Glass fiber composition, glass fiber and preparation method thereof

Abstract

The invention provides a glass fiber composition. The glass fiber composition comprises the following components: 36.0-46.0 wt% of SiO2; the content of Al2O3 is 0.5 to 6.0 percent by weight; 15.0 to 30.0 wt% of TiO2 (titanium dioxide); baO: 20.0 wt% to 35.0 wt%; r2O3: 0.5 to 15.0 wt%; 0 to 5.0 wt% of CaO; wherein R < 2 > O < 3 > is at least one of La2O3 and Y2O3. The specific raw materials are combined with a specific ratio, so that the final glass fiber composition has the dielectric constant of more than 9.5 and the dielectric loss of less than 0.0044 at the high frequency of 10GHz, and is beneficial to application in the fields of high-frequency communication, microwave electronics and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of glass fibers, and in particular to a glass fiber composition, glass fibers and a preparation method thereof. Background Art

[0002] Over the past decade, the electronic information industry has experienced rapid growth, and the demand for miniaturization and portability of electronic devices and microwave circuits has grown. This has driven a shift toward higher capacity and smaller printed circuit boards (PCBs). The key to achieving this goal lies in increasing the dielectric constant of PCB materials, as device size is inversely proportional to the material's dielectric constant.

[0003] Currently, the dielectric constant of conventional printed circuit board resins is generally below 4.0. Using resins with a dielectric constant above 10.0 results in a dramatic increase in dielectric loss. The dielectric constant of E-glass fiber used in circuit boards is approximately 7.0, which cannot meet the requirements of miniaturization. Furthermore, with the increasing speed and frequency of signal transmission and the shortening of transmission distances, circuit components need to be denser. Embedding passive components has become a key technology, shortening line lengths and improving electrical characteristics.

[0004] Common alkali-free glass fiber cloth on the market has a relatively low dielectric constant and low capacitance, which limits the development of embedded capacitance materials. To meet market demand and achieve miniaturization, high capacity, and portability of electronic devices, it is necessary to develop dielectric materials with high energy storage density and low loss. Currently, most research on high-dielectric glass fiber is conducted at low frequencies. Because the dielectric constant decreases with increasing frequency, the dielectric constant at high frequencies of 10 GHz is low and the dielectric loss is high, which cannot truly meet the application scenarios of high-dielectric glass fiber.

[0005] Therefore, it is very necessary to provide a glass fiber with high dielectric constant, low dielectric loss, low production difficulty and environmental friendliness. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a glass fiber composition. The glass fiber composition provided by the present invention has the characteristics of high dielectric constant and low dielectric loss.

[0007] The present invention provides a glass fiber composition comprising:

[0008] SiO2: 36.0~46.0wt%;

[0009] Al2O3: 0.5~6.0wt%;

[0010] TiO2: 15.0~30.0wt%;

[0011] BaO: 20.0~35.0wt%;

[0012] R2O3: 0.5~15.0wt%;

[0013] CaO: 0~5.0wt%;

[0014] Wherein R2O3 is at least one of La2O3 and Y2O3.

[0015] In some specific embodiments of the present invention, the total content of SiO2 and Al2O3 is 37.5-51.0 wt%; the total content of TiO2+R2O3 is 16.0-44.0 wt%.

[0016] In some specific embodiments of the present invention, in the glass fiber composition:

[0017] SiO2: 37.0~45.2wt%;

[0018] Al2O3: 0.8~5.8wt%;

[0019] TiO2: 15.8~29wt%;

[0020] BaO: 21.0~34.0wt%;

[0021] R2O3: 0.8~14.5wt%;

[0022] CaO: 0-4.5wt%;

[0023] Among them, R2O3 is at least one of La2O3 and Y2O3; the total content of SiO2 and Al2O3 is: 38.5~50.5wt%; the total content of TiO2+R2O3 is: 17.0~43.2wt%.

