2O+K2O 0~1%。

[0016] Preferably, the low dielectric constant glass fiber prepared at a low temperature comprises the following components in terms of weight percentage:

[0017] SiO2 56.5~61%;

[0018] Al2O3 14~16%;

[0019] B2O3 8~12%;

[0020] CeO2 1~4%;

[0021] P2O5 0.5~2%;

[0022] MgO+CaO 12~13%;

[0023] Li2O+Na2O+K2O 0~1%。

[0024] Further preferably, the low-temperature-preparable low dielectric constant glass fiber comprises the following components in percentage by weight:

[0025] SiO2 56.5-61%;

[0026] Al2O3 15%;

[0027] B2O3 10%;

[0028] CeO2 1-4%;

[0029] P2O5 0.5-2%;

[0030] MgO 11%;

[0031] CaO 1.5%.

[0032] Further preferably, the mass ratio of CeO2 to P2O5 is 2:1.

[0033] The method for preparing the low dielectric constant glass fiber comprises the following steps:

[0034] (1) Weigh the raw materials according to the percentage by weight, crush and sieve the raw materials, and mix them to obtain a mixture;

[0035] (2) Put the mixture obtained in step (1) into a glass kiln, and stir and melt it at 1400-1500°C to obtain a glass liquid which is clarified and homogenized;

[0036] (3) The clarified and homogenized glass liquid obtained in step (2) is drawn through a platinum-gold bushing at a temperature of 1250-1320°C, cooled and solidified to obtain a low dielectric constant glass fiber.

[0037] Further, the cooling and solidification in step (3) means cooling to room temperature by using cooling air and cooling water in sequence.

[0038] Further preferably, the cooling and solidification in step (3) means first cooling to 850-600°C by using a silicon sol atomized infiltration liquid, and then cooling to room temperature by using cooling water.

[0039] Further preferably, the silicon sol atomized infiltration liquid means a cooling vapor mist formed by atomizing an alkaline silicon sol aqueous solution with a mass concentration of 0.5%-5%.

[0040] In the present application, SiO2 exists in the glass as a glass network former, and the irregular network structure formed by silicon-oxygen tetrahedron is the structural framework of the glass, which plays a key role in the network structure and performance of the glass, and is the component with the highest content in the glass. If the content of SiO2 is increased, the number of bridge oxygen in the glass structure is increased, the glass linkage is more compact, and the glass structure is more stable, which is not easy to polarize under the action of an external electric field, and is not easy to produce conductance and relaxation loss, which is beneficial to the reduction of the dielectric constant and dielectric loss. However, when the content of SiO2 is too high, the high-temperature viscosity of the glass is relatively increased, which leads to the need to greatly increase the temperature required for glass melting and fiber drawing, and the increase of the melting temperature reduces the service life of the refractory material in the glass kiln; at the same time, it also makes it difficult to clear the glass bubble.

[0041] In the present application, Al2O3 also exists in the glass structure as an intermediate. A small amount of Al 3+ enters the glass network in the form of [AlO4] tetrahedron, which can enhance the network structure and has a certain network supplementing effect. Al 3+ can combine with free oxygen to form [AlO5] and [AlO6] polyhedron, and appropriate addition can reduce the tendency of glass phase separation and crystallization, and can improve the chemical stability of the glass and be beneficial to the formation of the fiber; however, the introduction of excessive amount will increase the viscosity of the glass, and also increase the dielectric constant and dielectric loss.

[0042] In the present application, B2O3 exists in the glass as a glass network intermediate. When the glass contains sufficient free oxygen, B 3+ participates in the network structure in the form of [BO4] and plays a role in connecting the network. When the content of the glass component network outer body is low and cannot provide sufficient free oxygen, B 3+ exists in the form of [BO3] triangle and does not enter the glass network. Since the B-O bond energy is higher than the Si-O bond energy, the glass is not easy to polarize, and the appropriate addition of B 3+ is beneficial to improve the dielectric performance of the glass, and the addition of boron can reduce the high-temperature viscosity of the glass, which is beneficial to industrial production; however, the excessive content of boron in the glass component will cause serious volatilization of boron, which will cause instability of the glass component and environmental pollution, etc.

