CN117700113A - Glass fiber composition for high-frequency high-speed substrate and application thereof - Google Patents
Glass fiber composition for high-frequency high-speed substrate and application thereof Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000000758 substrate Substances 0.000 title claims abstract description 41
- 239000011521 glass Substances 0.000 claims abstract description 85
- 239000000156 glass melt Substances 0.000 claims abstract description 14
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 11
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 239000008395 clarifying agent Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 238000012360 testing method Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 7
- 239000006060 molten glass Substances 0.000 claims description 4
- 238000005491 wire drawing Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000012779 reinforcing material Substances 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 21
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 12
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052810 boron oxide Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000000835 fiber Substances 0.000 description 2
- 239000006025 fining agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008284 Si—F Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
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- UFQXGXDIJMBKTC-UHFFFAOYSA-N oxostrontium Chemical compound [Sr]=O UFQXGXDIJMBKTC-UHFFFAOYSA-N 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to the technical field of glass fibers, in particular to a glass fiber composition for a high-frequency high-speed substrate and application thereof, wherein the composition comprises the following components in percentage by mass: siO (SiO) 2 51.0％‑57.0％，Al 2 O 3 3.0％‑8.0％，B 2 O 3 25.0％‑32.0％，RO 3.0％‑7.0％，La 2 O 3 0.9％‑1.5％，Y 2 O 3 0‑1.5％，TiO 2 1.0％‑2.0％，F 2 2.0% -3.0% and 0.3% -1.0% of glass melt clarifying agent; wherein RO comprises 0.2 to 1.0 percent of CaO,0 to 0.8 percent of MgO,0.5 to 3.2 percent of SrO,0 to 1.5 percent of BaO,0 to 3.2 percent of ZnO, and the contents of BaO and ZnO are different from each other to be 0; the present invention provides a glass composition for forming glass fibers and can be economically formed into glass fibers by continuous fiberization, is suitable for a high frequency high speed electronics ccl\pcb board reinforcing material, and preferably has a low dielectric constant and an extremely low dielectric loss tangent at 10G frequency.
Description
Technical Field
The invention relates to the technical field of glass fibers, in particular to a glass fiber composition for a high-frequency high-speed substrate and application thereof.
Background
The rapid development of internet of things (IoT), fifth generation (5G) and sixth generation mobile communication technologies (6G technologies) has put forward higher requirements on the performance of high-frequency communication copper-clad Plates (PCBs). The speed of large-scale data processing and data transmission is higher and higher, the frequency of signal processing and transmission is higher and higher, an electronic information system is continuously developed towards a high-frequency high-speed direction, and a new generation of high-speed routers, high-speed exchangers, communication base stations, high-end servers and the like on the market have great demands on copper-clad plates of high-frequency high-speed lines. To prepare a PCB board with excellent properties, it is necessary to have a low dielectric constant and low dielectric loss from the power consumption requirement to the signal reception, in addition to a thin substrate thickness, good workability, and a low thermal expansion coefficient as much as possible. Therefore, glass fiber is also required to have as low a dielectric constant and dielectric loss as possible as a reinforcing material for PCB.
The Chinese patent invention ZL 202210423804.7 provides a low dielectric glass fiber composition for high-frequency working conditions and application thereof, and the composition comprises the following components in mass content: siO (SiO) 2 54.0-60.0％，Al 2 O 3 9.0-12.0％，B 2 O 3 20.0-23.0％，RO 6.0-9.6％，TiO 2 1.0-2.0％，Li 2 O0.08-0.12% and F 2 0.5-1.2%; wherein RO comprises CaO 1.1-2.1%, srO 0.0-3.0%, baO 0.0-4.0% and ZnO 3.2-4.5%. The glass fiber composition for high-frequency working conditions has low wire drawing temperature, good processability and excellent dielectric property, low dielectric constant and low dielectric loss under high-frequency working conditions, and the dielectric constant under 10G test frequency<4.42 dielectric loss tangent<0.00165。
It should be noted that there is a complex relationship between the dielectric loss of glass and the frequency of electromagnetic waves. In general, in a low frequency range, the dielectric loss tangent of glass is relatively low, and in a high frequency range, the dielectric loss tangent is significantly increased, and thus, with the advent of terahertz (0.1-10 THz) communication technology, the dielectric constant and dielectric loss of materials need to be further reduced. The invention is a further extension of the patent ZL 202210423804.7 of the invention, and aims to further reduce the high-frequency dielectric constant and dielectric loss tangent of glass.
