CN115321824A - Low-dielectric glass fiber capable of being formed at low temperature - Google Patents
Low-dielectric glass fiber capable of being formed at low temperature Download PDFInfo
- Publication number
- CN115321824A CN115321824A CN202211104757.6A CN202211104757A CN115321824A CN 115321824 A CN115321824 A CN 115321824A CN 202211104757 A CN202211104757 A CN 202211104757A CN 115321824 A CN115321824 A CN 115321824A
- Authority
- CN
- China
- Prior art keywords
- glass fiber
- glass
- low
- cooling
- silica sol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003365 glass fiber Substances 0.000 title claims abstract description 118
- 239000011521 glass Substances 0.000 claims abstract description 78
- 238000001816 cooling Methods 0.000 claims abstract description 48
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims abstract description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 17
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 17
- 239000000498 cooling water Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 31
- 239000006060 molten glass Substances 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000003595 mist Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 16
- 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 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 10
- 230000009471 action Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000000889 atomisation Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 239000005407 aluminoborosilicate glass Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012681 fiber drawing Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 210000001808 exosome Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
-
- 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
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/42—Coatings containing inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention belongs to the technical field of electronic glass fiber materials, and discloses a low-dielectric glass fiber capable of being formed at a low temperature. The preparation method of the low dielectric glass fiber comprises the following steps: according to SiO 2 55～65％，Al 2 O 3 10～20％，B 2 O 3 5～15％，La 2 O 3 0.1～5％，MgO+CaO 10～15％，Li 2 O+Na 2 O+K 2 Mixing the raw materials according to the proportion of 0-1% of O, stirring and melting at 1400-1550 ℃, clarifying and homogenizing, then drafting at 1250-1350 ℃, and sequentially cooling by using a silica sol atomized soaking solution and cooling water and rapidly cooling and solidifying to obtain the glass fiber with low dielectric constant. The invention solves the problems of melting temperature and filamentation of the glass fiber by adjusting the component composition of the glass fiber and adopting the silica sol atomized impregnating solution as cooling steam fog for coolingThe contradiction between the temperature and the dielectric property of the glass is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of electronic glass fiber materials, and particularly relates to a low-dielectric glass fiber capable of being formed at low temperature.
Background
Electronic glass fiber is a key basic source material in the industries of electronic information, aerospace and the like, almost appears in each electronic component and is spread in various fields of national economy and national defense and military industry. Electronic glass fiber cloth (electronic cloth for short) woven by electronic glass fiber is an indispensable basic material for Copper Clad Laminate (CCL) and Printed Circuit Board (PCB) industries, and the performance of the electronic glass fiber cloth determines important performances such as electrical performance, mechanical performance, dimensional stability and the like of the CCL and the PCB to a great extent.
The development of the fifth generation communication (5G) industry has been driven by the rapid development of communication devices, mobile terminals, and the need for large data technologies since the 21 st century. On a PCB (printed circuit board) of a 5G communication integrated circuit, if the existing electronic-grade glass fiber is used, the larger dielectric constant (about 6.7) of the glass fiber can seriously reduce the transmission rate of electromagnetic signals and cause large dielectric loss, so that the signals are partially converted into heat energy loss in the transmission process, the strength of the signals is reduced, the exchange speed and the transmission efficiency of PCB high-frequency electric signals are limited finally, and the requirements of the 5G industry cannot be met.
In fact, the transmission rate and stability of the electrical signal in the PCB are closely related to the dielectric properties of the latter, where the signal transmission rate (V) is p ) And relative dielectric constant (D) k ) The relationship of (a) is as follows:
the relationship between signal loss (L) and dielectric properties and frequency of the PCB is expressed as:
in the formula: k is constant, f is frequency, C is speed of light, D f Is the dielectric loss, i.e., the dielectric loss tangent.