[0043] In the present application, alkaline earth metal oxides MgO+CaO and alkali metal oxides Li2O+Na2O+K2O do not participate in the composition of the glass network structure as the glass network outer body. The role of the addition is to provide free oxygen to destroy the bridge oxygen bond, reduce the glass melting temperature and fiber forming temperature, and be beneficial to the industrial production of the glass. However, it will also increase the dielectric constant and dielectric loss, especially the increase of the content of alkali metal oxides will seriously affect the dielectric performance of the glass.

[0044] The improvement principle of the present application is that CeO2 and P2O5 are introduced simultaneously: the cerium ion has a large field strength, can link multiple non-bridging oxygen to play a role in network complementation, and in addition, due to its large field strength, the bridge oxygen bond near it and the group connected to it will be offset, so that the bridge oxygen bond strength is weakened. Based on the above analysis, it can be known that the introduction of cerium oxide in the glass raw material can make the batch easily melt to form a glass liquid and reduce the high temperature viscosity of the glass liquid, which is beneficial to the industrial production of glass fibers. However, the introduction of cerium oxide will increase the dielectric constant and dielectric loss to a certain extent. By further introducing diaphosphorus pentoxide, the phosphorus element has an ion radius comparable to that of silicon, which can maintain good dielectric properties to a certain extent, and the phosphorus-oxygen ion bond is relatively weak, which can reduce the high temperature viscosity of the glass liquid to a certain extent. However, the introduction of too much phosphorus element will generate phosphorus eutectic, which will cause the glass to crystallize and lose transparency, and affect the mechanical properties. By introducing a certain content range of cerium oxide and diaphosphorus pentoxide, it is found that compared with the performance of pure cerium oxide or diaphosphorus pentoxide, the performance of the two combined oxides is significantly improved in terms of reducing the melting temperature and fiberizing temperature, which shows that the two combined oxides have a significant synergistic effect in improving the dielectric properties of glass fibers and reducing the melting temperature.

[0045] Compared with the prior art, the present application has the following advantages:

[0046] By simultaneously introducing CeO2 and P2O5 in aluminum-boron-silicon glass, through the synergistic effect of the two, the dielectric properties of glass fibers can be significantly improved while further reducing the melting temperature and fiberizing temperature. DETAILED DESCRIPTION

[0047] The present application will be further described in detail below in conjunction with examples, but the embodiments of the present application are not limited thereto.

[0048] Example 1

[0049] A low dielectric constant glass fiber that can be prepared at a low temperature is prepared by the following method:

[0050] (1) The raw materials in the formula amount are crushed, sieved and mixed according to Table 1 to obtain a mixture.

[0051] (2) The mixture obtained in step (1) is put into a glass kiln and stirred and melted at 1500 DEG C to obtain a glass liquid which is clarified and homogenized.

[0052] (3) The glass liquid clarified and homogenized in step (2) is flowed through a glass fiber forming channel to a platinum-gold bushing at a temperature of 1310 DEG C, the molten glass liquid is flowed out of the bushing under the action of high-speed drawing force and is rapidly cooled and solidified under the cooling of cooling air and cooling water to obtain a low dielectric constant glass fiber.

[0053] Example 2

[0054] A low dielectric constant glass fiber prepared at low temperature is prepared by the following method:

[0055] (1) The raw materials in the formula amount are crushed, sieved and mixed according to Table 1 to obtain a mixture.

[0056] (2) The mixture obtained in step (1) is put into a glass kiln and stirred and melted at 1480°C, and the obtained glass liquid is clarified and homogenized.

[0057] (3) The glass liquid clarified and homogenized in step (2) is flowed through a glass fiber forming channel to a platinum-gold bushing with a temperature of 1295°C, the molten glass liquid is flowed out through a bushing under the action of high-speed drawing force, and is rapidly cooled and solidified under the cooling of cooling air and cooling water to obtain a low dielectric constant glass fiber.

[0058] Example 3

[0059] A low dielectric constant glass fiber prepared at low temperature is prepared by the following method:

[0060] (1) The raw materials in the formula amount are crushed, sieved and mixed according to Table 1 to obtain a mixture.