Disclosure of Invention
The present invention aims to provide a glass fiber composition for a high-frequency and high-speed substrate and an application thereof, which can solve the technical problems.
The invention provides a glass fiber composition for a high-frequency high-speed substrate, which comprises the following components in percentage by mass: siO (SiO) 2 51.0％-57.0％，Al 2 O 3 3.0％-8.0％，B 2 O 3 25.0％-32.0％，RO 3.0％-7.0％，La 2 O 3 0.9％-1.5％，Y 2 O 3 0-1.5％，TiO 2 1.0％-2.0％，F 2 2.0% -3.0% and 0.5-1.0% of glass melt clarifying agent; wherein RO comprises 0.2 to 1.0 percent of CaO,0 to 0.8 percent of MgO,0.5 to 3.2 percent of SrO,0 to 1.5 percent of BaO,0 to 3.2 percent of ZnO, and the contents of BaO and ZnO are different from each other to be 0;
after the glass fiber composition for high-frequency high-speed substrates is melted into homogeneous glass, the amounts of non-bridging oxygen NBO and bridging oxygen BO contained in the structure satisfy the following relationship:
preferably, the composition comprises the following components in percentage by mass: siO (SiO) 2 52.0％-54.5％，Al 2 O 3 5.0％-8.0％，B 2 O 3 26.5％-31.5％，RO 3.5％-5.5％，La 2 O 3 0.9％-1.5％，Y 2 O 3 0-1.5％，TiO 2 1.0％-2.0％，F 2 2.0% -3.0% and 0.3% -1.0% of glass melt clarifying agent; wherein RO comprises 0.5% -1.0% of CaO, 0% -0.5% of MgO, 1.0% -3.0% of SrO, 0% -1.0% of BaO, 0% -3.0% of ZnO, and the contents of BaO and ZnO are different from each other to be 0.
Preferably, the corresponding drawing temperature at 1000 poise is less than or equal to 1438 ℃ in the melting process.
In a low dielectric multi-glass composition system,there are conductance losses, relaxation losses, ionization losses, structural losses. When a glass sample is subjected to room temperature and high frequency environment, the main dielectric loss is in the form of structural loss, and the size of the dielectric loss is related to the tightness of a network structure inside the glass. O in glass network 2- Ions mainly exist in a glass network structure in three forms of Bridged Oxygen (BO), non-bridged oxygen (NBO) and free oxygen, and the lower the non-bridged oxygen content in the glass network is, the better the network integrity is, the lower the dielectric loss is; conversely, when the glass network is looser, the worse the integrity, the more defects, the greater the dielectric loss of the glass. The dielectric loss tangent value of the glass structure can be effectively reduced by controlling and reducing the content of non-bridging oxygen in the glass structure.
The glass fiber compositions of the present invention are generally composed of a plurality of oxides, including silica (SiO 2 ) Boron oxide (B) 2 O 3 ) Alumina (Al) 2 O 3 ) Calcium oxide (CaO), strontium oxide (SrO), magnesium oxide (MgO), barium oxide (BaO), zinc oxide (ZnO), titanium oxide (TiO) 2 ) Lanthanum oxide (La) 2 O 3 ) Yttria (Y) 2 O 3 ) F (F) 2 . Additional oxides as described below may be included without departing from the true scope of the present invention. The glass fiber of the present invention preferably has a dielectric constant of less than 4.2 and a dielectric loss tangent of 0.0013 or less at a frequency of 10GHz at room temperature. The glass composition has the ability to form continuous fibers due to the positive difference (Δt3) between the drawing temperature and the liquidus temperature.