In order to meet the development of 5G, higher requirements are put on the copper clad laminate for the printed circuit board, and a CCL (CCL) plate with a low dielectric constant and glass fiber with a low dielectric constant are urgently required to be searched. The lower its dielectric constant, the faster the signal transmission speed. Generally, the PCB is mainly composed of three parts of a resin substrate, a glass fiber reinforced material and a filler, and the main way for optimizing the dielectric property of the PCB is to reduce the D of the components of the PCB k And D f . Formerly high frequency PCB was mainly manufactured by reducing D of resin base material k And D f The dielectric property of the PCB is changed more and more limitedly by the mode along with the continuous enhancement of research and development technology, so that research and development personnel in China and abroad begin to carry out large treatment on the glass fiber reinforced material of the PCBResearch and development of low dielectric glass fiber reinforced materials for PCB with lower D k And D f 。
The glass fiber has the advantages of good insulation property, good heat resistance, good corrosion resistance, high mechanical strength and the like, and is widely used as a PCB (printed circuit board) reinforcing material (for example, the traditional FR-4 adopts E glass fiber to reinforce and modify epoxy resin). E glass fiber having a dielectric constant of 6.7 and a dielectric loss of about 10 -3 . In recent decades, with the rapid development of the electronic information industry, the E glass fiber has not been able to meet the requirements of the current stage. Among various glass materials, the dielectric constant of quartz glass is as low as 3.8, the dielectric constant is optimal, but the quartz glass cannot be industrially produced in large scale due to overhigh melting temperature and filament leakage operation temperature; the dielectric constant of the D glass fiber was 4.1, and the dielectric loss was 8X 10 -4 On the other hand, there are the following disadvantages: the drilling performance is poor, the subsequent processing is not facilitated, the manufacturability is poor, the production cost is high, the water resistance is poor, only a small amount of the drilling fluid is used in military industry, and the drilling fluid is difficult to be widely applied to the civil field.
Japan and the United states have been leading in the world in developing low dielectric glass fibers and new varieties. The Nittobo company of Japan develops a novel low-dielectric constant glass fiber by adjusting the proportion of oxides in the basic components of E glass: the dielectric constant of the NE glass fiber is remarkably reduced and is about 4.4 under the condition of 1 MHz. The acid resistance and the alkali resistance of the NE glass are equivalent to those of the E glass, and the water resistance of the NE glass is obviously enhanced compared with that of the D glass fiber. A glass fiber having a low dielectric constant and low dielectric loss, produced by AGY of U.S. and having a dielectric constant of less than 5,SiO 2 The content is lower than 60%, so that the defect of poor melting property of the D glass fiber is overcome to a certain extent while the excellent dielectric property is maintained. Technology blockade and product monopoly policy are adopted abroad to China to always limit the development of low dielectric glass fiber in China. The formula of the low dielectric glass fiber in China needs to be researched, and the industrial production technology of the low dielectric glass fiber needs to be broken through.
Patent CN 101269915A discloses a low dielectric glass fiber which can be formed at low temperature and whose composition comprises the following components by weight percentageRepresents: 50-60% SiO 2 7-15% of Al 2 O 3 25-30% of B 2 O 3 0-0.5% of Na 2 O,0-0.5% of K 2 O,0.5-2% of Li 2 O, caO 0-5%, mgO 0-5%, znO 0-5%, tiO 0.5-3% 2 (ii) a The content of CaO, mgO and ZnO is 0-8%; in addition, 0.01 to 0.33 times (mol) of B is added 2 O 3 La of 2 O 3 . This patent is based on the addition of TiO 2 Reducing high temperature viscosity, adding high content (25-30%) B 2 O 3 The lanthanum oxide is used for reducing the high-temperature viscosity of the glass and reducing the dielectric constant and dielectric loss, the volatilization amount of boron oxide in the melting process of batch materials can be reduced by adding a certain amount of lanthanum oxide, and meanwhile, the water resistance of the glass can be improved by adding the lanthanum oxide.
Patent CN 103482876A discloses a low dielectric constant glass fiber for printed circuit board, comprising the following components by mass percent: siO 2 2 48％～53％；Al 2 O 3 13％～16％；B 2 O 3 19％～25％；P 2 O 5 0.5％～2％；CaO 5.0％～8.5％；La 2 O 3 0.5％～8％；ZnO 0.5％～2.5％；TiO 2 0.5％～2％；Na 2 O、K 2 O and Li 2 O is less than 1 percent; SO (SO) 3 Less than 0.45%; fe 2 O 3 Less than 0.45 percent. This patent also teaches the use of high levels of B 2 O 3 The glass is used for reducing the high-temperature viscosity of the glass and reducing the dielectric constant and dielectric loss; adding P 2 O 5 Dielectric loss is reduced; adding TiO 2 And La 2 O 3 And reduction of SiO 2 The content is 48 to 53 percent to reduce the high-temperature viscosity.
Patent CN 102718406A discloses a low dielectric constant glass fiber with low drawing temperature, which comprises the following raw materials by weight percent: 48 to 55 weight percent of SiO 2 (ii) a 12 to 16 weight percent of Al 2 O 3 (ii) a 22 to 27 weight percent of B 2 O 3 (ii) a 3-7 wt% CaO;0.5wt% -6 wt% of La 2 O 3 (ii) a 0 to 2wt% of CaF 2 (ii) a 0 to 1wt% of Na 2 O、K 2 O and Li 2 O，Na 2 O、K 2 O and Li 2 Mixing O in any proportion; 0 to 0.45wt% of MgO;0 to 0.45wt% of SO 3 (ii) a 0 to 0.45wt% of TiO 2 (ii) a 0 to 0.45wt% of Fe 2 O 3 . This patent also teaches the use of high levels of B 2 O 3 The glass is used for reducing the high-temperature viscosity of the glass and reducing the dielectric constant and dielectric loss; and adding CaF 2 、TiO 2 And La 2 O 3 And reduction of SiO 2 The content is 48 to 55 percent to reduce the high-temperature viscosity.