[0061] (2) The mixture obtained in step (1) is put into a glass kiln and stirred and melted at 1450°C, and the obtained glass liquid is clarified and homogenized.

[0062] (3) The glass liquid clarified and homogenized in step (2) is flowed through a glass fiber forming channel to a platinum-gold bushing with a temperature of 1270°C, the molten glass liquid is flowed out through a bushing under the action of high-speed drawing force, and is rapidly cooled and solidified under the cooling of cooling air and cooling water to obtain a low dielectric constant glass fiber.

[0063] Example 4

[0064] A low dielectric constant glass fiber prepared at low temperature is prepared by the following method:

[0065] (1) The raw materials in the formula amount are crushed, sieved and mixed according to Table 1 to obtain a mixture.

[0066] (2) The mixture obtained in step (1) is put into a glass kiln and stirred and melted at 1430°C, and the obtained glass liquid is clarified and homogenized.

[0067] (3) The step (2) clarified homogenized glass liquid flows through the glass fiber forming channel to the platinum gold sieve plate with the temperature of 1255℃, the molten glass liquid flows out through the nozzle and is drawn under the high speed drawing force, and is rapidly cooled and solidified under the cooling air and cooling water to obtain the low dielectric constant glass fiber.

[0068] Example 5

[0069] A low dielectric constant glass fiber prepared at low temperature is prepared by the following method:

[0070] (1) The raw materials in the formula amount are crushed, sieved and mixed according to Table 1 to obtain a mixture.

[0071] (2) The mixture obtained in step (1) is put into a glass kiln and stirred and melted at 1430℃ to obtain a glass liquid which is clarified and homogenized.

[0072] (3) The step (2) clarified homogenized glass liquid flows through the glass fiber forming channel to the platinum gold sieve plate with the temperature of 1255℃, the molten glass liquid flows out through the nozzle and is drawn under the high speed drawing force, and is rapidly cooled and solidified under the cooling air and cooling water to obtain the low dielectric constant glass fiber.

[0073] Comparative Examples 1-9

[0074] A glass fiber of Comparative Examples 1-9 is prepared by the following method:

[0075] (1) The raw materials in the formula amount are crushed, sieved and mixed according to Table 1 to obtain a mixture.

[0076] (2) The mixture obtained in step (1) is put into a glass kiln and stirred and melted at 1430℃ to obtain a glass liquid which is clarified and homogenized.

[0077] (3) The step (2) clarified homogenized glass liquid flows through the glass fiber forming channel to the platinum gold sieve plate with the temperature of 1255℃, the molten glass liquid flows out through the nozzle and is drawn under the high speed drawing force, and is rapidly cooled and solidified under the cooling air and cooling water to obtain the low dielectric constant glass fiber.

[0078] Table 1 Weight percentage composition of glass fiber of Examples 1-5 and Comparative Examples 1-9

[0079]

[0080]

[0081] The glass fibers obtained in the above examples and comparative examples were tested for performance. In the glass fiber industry, some characteristic temperatures are defined by the viscosity of the glass, among which the two important temperatures are "melting temperature" and "fiberizing temperature", which correspond to the temperatures at which the viscosity of the glass melt is 100P and 1000P, respectively. The "melting temperature" is the highest temperature experienced by the glass during melting; the "fiberizing temperature" is the temperature at which the glass liquid begins to be drawn into fibers, and at this temperature the 1000P viscosity of the glass liquid is most suitable for fiberizing. The dielectric constant and dielectric loss were tested using a vector network analyzer under the condition of 10 GHz; the glass viscosity was determined using a high-temperature viscometer; and based on the viscosity measurement results, the melting temperature corresponding to the 100P viscosity and the fiberizing temperature corresponding to the 1000P viscosity of the glass were obtained. The test results are shown in Table 2 below.