Unless otherwise indicated, the terms and test methods used in the specification and claims are as follows:
"dielectric constant (D) k ) "represents the ability of a medium to store electrical energy in an electric field. The electrical energy consumed per unit time by a dielectric under the action of an electric field is called "dielectric loss (D f ) Or dielectric loss tangent). The invention uses a network analyzer to measure the resonant frequency and the Q value of the resonant cavity clamp, is blank set at the beginning of the test, then loads the tested sample, and calculates the dielectric constant D through the measurements when the volume of the sample and other parameters of the resonant cavity are known k And dielectric loss D f 。
"liquidus temperature T liq "refers to the temperature of equilibrium between a liquid glass melt and its primary crystalline phase, at all temperatures above the liquidus, where crystals are absent from the glass melt and below the liquidus, where crystals may form in the melt. Thus, the liquidus temperature provides a lower temperature limit above which the glass can be continuously fibrillated. The measuring method comprises the following steps: and (3) placing a glass sample to be measured with the size of 10 x 10mm into a gradient furnace which is heated to 800-1300 ℃, performing heat treatment for 8 hours, and then taking out and cooling to room temperature to obtain the cooled glass. The crystallization condition inside the cooled glass is observed by a polarizing microscope: if crystallization exists in the range within 2 mm from the surface of the cooled glass, judging that the temperature of the melting treatment is lower than the liquidus temperature of the glass sample to be detected; if crystallization does not exist in the cooled glass, judging that the temperature of the melting treatment is higher than the liquidus temperature of the glass sample to be measured; if no devitrification exists in the region within 2 mm from the surface of the cooled glass, but no devitrification exists in the region outside 2 mm from the surface of the cooled glass, the temperature at that position in the gradient furnace is taken as the liquidus temperature T of the glass sample to be measured liq 。
The term "drawing temperature" or "T 3 The temperature "refers to the temperature at which the viscosity of the glass is equal to 1000 poise. The large difference between the glass draw temperature and liquidus temperature represents a wider fiber forming process window, the greater the process flexibility during glass fiber formation, the less likely it is that devitrification (crystallization) of the glass melt will occur during melting and fiberizing.
High temperature viscosity test: a BROOKFIELD rotational high temperature viscometer was used in the united states. After the glass to be measured is crushed into proper granularity, 100 g is weighed and placed in a platinum crucible, then the platinum crucible is placed in a high-temperature heating furnace, the position of a platinum rotor is adjusted to be positioned at the center of the platinum crucible, the platinum crucible is heated by a program, the temperature is kept for a period of time after the temperature is raised to a high temperature, the temperature is reduced by the program, the torque of the rotor is recorded every time the temperature reaches a set temperature, and the torque is converted into a corresponding glass viscosity value at the temperature.
Terminology"bridged versus non-bridged": o in glass structure 2- Ions exist mainly in three forms, bridged Oxygen (BO), non-bridged oxygen (NBO) and free oxygen. According to the X-ray photoelectron spectrum XPS spectrum O1s peak-splitting fitting result of the glass sample, the free oxygen content in the glass microstructure is low and negligible relative to the bridge oxygen and the non-bridge oxygen, so that only the bridge oxygen and the non-bridge oxygen content in the glass structure are quantitatively compared. The binding energy of non-bridging oxygen (NBO) is slightly smaller than that of Bridging Oxygen (BO), the electron binding energy of non-bridging oxygen is 530-531eV, the electron binding energy of bridging oxygen is 531-533eV, the energy spectrum is corrected by taking C1s spectral line (284.80 eV) as an internal standard, after background is subtracted, the spectrum is subjected to peak-by-peak fitting on O1s spectrum of a glass sample by adopting a Gaussian-Lorentz function, and the change of NBO and BO content in the microstructure of the glass sample can be quantitatively analyzed.
In the glass fiber composition of the present invention: contains 51.0wt% to 57.0wt% of SiO 2 . In this composition system, if SiO 2 If the content is less than 51.0wt%, the dielectric constant of the glass becomes large, and if the content exceeds 57wt%, the high-temperature viscosity of the glass becomes too high, so that the glass becomes more refractory and clear, and the drawing temperature increases, and breakage is easily generated during the drawing. Therefore, the silica content is preferably between 51.0wt% and 57.0wt% of the total glass composition. Furthermore, when combined with other ingredients described herein, a silica content of between 51.0wt% and 57.0wt% generally results in glass fibers having desirably low dielectric constants as well as low dielectric losses.