As can be seen from the above prior art, the reduction of the high temperature viscosity and the reduction of the dielectric constant of glass is generally achieved by adding a high B content 2 O 3 To be implemented. But with a high content of B 2 O 3 There is a greater rate of boron volatilization with limited improvement. Therefore, there is a need to find other ways to reduce the dielectric constant and dielectric loss.
Disclosure of Invention
In view of the above disadvantages and shortcomings of the prior art, the present invention is primarily directed to a method for preparing low dielectric glass fibers that can be formed at low temperature. According to the method, lanthanum oxide is introduced into the aluminoborosilicate glass, and the basic components of the aluminoborosilicate glass are adjusted, so that the obtained glass fiber has the characteristics of low dielectric constant and low dielectric loss performance, and has low melting temperature and filament forming temperature and excellent processing performance. Further cooling by using the silica sol atomized impregnating solution as cooling steam fog, and generating SiO on the surface of the glass fiber 2 The surface coating or composite structure proves that the dielectric property of the glass fiber can be further obviously improved, and the melting process of the glass fiber and the mechanical property of the glass fiber matrix are not influenced.
Another object of the present invention is to provide a low dielectric glass fiber prepared by the above method.
The purpose of the invention is realized by the following technical scheme:
a preparation method of low-dielectric glass fiber capable of being formed at low temperature comprises the following preparation steps:
(1) In terms of weight percent, as SiO 2 55～65％，Al 2 O 3 10～20％，B 2 O 3 5～15％，La 2 O 3 0.1～5％，MgO+CaO 10～15％，Li 2 O+Na 2 O+K 2 Crushing, sieving and mixing the raw materials according to the proportion of 0-1% of O to obtain a mixture;
(2) Putting the mixture obtained in the step (1) into a glass kiln, stirring and melting at 1400-1550 ℃, and clarifying and homogenizing the obtained molten glass;
(3) And (3) enabling the clarified and homogenized glass liquid in the step (2) to flow through a glass fiber forming channel until a platinum bushing with the temperature of 1250-1350 ℃ is drafted, and then sequentially cooling by using a silica sol atomized soaking liquid and rapidly cooling and solidifying by using cooling water to obtain the low dielectric glass fiber.
More preferably, the atomized silica sol immersion liquid is cooling mist formed by atomizing an alkaline silica sol aqueous solution with the mass concentration of 0.5-5%.
More preferably, the cooling of the silica sol atomized impregnation liquid is to cool the drawn glass fiber to 850 to 600 ℃, and the rapid cooling of the cooling water is to cool the glass fiber cooled by the silica sol atomized impregnation liquid to normal temperature by the cooling water.
Further, siO in step (1) 2 57-63% of Al 2 O 3 Content of 14-16%, B 2 O 3 The content is 9-12 wt%; siO is preferred 2 58.05 to 61.05 percent of Al 2 O 3 Content 15.02%, B 2 O 3 The content is 10 percent; more preferably SiO 2 61.05% of Al 2 O 3 Content 15.02%, B 2 O 3 The content is 10%.
Further, the content of MgO + CaO in the step (1) is 11-14%; preferably, the MgO content is 10 to 13%, the CaO content is 0 to 3%, more preferably, the MgO content is 12.57%, and the CaO content is 0.17%.
Further, na in step (1) 2 The content of O is 0 to 0.3 percent; preferably Na 2 O content 0.17%, li 2 O and K 2 O containsThe amount is 0.
Further, la in step (1) 2 O 3 The content is 1-4%.
Further preferably, the raw materials in the step (1) are in the following proportion: siO 2 2 58.05～61.05％，Al 2 O 3 15.02％，B 2 O 3 10％，MgO 12.57％，CaO 0.17％，Na 2 O 0.17％。
Still more preferably, the raw materials in step (1) are in the following proportions: siO 2 2 61.05％，Al 2 O 3 15.02％，B 2 O 3 10％，MgO 12.57％，CaO 0.17％，Na 2 O 0.17％，La 2 O 3 1％。
A low-dielectric glass fiber which can be molded at low temperature is prepared by the method.