[0024] In some specific embodiments of the present invention, in the glass fiber composition:

[0025] SiO2: 38.0~43.5wt%;

[0026] Al2O3: 2~5.8wt%;

[0027] TiO2: 16.8~27wt%;

[0028] BaO: 22.0-30.0 wt%;

[0029] R2O3: 1~13wt%;

[0030] CaO: 0~4.4wt%.

[0031] In some specific embodiments of the present invention, in the glass fiber composition:

[0032] SiO2: 38.0~42.8wt%;

[0033] Al2O3: 3.5~5.8wt%;

[0034] TiO2: 18.1~24.2wt%;

[0035] BaO: 24.1-28.6 wt%;

[0036] R2O3: 1.2~10.3wt%;

[0037] CaO: 0~4.2wt%.

[0038] The present invention provides a glass fiber prepared from the glass fiber composition described in any one of the above technical solutions.

[0039] In some specific embodiments of the present invention, the diameter of the glass fiber is 3 to 25 μm.

[0040] The present invention provides a method for preparing glass fiber, comprising:

[0041] A) preparing the glass fiber raw material according to any one of the above technical solutions;

[0042] B) heating and melting the raw material platinum-rhodium alloy in a crucible, and after melting, clarifying, and homogenizing, pouring out and cooling to obtain glass blocks or glass beads;

[0043] C) pouring the glass blocks or glass beads into a platinum-rhodium alloy crucible and keeping the crucible warm to obtain molten glass;

[0044] D) Draw the glass liquid to obtain glass fiber.

[0045] In some specific embodiments of the present invention, the holding temperature in step C) is 1400-1500° C., and the holding time is 5-6 hours.

[0046] The present invention provides a circuit board, the raw material of which includes the glass fiber described in the above technical solution.

[0047] Compared to the prior art, the present invention provides a glass fiber composition comprising: 36.0-46.0 wt% SiO2; 0.5-6.0 wt% Al2O3; 15.0-30.0 wt% TiO2; 20.0-35.0 wt% BaO; 0.5-15.0 wt% R2O3; and 0-5.0 wt% CaO; wherein R2O3 is at least one of La2O3 and Y2O3. By combining the above-mentioned specific raw materials with specific proportions, the present invention achieves a dielectric constant greater than 9.5 and a dielectric loss less than 0.0044 at a high frequency of 10 GHz, facilitating applications in high-frequency communications, microwave electronics, and other fields. DETAILED DESCRIPTION

[0048] The present invention provides a glass fiber composition, glass fiber, and a method for preparing the same. Those skilled in the art can refer to the contents herein and appropriately modify the process parameters to achieve the desired results. It should be noted that all similar substitutions and modifications are obvious to those skilled in the art and fall within the scope of protection of the present invention. The methods and applications of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately alter and combine the methods and applications herein without departing from the content, spirit, and scope of the present invention to implement and apply the technology of the present invention.

[0049] The present invention provides a glass fiber composition comprising:

[0050] SiO2: 36.0~46.0wt%;

[0051] Al2O3: 0.5~6.0wt%;

[0052] TiO2: 15.0~30.0wt%;

[0053] BaO: 20.0~35.0wt%;

[0054] R2O3: 0.5~15.0wt%;

[0055] CaO: 0~5.0wt%;

[0056] Wherein R2O3 is at least one of La2O3 and Y2O3.

[0057] The sum of the aforementioned glass components is 100 wt%. The glass fiber produced using these components achieves a dielectric constant greater than 9.5 and a dielectric loss less than 0.0044 at a high frequency of 10 GHz. This establishes a new high-dielectric-constant, low-dielectric-loss glass fiber composition system. The glass fiber produced using this system exhibits excellent dielectric properties at high frequencies, is easy to produce, has cost advantages, and is environmentally friendly.

[0058] In some specific embodiments of the present invention, the total content of SiO2 and Al2O3 is 37.5-51.0 wt%; the total content of TiO2+R2O3 is 16.0-44.0 wt%.