The glass fibers of the present invention also typically contain from 25.0wt% to 32.0wt% of B 2 O 3 . Boron oxide exceeding 32.0wt% may cause excessive volatilization during melting, low glass strength and poor mechanical properties; but also increases the non-bridging oxygen content in the structure and phase separation occurs. Furthermore, boron oxide below 25.0wt% may result in an increase in dielectric constant. Thus, when combined with other ingredients described herein, preferably the boron oxide content is greater than 25.0wt% and not greater than 32.0wt% generally results in glass fibers having a desirably low dielectric constant and very low dielectric loss.
The glass fibers of the present invention generally comprise3.0wt% to 8.0wt% of Al 2 O 3 . In the present invention, too low an amount of alumina (e.g., less than 3.0 wt.%) may result in easy breakage during drawing, affecting glass fiber formation; whereas when the alumina content is higher than 8.0wt%, the non-bridging oxygen content increases, increasing the dielectric constant and dielectric loss tangent. Thus, when combined with other ingredients described herein, preferably 5.2wt% to 7.8wt% alumina generally produces glass fibers having desirably low dielectric constants as well as extremely low dielectric loss tangents.
The glass fiber composition of the present invention contains divalent metal oxide (RO) in an amount of 3.0wt% to 7.0wt%, wherein RO is selected from CaO, mgO, srO, baO and ZnO. Specifically, the composite material comprises 0.2 to 1.0 weight percent of CaO,0.0 to 0.8 weight percent of MgO,0.5 to 3.2 weight percent of SrO,0.0 to 1.5 weight percent of BaO and 0.0 to 3.2 weight percent of ZnO. RO is taken as a glass network external body and is a provider of free oxygen, the melting temperature and high-temperature viscosity of glass can be reduced, and the clarification and uniformity in the glass melting process are ensured so as to meet the requirements of glass fiber production and processing, so that the total mass percent of RO generally affects the liquidus temperature, the high-temperature viscosity and the dielectric property of the glass. In the present invention, when the RO content is less than 3.0wt%, it is difficult to melt glass, and the viscosity of the high temperature glass melt increases, and it is difficult to clarify and homogenize the glass. Above 7.0wt% the dielectric constant and dielectric loss will increase rapidly. Thus, when combined with other ingredients described herein, RO levels of preferably 3.5wt% to 5.5wt% generally result in glass fibers having desirably low dielectric constants as well as low dielectric losses.
The glass fibers of the present invention generally contain from 1.0wt% to 2.0wt% TiO 2 . Small amount of TiO 2 Can reduce the high-temperature viscosity and improve the acid resistance of the glass, but TiO 2 Too high a content may cause the glass to be easily phase-separated.
The glass fibers of the present invention generally contain 0.0wt% to 2.0wt% La 2 O 3 Or 0.0wt% to 1.5wt% Y 2 O 3 . Small amount of La 2 O 3 、Y 2 O 3 The introduction of (2) can lower the dielectric constant and dielectric loss tangent of the glass due to rare earth ionsThe field is strong, and the field has stronger attraction to anion groups in the glass, so that the field is shown to have an accumulation effect on the glass structure, and the polymerization degree of the glass structure is increased. When the content exceeds a certain value, the free oxygen has a depolymerization effect on the network, and excessive introduction of the free oxygen damages the network structure, so that the glass structure tends to be loose. Thus, when combined with other ingredients described herein, preferably 0.9wt% to 2.0wt% La 2 O 3 Or 0.0wt% to 1.5wt% Y 2 O 3 Glass fibers having a low dielectric constant and an extremely low dielectric loss tangent are generally produced.