The main technical means in the invention is to introduce lanthanum oxide (La) into the glass component 2 O 3 )，La 2 O 3 The introduction of the glass fiber can obviously reduce the high-temperature viscosity of the glass fiber and is beneficial to the industrial production of the glass. Rare earth element La 2 O 3 The high-strength bridge has high field strength and small radius, can link a plurality of non-bridge oxygens to play a role in supplementing a network, and can weaken the strength of the bridge oxygen bond because the high field strength can shift the bridge oxygen bond near the high-strength bridge and the bridge oxygen bond of a group connected with the high-strength bridge. Based on the above analysis, it can be seen that: at high temperature, la 2 O 3 The chemical bond is easy to break, so that the batch can be easily melted to generate molten glass and the high-temperature viscosity of the molten glass is reduced; at low temperature, la 2 O 3 The network-repairing function of (A) plays a major role in compacting the network structure of the glass to inhibit the movement of alkali metals and alkaline earth metals, and La 2 O 3 The linkage of non-bridge oxygen can greatly reduce the polarization of non-bridge oxygen, so that the rare earth element La 2 O 3 The influence of the addition of (2) on the dielectric properties is smaller than that of oxides such as alkali metals and alkaline earth metals. Wherein La 2 O 3 If too much is introduced, the radius of the glass will be large, and the network structure of the glass will be destroyed, so La 2 O 3 It should be added in proper amount. The invention limits La 2 O 3 The content is less than 5wt%, preferablyIs selected as La 2 O 3 The content is less than 4 percent.
SiO 2 The glass exists as a glass network forming body, an irregular network structure formed by silica tetrahedrons is used as a structural framework of the glass, plays a key role in the network structure constitution and the performance of the glass, and is a component with the highest content in the glass. If SiO is added 2 The content of (2) can increase the quantity of the bridge oxygen in the glass structure, the glass link is tighter, the glass structure is more stable, the polarization is not easy to occur under the action of an external electric field, the losses such as conductance and relaxation are not easy to generate, and the reduction of dielectric constant and dielectric loss is facilitated. But when SiO 2 The content is too high, the high-temperature viscosity of the glass is relatively increased, so that the temperature required by glass melting and glass fiber drawing needs to be greatly increased, and the service life of the refractory material in the glass kiln can be shortened due to the increase of the melting temperature; meanwhile, the glass is difficult to remove bubbles and clarify, and for industrial production of glass fibers, on one hand, bubbles in the glass liquid can cause breakage of the glass fibers and reduce the production efficiency and quality of the fibers, and on the other hand, tiny bubbles in the glass liquid can cause the glass fibers to be hollow, so that the insulating property of the PCB made of the glass fibers is greatly reduced. Therefore, the SiO also meets the requirements of glass fiber production under the condition of ensuring the performance of the glass fiber 2 The content should not be too high. The invention determines SiO through experimental research 2 The content is 55 to 65wt%, and the preferable content is SiO 2 57 to 63 wt.%, more preferably SiO 2 58.05～61.05wt％。
B 2 O 3 Present in glass as a former of the glass network intermediate. When the glass contains enough free oxygen, B 3+ With [ BO ] 4 ]The form participates in the network structure, and plays a role of connecting the network. B when the glass component network has a low exosome content and does not provide sufficient free oxygen 3+ With [ BO ] 3 ]The triangular form exists and does not enter the glass network. Because the bond energy of B-O bond is higher than that of Si-O bond, the glass is not easy to polarize, and B is added in a proper amount 3+ The dielectric property of the glass is improved, and the high-temperature viscosity of the glass is reduced by adding boron, so that the industrial production is facilitated;however, too high boron content in the glass component leads to severe boron volatilization, which causes problems of unstable glass component, environmental pollution and the like. Definition of the invention B 2 O 3 The content is 5 to 15wt%, preferably 9 to 12wt%.
Al 2 O 3 The glass structure is also present in the form of an intermediate. Small amount of Al 3+ With [ AlO ] 4 ]The tetrahedron enters the glass network, so that the network structure can be enhanced, and a certain net supplement effect is achieved. Al (Al) 3+ Can combine with free oxygen to form [ AlO 5 ]And [ AlO ] 6 ]The polyhedron is added in a proper amount, so that the tendency of phase separation and crystallization of the glass can be reduced, the chemical stability of the glass can be improved, and the glass fiber molding is facilitated; however, the excessive introduction of the inorganic filler causes a problem that the viscosity of the glass increases and the dielectric constant and dielectric loss increase. The invention limits Al 2 O 3 The content is 10 to 20wt%, preferably 14 to 16wt%.