[0059] The glass fiber composition provided by the present invention includes SiO2: 36.0~46.0wt%; specifically, it can be: 36.0wt%, 37.0wt%, 38.0wt%, 39.0wt%, 40.0wt%, 41.0wt%, 42.0wt%, 43.0wt%, 44.0wt%, 45.0wt%, 46.0wt%.

[0060] SiO2 is one of the main components of glass and the primary oxide that forms its skeleton. It not only directly affects the glass's high-temperature viscosity, strength, and crystallization temperature, but also forms a continuous glass network with strong bonds, preventing the glass from polarizing and causing conductivity loss even under the influence of an electric field. In high-dielectric glass fibers, this oxide indirectly affects properties such as the dielectric constant and dielectric loss.

[0061] This technical solution further limits the SiO2 content. When the SiO2 content is less than 34.0wt%, the glass viscosity is too low, resulting in poor processability of the resulting high-dielectric glass fiber, making it difficult to draw the fiber, and the glass is prone to devitrification. When the SiO2 content exceeds 46.0wt%, the dielectric constant is significantly reduced, greatly limiting its application range.

[0062] The glass fiber composition provided by the present invention includes Al2O3: 0.5-6.0 wt%; specifically, it can be:

[0063] 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt%, 5.0wt%, 5.5wt%, 6.0wt%.

[0064] Al2O3 is a glass network intermediate. Adding a certain amount of Al2O3 can effectively improve the chemical stability of the glass. However, adding too much will increase the crystallization tendency of the glass and increase the dielectric loss.

[0065] The glass fiber composition provided by the present invention includes TiO2: 15.0-30.0 wt%; specifically, it can be:

[0066] 15.0wt%, 16.0wt%, 17.0wt%, 18.0wt%, 19.0wt%, 20.0wt%, 21.0wt%, 22.0wt%, 23.0wt%, 24.0wt%, 25.0wt%, 26.0wt%, 27.0wt%, 28.0wt%, 29.0wt%, 30.0wt%;

[0067] TiO2 is a glass network body, titanium ions are often Ti 3+ or Ti 4+ Titanium exists in glass, often as tetrahedrons (TiO4) or octahedrons (TiO6) within the glass network. Titanium ions have a strong polarization effect, significantly increasing the dielectric constant of glass. They also improve the acid resistance of glass fibers and reduce the thermal expansion coefficient.

[0068] In this technical solution, the TiO2 content is limited to 15.0-30.0wt%. When the TiO2 content is less than 15.0wt%, the dielectric constant is limited, and the chemical stability of the formed glass fiber is poor. When the TiO2 content is higher than 30.0wt%, the crystallization temperature of the glass is greatly increased, increasing the tendency of crystallization, making it difficult to form glass fibers.

[0069] The glass fiber composition provided by the present invention includes BaO: 20.0-35.0 wt%; specifically, it can be:

[0070] 20.0wt%, 21.0wt%, 22.0wt%, 23.0wt%, 24.0wt%, 25.0wt%, 26.0wt%, 27.0wt%, 28.0wt%, 29.0wt%, 30.0wt%, 31.0wt%, 32.0wt%, 33.0wt%, 34.0wt%, 35.0wt%;

[0071] BaO is an alkaline earth oxide that exists as a network exosome within the glass structure. Barium has the highest atomic number and largest ionic radius among the alkaline earth metal elements, which determines that this oxide can increase the density, chemical stability, and dielectric constant of glass.

[0072] In this technical solution, the BaO content is limited to 20.0-35.0wt%. When the BaO content is higher than 35.0wt%, the dielectric constant can be increased, but the viscosity of the glass is too low, making it difficult to draw. When the BaO content is lower than 20.0wt%, the dielectric constant of the resulting glass fiber is low, and the viscosity of the glass is too high at high temperatures, making the drawing process too difficult.