The glass fibers of the present invention also typically contain 2.0wt% to 3.0wt% F 2 . Can be made of AlF 3 And/or CaF 2 Introduction due to F - Radius of ionWith O 2- Radius of ion->Near, can replace O in a glass Si-O network under the condition of not influencing the occupation of other ions 2- When a pair of Si-F bonds are used instead of Si-O-Si bonds, the polarity of Si-O-Si is reduced, and thus the dielectric constant can be reduced, and the high-temperature viscosity of the molten glass is lowered. F (F) 2 The content will affect the [ SiO ] content in the glass structure 4 ]、[BO 3 ]/[BO 4 ]，[AlO 6 ]/[AlO 4 ]The amount of isostructural groups and the non-bridging oxygen (NBO) content in the glass silica network, in the present invention, when combined with other ingredients described herein, preferably 2.0wt% to 3.0wt% F 2 The content generally produces glass fibers having desirably low dielectric constants and very low loss tangents, and can effectively reduce the high temperature viscosity of the glass melt, thereby reducing the drawing temperature.
Additional oxides may be present in the glass fibers and compositions of the present invention as fining agents or with other raw material components as well as with minor amounts of impurities that are not intentionally added without departing from the scope of the present invention. For example, oxides may be present including, but not limited to, iron oxidesFe 2 O 3 ) Zirconium oxide (ZrO) 2 ) Tin oxide (SnO) 2 ) Sodium oxide (Na) 2 O), potassium oxide (K) 2 O), magnesium oxide (MgO), chromium oxide (Cr 2 O 3 ) Etc., the total amount of additional oxide is less than 1.0wt%.
The invention also provides a glass fiber for a high-frequency high-speed substrate, which is prepared from the glass fiber composition for the high-frequency high-speed substrate.
Preferably, the glass fiber for high frequency and high speed substrate of the present invention has a dielectric loss of <0.0013 at a 10G test frequency.
Preferably, the glass fiber for high frequency and high speed substrate of the present invention has a dielectric constant <4.2 at a test frequency of 10G.
More preferably, the frequency is 10GHz, and has a dielectric constant less than 4.0 and a dielectric loss less than or equal to 0.0010.
The method for preparing the glass fiber for the high-frequency high-speed substrate is not strictly limited, and the conventional method in the field can be adopted. Specifically, the invention also provides a preparation method of the glass fiber for the high-frequency high-speed substrate, which comprises the following steps: a glass fiber composition for high-frequency high-speed substrates is provided into a glass melting furnace, and the glass fiber composition for high-frequency high-speed substrates is heated to a temperature exceeding the liquidus temperature to continuously fibrillate molten glass, thereby producing glass fibers for high-frequency high-speed substrates having a low dielectric constant and a low dielectric loss.
Further, the present invention provides a method for preparing glass fiber for high-frequency and high-speed substrate, comprising the steps of: the glass fiber composition for the high-frequency high-speed substrate is melted, clarified and homogenized in a kiln, then flows out of the Pt bushing plate at the temperature of 1378-1438 ℃, and the glass liquid flowing out of the bushing plate is stretched into filaments at a high speed by a wire drawing machine and is wound and molded to obtain the glass fiber for the high-frequency high-speed substrate.
The invention also provides application of the glass fiber composition for the high-frequency high-speed substrate in preparing a printed circuit board or a laminated board for high-speed communication. In particular, the glass fibers of the present invention are useful in glass fiber reinforced articles such as copper clad laminates, printed circuit boards, and the like. In addition, the glass fiber product of the present invention can be applied to woven fabrics, non-woven fabrics, unidirectional fabrics, chopped strands, chopped strand mats, composite materials, communication signal transmission media, and the like.
The invention has the beneficial effects that:
the present invention provides a glass composition for forming glass fibers and can be economically formed into glass fibers by continuous fiberization, is suitable for a high frequency high speed electronics ccl\pcb board reinforcing material, and preferably has a low dielectric constant and an extremely low dielectric loss tangent at 10G frequency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIGS. 1-4 are O1s XPS fit maps for examples 1, 2, 8, and 9, respectively, of the present invention.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular forms also include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples 1 to 10
The glass fiber composition for the high-frequency high-speed substrate comprises the following components in parts by mass: siO (SiO) 2 51.0％-57.0％，Al 2 O 3 3.0％-8.0％，B 2 O 3 25.0％-32.0％，RO 3.0％-7.0％，La 2 O 3 0.9％-1.5％，Y 2 O 3 0-1.5％，TiO 2 1.0％-2.0％，F 2 2.0% -3.0% and 0.5-1.0% of glass melt clarifying agent; wherein RO comprises 0.2 to 1.0 percent of CaO,0 to 0.8 percent of MgO,0.5 to 3.2 percent of SrO,0 to 1.5 percent of BaO and 0 to 3.2 percent of ZnO.