Alkaline earth metal oxides MgO, caO and alkali metal oxides Na 2 O as an outer body of the glass network does not participate in the composition of the glass network structure. The function of adding the oxygen-free glass is to provide free oxygen to destroy oxygen-bridge bonds, reduce the melting temperature and fiber forming temperature of the glass and be beneficial to the industrial production of the glass. However, the amount of the alkali metal oxide is also minimized because the dielectric constant and dielectric loss are increased, and the dielectric properties of the glass are seriously affected by the increased amount of the alkali metal oxide. The invention limits the MgO + CaO content to 10-15 wt%, li 2 O+Na 2 O+K 2 O content is 0-1 wt%, preferably CaO + MgO 11-14 wt%, caO 0-3 wt%, mgO 10-13 wt%, li 2 O+Na 2 O+K 2 O 0～0.3wt％。
The cooling effect of the silica sol atomized impregnating solution is mainly to generate SiO on the surface of the glass fiber 2 Surface coating or composite structures. If SiO is added to the glass fiber matrix as described above 2 The content of (b) is favorable for reduction of dielectric constant and dielectric loss. But when SiO 2 Too high a content can have a great impact on the processing and quality of the glass fibers. The invention adopts the silica sol atomization impregnating solution to cool and generate SiO in the cooling process of the drawn glass fiber 2 The surface coating or composite structure does not influence the glass melting and glass fiber drawing processes, and can achieve the purpose of further reducing the dielectric constant and the dielectric loss.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention introduces lanthanum oxide with lower content into the aluminoborosilicate glass and controls SiO 2 The content is in a higher range and B is adjusted 2 O 3 The content is in a lower range, the glass fiber with low dielectric constant and low dielectric loss performance can be obtained, meanwhile, the melting temperature and the filament forming temperature can be controlled within an easy processing range, and the preparation method has the advantages of low preparation cost and good dielectric property.
(2) In the preparation method of the glass fiber, siO can be generated on the surface of the glass fiber by cooling by using the silica sol atomized impregnating solution as cooling steam fog 2 The surface coating or composite structure proves that the dielectric property of the glass fiber can be obviously improved, and the melting process of the glass fiber and the mechanical property of the glass fiber matrix are not influenced.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) According to Table 1 (where Fe 2 O 3 Is an impurity component), the raw materials with the formula amount are crushed, sieved and mixed to obtain a mixture.
(2) And putting the obtained mixture into a glass kiln, stirring and melting at 1520 ℃, and clarifying and homogenizing the obtained molten glass.
(3) Enabling the clarified and homogenized glass liquid to flow through a glass fiber forming channel to a platinum bushing plate with the temperature of 1310-1350 ℃, enabling the molten glass liquid to flow out through a bushing nozzle and be drawn under the action of high-speed drawing force, cooling the drawn glass fiber to about 750 ℃ through silica sol atomized soaking liquid, wherein the silica sol atomized soaking liquid is cooling vapor fog formed by atomizing an alkaline silica sol water solution with the mass concentration of 4%, and then rapidly cooling and solidifying the glass fiber under the cooling of cooling water.
Treating the obtained glass fiber, and testing the dielectric constant and the dielectric loss by using a vector network analyzer under the condition of 10 Ghz; the glass viscosity was measured using a high temperature viscometer, and the measurement results are shown in Table 2.
Example 2
(1) The raw materials in the formula amount are crushed, sieved and mixed according to the table 1 to obtain a mixture.
(2) And putting the obtained mixture into a glass kiln, stirring and melting at the melting temperature of 1490 ℃, and clarifying and homogenizing the obtained molten glass.
(3) Enabling the clarified and homogenized glass liquid to flow through a glass fiber forming channel to a platinum bushing plate with the temperature of 1280-1320 ℃, enabling the molten glass liquid to flow out through a bushing nozzle and be drawn under the action of high-speed drawing force, cooling the drawn glass fiber to about 750 ℃ through silica sol atomized soaking liquid, enabling the silica sol atomized soaking liquid to be cooling vapor formed after atomization of alkaline silica sol water solution with the mass concentration of 4%, and then cooling and solidifying rapidly by cooling water to obtain the glass fiber.
Treating the obtained glass fiber, and testing the dielectric constant and the dielectric loss by using a vector network analyzer under the condition of 10 Ghz; the glass viscosity was measured using a high temperature viscometer, and the measurement results are shown in Table 2.
Example 3
(1) The raw materials in the formula amount are crushed, sieved and mixed according to the table 1 to obtain a mixture.
(2) And putting the obtained mixture into a glass kiln, stirring and melting at 1470 ℃, and clarifying and homogenizing the obtained molten glass.