[0073] The glass fiber composition provided by the present invention includes R2O3: 0.5-15.0 wt%; specifically, it can be:

[0074] 0.5wt%, 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt%, 5.0wt%, 6.0wt%, 7.0wt%, 8.0wt%, 9.0wt%, 10.0wt%, 11.0wt%, 12.0wt%, 13.0wt%, 14.0wt%, 15.0wt%

[0075] R2O3 is also introduced in this technical solution. R2O3 is at least one of La2O3 and Y2O3. 3+ While the ion field is strong, its fewer 4f and 5d electron orbitals give it greater deformability and increased electronic polarization, leading to increased polarization within the glass and thus improving the dielectric constant. Furthermore, the addition of a certain amount of R₂O₃ can act as a "network filler," reducing the number of non-bridging oxygen atoms in the glass network, strengthening the glass network structure, and improving the structural stability of the glass. A stable glass structure facilitates charge storage and transfer.

[0076] In this technical solution, the content of R2O3 is limited to 0.5-15.0 wt %. Too high R2O3 will easily increase the tendency of glass crystallization and increase the cost of glass fiber, while too low R2O3 will have limited effect on improving the dielectric constant.

[0077] The glass fiber composition provided by the present invention includes CaO: 0-5.0 wt%, specifically 0 wt%, 1.0 wt%, 2.0 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%. The present invention can select a range between any two of the above values.

[0078] In this technical solution, CaO is introduced, which is also an alkaline earth oxide. Introducing a certain amount of CaO can adjust the high temperature viscosity of the glass and increase the overall stability of the glass. 2+ and Ba 2+ It can produce a synergistic effect, limit the movement of ions, and reduce the tendency of glass crystallization. The CaO content in this technical solution is limited to 0-5.0wt%.

[0079] In some specific embodiments of the present invention, in the glass fiber composition:

[0080] SiO2: 37.0~45.2wt%;

[0081] Al2O3: 0.8~5.8wt%;

[0082] TiO2: 15.8~29wt%;

[0083] BaO: 21.0~34.0wt%;

[0084] R2O3: 0.8~14.5wt%;

[0085] CaO: 0-4.5wt%;

[0086] Among them, R2O3 is at least one of La2O3 and Y2O3; the total content of SiO2 and Al2O3 is: 38.5~50.5wt%; the total content of TiO2+R2O3 is: 17.0~43.2wt%.

[0087] In some specific embodiments of the present invention, in the glass fiber composition:

[0088] SiO2: 38.0~43.5wt%;

[0089] Al2O3: 2~5.8wt%;

[0090] TiO2: 16.8~27wt%;

[0091] BaO: 22.0-30.0 wt%;

[0092] R2O3: 1~13wt%;

[0093] CaO: 0~4.4wt%.

[0094] In some specific embodiments of the present invention, in the glass fiber composition:

[0095] SiO2: 38.0~42.8wt%;

[0096] Al2O3: 3.5~5.8wt%;

[0097] TiO2: 18.1~24.5wt%;

[0098] BaO: 24.1-28.6 wt%;

[0099] R2O3: 1.2~10.3wt%;

[0100] CaO: 0~4.2wt%.

[0101] In some specific embodiments of the present invention, in the glass fiber composition:

[0102] SiO2: 38.2~40.9wt%;

[0103] Al2O3: 3.6~4.8wt%;

[0104] TiO2: 22.1~24.5wt%;

[0105] BaO: 26-28.6 wt%;

[0106] R2O3: 1.2~6.5wt%;

[0107] CaO: 1.1~3.3wt%.

[0108] The present invention provides a glass fiber prepared from the glass fiber composition described in any one of the above technical solutions.

[0109] The present invention has no particular limitation on the preparation method of the glass fiber, and the method may be a method well known in the art, including a tank kiln method and a crucible kiln method. The specific method may be prepared as follows:

[0110] In some specific embodiments of the present invention, the diameter of the glass fiber is 3 to 25 μm.