Table 1 below shows an example of a glass fiber composition of the present invention.
The glass composition of the invention is used for preparing glass fibers, which comprises (1) firstly, uniformly mixing batch materials, and adding the batch materials into a kiln for melting, clarifying and homogenizing; (2) And (3) at the drawing temperature of 1378-1438 ℃, the molten glass flows out of the Pt bushing, is drawn at a high speed by a drawing machine, and is wound and molded in a certain direction to obtain the glass fiber.
TABLE 1 composition (wt%) of glass fiber composition for high-frequency and high-speed substrates in each example
TABLE 2 microstructure characteristics and Properties of glass fibers for high frequency high speed substrates of examples
TABLE 3 composition (wt%) of glass fiber compositions of comparative examples
Table 4 microstructure characteristics and properties of glass fibers of each comparative example
As shown in Table 1, the glass composition of the present invention contains 52.0wt% to 54.5wt% of SiO 2 3.0wt% to 8.0wt% of Al 2 O 3 25.0wt% to 32.0wt% of B 2 O 3 . The glass further includes a plurality of divalent metal oxides (RO) in a total amount controlled to be 3.0wt% to 7.0wt%, wherein RO is selected from CaO, mgO, srO, baO and ZnO. Specifically, the composite material comprises 0.2-1.0 wt% of CaO, 0.0-0.8 wt% of MgO, 0.5-3.2 wt% of SrO, 0.0-1.5 wt% of BaO and 0.0-3.2 wt% of ZnO. The glass composition contains 0.9wt% to 1.5wt% of La 2 O 3 0.0wt% to 1.5wt% of Y 2 O 3 1.0 to 2.0wt% of TiO 2 2.0wt% to 3.0wt% of F 2 And 0.5wt% to 1.0wt% of a glass melt fining agent. Glass and glass fibers formed using these glass compositions have properties as shown in Table 2, and have a dielectric constant of 4.2 or less, a dielectric loss of 0.0013 or less, a drawing temperature of 1438 ℃ or less, and all glass and glass fiber samples are transparent and no phase separation occurs at a test frequency of 10 GHz. In the examples, the glasses satisfying the above composition and within the structural feature boundaries were obtained with a dielectric constant of 4.2 or less and a low dielectric loss tangent of 0.0013 or less at a test frequency of 10G. The preferred composition is at room temperature, frequencyThe dielectric constant of 10GHz is less than 4.0 and the dielectric loss tangent of 0.0010 or less.
The compositions of the comparative examples are shown in tables 3 and 4, respectively.
In comparative example 1, an Al is shown 2 O 3 Glass compositions having a non-bridging oxygen ratio of greater than 0.37, a dielectric constant of greater than 4.30, and a dielectric loss of greater than 0.0014, in amounts exceeding 8.0 wt.%.
In comparative example 2, an Al is shown 2 O 3 Glass compositions having a content of less than 3.5% by weight are susceptible to breakage during continuous drawing of glass.
In comparative example 3, a SiO is shown 2 A glass composition having a content of greater than 55.0wt% has a dielectric constant of 4.156 and a dielectric loss of 0.00124, and a significant phase separation behavior occurs after the glass has been melt cooled.
In comparative example 4, a SiO is shown 2 A glass composition having a non-bridging oxygen ratio of greater than 0.37, a dielectric constant of greater than 4.60, and a dielectric loss of greater than 0.002, in an amount of less than 52.0 wt%.
In comparative example 5, a B is shown 2 O 3 A glass composition having a non-bridging oxygen ratio of greater than 0.37, a dielectric constant of greater than 4.20, and a dielectric loss of greater than 0.0016, in an amount of less than 25.0 wt%.
In comparative example 6, a B is shown 2 O 3 A glass composition having a content of greater than 32.0wt% exhibits significant phase separation behavior upon cooling of the glass melt.