(3) The method comprises the steps of enabling clarified and homogenized glass liquid to flow through a glass fiber forming channel to a platinum bushing plate with the temperature of 1270-1310 ℃, enabling molten glass liquid to flow out through a bushing nozzle and be drawn under the action of high-speed drawing force, cooling drawn glass fibers to 750 ℃ through silica sol atomization impregnating solution, enabling the silica sol atomization impregnating solution to be cooling vapor mist formed by atomization of alkaline silica sol water solution with the mass concentration of 4%, and then cooling and rapidly cooling and solidifying the glass fibers under the cooling action of cooling water to obtain the glass fibers.
Treating the obtained glass fiber, and testing the dielectric constant and the dielectric loss by using a vector network analyzer under the condition of 10 Ghz; the glass viscosity was measured using a high temperature viscometer, and the measurement results are shown in Table 2.
Example 4
(1) The raw materials in the formula amount are crushed, sieved and mixed according to the table 1 to obtain a mixture.
(2) And putting the obtained mixture into a glass kiln, stirring and melting at 1450 ℃, and clarifying and homogenizing the obtained molten glass.
(3) The clarified and homogenized glass liquid flows through a glass fiber forming channel to a platinum bushing plate with the temperature of 1250-1290 ℃, the molten glass liquid flows out through a bushing nozzle and is drawn under the action of high-speed drawing force, the drawn glass fiber is cooled to about 750 ℃ through silica sol atomized impregnation liquid, the silica sol atomized impregnation liquid is cooling vapor fog formed by atomizing an alkaline silica sol water solution with the mass concentration of 4%, and then the glass fiber is obtained by rapid cooling and solidification under the cooling of cooling water.
Treating the obtained glass fiber, and testing the dielectric constant and the dielectric loss by using a vector network analyzer under the condition of 10 Ghz; the glass viscosity was measured using a high temperature viscometer, and the measurement results are shown in Table 2.
Comparative example 1
Compared with the embodiment 4, the rapid cooling of the drawn glass fiber under cooling by adopting cooling air and cooling water replaces the cooling of the silica sol atomized soaking liquid and the rapid cooling of the cooling water, and the specific steps are as follows:
(1) The raw materials in the formula amount are crushed, sieved and mixed according to the table 1 to obtain a mixture.
(2) Putting the obtained mixture into a glass kiln, stirring and melting at 1450 ℃, and clarifying and homogenizing the obtained molten glass.
(3) The clarified and homogenized glass liquid flows through a glass fiber forming channel to a platinum bushing plate with the temperature of 1250-1290 ℃, the molten glass liquid flows out through a bushing nozzle and is drawn under the action of high-speed drawing force, the drawn glass fiber is cooled to about 750 ℃ by cooling air, and then is rapidly cooled and solidified by cooling water to obtain the glass fiber.
Comparative example 2
In comparison with example 1, in this comparative example, la was not added 2 O 3 ，SiO 2 The content is 62.05 percent, the other components and the preparation method are the same, and the specific formula components are shown in table 1.
TABLE 1 glass compositions of examples and comparative examples
TABLE 2 dielectric constant, dielectric loss, and temperature for 1000P viscosity and 100P viscosity for the glass fibers of examples and comparative examples
As can be seen from the results of examples 1 to 4 and comparative example 2, as La 2 O 3 Increase in addition amount and SiO 2 With a corresponding decrease in the content, the dielectric constant tends to increase while the melting temperature and the filament forming temperature tend to decrease. As can be seen from the results of example 4 and comparative example 1, the fused glass fiber filaments are cooled by using the silica sol atomized impregnating solution as the cooling vapor, and the dielectric properties of the glass fibers can be remarkably improved under the condition of not changing the fusing temperature.
Example 5
(1) The raw materials with the same formula amount as in example 4 are crushed, sieved and mixed to obtain a mixture.
(2) And putting the obtained mixture into a glass kiln, stirring and melting at 1450 ℃, and clarifying and homogenizing the obtained molten glass.
(3) The clarified and homogenized glass liquid flows through a glass fiber forming channel to a platinum bushing plate with the temperature of 1250-1290 ℃, the molten glass liquid flows out through a bushing nozzle and is drawn under the action of high-speed drawing force, the drawn glass fiber is cooled to about 750 ℃ through silica sol atomized soaking liquid, the silica sol atomized soaking liquid is cooling vapor fog formed by atomizing alkaline silica sol water solutions with the mass concentration of 0.5%, 1%, 2%, 3%, 4% and 5%, and then the glass fiber is obtained by rapid cooling and solidification under the cooling of cooling water.