[0111] The present invention provides a method for preparing glass fiber, comprising:

[0112] A) preparing the glass fiber raw material according to any one of the above technical solutions;

[0113] B) heating and melting the raw material platinum-rhodium alloy in a crucible, and after melting, clarifying, and homogenizing, pouring out and cooling to obtain glass blocks or glass beads;

[0114] C) pouring the glass blocks or glass beads into a platinum-rhodium alloy crucible and keeping the crucible warm to obtain molten glass;

[0115] D) Draw the glass liquid to obtain glass fiber.

[0116] The method for preparing glass fiber provided by the present invention first prepares raw materials for the glass fiber according to any one of the above technical solutions.

[0117] The raw material platinum-rhodium alloy is heated and melted in a crucible, and after the melting, clarification and homogenization stages, it is cooled to obtain glass blocks or glass beads;

[0118] The raw materials are poured into a platinum-rhodium alloy crucible and heated to melt at a melting temperature of 1400-1500°C. After the melting, clarification and homogenization stages, the raw materials are poured out and cooled to obtain glass blocks or glass beads.

[0119] Pour the glass blocks or glass beads into a platinum-rhodium alloy crucible and keep it warm to obtain glass liquid;

[0120] In some specific embodiments of the present invention, the holding temperature is 1400-1500°C, and the holding time is 5-6 hours, specifically 1400°C, 1410°C, 1420°C, 1430°C, 1440°C, 1450°C, 1460°C, 1470°C, 1480°C, 1490°C, or 1500°C.

[0121] The present invention provides a circuit board, the raw material of which includes the glass fiber described in the above technical solution.

[0122] The glass fiber produced by the present invention achieves a dielectric constant greater than 9.5 and a dielectric loss less than 0.0044 at a high frequency of 10 GHz. The excellent dielectric properties are of great significance to high-frequency communications, microwave electronics and other fields, and can meet the needs of high-end applications such as high-speed data transmission and low-loss signal transmission.

[0123] In terms of environmental protection, the glass components of the present invention do not contain harmful substances such as lead oxide (PbO) and volatile substances such as boron oxide (B2O3). The glass fiber produced has minimal impact on the environment and meets the current and future high standards for green and sustainable development materials.

[0124] In terms of cost control, the present invention does not contain relatively expensive rare earth metal oxides such as Nb2O5 and Ho2O3, thereby effectively reducing production costs and facilitating large-scale production.

[0125] The high dielectric constant and low dielectric loss glass fiber of the present invention has low production difficulty and is easy to produce and apply.

[0126] It should be understood that the expression "one or more of" includes individually each of the items recited after the expression and various combinations of two or more of the recited items, unless otherwise apparent from the context and usage. The expression "and / or" in conjunction with three or more recited items should be understood to have the same meaning, unless otherwise apparent from the context.

[0127] The terms "comprising", "having" or "containing", including their grammatical synonyms, should generally be understood as open and non-restrictive, e.g., not excluding other unrecited elements or steps, unless otherwise specifically stated or understood from the context.

[0128] In this application, the term "and / or" describes the association relationship between associated objects, indicating that three relationships may exist. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0129] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single or plural items.

[0130] It should be understood that the order of steps or the order in which certain actions are performed are not important as long as the present invention remains operable. Additionally, two or more steps or actions may be performed simultaneously.

[0131] The use of any and all examples or exemplary language, such as "such as" or "including," herein is intended merely to better illustrate the invention and does not limit the scope of the invention unless otherwise claimed. No language in this specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0132] In addition, the numerical ranges and parameters used to define the present invention are approximate values. The relevant numerical values in the specific examples have been presented as accurately as possible. However, any numerical value inherently inevitably contains standard deviations due to individual testing methods. Therefore, unless otherwise expressly stated, all ranges, amounts, values, and percentages used in this disclosure should be understood to be modified by the word "about." As used herein, "about" generally means that the actual value is within plus or minus 10%, 5%, 1%, or 0.5% of a specified value or range.

[0133] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0134] Some cases are described in the embodiments and comparative examples of the present invention, wherein the embodiments illustrate certain implementations of the present invention. However, this does not mean that the effects of the present invention can only be achieved in these cases.

[0135] To further illustrate the present invention, a glass fiber composition, glass fiber and preparation method thereof provided by the present invention are described in detail below with reference to examples.

[0136] Examples 1-18

[0137] The following example was prepared using the following method: All raw materials were mixed according to the corresponding formula components. The homogeneous mixture was poured into a platinum crucible and then heated in a high-temperature muffle furnace at 1450°C for 6 hours. After clarification and homogenization, a glass solution was formed. The glass solution was poured into a preheated graphite mold and cooled to produce a glass block. The glass block was then annealed in a muffle furnace at 650°C for 4-6 hours to eliminate internal stress. After annealing, the glass block was cut into glass strips approximately 30 mm long, 2 mm wide, and 2 mm thick.

[0138] The glass specimens were placed in relevant testing equipment, the frequency was set to 1-10 GHz, and the dielectric constant and dielectric loss of the specimens were tested. The results are shown in Tables 1 and 2.

[0139] Table 1 Examples 1-9

[0140]

[0141]

[0142] Table 2 Examples 10-18

[0143]

[0144] Table 3 Comparative Examples 1-9

[0145]

[0146] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A glass fiber composition, characterized in that include: SiO2: 36.0~46.0wt%; Al2O3: 0.5~6.0wt%; TiO2: 15.0~30.0wt%; BaO: 20.0~35.0wt%; R2O3: 0.5~15.0wt%; CaO: 0~5.0wt%; Wherein R2O3 is at least one of La2O3 and Y2O3.

2. The composition according to claim 1, characterized in that The total content of SiO2 and Al2O3: 37.5~51.0wt%; the total content of TiO2+R2O3: 16.0~44.0wt%.

3. The composition according to claim 1, characterized in that In the glass fiber composition: SiO2: 37.0~45.2wt%; Al2O3: 0.8~5.8wt%; TiO2: 15.8~29wt%; BaO: 21.0~34.0wt%; R2O3: 0.8~14.5wt%; CaO: 0-4.5wt%; Among them, R2O3 is at least one of La2O3 and Y2O3; the total content of SiO2 and Al2O3 is: 38.5~50.5wt%; the total content of TiO2+R2O3 is: 17.0~43.2wt%.

4. The composition according to claim 3, characterized in that In the glass fiber composition: SiO2: 38.0~43.5wt%; Al2O3: 2~5.8wt%; TiO2: 16.8~27wt%; BaO: 22.0-30.0 wt%; R2O3: 1~13wt%; CaO: 0~4.4wt%.

5. The composition according to claim 4, characterized in that In the glass fiber composition: SiO2: 38.0~42.8wt%; Al2O3: 3.5~5.8wt%; TiO2: 18.1~24.2wt%; BaO: 24.1-28.6 wt%; R2O3: 1.2~10.3wt%; CaO: 0~4.2wt%.

6. A glass fiber, characterized in that The glass fiber composite is prepared from the glass fiber composition according to any one of claims 1 to 5.

7. The glass fiber according to claim 6, characterized in that The diameter of the glass fiber is 3 to 25 μm.

8. A method for preparing glass fiber, characterized in that: include: A) a glass fiber raw material according to any one of claims 1 to 5; B) heating and melting the raw material platinum-rhodium alloy in a crucible, and after melting, clarifying, and homogenizing, pouring out and cooling to obtain glass blocks or glass beads; C) pouring the glass blocks or glass beads into a platinum-rhodium alloy crucible and keeping the crucible warm to obtain molten glass; D) Draw the glass liquid to obtain glass fiber.

9. The preparation method according to claim 8, characterized in that In step C), the holding temperature is 1400-1500° C. and the holding time is 5-6 hours.

10. A circuit board, characterized in that: The raw material includes the glass fiber according to claim 6.

Images