In comparative example 7, an F is shown 2 A glass composition having a non-bridging oxygen ratio of greater than 0.37, a dielectric constant of greater than 4.40, and a dielectric loss of greater than 0.0017, in an amount of less than 2.0 wt%.
In comparative example 8, an F is shown 2 A glass composition having a content of greater than 3.0wt% exhibits significant phase separation behavior upon cooling of the glass melt.
In comparative example 9, a Y is shown 2 O 3 A glass composition having a content of greater than 2.0wt% exhibits significant phase separation behavior after the glass has been melt cooled.
In comparative example 10, a La was shown 2 O 3 A glass composition having a content of greater than 2.0wt% exhibits significant phase separation behavior after the glass has been melt cooled.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A glass fiber composition for a high-frequency high-speed substrate is characterized by comprising the following components in parts by mass: siO (SiO) 2 51.0％-57.0％，Al 2 O 3 3.0％-8.0％，B 2 O 3 25.0％-32.0％，RO 3.0％-7.0％，La 2 O 3 0.9％-1.5％，Y 2 O 3 0-1.5％，TiO 2 1.0％-2.0％，F 2 2.0% -3.0% and 0.3% -1.0% of glass melt clarifying agent; wherein RO comprises 0.2 to 1.0 percent of CaO,0 to 0.8 percent of MgO,0.5 to 3.2 percent of SrO,0 to 1.5 percent of BaO,0 to 3.2 percent of ZnO, and the contents of BaO and ZnO are different from each other to be 0;
after the glass fiber composition for high-frequency high-speed substrates is melted into homogeneous glass, the amounts of non-bridging oxygen NBO and bridging oxygen BO contained in the structure satisfy the following relationship:
2. the glass fiber composition for high-frequency and high-speed substrates according to claim 1, comprising the following components in mass content: siO (SiO) 2 52.0％-54.5％，Al 2 O 3 5.0％-8.0％，B 2 O 3 26.5％-31.5％，RO 3.5％-5.5％，La 2 O 3 0.9％-1.5％，Y 2 O 3 0-1.5％，TiO 2 1.0％-2.0％，F 2 2.0% -3.0% and 0.5-1.0% of glass melt clarifying agent; wherein RO comprises 0.5% -1.0% of CaO, 0% -0.5% of MgO, 1.0% -3.0% of SrO, 0% -1.0% of BaO, 0% -3.0% of ZnO, and the contents of BaO and ZnO are different from each other to be 0.
3. The glass fiber composition for high-frequency and high-speed substrates according to claim 1, wherein the drawing temperature at 1000 poise is not more than 1438 ℃.
4. A glass fiber for a high-frequency and high-speed substrate, which is produced from the glass fiber composition for a high-frequency and high-speed substrate according to claim 1.
5. The glass fiber for high-frequency and high-speed substrates according to claim 4, wherein dielectric loss at 10G test frequency is <0.0013.
6. The glass fiber for high-frequency and high-speed substrates according to claim 4, wherein a dielectric constant at a test frequency of 10G is <4.2.
7. The method for producing a glass fiber for a high-frequency and high-speed substrate according to any one of claims 4 to 6, comprising the steps of: a glass fiber composition for high-frequency high-speed substrates is supplied into a glass melting furnace, and the glass fiber composition for high-frequency high-speed substrates is heated to a temperature exceeding the liquidus temperature to continuously fibrillate molten glass, thereby producing glass fibers for high-frequency high-speed substrates.
8. The method for producing a glass fiber for a high-frequency and high-speed substrate according to claim 7, comprising the steps of: the glass fiber composition for the high-frequency high-speed substrate is melted, clarified and homogenized in a kiln, then flows out of the Pt bushing plate at the temperature of 1378-1438 ℃, and the glass liquid flowing out of the bushing plate is stretched into filaments at a high speed by a wire drawing machine and is wound and molded to obtain the glass fiber for the high-frequency high-speed substrate.
9. Use of the glass fiber composition for high-frequency and high-speed substrates according to claims 1 to 3 for the production of printed circuit boards or laminates for communications.
10. Use of the glass fiber for high frequency and high speed substrates as claimed in claims 4-6 for the preparation of printed circuit boards or laminates for communications.
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