In this example, the glass composition was the same as in example 4, and the viscosity at 1000P was 1268 ℃ which is the fiber forming temperature of the glass fiber, and the viscosity at 100P was 1443 ℃ which is the melting temperature of the glass fiber. The dielectric properties of the glass fibers obtained by cooling the atomized impregnating solution of silica sol with different concentrations are shown in the following table 3.
TABLE 3 dielectric properties of glass fibers obtained by cooling silica sol atomized impregnating solution with different concentrations
As can be seen from the results in Table 3, when the atomized impregnating solution of silica sol is used as cooling mist to cool the molten glass fiber, the dielectric constant and the dielectric loss both tend to decrease with the increase of the concentration of silica sol within a certain range.
From the above results, it can be seen that lanthanum oxide (La) having a large field strength and a small radius is introduced into the glass composition 2 O 3 ) The melting temperature and the filament forming temperature can be obviously reduced, and the fused glass fiber filaments are cooled by using the silica sol atomized impregnating solution as cooling vapor, so that the dielectric property of the glass fibers can be obviously improved. Through the combination of the two, the glass fiber with low dielectric constant and low dielectric loss performance can be obtained, and meanwhile, the melting temperature and the filamentation temperature can be controlled within the easy processing range to realize the melting and filamentationThe contradiction between the glass fiber melting temperature, the filament forming temperature and the glass dielectric property is solved, and the method is suitable for industrial production.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of low-dielectric glass fiber capable of being formed at low temperature is characterized by comprising the following preparation steps:
(1) In terms of weight percent, as SiO 2 55～65％，Al 2 O 3 10～20％，B 2 O 3 5～15％，La 2 O 3 0.1～5％，MgO+CaO 10～15％，Li 2 O+Na 2 O+K 2 Crushing, sieving and mixing the raw materials according to the proportion of 0-1% of O to obtain a mixture;
(2) Putting the mixture obtained in the step (1) into a glass kiln, stirring and melting at 1400-1550 ℃, and clarifying and homogenizing the obtained molten glass;
(3) And (3) enabling the clarified and homogenized glass liquid in the step (2) to flow through a glass fiber forming channel until a platinum bushing with the temperature of 1250-1350 ℃ is drafted, and then sequentially cooling by using a silica sol atomized soaking liquid and rapidly cooling and solidifying by using cooling water to obtain the low dielectric glass fiber.
2. The method for preparing low dielectric glass fiber capable of being formed at low temperature according to claim 1, wherein the atomized silica sol immersion liquid is cooling mist formed by atomizing 0.5-5% alkali silica sol water solution.
3. The method for preparing low dielectric glass fiber capable of being formed at low temperature according to claim 1 or 2, wherein the cooling of the silica sol atomized soaking solution is to cool the drawn glass fiber to 850-600 ℃, and the rapid cooling of the cooling water is to cool the glass fiber cooled by the silica sol atomized soaking solution to normal temperature by the cooling water.
4. The method of claim 1, wherein in step (1), siO is used as the material of the low dielectric glass fiber 2 57 to 63 percent of Al 2 O 3 Content of 14-16%, B 2 O 3 9-12 wt% of La 2 O 3 1-4% of MgO + CaO, 11-14% of Na 2 The content of O is 0 to 0.3 percent.
5. The method of claim 4, wherein SiO is used to form low-k glass fibers 2 58.05 to 61.05 percent of Al 2 O 3 Content 15.02%, B 2 O 3 10 percent of MgO, 10 to 13 percent of MgO and 0 to 3 percent of CaO.
6. The method of claim 5, wherein SiO is used to form low-k glass fibers 2 58.05 to 61.05 percent of Al 2 O 3 Content 15.02%, B 2 O 3 10% of MgO, 12.57% of CaO, 0.17% of CaO, na 2 The O content was 0.17%.