[0082] Table 2 Performance test results of glass fibers of Examples 1-5 and Comparative Examples 1-9

[0083]

[0084] From the comparison results of Examples 1-4 and Comparative Example 1, it can be seen that, by simultaneously introducing CeO2 and P2O5, the present application can maintain the dielectric constant and dielectric loss in a lower range while reducing the melting temperature and fiberizing temperature. With the gradual increase of the content of CeO2 and P2O5, the melting temperature and fiberizing temperature both show a significant downward trend, while the dielectric constant and dielectric loss are stably maintained in a lower range and do not show an upward trend. From the comparison results of Comparative Examples 2-5 and Comparative Example 1, it can be seen that, with the increase of the content of pure CeO2, the melting temperature and fiberizing temperature both show a significant downward trend, but the degree of reduction is less than that of Examples 1-4 under the same content (the same content of CeO2 or the same total content of CeO2+P2O5); with the increase of the content of pure CeO2, the dielectric constant and dielectric loss both show a certain degree of increase. The above results show that the addition of P2O5 in the present application is beneficial to inhibit the deterioration of dielectric properties caused by the introduction of CeO2, and can further promote the effect of reducing the high-temperature viscosity of the glass. From the comparison results of Comparative Examples 6-9 and Comparative Example 1, it can be seen that, with the increase of the content of pure P2O5, the melting temperature and fiberizing temperature both show a downward trend, but the degree of reduction is less than that of Examples 1-4 under the same content (the same content of CeO2 or the same total content of CeO2+P2O5), further illustrating that CeO2 and P2O5 have a good synergistic effect in reducing the melting temperature and fiberizing temperature. With the increase of the content of pure P2O5, the dielectric constant and dielectric loss both show a trend of first decreasing and then increasing, while in Examples 1-4, with the gradual increase of the content of P2O5, the dielectric constant and dielectric loss do not show a corresponding upward trend, indicating that the simultaneous introduction of CeO2 and P2O5 has a different effect on the dielectric properties of aluminum-boron-silicon glass fiber compared to the pure introduction of P2O5, and the complex oxide structure mechanism needs to be further studied. From the comparison results of Example 5 and Example 4, it can be seen that, by further using a silicon sol atomized immersion liquid as a cooling vapor to cool the molten glass fiber, the dielectric properties of the glass fiber can be further improved without affecting the melting and fiberizing process.

[0085] The above examples are preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application shall be equivalent replacement methods and shall be included in the protection scope of the present application.

Claims

1. A low dielectric constant glass fiber that can be produced at low temperatures, characterized in that, By weight percentage, the following components are included: SiO2 56.5~61%; Al2O3 15%; B2O3 10%; CeO2 1~4%; P2O5 0.5~2%; MgO 11%; CaO 1.5%.

2. The low dielectric constant glass fiber prepared at low temperature according to claim 1, wherein, The mass ratio of CeO2 to P2O5 is 2:

1.

3. A method of making a low dielectric constant glass fiber that can be made at low temperatures according to claim 1 or 2, characterized in that, The following preparation steps are included: (1) Each raw material is weighed by weight percentage, and the raw materials are crushed, sieved, and mixed to obtain a mixture; (2) The mixture obtained in step (1) is put into a glass kiln, and is stirred and melted at 1400~1500℃, and the obtained glass liquid is clarified and homogenized; (3) The glass liquid clarified and homogenized in step (2) flows through a glass fiber forming channel to a platinum gold sieve plate with a temperature of 1250~1320℃, is drawn, and is cooled and solidified to obtain low dielectric glass fiber.

4. The method of claim 3, wherein the low dielectric constant glass fiber is prepared at a low temperature. The cooling and solidification in step (3) means that cooling air and cooling water are used in sequence to cool to room temperature and solidify.

5. The method of claim 3, wherein the low dielectric constant glass fiber is prepared at a low temperature, and the low dielectric constant glass fiber has a dielectric constant of 3.5 or less at 1 MHz. The cooling and solidification in step (3) means that a silicon sol atomized infiltration liquid is used to cool to 850~600℃ first, and then cooling water is used to cool to room temperature and solidify.

6. The method of claim 5, wherein the low dielectric constant glass fiber is prepared at a low temperature. The silicon sol atomized infiltration liquid refers to a cooling vapor mist formed by atomizing an alkaline silicon sol aqueous solution with a mass concentration of 0.5%~5%.

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