7. The low dielectric glass fiber capable of being formed at low temperature according to claim 6, wherein the raw material components are as follows: siO 2 2 61.05％，Al 2 O 3 15.02％，B 2 O 3 10％，MgO 12.57％，CaO 0.17％，Na 2 O 0.17％，La 2 O 3 1％。
8. A low dielectric glass fiber which can be formed at low temperature, characterized by being obtained by the method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211104757.6A CN115321824B (en) | 2022-09-09 | 2022-09-09 | Low-dielectric glass fiber capable of being molded at low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211104757.6A CN115321824B (en) | 2022-09-09 | 2022-09-09 | Low-dielectric glass fiber capable of being molded at low temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115321824A true CN115321824A (en) | 2022-11-11 |
| CN115321824B CN115321824B (en) | 2023-11-17 |
Family
ID=83929172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211104757.6A Active CN115321824B (en) | 2022-09-09 | 2022-09-09 | Low-dielectric glass fiber capable of being molded at low temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115321824B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115959834A (en) * | 2023-01-31 | 2023-04-14 | 华润水泥技术研发有限公司 | High-strength alkali-resistant basalt fiber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298531A (en) * | 2017-07-07 | 2017-10-27 | 重庆理工大学 | Glass fiber with low dielectric constant and preparation method thereof |
| CN107620208A (en) * | 2017-09-27 | 2018-01-23 | 中国人民解放军国防科技大学 | Nitride fiber impregnating compound and coating method thereof |
| CN108409150A (en) * | 2018-03-28 | 2018-08-17 | 济南大学 | A kind of doping Pr2O3Dielectric glass fibre and preparation method thereof |
| CN110451811A (en) * | 2019-09-03 | 2019-11-15 | 济南大学 | A kind of doping Yb2O3The low dielectric glass of free-floride and preparation method thereof |
| CN111635128A (en) * | 2020-07-08 | 2020-09-08 | 韦杰 | Preparation method of high-strength cold-resistant modified glass wool fiber material |
-
2022
- 2022-09-09 CN CN202211104757.6A patent/CN115321824B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298531A (en) * | 2017-07-07 | 2017-10-27 | 重庆理工大学 | Glass fiber with low dielectric constant and preparation method thereof |
| CN107620208A (en) * | 2017-09-27 | 2018-01-23 | 中国人民解放军国防科技大学 | Nitride fiber impregnating compound and coating method thereof |
| CN108409150A (en) * | 2018-03-28 | 2018-08-17 | 济南大学 | A kind of doping Pr2O3Dielectric glass fibre and preparation method thereof |
| CN110451811A (en) * | 2019-09-03 | 2019-11-15 | 济南大学 | A kind of doping Yb2O3The low dielectric glass of free-floride and preparation method thereof |
| CN111635128A (en) * | 2020-07-08 | 2020-09-08 | 韦杰 | Preparation method of high-strength cold-resistant modified glass wool fiber material |
Non-Patent Citations (1)
| Title |
|---|
| 朱晓燕: "低介电玻璃纤维组合物技术简介", 《科技视界》, vol. 17, pages 94 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115959834A (en) * | 2023-01-31 | 2023-04-14 | 华润水泥技术研发有限公司 | High-strength alkali-resistant basalt fiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115321824B (en) | 2023-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5789329A (en) | Boron-free glass fibers | |
| US6136735A (en) | Glass fibres for reinforcing organic and/or inorganic materials | |
| CN101012105B (en) | Glass fiber with low permittivity | |
| CN102276153B (en) | Composition for high-property heat-resisting corrosion-resisting glass fiber | |
| CN112047626B (en) | Low bubble number, low dielectric constant glass composition and glass fiber made therefrom | |
| JP2004525066A (en) | Low dielectric constant strengthening glass yarn | |
| CA3017536C (en) | High performance glass fiber composition, and glass fiber and composite material thereof | |
| JPS62226839A (en) | Glass fiber having low dielectric constant | |
| TW201012771A (en) | Glass fiber composition and printed circuit board made from the glass fiber composition | |
| CN110395912B (en) | Low-dielectric-constant electronic-grade glass fiber and preparation method thereof | |
| CN101696089A (en) | Glass fiber with low dielectric constant for high frequency high-density circuit board | |
| CN115321824B (en) | Low-dielectric glass fiber capable of being molded at low temperature | |
| CN107531552B (en) | High-performance glass fiber composition, and glass fiber and composite material thereof | |
| JP4695066B2 (en) | Glass strand capable of reinforcing organic and / or inorganic materials, method for producing said strand and composition used | |
| CN110451811A (en) | A kind of doping Yb2O3The low dielectric glass of free-floride and preparation method thereof | |
| CN111943515A (en) | Low-dielectric-constant glass fiber and preparation method thereof | |
| CN102863152B (en) | Glass fiber for printed circuit board | |
| CN113754295B (en) | Low-dielectric modified glass fiber and preparation method and application thereof | |
| JP2024520955A (en) | Glass fiber composition with low dielectric loss | |
| CN107056075A (en) | Glass fiber compound and glass fibre | |
| CN115806391B (en) | Glass fiber with low expansion coefficient and preparation method thereof | |
| CN115304282A (en) | Low-dielectric-constant glass fiber containing lanthanum oxide | |
| CN108409150B (en) | Pr-doped optical fiber2O3Low dielectric glass fiber and its preparation method | |
| CN109956673A (en) | Continuous glass fibre and preparation method thereof | |
| CN112250311B (en) | Low-dielectric glass fiber composition, low-dielectric glass fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |