WO2022088452A1 - Acid-resistant glass fiber composition, and acid-resistant glass fiber and preparation method therefor - Google Patents

Acid-resistant glass fiber composition, and acid-resistant glass fiber and preparation method therefor Download PDF

Info

Publication number
WO2022088452A1
WO2022088452A1 PCT/CN2020/138556 CN2020138556W WO2022088452A1 WO 2022088452 A1 WO2022088452 A1 WO 2022088452A1 CN 2020138556 W CN2020138556 W CN 2020138556W WO 2022088452 A1 WO2022088452 A1 WO 2022088452A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass fiber
acid
content
present
resistant glass
Prior art date
Application number
PCT/CN2020/138556
Other languages
French (fr)
Chinese (zh)
Inventor
宋朋泽
李刚
Original Assignee
浙江鸿盛新材料科技集团股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 浙江鸿盛新材料科技集团股份有限公司 filed Critical 浙江鸿盛新材料科技集团股份有限公司
Publication of WO2022088452A1 publication Critical patent/WO2022088452A1/en

Links

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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium

Definitions

  • the invention relates to the technical field of special glass fibers, in particular to an acid-resistant glass fiber composition, an acid-resistant glass fiber and a preparation method thereof.
  • Glass fiber is an inorganic fiber material with excellent properties such as temperature resistance and corrosion resistance, high strength and low elongation, and a lower price.
  • the production cost of glass fiber has been significantly reduced. Therefore, the scope and amount of glass fiber are continuously expanded, and are widely used in aerospace, automobile, construction, electronics, electrical, chemical industry. , metallurgy, environmental protection, national defense and other industries; glass fiber reinforced organic polymer materials can be used to produce composite materials with excellent performance; glass fibers can also be used to strengthen inorganic materials (such as cement), and are used in road, bridge construction and other fields.
  • Alkali-free glass fiber belongs to alumino-borosilicate glass fiber. It has good tensile strength and electrical insulation properties, but because the glass composition contains a certain amount of boron and fluorine, the structural skeleton is loose and incomplete, and its acid corrosion resistance is relatively high. Poor, the composite material prepared from it is easily eroded by acid in an acidic environment and peeled off from the resin matrix, rapidly losing strength.
  • Medium-alkali glass fiber belongs to the composition of sodium calcium silicate and has good chemical stability. However, due to its high alkali content, it cannot be used as an electrical insulating material, and its physical properties such as tensile strength are relatively poor.
  • the technical problem to be solved by the present invention is to provide an acid-resistant glass fiber composition, an acid-resistant glass fiber and a preparation method thereof, and the glass fiber prepared by the glass fiber composition has good physical properties and chemical properties, Especially with high acid resistance.
  • the invention provides an acid-resistant glass fiber composition, comprising:
  • Preferred include:
  • Preferred include:
  • Preferred include:
  • Preferred include:
  • the present invention also provides an acid-resistant glass fiber prepared from the above-mentioned acid-resistant glass fiber composition.
  • the acid-resistant glass fiber has a diameter of 3-17 ⁇ m.
  • the present invention also provides a preparation method of acid-resistant glass fiber, comprising;
  • the raw materials are melted to obtain glass liquid
  • the glass liquid is drawn to obtain acid-resistant glass fibers.
  • the melting temperature ranges from 1300°C to 1550°C; the drawing temperature ranges from 1150°C to 1250°C.
  • the invention provides an acid-resistant glass fiber composition, comprising: SiO 2 55.2-64.5 wt %; Al 2 O 3 4.5-8.5 wt %; Na 2 O 9.8-17.5 wt %; CaO 10.8-15.8 wt % ; B 2 O 3 1.1-3.2 wt %; ZrO 0.3-1.5 wt %; K 2 O 1.5-5.5 wt %; MgO 0.15-0.7 wt %; Fe 2 O 3 0.18-0.68 wt %.
  • the present invention optimizes the internal structure of the glass fiber by precisely regulating the content range of the four main components, SiO 2 , Al 2 O 3 , Na 2 O and CaO, and ensures that the glass fiber has good mechanical properties, good resistance to Corrosion properties and forming properties overcome the difficulty of obtaining high-performance glass fibers with low production difficulty; at the same time, by properly introducing appropriate K 2 O, MgO, ZrO, B 2 O 3 , Fe 2 O 3 components, further improvement
  • the glass fiber forming operation reduces the difficulty of forming operation, improves the mechanical properties and corrosion resistance of the glass fiber, especially the acid resistance; and the glass fiber component obtained by the present invention does not contain boron, fluorine and harmful clarifying agent, and prolongs the refractory of the kiln.
  • the service life of the material realizes energy saving, environmental protection and emission reduction, and also ensures that the glass fiber is easy to realize industrial production.
  • the invention provides an acid-resistant glass fiber composition, comprising:
  • the acid-resistant glass fiber composition provided by the invention enables the glass fiber to have the characteristics of acid resistance and low cost of the medium-alkali glass fiber on the basis of maintaining the high physical properties of the alkali-free glass fiber, and at the same time, it is easy to realize the large-scale industrialization of the kiln method. Production.
  • the glass fiber composition provided by the present invention is mainly composed of SiO 2 , Al 2 O 3 , Na 2 O and CaO, wherein the content of SiO 2 is preferably 57.3-64.5 wt %, more preferably 59.5-61.5 wt %, and even more preferably
  • the SiO 2 content is preferably 55.2 wt %; in some embodiments provided by the present invention, the SiO 2 content is preferably 64.5 wt %;
  • the SiO 2 content is preferably 60.5 wt %; in some embodiments provided by the present invention, the SiO 2 content is preferably 61.5 wt %; in some embodiments provided by the present invention , the SiO 2 content is preferably 57.3 wt %; in other embodiments provided by the present invention, the SiO 2 content is preferably 61 wt %.
  • the content of the Al 2 O 3 is preferably 5.5-8.5 wt %, more preferably 6.0-7.3 wt %, more preferably 6.0-7.1 wt %, still more preferably 6.0-6.8 wt %, most preferably 6.0-6.5 wt % %; in some embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 8.5 wt %; in some embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 5.5 wt %; In some embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 6.5 wt %; in some embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 6 wt %; in the present invention In some provided embodiments, the content of the Al 2 O 3 is preferably 6.8 wt %; in other embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 7.1 wt %.
  • the content of the Na 2 O is preferably 9.8-16.05 wt %, more preferably 9.8-13 wt %, and still more preferably 9.8-12 wt %; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 9.8-16.05 wt % 12.8wt%; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 13wt%; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 12wt%; In some embodiments provided by the present invention, the content of the Na 2 O is preferably 9.8 wt %; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 12.5 wt %; In the embodiment, the content of the Na 2 O is preferably 16.05 wt %; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 13 wt %.
  • the CaO content is preferably 10.8-15.5wt%, more preferably 11.3-15.5wt%, most preferably 13-15wt%; in some embodiments provided by the present invention, the CaO content is preferably 14.8wt% ; in some embodiments provided by the present invention, the content of the CaO is preferably 11.3wt%; in some embodiments provided by the present invention, the content of the CaO is preferably 13wt%; in some embodiments provided by the present invention , the CaO content is preferably 15wt%; in some embodiments provided by the present invention, the CaO content is preferably 13.5wt%; in some embodiments provided by the present invention, the CaO content is preferably 14 wt %; in other embodiments provided by the present invention, the content of the CaO is preferably 14.5 wt %.
  • the components of K 2 O, MgO, ZrO, B 2 O 3 and Fe 2 O 3 also added to the glass fiber composition provided by the present invention further improve the forming operation of the glass fiber.
  • the K 2 O content is preferably 1.5-3.5 wt %; in some embodiments provided by the present invention, the K 2 O content is preferably 5.5 wt %; in some embodiments provided by the present invention, the K 2 O content is preferably 5.5 wt %
  • the content of K 2 O is preferably 3 wt %; in some embodiments provided by the present invention, the content of K 2 O is preferably 3.5 wt %; in some embodiments provided by the present invention, the content of K 2 O Preferably, it is 3.5wt%; in some embodiments provided by the present invention, the content of K 2 O is preferably 2.55wt%; in some embodiments provided by the present invention, the content of K 2 O is preferably 3.1wt% %; in other embodiments provided by the present invention, the content of the K 2 O is preferably 1.5 wt %.
  • the content of the B 2 O 3 is preferably 1.3-3.2 wt %, more preferably 1.5-3.2 wt %, more preferably 1.6-3.2 wt %, most preferably 1.6-2.8 wt %; in some implementations provided by the present invention
  • the content of the B 2 O 3 is preferably 1.5 wt %; in some embodiments provided by the present invention, the content of the B 2 O 3 is preferably 1.3 wt %; in some embodiments provided by the present invention , the content of the B 2 O 3 is preferably 2.3 wt %; in some embodiments provided by the present invention, the content of the B 2 O 3 is preferably 2.8 wt %; in some embodiments provided by the present invention, the The content of the B 2 O 3 is preferably 3.2 wt %; in some embodiments provided by the present invention, the content of the B 2 O 3 is preferably 1.6 wt %; in other embodiments provided by the present invention, the The content of B 2 O 3
  • the content of the ZrO is preferably 0.3-1.25wt%, more preferably 0.35-1.25wt%, and more preferably 0.4-1.25wt%; in some embodiments provided by the present invention, the ZrO content is preferably 0.32wt% %; in some embodiments provided by the present invention, the content of the ZrO is preferably 0.5wt%; in some embodiments provided by the present invention, the content of the ZrO is preferably 1.25wt%; In the embodiments, the content of the ZrO is preferably 0.45wt%; in some embodiments provided by the present invention, the content of the ZrO is preferably 0.35wt%; in some embodiments provided by the present invention, the ZrO content The content is preferably 0.4 wt %; in other embodiments provided by the present invention, the content of the ZrO is preferably 0.42 wt %.
  • the content of the MgO is preferably 0.15-0.6wt%, more preferably 0.15-0.5wt%, more preferably 0.38-0.5wt%, most preferably 0.4-0.5wt%; in some embodiments provided by the present invention,
  • the content of the MgO is preferably 0.7wt%; in some embodiments provided by the present invention, the content of the MgO is preferably 0.52wt%; in some embodiments provided by the present invention, the content of the MgO is preferably 0.4 wt%; in some embodiments provided by the present invention, the content of the MgO is preferably 0.5wt%; in some embodiments provided by the present invention, the content of the MgO is preferably 0.38wt%; In some embodiments, the content of the MgO is preferably 0.15 wt %; in other embodiments provided by the present invention, the content of the MgO is preferably 0.45 wt %.
  • the content of the Fe 2 O 3 is preferably 0.22-0.68wt%, more preferably 0.22-0.55wt%, more preferably 0.3-0.55wt%, most preferably 0.43-0.55wt%; in some implementations provided in the present invention
  • the content of Fe 2 O 3 is preferably 0.68wt%; in some embodiments provided by the present invention, the content of Fe 2 O 3 is preferably 0.38wt%; in some embodiments provided by the present invention , the content of Fe 2 O 3 is preferably 0.55wt%; in some embodiments provided by the present invention, the content of Fe 2 O 3 is preferably 0.45wt%; in some embodiments provided by the present invention, the The Fe 2 O 3 content is preferably 0.22 wt %; in some embodiments provided by the present invention, the Fe 2 O 3 content is preferably 0.3 wt %; in other embodiments provided by the present invention, the Fe 2 O 3 content is preferably 0.3 wt %
  • the content of Fe 2 O 3 is preferably
  • the present invention also includes other unavoidable impurities.
  • the invention optimizes the internal structure of the glass fiber by precisely regulating the content range of the four main components of SiO 2 , Al 2 O 3 , Na 2 O and CaO, ensures that the glass fiber has good mechanical properties, corrosion resistance and forming properties, and overcomes the It solves the problem of obtaining high-performance glass fibers with lower production difficulty; at the same time, by properly introducing appropriate K 2 O, MgO, ZrO, B 2 O 3 , Fe 2 O 3 components, the forming operation of glass fibers is further improved, reducing the The molding operation is difficult, and the mechanical properties and corrosion resistance of the glass fiber are improved; and the glass fiber obtained by the present invention does not contain boron, fluorine and harmful clarifying agents, prolongs the service life of the furnace refractory material, and realizes energy saving, environmental protection and emission reduction.
  • the glass fiber is easy to achieve industrial production (the forming temperature does not exceed 1230 ° C, the upper limit temperature of crystallization is lower than 1130 ° C, and the temperature range of wire drawing forming operation is greater than 70 ° C).
  • the present invention also provides a glass fiber prepared from the above-mentioned glass fiber composition; the diameter of the glass fiber is preferably 3-17 ⁇ m.
  • the present invention also provides a method for preparing glass fiber, which includes: preparing raw materials according to the above-mentioned glass fiber composition; fusing the raw materials to obtain glass liquid; drawing the glass liquid to obtain glass fibers.
  • the raw materials are prepared according to the above-mentioned glass fiber composition; in the present invention, the above-mentioned glass fiber composition is preferably derived from pyrophyllite, quartz sand, calcite, potassium feldspar, sodium oxide, calcium oxide, zircon, monetite and soda ash. raw material.
  • the raw material is melted to obtain molten glass; in the present invention, the melting is preferably carried out in a kiln; the raw material is preferably transported into the kiln by a conveying device; the conveying device is preferably a pneumatic conveying device; the melting Preferably, pure oxygen combustion, all-electric melting or pure oxygen combustion electric boosting is used for the preparation; the temperature of the melting is preferably 1300°C to 1550°C, more preferably 1400°C to 1550°C, and more preferably 1450°C to 1550°C.
  • the glass liquid is drawn to obtain glass fibers;
  • the drawing is preferably through a drawing bushing and a wire drawing machine;
  • the drawing bushing is preferably a platinum-rhodium alloy drawing bushing;
  • the drawing temperature is the drawing bushing
  • the temperature of the plate is preferably 1150°C to 1250°C, and more preferably 1180°C to 1230°C.
  • raw materials are used to melt glass liquid, and pure oxygen combustion, all-electric melting or pure oxygen combustion and electric-assisted melting can be used for furnace melting to form a homogeneous glass solution, which greatly reduces the melting cost;
  • Furnace and kiln passages can be composed of refractory materials with high temperature resistance and glass erosion resistance, such as dense zirconium bricks, fused mullite bricks, sintered zirconium corundum bricks, fused chromium zirconium corundum bricks, fused quartz bricks, Fused zircon bricks, etc.
  • the technologies not described in the embodiments refer to the prior art.
  • an acid-resistant glass fiber composition, acid-resistant glass fiber and a preparation method thereof provided by the present invention are described in detail below with reference to the examples.
  • a kind of acid-resistant glass fiber composition, its main component and its weight content are:
  • SiO 2 55.2%, Al 2 O 3 : 8.5%, Na 2 O: 12.8%, CaO: 14.8%, K 2 O: 5.5%, B 2 O 3 : 1.5%, ZrO: 0.32%, MgO: 0.70% , Fe 2 O 3 : 0.68%.
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through testing and calculation.
  • Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch.
  • the batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted in a kiln with pure oxygen combustion at 1510° C. to obtain a clear and homogenized glass liquid.
  • the melted glass liquid flows to the drawing channel and drawing forming system to directly draw glass fibers.
  • the drawing bushing temperature is 1210°C to draw continuous glass fibers.
  • the diameter of the glass fibers is 17 ⁇ m ⁇ 0.5 ⁇ m.
  • a kind of glass fiber composition, its main component and its weight content are:
  • SiO 2 64.5%, Al 2 O 3 : 5.5%, Na 2 O: 13.0%, CaO: 11.3%, K 2 O: 3.0%, B 2 O 3 : 1.3%, ZrO: 0.50%, MgO: 0.52% , Fe 2 O 3 : 0.38%.
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through testing and calculation.
  • Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch.
  • the batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted at 1450°C in a kiln with pure oxygen combustion and electric melting to obtain a clarified and homogenized glass liquid.
  • the molten glass flows to the drawing channel and drawing forming system to directly draw glass fibers, and the drawing bushing temperature is 1230°C to draw continuous glass fibers.
  • the diameter of the glass fibers is 11 ⁇ m ⁇ 0.5 ⁇ m.
  • a kind of glass fiber composition, its main component and its weight content are:
  • SiO 2 60.5%, Al 2 O 3 : 6.5%, Na 2 O: 12.0%, CaO: 13.0%, K 2 O: 3.5%, B 2 O 3 : 2.3%, ZrO: 1.25%, MgO: 0.4% , Fe 2 O 3 : 0.55%.
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through testing and calculation.
  • Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch.
  • the batch material is transported to the kiln front warehouse by a pneumatic conveying system, fed by an automatic feeder, and melted in a kiln with pure oxygen combustion at 1550° C. to obtain a clarified and homogenized glass liquid.
  • the melted glass liquid flows to the drawing channel and the drawing forming system to directly draw glass fibers, and the drawing bushing temperature is 1180° C. to draw continuous glass fibers.
  • the diameter of the glass fibers is 3 ⁇ m ⁇ 0.5 ⁇ m.
  • a kind of glass fiber composition, its main component and its weight content are:
  • SiO 2 61.5%, Al 2 O 3 : 6.0%, Na 2 O: 9.8%, CaO: 15.0%, K 2 O: 3.5%, B 2 O 3 : 2.8%, ZrO: 0.45%, MgO: 0.50% , Fe 2 O 3 : 0.45%.
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through testing and calculation.
  • Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch.
  • the batch material is transported to the kiln front warehouse by a pneumatic conveying system, fed by an automatic feeder, and melted in a kiln with pure oxygen combustion at 1500° C. to obtain a clarified and homogenized glass liquid.
  • the molten glass flows to the drawing channel and drawing forming system to directly draw glass fibers, and the drawing bushing temperature is 1200°C to draw continuous glass fibers.
  • the diameter of the glass fibers is 5 ⁇ m ⁇ 0.5 ⁇ m.
  • a kind of glass fiber composition, its main component and its weight content are:
  • SiO 2 60.5%, Al 2 O 3 : 6.8%, Na 2 O: 12.5%, CaO: 13.5%, K 2 O: 2.55%, B 2 O 3 : 3.2%, ZrO: 0.35%, MgO: 0.38% , Fe 2 O 3 : 0.22%.
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through testing and calculation.
  • Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch.
  • the batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted at 1480°C in an all-electric melting furnace to obtain a clarified and homogenized glass liquid.
  • Continuous HS fibers with a diameter of 13 ⁇ m ⁇ 0.5 ⁇ m were drawn through a wire drawing channel at a bushing temperature of 1175°C.
  • a kind of glass fiber composition, its main component and its weight content are:
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through testing and calculation.
  • Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch.
  • the batches are transported to the front silo of the kiln by a pneumatic conveying system, fed by an automatic feeder, and melted at 1510°C by an all-electric melting furnace to obtain a clear and homogenized glass liquid.
  • Continuous HS fibers with a diameter of 9 ⁇ m ⁇ 0.5 ⁇ m were drawn through a wire drawing channel at a bushing temperature of 1190°C.
  • a kind of glass fiber composition, its main component and its weight content are:
  • SiO 2 61.0%, Al 2 O 3 : 6.5%, Na 2 O: 13.0%, CaO: 14.5%, K 2 O: 1.5%, B 2 O 3 : 2.2%, ZrO: 0.42%, MgO: 0.45% , Fe 2 O 3 : 0.43%.
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through testing and calculation.
  • Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch.
  • the batches are transported to the kiln front warehouse through a pneumatic conveying system, fed by an automatic feeder, and melted at 1500°C in an all-electric melting furnace to obtain a clear and homogenized glass liquid.
  • Continuous HS fibers with a diameter of 6 ⁇ m ⁇ 0.5 ⁇ m were drawn through a wire drawing channel at a bushing temperature of 1205°C.
  • a kind of HS fiber composition, its main component and its weight content are:
  • SiO 2 68.0%, Al 2 O 3 : 4.5%, Na 2 O: 12.8%, CaO: 11.2%, K 2 O: 1.5%, B 2 O 3 : 1.2%, ZrO: 0.32%, MgO: 0.25% , Fe 2 O 3 : 0.23%.
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through detection and calculation, and then accurately measured by the weighing system, and uniformly mixed through the mixing system to form batches.
  • the batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted at 1500°C using an all-electric melting furnace to obtain a clear and homogenized glass liquid.
  • the glass liquid is made into glass balls by a ball making machine, and then the glass balls are melted at 1350 ° C in a platinum-substituting furnace, and drawn at a temperature of 1180 ° C with a wire drawing bushing to make continuous HS fibers.
  • the diameter of the HS fibers is 6 ⁇ m ⁇ 0.5 ⁇ m.
  • SiO 2 58.2%, Al 2 O 3 : 8.5%, Na 2 O: 9.0%, CaO: 16.6%, K 2 O: 4.5%, B 2 O 3 : 1.5%, ZrO: 0.32%, MgO: 0.70% , Fe 2 O 3 : 0.68%.
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through detection and calculation, and then accurately measured by the weighing system, and uniformly mixed through the mixing system to make batches.
  • the batch material is transported to the kiln front warehouse through a pneumatic conveying system, fed by an automatic feeder, and melted at 1510° C. using a pure oxygen combustion kiln to obtain a clarified and homogenized glass liquid.
  • the melted glass liquid flows to the drawing channel and the drawing forming system is directly drawn into HS fibers, and the drawing bushing temperature is 1210 °C to make continuous HS fibers.
  • the diameter of the HS fibers is 6 ⁇ m ⁇ 0.5 ⁇ m.
  • a kind of HS fiber composition, its main component and its weight content are:
  • SiO 2 61.5%, Al 2 O 3 : 10.5%, Na 2 O: 13.0%, CaO: 8.8%, K 2 O: 3.0%, B 2 O 3 : 1.8%, ZrO: 0.50%, MgO: 0.52% , Fe 2 O 3 : 0.38%.
  • the preparation method of glass fiber is as follows:
  • the proportioning requirements of various raw materials are obtained through detection and calculation, and then accurately measured by the weighing system, and uniformly mixed through the mixing system to form batches.
  • the batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted at 1450°C in a kiln with pure oxygen combustion and electric melting to obtain a clear and homogenized glass liquid.
  • the molten glass flows to the drawing channel and the drawing forming system is directly drawn into HS fibers, and the drawing bushing temperature is 1230°C to make continuous HS fibers.
  • the diameter of the HS fibers is 9 ⁇ m ⁇ 0.5 ⁇ m.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (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)
  • Manufacturing & Machinery (AREA)
  • Glass Compositions (AREA)

Abstract

An acid-resistant glass fiber composition. By accurately regulating the content ranges of four main components, i.e., SiO2, Al2O3, Na2O, and CaO, the internal structure of a glass fiber is optimized, it is ensured that the glass fiber has good mechanical property, corrosion resistance, and forming property, and the problem of being difficult in obtaining a high-performance glass fiber under the condition of low production difficulty is solved. Moreover, by properly introducing an appropriate amount of components, i.e., K2O, MgO, ZrO, B2O3, and Fe2O3, the forming operation of the glass fiber is further improved, the forming operation difficulty is reduced, and the mechanical property and corrosion resistance, particularly the acid resistance, of the glass fiber are improved.

Description

一种耐酸性玻璃纤维组合物、耐酸性玻璃纤维及其制备方法Acid-resistant glass fiber composition, acid-resistant glass fiber and preparation method thereof
本申请要求于2020年10月26日提交中国专利局、申请号为202011156449.9、发明名称为“一种耐酸性玻璃纤维组合物、耐酸性玻璃纤维及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on October 26, 2020 with the application number 202011156449.9 and the invention titled "An acid-resistant glass fiber composition, acid-resistant glass fiber and its preparation method", The entire contents of which are incorporated herein by reference.
技术领域technical field
本发明涉及于特种玻璃纤维技术领域，尤其涉及一种耐酸性玻璃纤维组合物、耐酸性玻璃纤维及其制备方法。The invention relates to the technical field of special glass fibers, in particular to an acid-resistant glass fiber composition, an acid-resistant glass fiber and a preparation method thereof.
背景技术Background technique
玻璃纤维属于无机纤维材料，具有耐温耐腐、高强低伸等优异的性能和较低的价格。大规模池窑法生产玻璃纤维的技术取得突破后，显著降低了玻璃纤维的生产成本，因此玻璃纤维的使用范围和使用量不断扩大，广泛应用在航空航天、汽车、建筑、电子、电气、化工、冶金、环境保护、国防等行业；采用玻璃纤维增强有机高分子材料可制得性能优良的复合材料；玻璃纤维也可用于增强无机材料(例如水泥)，在道路、桥梁建设等领域获得应用。Glass fiber is an inorganic fiber material with excellent properties such as temperature resistance and corrosion resistance, high strength and low elongation, and a lower price. After a breakthrough in the technology of glass fiber production by large-scale pool kiln method, the production cost of glass fiber has been significantly reduced. Therefore, the scope and amount of glass fiber are continuously expanded, and are widely used in aerospace, automobile, construction, electronics, electrical, chemical industry. , metallurgy, environmental protection, national defense and other industries; glass fiber reinforced organic polymer materials can be used to produce composite materials with excellent performance; glass fibers can also be used to strengthen inorganic materials (such as cement), and are used in road, bridge construction and other fields.
目前应用较为广泛的是无碱玻纤和中碱玻纤。无碱玻纤属于铝硼硅酸盐玻纤，它的拉伸强度、电绝缘性能很好，但因其玻璃成分中含有一定量的硼、氟，结构骨架松散，不够完整，耐酸侵蚀性能较差，由其制备的复合材料在酸性环境下容易被酸侵蚀而与树脂基体剥离，迅速失去强度。中碱玻纤属于钠钙硅酸盐成分，化学稳定性较好，但因其含碱量高，不能作电绝缘材料，同时拉伸强度等物性指标相对较差。At present, the most widely used are alkali-free glass fiber and medium-alkali glass fiber. Alkali-free glass fiber belongs to alumino-borosilicate glass fiber. It has good tensile strength and electrical insulation properties, but because the glass composition contains a certain amount of boron and fluorine, the structural skeleton is loose and incomplete, and its acid corrosion resistance is relatively high. Poor, the composite material prepared from it is easily eroded by acid in an acidic environment and peeled off from the resin matrix, rapidly losing strength. Medium-alkali glass fiber belongs to the composition of sodium calcium silicate and has good chemical stability. However, due to its high alkali content, it cannot be used as an electrical insulating material, and its physical properties such as tensile strength are relatively poor.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明要解决的技术问题在于提供一种耐酸性玻璃纤维组合物、耐酸性玻璃纤维及其制备方法，该玻璃纤维组合物制备的玻璃纤维具有较好的物理性能与化学性能，尤其是具有较高的耐酸性能。In view of this, the technical problem to be solved by the present invention is to provide an acid-resistant glass fiber composition, an acid-resistant glass fiber and a preparation method thereof, and the glass fiber prepared by the glass fiber composition has good physical properties and chemical properties, Especially with high acid resistance.
本发明提供了一种耐酸性玻璃纤维组合物，包括：The invention provides an acid-resistant glass fiber composition, comprising:
Figure PCTCN2020138556-appb-000001
Figure PCTCN2020138556-appb-000001
Figure PCTCN2020138556-appb-000002
Figure PCTCN2020138556-appb-000002
优选的，包括：Preferred include:
Figure PCTCN2020138556-appb-000003
Figure PCTCN2020138556-appb-000003
优选的，包括：Preferred include:
Figure PCTCN2020138556-appb-000004
Figure PCTCN2020138556-appb-000004
优选的，包括：Preferred include:
Figure PCTCN2020138556-appb-000005
Figure PCTCN2020138556-appb-000005
Figure PCTCN2020138556-appb-000006
Figure PCTCN2020138556-appb-000006
优选的，包括：Preferred include:
Figure PCTCN2020138556-appb-000007
Figure PCTCN2020138556-appb-000007
本发明还提供了一种耐酸性玻璃纤维，由上述的耐酸性玻璃纤维组合物制备得到。The present invention also provides an acid-resistant glass fiber prepared from the above-mentioned acid-resistant glass fiber composition.
优选的，所述耐酸性玻璃纤维的直径为3～17μm。Preferably, the acid-resistant glass fiber has a diameter of 3-17 μm.
本发明还提供了一种耐酸性玻璃纤维的制备方法，包括；The present invention also provides a preparation method of acid-resistant glass fiber, comprising;
按照上述的耐酸性玻璃纤维组合物配制原料；Prepare raw materials according to the above-mentioned acid-resistant glass fiber composition;
将原料熔制得到玻璃液；The raw materials are melted to obtain glass liquid;
将所述玻璃液拉制，得到耐酸性玻璃纤维。The glass liquid is drawn to obtain acid-resistant glass fibers.
优选的，所述熔制的温度为1300℃～1550℃；所述拉制温度为1150℃～1250℃。Preferably, the melting temperature ranges from 1300°C to 1550°C; the drawing temperature ranges from 1150°C to 1250°C.
本发明提供了一种耐酸性玻璃纤维组合物，包括：SiO 255.2～64.5wt％；Al 2O 34.5～8.5wt％；Na 2O9.8～17.5wt％；CaO10.8～15.8wt％；B 2O 31.1～3.2wt％；ZrO0.3～1.5wt％；K 2O1.5～5.5wt％；MgO0.15～0.7wt％；Fe 2O 30.18～0.68wt％。 与现有技术相比，本发明通过精确调控SiO 2、Al 2O 3、Na 2O、CaO四种主组分的含量范围，优化玻璃纤维内部结构，保证玻璃纤维具有良好的力学性能、耐腐蚀性能和成型性能，克服了在较低生产难度下获得高性能玻璃纤维的难题；同时通过适当引入适量的K 2O、MgO、ZrO、B 2O 3、Fe 2O 3组分，进一步改善玻璃纤维的成型作业，降低成型作业难度，提高玻璃纤维的机械性能和耐腐蚀性能，尤其是耐酸性；并且本发明得到的玻璃纤维成分中不含硼、氟及有害澄清剂，延长窑炉耐火材料使用寿命，实现了节能、环保、减排，还保证了玻璃纤维易于实现工业化生产。 The invention provides an acid-resistant glass fiber composition, comprising: SiO 2 55.2-64.5 wt %; Al 2 O 3 4.5-8.5 wt %; Na 2 O 9.8-17.5 wt %; CaO 10.8-15.8 wt % ; B 2 O 3 1.1-3.2 wt %; ZrO 0.3-1.5 wt %; K 2 O 1.5-5.5 wt %; MgO 0.15-0.7 wt %; Fe 2 O 3 0.18-0.68 wt %. Compared with the prior art, the present invention optimizes the internal structure of the glass fiber by precisely regulating the content range of the four main components, SiO 2 , Al 2 O 3 , Na 2 O and CaO, and ensures that the glass fiber has good mechanical properties, good resistance to Corrosion properties and forming properties overcome the difficulty of obtaining high-performance glass fibers with low production difficulty; at the same time, by properly introducing appropriate K 2 O, MgO, ZrO, B 2 O 3 , Fe 2 O 3 components, further improvement The glass fiber forming operation reduces the difficulty of forming operation, improves the mechanical properties and corrosion resistance of the glass fiber, especially the acid resistance; and the glass fiber component obtained by the present invention does not contain boron, fluorine and harmful clarifying agent, and prolongs the refractory of the kiln. The service life of the material realizes energy saving, environmental protection and emission reduction, and also ensures that the glass fiber is easy to realize industrial production.
具体实施方式Detailed ways
为了进一步了解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。In order to further understand the present invention, the preferred embodiments of the present invention are described below with reference to examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.
本发明提供了一种耐酸性玻璃纤维组合物，包括：The invention provides an acid-resistant glass fiber composition, comprising:
Figure PCTCN2020138556-appb-000008
Figure PCTCN2020138556-appb-000008
本发明提供的耐酸性玻璃纤维组合物使玻璃纤维能够在保持无碱玻璃纤维高物理性能的基础上，具有中碱玻璃纤维的耐酸性、成本低等特点，同时易于实现池窑法大规模工业化生产。The acid-resistant glass fiber composition provided by the invention enables the glass fiber to have the characteristics of acid resistance and low cost of the medium-alkali glass fiber on the basis of maintaining the high physical properties of the alkali-free glass fiber, and at the same time, it is easy to realize the large-scale industrialization of the kiln method. Production.
本发明提供的玻璃纤维组合物以SiO 2、Al 2O 3、Na 2O与CaO为主成分，其中SiO 2的含量优选为57.3～64.5wt％，更优选为59.5～61.5wt％，再优选为60.5～61.5wt％；在本发明提供的一些实施例中，所述SiO 2含量优选为55.2wt％；在本发明提供的一些实施例中，所述SiO 2含量优选为64.5wt％；在本 发明提供的一些实施例中，所述SiO 2含量优选为60.5wt％；在本发明提供的一些实施例中，所述SiO 2含量优选为61.5wt％；在本发明提供的一些实施例中，所述SiO 2含量优选为57.3wt％；在本发明提供的另一些实施例中，所述SiO 2含量优选为61wt％。 The glass fiber composition provided by the present invention is mainly composed of SiO 2 , Al 2 O 3 , Na 2 O and CaO, wherein the content of SiO 2 is preferably 57.3-64.5 wt %, more preferably 59.5-61.5 wt %, and even more preferably In some embodiments provided by the present invention, the SiO 2 content is preferably 55.2 wt %; in some embodiments provided by the present invention, the SiO 2 content is preferably 64.5 wt %; In some embodiments provided by the present invention, the SiO 2 content is preferably 60.5 wt %; in some embodiments provided by the present invention, the SiO 2 content is preferably 61.5 wt %; in some embodiments provided by the present invention , the SiO 2 content is preferably 57.3 wt %; in other embodiments provided by the present invention, the SiO 2 content is preferably 61 wt %.
所述Al 2O 3的含量优选为5.5～8.5wt％，更优选为6.0～7.3wt％，再优选为6.0～7.1wt％，再优选为6.0～6.8wt％，最优选为6.0～6.5wt％；在本发明提供的一些实施例中，所述Al 2O 3的含量优选为8.5wt％；在本发明提供的一些实施例中，所述Al 2O 3的含量优选为5.5wt％；在本发明提供的一些实施例中，所述Al 2O 3的含量优选为6.5wt％；在本发明提供的一些实施例中，所述Al 2O 3的含量优选为6wt％；在本发明提供的一些实施例中，所述Al 2O 3的含量优选为6.8wt％；在本发明提供的另一些实施例中，所述Al 2O 3的含量优选为7.1wt％。 The content of the Al 2 O 3 is preferably 5.5-8.5 wt %, more preferably 6.0-7.3 wt %, more preferably 6.0-7.1 wt %, still more preferably 6.0-6.8 wt %, most preferably 6.0-6.5 wt % %; in some embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 8.5 wt %; in some embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 5.5 wt %; In some embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 6.5 wt %; in some embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 6 wt %; in the present invention In some provided embodiments, the content of the Al 2 O 3 is preferably 6.8 wt %; in other embodiments provided by the present invention, the content of the Al 2 O 3 is preferably 7.1 wt %.
所述Na 2O的含量优选为9.8～16.05wt％，更优选为9.8～13wt％，再优选为9.8～12wt％；在本发明提供的一些实施例中，所述Na 2O的含量优选为12.8wt％；在本发明提供的一些实施例中，所述Na 2O的含量优选为13wt％；在本发明提供的一些实施例中，所述Na 2O的含量优选为12wt％；在本发明提供的一些实施例中，所述Na 2O的含量优选为9.8wt％；在本发明提供的一些实施例中，所述Na 2O的含量优选为12.5wt％；在本发明提供的一些实施例中，所述Na 2O的含量优选为16.05wt％；在本发明提供的一些实施例中，所述Na 2O的含量优选为13wt％。 The content of the Na 2 O is preferably 9.8-16.05 wt %, more preferably 9.8-13 wt %, and still more preferably 9.8-12 wt %; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 9.8-16.05 wt % 12.8wt%; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 13wt%; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 12wt%; In some embodiments provided by the present invention, the content of the Na 2 O is preferably 9.8 wt %; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 12.5 wt %; In the embodiment, the content of the Na 2 O is preferably 16.05 wt %; in some embodiments provided by the present invention, the content of the Na 2 O is preferably 13 wt %.
所述CaO的含量优选为10.8～15.5wt％，更优选为11.3～15.5wt％，最优选为13～15wt％；在本发明提供的一些实施例中，所述CaO的含量优选为14.8wt％；在本发明提供的一些实施例中，所述CaO的含量优选为11.3wt％；在本发明提供的一些实施例中，所述CaO的含量优选为13wt％；在本发明提供的一些实施例中，所述CaO的含量优选为15wt％；在本发明提供的一些实施例中，所述CaO的含量优选为13.5wt％；在本发明提供的一些实施例中，所述CaO的含量优选为14wt％；在本发明提供的另一些实施例中，所述CaO的含量优选为14.5wt％。The CaO content is preferably 10.8-15.5wt%, more preferably 11.3-15.5wt%, most preferably 13-15wt%; in some embodiments provided by the present invention, the CaO content is preferably 14.8wt% ; in some embodiments provided by the present invention, the content of the CaO is preferably 11.3wt%; in some embodiments provided by the present invention, the content of the CaO is preferably 13wt%; in some embodiments provided by the present invention , the CaO content is preferably 15wt%; in some embodiments provided by the present invention, the CaO content is preferably 13.5wt%; in some embodiments provided by the present invention, the CaO content is preferably 14 wt %; in other embodiments provided by the present invention, the content of the CaO is preferably 14.5 wt %.
本发明提供的玻璃纤维组合物中还添加的K 2O、MgO、ZrO、B 2O 3、Fe 2O 3 组分进一步改善玻璃纤维的成型作业。 The components of K 2 O, MgO, ZrO, B 2 O 3 and Fe 2 O 3 also added to the glass fiber composition provided by the present invention further improve the forming operation of the glass fiber.
所述K 2O的含量优选为1.5～3.5wt％；在本发明提供的一些实施例中，所述K 2O的含量优选为5.5wt％；在本发明提供的一些实施例中，所述K 2O的含量优选为3wt％；在本发明提供的一些实施例中，所述K 2O的含量优选为3.5wt％；在本发明提供的一些实施例中，所述K 2O的含量优选为3.5wt％；在本发明提供的一些实施例中，所述K 2O的含量优选为2.55wt％；在本发明提供的一些实施例中，所述K 2O的含量优选为3.1wt％；在本发明提供的另一些实施例中，所述K 2O的含量优选为1.5wt％。 The K 2 O content is preferably 1.5-3.5 wt %; in some embodiments provided by the present invention, the K 2 O content is preferably 5.5 wt %; in some embodiments provided by the present invention, the K 2 O content is preferably 5.5 wt % The content of K 2 O is preferably 3 wt %; in some embodiments provided by the present invention, the content of K 2 O is preferably 3.5 wt %; in some embodiments provided by the present invention, the content of K 2 O Preferably, it is 3.5wt%; in some embodiments provided by the present invention, the content of K 2 O is preferably 2.55wt%; in some embodiments provided by the present invention, the content of K 2 O is preferably 3.1wt% %; in other embodiments provided by the present invention, the content of the K 2 O is preferably 1.5 wt %.
所述B 2O 3的含量优选为1.3～3.2wt％，更优选为1.5～3.2wt％，再优选为1.6～3.2wt％，最优选为1.6～2.8wt％；在本发明提供的一些实施例中，所述B 2O 3的含量优选为1.5wt％；在本发明提供的一些实施例中，所述B 2O 3的含量优选为1.3wt％；在本发明提供的一些实施例中，所述B 2O 3的含量优选为2.3wt％；在本发明提供的一些实施例中，所述B 2O 3的含量优选为2.8wt％；在本发明提供的一些实施例中，所述B 2O 3的含量优选为3.2wt％；在本发明提供的一些实施例中，所述B 2O 3的含量优选为1.6wt％；在本发明提供的另一些实施例中，所述B 2O 3的含量优选为2.2wt％。 The content of the B 2 O 3 is preferably 1.3-3.2 wt %, more preferably 1.5-3.2 wt %, more preferably 1.6-3.2 wt %, most preferably 1.6-2.8 wt %; in some implementations provided by the present invention In an example, the content of the B 2 O 3 is preferably 1.5 wt %; in some embodiments provided by the present invention, the content of the B 2 O 3 is preferably 1.3 wt %; in some embodiments provided by the present invention , the content of the B 2 O 3 is preferably 2.3 wt %; in some embodiments provided by the present invention, the content of the B 2 O 3 is preferably 2.8 wt %; in some embodiments provided by the present invention, the The content of the B 2 O 3 is preferably 3.2 wt %; in some embodiments provided by the present invention, the content of the B 2 O 3 is preferably 1.6 wt %; in other embodiments provided by the present invention, the The content of B 2 O 3 is preferably 2.2 wt %.
所述ZrO的含量优选为0.3～1.25wt％，更优选为0.35～1.25wt％，再优选为0.4～1.25wt％；在本发明提供的一些实施例中，所述ZrO的含量优选为0.32wt％；在本发明提供的一些实施例中，所述ZrO的含量优选为0.5wt％；在本发明提供的一些实施例中，所述ZrO的含量优选为1.25wt％；在本发明提供的一些实施例中，所述ZrO的含量优选为0.45wt％；在本发明提供的一些实施例中，所述ZrO的含量优选为0.35wt％；在本发明提供的一些实施例中，所述ZrO的含量优选为0.4wt％；在本发明提供的另一些实施例中，所述ZrO的含量优选为0.42wt％。The content of the ZrO is preferably 0.3-1.25wt%, more preferably 0.35-1.25wt%, and more preferably 0.4-1.25wt%; in some embodiments provided by the present invention, the ZrO content is preferably 0.32wt% %; in some embodiments provided by the present invention, the content of the ZrO is preferably 0.5wt%; in some embodiments provided by the present invention, the content of the ZrO is preferably 1.25wt%; In the embodiments, the content of the ZrO is preferably 0.45wt%; in some embodiments provided by the present invention, the content of the ZrO is preferably 0.35wt%; in some embodiments provided by the present invention, the ZrO content The content is preferably 0.4 wt %; in other embodiments provided by the present invention, the content of the ZrO is preferably 0.42 wt %.
所述MgO的含量优选为0.15～0.6wt％，更优选为0.15～0.5wt％，再优选为0.38～0.5wt％，最优选为0.4～0.5wt％；在本发明提供的一些实施例中，所述MgO的含量优选为0.7wt％；在本发明提供的一些实施例中，所述MgO的含量优选为0.52wt％；在本发明提供的一些实施例中，所述MgO的含量优选为0.4wt％；在本发明提供的一些实施例中，所述MgO的含量优选为0.5wt％； 在本发明提供的一些实施例中，所述MgO的含量优选为0.38wt％；在本发明提供的一些实施例中，所述MgO的含量优选为0.15wt％；在本发明提供的另一些实施例中，所述MgO的含量优选为0.45wt％。The content of the MgO is preferably 0.15-0.6wt%, more preferably 0.15-0.5wt%, more preferably 0.38-0.5wt%, most preferably 0.4-0.5wt%; in some embodiments provided by the present invention, The content of the MgO is preferably 0.7wt%; in some embodiments provided by the present invention, the content of the MgO is preferably 0.52wt%; in some embodiments provided by the present invention, the content of the MgO is preferably 0.4 wt%; in some embodiments provided by the present invention, the content of the MgO is preferably 0.5wt%; in some embodiments provided by the present invention, the content of the MgO is preferably 0.38wt%; In some embodiments, the content of the MgO is preferably 0.15 wt %; in other embodiments provided by the present invention, the content of the MgO is preferably 0.45 wt %.
所述Fe 2O 3的含量优选为0.22～0.68wt％，更优选为0.22～0.55wt％，再优选为0.3～0.55wt％，最优选为0.43～0.55wt％；在本发明提供的一些实施例中，所述Fe 2O 3的含量优选为0.68wt％；在本发明提供的一些实施例中，所述Fe 2O 3的含量优选为0.38wt％；在本发明提供的一些实施例中，所述Fe 2O 3的含量优选为0.55wt％；在本发明提供的一些实施例中，所述Fe 2O 3的含量优选为0.45wt％；在本发明提供的一些实施例中，所述Fe 2O 3的含量优选为0.22wt％；在本发明提供的一些实施例中，所述Fe 2O 3的含量优选为0.3wt％；在本发明提供的另一些实施例中，所述Fe 2O 3的含量优选为0.43wt％。 The content of the Fe 2 O 3 is preferably 0.22-0.68wt%, more preferably 0.22-0.55wt%, more preferably 0.3-0.55wt%, most preferably 0.43-0.55wt%; in some implementations provided in the present invention In example, the content of Fe 2 O 3 is preferably 0.68wt%; in some embodiments provided by the present invention, the content of Fe 2 O 3 is preferably 0.38wt%; in some embodiments provided by the present invention , the content of Fe 2 O 3 is preferably 0.55wt%; in some embodiments provided by the present invention, the content of Fe 2 O 3 is preferably 0.45wt%; in some embodiments provided by the present invention, the The Fe 2 O 3 content is preferably 0.22 wt %; in some embodiments provided by the present invention, the Fe 2 O 3 content is preferably 0.3 wt %; in other embodiments provided by the present invention, the Fe 2 O 3 content is preferably 0.3 wt % The content of Fe 2 O 3 is preferably 0.43 wt %.
本发明还包括其他不可避免的杂质。The present invention also includes other unavoidable impurities.
本发明通过精确调控SiO 2、Al 2O 3、Na 2O、CaO四种主组分的含量范围，优化玻璃纤维内部结构，保证玻璃纤维具有良好的力学性能、耐腐蚀性能和成型性能，克服了在较低生产难度下获得高性能玻璃纤维的难题；同时通过适当引入适量的K 2O、MgO、ZrO、B 2O 3、Fe 2O 3组分，进一步改善玻璃纤维的成型作业，降低成型作业难度，提高玻璃纤维的机械性能和耐腐蚀性能；并且本发明得到的玻璃纤维成分中不含硼、氟及有害澄清剂，延长窑炉耐火材料使用寿命，实现了节能、环保、减排，还保证了玻璃纤维易于实现工业化生产(其成型温度不超过1230℃，析晶上限温度低于1130℃，拉丝成型作业温度区间大于70℃)。 The invention optimizes the internal structure of the glass fiber by precisely regulating the content range of the four main components of SiO 2 , Al 2 O 3 , Na 2 O and CaO, ensures that the glass fiber has good mechanical properties, corrosion resistance and forming properties, and overcomes the It solves the problem of obtaining high-performance glass fibers with lower production difficulty; at the same time, by properly introducing appropriate K 2 O, MgO, ZrO, B 2 O 3 , Fe 2 O 3 components, the forming operation of glass fibers is further improved, reducing the The molding operation is difficult, and the mechanical properties and corrosion resistance of the glass fiber are improved; and the glass fiber obtained by the present invention does not contain boron, fluorine and harmful clarifying agents, prolongs the service life of the furnace refractory material, and realizes energy saving, environmental protection and emission reduction. , it also ensures that the glass fiber is easy to achieve industrial production (the forming temperature does not exceed 1230 ° C, the upper limit temperature of crystallization is lower than 1130 ° C, and the temperature range of wire drawing forming operation is greater than 70 ° C).
本发明还提供了一种由上述玻璃纤维组合物制备的玻璃纤维；所述玻璃纤维的直径优选为3～17μm。The present invention also provides a glass fiber prepared from the above-mentioned glass fiber composition; the diameter of the glass fiber is preferably 3-17 μm.
本发明还提供了一种玻璃纤维的制备方法，包括：按照上述的玻璃纤维组合物配制原料；将原料熔制得到玻璃液；将所述玻璃液拉制，得到玻璃纤维。The present invention also provides a method for preparing glass fiber, which includes: preparing raw materials according to the above-mentioned glass fiber composition; fusing the raw materials to obtain glass liquid; drawing the glass liquid to obtain glass fibers.
其中，本发明对所有原料的来源并没有特殊的限制，为市售即可。Wherein, in the present invention, there is no special restriction on the sources of all raw materials, and they can be commercially available.
按照上述的玻璃纤维组合物配制原料；在本发明中上述玻璃纤维组合物优选来源于叶腊石、石英砂、方解石、钾长石、氧化钠、氧化钙、锆英石、硼钙石与纯碱，配制原料。The raw materials are prepared according to the above-mentioned glass fiber composition; in the present invention, the above-mentioned glass fiber composition is preferably derived from pyrophyllite, quartz sand, calcite, potassium feldspar, sodium oxide, calcium oxide, zircon, monetite and soda ash. raw material.
将原料熔制得到玻璃液；在本发明中，所述熔制优选在窑炉内进行；所述原料优选通过输送设备输送至窑炉内；所述输送设备优选为气力输送设备；所述熔制优选采用纯氧燃烧、全电熔或纯氧燃烧电助熔；所述熔制的温度优选为1300℃～1550℃，更优选为1400℃～1550℃，再优选为1450℃～1550℃。The raw material is melted to obtain molten glass; in the present invention, the melting is preferably carried out in a kiln; the raw material is preferably transported into the kiln by a conveying device; the conveying device is preferably a pneumatic conveying device; the melting Preferably, pure oxygen combustion, all-electric melting or pure oxygen combustion electric boosting is used for the preparation; the temperature of the melting is preferably 1300°C to 1550°C, more preferably 1400°C to 1550°C, and more preferably 1450°C to 1550°C.
将所述玻璃液拉制，得到玻璃纤维；所述拉制优选为通过拉丝漏板与拉丝机；所述拉丝漏板优选为铂铑合金拉丝漏板；所述拉制的温度，即拉丝漏板的温度优选为1150℃～1250℃，更优选为1180℃～1230℃。The glass liquid is drawn to obtain glass fibers; the drawing is preferably through a drawing bushing and a wire drawing machine; the drawing bushing is preferably a platinum-rhodium alloy drawing bushing; the drawing temperature is the drawing bushing The temperature of the plate is preferably 1150°C to 1250°C, and more preferably 1180°C to 1230°C.
在本发明中原料熔制玻璃液，可采用纯氧燃烧、全电熔或纯氧燃烧电助融的方式进行窑炉熔制，形成均质玻璃溶液，大幅度降低了熔制成本；窑炉、窑炉通路，可采用具有耐高温、耐玻璃液侵蚀的耐火材料组成，如致密锆砖，电熔莫来石砖、烧结锆刚玉砖、电熔铬锆刚玉砖、电熔石英砖、电熔锆英石砖等。实施例未说明的技术均参照现有技术。In the present invention, raw materials are used to melt glass liquid, and pure oxygen combustion, all-electric melting or pure oxygen combustion and electric-assisted melting can be used for furnace melting to form a homogeneous glass solution, which greatly reduces the melting cost; Furnace and kiln passages can be composed of refractory materials with high temperature resistance and glass erosion resistance, such as dense zirconium bricks, fused mullite bricks, sintered zirconium corundum bricks, fused chromium zirconium corundum bricks, fused quartz bricks, Fused zircon bricks, etc. The technologies not described in the embodiments refer to the prior art.
为了进一步说明本发明，以下结合实施例对本发明提供的一种耐酸性玻璃纤维组合物、耐酸性玻璃纤维及其制备方法进行详细描述。In order to further illustrate the present invention, an acid-resistant glass fiber composition, acid-resistant glass fiber and a preparation method thereof provided by the present invention are described in detail below with reference to the examples.
以下实施例中所用的试剂均为市售。The reagents used in the following examples are all commercially available.
实施例1Example 1
一种耐酸性玻璃纤维组合物，其主要组分及其重量含量为：A kind of acid-resistant glass fiber composition, its main component and its weight content are:
SiO 2：55.2％、Al 2O 3：8.5％、Na 2O：12.8％、CaO：14.8％、K 2O：5.5％、B 2O 3：1.5％、ZrO：0.32％、MgO：0.70％、Fe 2O 3：0.68％。 SiO 2 : 55.2%, Al 2 O 3 : 8.5%, Na 2 O: 12.8%, CaO: 14.8%, K 2 O: 5.5%, B 2 O 3 : 1.5%, ZrO: 0.32%, MgO: 0.70% , Fe 2 O 3 : 0.68%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，以叶腊石、石英砂、方解石、钾长石、氧化钠、氧化钙、锆英石、硼钙石、纯碱为原料，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1510℃采用纯氧燃烧的窑炉熔制得到澄清、均化的玻璃液。熔制好的玻璃液流动至拉丝通道和拉丝成型系统直接拉制成玻璃纤维，拉丝漏板温度为1210℃的下拉制成连续玻璃纤维，所述玻璃纤维的直径为17μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through testing and calculation. , Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch. The batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted in a kiln with pure oxygen combustion at 1510° C. to obtain a clear and homogenized glass liquid. The melted glass liquid flows to the drawing channel and drawing forming system to directly draw glass fibers. The drawing bushing temperature is 1210°C to draw continuous glass fibers. The diameter of the glass fibers is 17 μm±0.5 μm.
实施例2Example 2
一种玻璃纤维组合物，其主要组分及其重量含量为：A kind of glass fiber composition, its main component and its weight content are:
SiO 2：64.5％、Al 2O 3：5.5％、Na 2O：13.0％、CaO：11.3％、K 2O：3.0％、B 2O 3：1.3％、ZrO：0.50％、MgO：0.52％、Fe 2O 3：0.38％。 SiO 2 : 64.5%, Al 2 O 3 : 5.5%, Na 2 O: 13.0%, CaO: 11.3%, K 2 O: 3.0%, B 2 O 3 : 1.3%, ZrO: 0.50%, MgO: 0.52% , Fe 2 O 3 : 0.38%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，以叶腊石、石英砂、方解石、钾长石、氧化钠、氧化钙、锆英石、硼钙石、纯碱为原料，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1450℃采用纯氧燃烧电助融的窑炉熔制得到澄清、均化的玻璃液。熔制好的玻璃液流动至拉丝通道和拉丝成型系统直接拉制成玻璃纤维，拉丝漏板温度为1230℃的下拉制成连续玻璃纤维，所述玻璃纤维的直径为11μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through testing and calculation. , Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch. The batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted at 1450°C in a kiln with pure oxygen combustion and electric melting to obtain a clarified and homogenized glass liquid. The molten glass flows to the drawing channel and drawing forming system to directly draw glass fibers, and the drawing bushing temperature is 1230°C to draw continuous glass fibers. The diameter of the glass fibers is 11 μm±0.5 μm.
实施例3Example 3
一种玻璃纤维组合物，其主要组分及其重量含量为：A kind of glass fiber composition, its main component and its weight content are:
SiO 2：60.5％、Al 2O 3：6.5％、Na 2O：12.0％、CaO：13.0％、K 2O：3.5％、B 2O 3：2.3％、ZrO：1.25％、MgO：0.4％、Fe 2O 3：0.55％。 SiO 2 : 60.5%, Al 2 O 3 : 6.5%, Na 2 O: 12.0%, CaO: 13.0%, K 2 O: 3.5%, B 2 O 3 : 2.3%, ZrO: 1.25%, MgO: 0.4% , Fe 2 O 3 : 0.55%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，以叶腊石、石英砂、方解石、钾长石、氧化钠、氧化钙、锆英石、硼钙石、纯碱为原料，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1550℃采用纯氧燃烧的窑炉熔制得到澄清、均化的玻璃液。熔制好的玻璃液流动至拉丝通道和拉丝成型系统直接拉制成玻璃纤维，拉丝漏板温度为1180℃的下拉制成连续玻璃纤维，所述玻璃纤维的直径为3μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through testing and calculation. , Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch. The batch material is transported to the kiln front warehouse by a pneumatic conveying system, fed by an automatic feeder, and melted in a kiln with pure oxygen combustion at 1550° C. to obtain a clarified and homogenized glass liquid. The melted glass liquid flows to the drawing channel and the drawing forming system to directly draw glass fibers, and the drawing bushing temperature is 1180° C. to draw continuous glass fibers. The diameter of the glass fibers is 3 μm ± 0.5 μm.
实施例4Example 4
一种玻璃纤维组合物，其主要组分及其重量含量为：A kind of glass fiber composition, its main component and its weight content are:
SiO 2：61.5％、Al 2O 3：6.0％、Na 2O：9.8％、CaO：15.0％、K 2O：3.5％、B 2O 3：2.8％、ZrO：0.45％、MgO：0.50％、Fe 2O 3：0.45％。 SiO 2 : 61.5%, Al 2 O 3 : 6.0%, Na 2 O: 9.8%, CaO: 15.0%, K 2 O: 3.5%, B 2 O 3 : 2.8%, ZrO: 0.45%, MgO: 0.50% , Fe 2 O 3 : 0.45%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，以叶腊石、石英砂、方解石、钾长石、氧化钠、氧化钙、锆英石、硼钙 石、纯碱为原料，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1500℃采用纯氧燃烧的窑炉熔制得到澄清、均化的玻璃液。熔制好的玻璃液流动至拉丝通道和拉丝成型系统直接拉制成玻璃纤维，拉丝漏板温度为1200℃的下拉制成连续玻璃纤维，所述玻璃纤维的直径为5μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through testing and calculation. , Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch. The batch material is transported to the kiln front warehouse by a pneumatic conveying system, fed by an automatic feeder, and melted in a kiln with pure oxygen combustion at 1500° C. to obtain a clarified and homogenized glass liquid. The molten glass flows to the drawing channel and drawing forming system to directly draw glass fibers, and the drawing bushing temperature is 1200°C to draw continuous glass fibers. The diameter of the glass fibers is 5 μm±0.5 μm.
实施例5Example 5
一种玻璃纤维组合物，其主要组分及其重量含量为：A kind of glass fiber composition, its main component and its weight content are:
SiO 2：60.5％、Al 2O 3：6.8％、Na 2O：12.5％、CaO：13.5％、K 2O：2.55％、B 2O 3：3.2％、ZrO：0.35％、MgO：0.38％、Fe 2O 3：0.22％。 SiO 2 : 60.5%, Al 2 O 3 : 6.8%, Na 2 O: 12.5%, CaO: 13.5%, K 2 O: 2.55%, B 2 O 3 : 3.2%, ZrO: 0.35%, MgO: 0.38% , Fe 2 O 3 : 0.22%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，以叶腊石、石英砂、方解石、钾长石、氧化钠、氧化钙、锆英石、硼钙石、纯碱为原料，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1480℃采用全电熔的窑炉熔制得到澄清、均化的玻璃液。通过拉丝通道，在1175℃的漏板温度下拉制成连续HS纤维，所述HS纤维的直径为13μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through testing and calculation. , Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch. The batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted at 1480°C in an all-electric melting furnace to obtain a clarified and homogenized glass liquid. Continuous HS fibers with a diameter of 13 μm ± 0.5 μm were drawn through a wire drawing channel at a bushing temperature of 1175°C.
实施例6Example 6
一种玻璃纤维组合物，其主要组分及其重量含量为：A kind of glass fiber composition, its main component and its weight content are:
SiO 2：57.3％、Al 2O 3：7.1％、Na 2O：16.05％、CaO：14.0％、K 2O：3.1％、B 2O 3：1.6％、ZrO：0.40％、MgO：0.15％、Fe 2O 3：0.30％。 SiO 2 : 57.3%, Al 2 O 3 : 7.1%, Na 2 O: 16.05%, CaO: 14.0%, K 2 O: 3.1%, B 2 O 3 : 1.6%, ZrO: 0.40%, MgO: 0.15% , Fe 2 O 3 : 0.30%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，以叶腊石、石英砂、方解石、钾长石、氧化钠、氧化钙、锆英石、硼钙石、纯碱为原料，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1510℃采用全电熔的窑炉熔制得到澄清、均化的玻璃液。通过拉丝通道，在1190℃的漏板温度下拉制成连续HS纤维，所述HS纤维的直径为9μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through testing and calculation. , Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch. The batches are transported to the front silo of the kiln by a pneumatic conveying system, fed by an automatic feeder, and melted at 1510°C by an all-electric melting furnace to obtain a clear and homogenized glass liquid. Continuous HS fibers with a diameter of 9 μm ± 0.5 μm were drawn through a wire drawing channel at a bushing temperature of 1190°C.
实施例7Example 7
一种玻璃纤维组合物，其主要组分及其重量含量为：A kind of glass fiber composition, its main component and its weight content are:
SiO 2：61.0％、Al 2O 3：6.5％、Na 2O：13.0％、CaO：14.5％、K 2O：1.5％、B 2O 3：2.2％、ZrO：0.42％、MgO：0.45％、Fe 2O 3：0.43％。 SiO 2 : 61.0%, Al 2 O 3 : 6.5%, Na 2 O: 13.0%, CaO: 14.5%, K 2 O: 1.5%, B 2 O 3 : 2.2%, ZrO: 0.42%, MgO: 0.45% , Fe 2 O 3 : 0.43%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，以叶腊石、石英砂、方解石、钾长石、氧化钠、氧化钙、锆英石、硼钙石、纯碱为原料，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1500℃采用全电熔的窑炉熔制得到澄清、均化的玻璃液。通过拉丝通道，在1205℃的漏板温度下拉制成连续HS纤维，所述HS纤维的直径为6μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through testing and calculation. , Soda ash as the raw material, and then accurately measured by the weighing system, uniformly mixed by the mixing system to make the batch. The batches are transported to the kiln front warehouse through a pneumatic conveying system, fed by an automatic feeder, and melted at 1500°C in an all-electric melting furnace to obtain a clear and homogenized glass liquid. Continuous HS fibers with a diameter of 6 μm ± 0.5 μm were drawn through a wire drawing channel at a bushing temperature of 1205°C.
对实施例1～7中得到的玻璃纤维的性能进行检测，得到结果见表1。The properties of the glass fibers obtained in Examples 1 to 7 were tested, and the results are shown in Table 1.
表1 玻璃纤维的产品性能Table 1 Product properties of glass fiber
Figure PCTCN2020138556-appb-000009
Figure PCTCN2020138556-appb-000009
对比例1Comparative Example 1
一种HS纤维组合物，其主要组分及其重量含量为：A kind of HS fiber composition, its main component and its weight content are:
SiO 2：68.0％、Al 2O 3：4.5％、Na 2O：12.8％、CaO：11.2％、K 2O：1.5％、B 2O 3：1.2％、ZrO：0.32％、MgO：0.25％、Fe 2O 3：0.23％。 SiO 2 : 68.0%, Al 2 O 3 : 4.5%, Na 2 O: 12.8%, CaO: 11.2%, K 2 O: 1.5%, B 2 O 3 : 1.2%, ZrO: 0.32%, MgO: 0.25% , Fe 2 O 3 : 0.23%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1500℃采用全电熔的窑炉熔制得到澄清、均化的玻璃液。将玻璃液通过制球机制成玻璃球，再将玻璃球采用代铂炉在1350℃下熔融，采用拉丝漏板，在1180℃的漏板温度下拉制成连续HS纤维，所述HS纤维的直径为6μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through detection and calculation, and then accurately measured by the weighing system, and uniformly mixed through the mixing system to form batches. The batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted at 1500°C using an all-electric melting furnace to obtain a clear and homogenized glass liquid. The glass liquid is made into glass balls by a ball making machine, and then the glass balls are melted at 1350 ° C in a platinum-substituting furnace, and drawn at a temperature of 1180 ° C with a wire drawing bushing to make continuous HS fibers. The diameter of the HS fibers is 6μm±0.5μm.
对比例2Comparative Example 2
SiO 2：58.2％、Al 2O 3：8.5％、Na 2O：9.0％、CaO：16.6％、K 2O：4.5％、B 2O 3：1.5％、ZrO：0.32％、MgO：0.70％、Fe 2O 3：0.68％。 SiO 2 : 58.2%, Al 2 O 3 : 8.5%, Na 2 O: 9.0%, CaO: 16.6%, K 2 O: 4.5%, B 2 O 3 : 1.5%, ZrO: 0.32%, MgO: 0.70% , Fe 2 O 3 : 0.68%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1510℃采用纯氧燃烧的窑炉熔制得到澄清、均化的玻璃液。熔制好的玻璃液流动至拉丝通道和拉丝成型系统直接拉制成HS纤维，拉丝漏板温度为1210℃的下拉制成连续HS纤维，所述HS纤维的直径为6μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through detection and calculation, and then accurately measured by the weighing system, and uniformly mixed through the mixing system to make batches. The batch material is transported to the kiln front warehouse through a pneumatic conveying system, fed by an automatic feeder, and melted at 1510° C. using a pure oxygen combustion kiln to obtain a clarified and homogenized glass liquid. The melted glass liquid flows to the drawing channel and the drawing forming system is directly drawn into HS fibers, and the drawing bushing temperature is 1210 ℃ to make continuous HS fibers. The diameter of the HS fibers is 6 μm ± 0.5 μm.
对比例3Comparative Example 3
一种HS纤维组合物，其主要组分及其重量含量为：A kind of HS fiber composition, its main component and its weight content are:
SiO 2：61.5％、Al 2O 3：10.5％、Na 2O：13.0％、CaO：8.8％、K 2O：3.0％、B 2O 3：1.8％、ZrO：0.50％、MgO：0.52％、Fe 2O 3：0.38％。 SiO 2 : 61.5%, Al 2 O 3 : 10.5%, Na 2 O: 13.0%, CaO: 8.8%, K 2 O: 3.0%, B 2 O 3 : 1.8%, ZrO: 0.50%, MgO: 0.52% , Fe 2 O 3 : 0.38%.
玻璃纤维的制备方法如下：The preparation method of glass fiber is as follows:
按照上述所列各配方的化学组成，通过检测和计算得出各种原料的配比需求量，再经过称量系统精确计量后，经由混合系统均匀混合制成配合料。所述配合料通过气力输送系统运送至窑炉窑前仓，采用自动加料机投料，在1450℃ 采用纯氧燃烧电助融的窑炉熔制得到澄清、均化的玻璃液。熔制好的玻璃液流动至拉丝通道和拉丝成型系统直接拉制成HS纤维，拉丝漏板温度为1230℃的下拉制成连续HS纤维，所述HS纤维的直径为9μm±0.5μm。According to the chemical composition of each formula listed above, the proportioning requirements of various raw materials are obtained through detection and calculation, and then accurately measured by the weighing system, and uniformly mixed through the mixing system to form batches. The batch material is transported to the front silo of the kiln through a pneumatic conveying system, fed by an automatic feeder, and melted at 1450°C in a kiln with pure oxygen combustion and electric melting to obtain a clear and homogenized glass liquid. The molten glass flows to the drawing channel and the drawing forming system is directly drawn into HS fibers, and the drawing bushing temperature is 1230°C to make continuous HS fibers. The diameter of the HS fibers is 9 μm±0.5 μm.
对对比例1～3中得到的玻璃纤维的性能进行检测，得到结果见表2。The properties of the glass fibers obtained in Comparative Examples 1 to 3 were tested, and the results are shown in Table 2.
表2 对比例1～3玻璃纤维性能检测结果Table 2 Comparative Examples 1-3 Glass Fiber Performance Test Results
Figure PCTCN2020138556-appb-000010
Figure PCTCN2020138556-appb-000010
以上对本发明所提供的一种聚合物粒子的制备方法进行了详细介绍。本文应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。The preparation method of the polymer particles provided by the present invention has been described in detail above. The principles and implementations of the present invention are described herein by using specific examples, and the descriptions of the above embodiments are only used to help understand the method and the core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can also be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (9)

  1. 一种耐酸性玻璃纤维组合物，其特征在于，包括：An acid-resistant glass fiber composition, comprising:
    Figure PCTCN2020138556-appb-100001
    Figure PCTCN2020138556-appb-100001
  2. 根据权利要求1所述的耐酸性玻璃纤维组合物，其特征在于，包括：The acid-resistant glass fiber composition according to claim 1, characterized in that, comprising:
    Figure PCTCN2020138556-appb-100002
    Figure PCTCN2020138556-appb-100002
  3. 根据权利要求1所述的耐酸性玻璃纤维组合物，其特征在于，包括：The acid-resistant glass fiber composition according to claim 1, characterized in that, comprising:
    Figure PCTCN2020138556-appb-100003
    Figure PCTCN2020138556-appb-100003
    Figure PCTCN2020138556-appb-100004
    Figure PCTCN2020138556-appb-100004
  4. 根据权利要求1所述的耐酸性玻璃纤维组合物，其特征在于，包括：The acid-resistant glass fiber composition according to claim 1, characterized in that, comprising:
    Figure PCTCN2020138556-appb-100005
    Figure PCTCN2020138556-appb-100005
  5. 根据权利要求1所述的耐酸性玻璃纤维组合物，其特征在于，包括：The acid-resistant glass fiber composition according to claim 1, characterized in that, comprising:
    Figure PCTCN2020138556-appb-100006
    Figure PCTCN2020138556-appb-100006
  6. 一种耐酸性玻璃纤维，其特征在于，由权利要求1～5任意一项所述的耐酸性玻璃纤维组合物制备得到。An acid-resistant glass fiber, characterized in that, it is prepared from the acid-resistant glass fiber composition according to any one of claims 1 to 5.
  7. 根据权利要求6所述的耐酸性玻璃纤维，其特征在于，所述耐酸性玻璃纤维的直径为3～17μm。The acid-resistant glass fiber according to claim 6, wherein the acid-resistant glass fiber has a diameter of 3 to 17 μm.
  8. 一种耐酸性玻璃纤维的制备方法，其特征在于，包括；A method for preparing acid-resistant glass fiber, comprising:
    按照权利要求1所述的耐酸性玻璃纤维组合物配制原料；The raw material for preparing the acid-resistant glass fiber composition according to claim 1;
    将原料熔制得到玻璃液；The raw materials are melted to obtain glass liquid;
    将所述玻璃液拉制，得到耐酸性玻璃纤维。The glass liquid is drawn to obtain acid-resistant glass fibers.
  9. 根据权利要求8所述的制备方法，其特征在于，所述熔制的温度为1300℃～1550℃；所述拉制温度为1150℃～1250℃。The preparation method according to claim 8, wherein the melting temperature is 1300°C-1550°C; the drawing temperature is 1150°C-1250°C.
PCT/CN2020/138556 2020-10-26 2020-12-23 Acid-resistant glass fiber composition, and acid-resistant glass fiber and preparation method therefor WO2022088452A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011156449.9A CN112174537A (en) 2020-10-26 2020-10-26 Acid-resistant glass fiber composition, acid-resistant glass fiber and preparation method thereof
CN202011156449.9 2020-10-26

Publications (1)

Publication Number Publication Date
WO2022088452A1 true WO2022088452A1 (en) 2022-05-05

Family

ID=73923846

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/138556 WO2022088452A1 (en) 2020-10-26 2020-12-23 Acid-resistant glass fiber composition, and acid-resistant glass fiber and preparation method therefor

Country Status (2)

Country Link
CN (1) CN112174537A (en)
WO (1) WO2022088452A1 (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853569A (en) * 1963-02-07 1974-12-10 Saint Gobain Silicate glass fiber compositions
CN101687691A (en) * 2007-05-23 2010-03-31 欧洲圣戈班技术结构公司 Glass yarns suitable for reinforcing organic and/or inorganic materials
US20110203645A1 (en) * 2008-10-31 2011-08-25 Asahi Glass Company, Limited Solar cell
CN102390934A (en) * 2011-08-10 2012-03-28 巨石集团有限公司 Glass fiber compound
CN108840574A (en) * 2018-09-21 2018-11-20 辽宁新洪源环保材料有限公司 A kind of 50,000 tons of spun yarn tank furnace glass compositions
CN109133654A (en) * 2018-09-21 2019-01-04 辽宁新洪源环保材料有限公司 A kind of high-performance perlite fiber and preparation method thereof
CN110407474A (en) * 2018-04-26 2019-11-05 佛山市嘉懿行农业科技有限公司 A kind of high-performance glass fiber

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853569A (en) * 1963-02-07 1974-12-10 Saint Gobain Silicate glass fiber compositions
CN101687691A (en) * 2007-05-23 2010-03-31 欧洲圣戈班技术结构公司 Glass yarns suitable for reinforcing organic and/or inorganic materials
US20110203645A1 (en) * 2008-10-31 2011-08-25 Asahi Glass Company, Limited Solar cell
CN102390934A (en) * 2011-08-10 2012-03-28 巨石集团有限公司 Glass fiber compound
CN110407474A (en) * 2018-04-26 2019-11-05 佛山市嘉懿行农业科技有限公司 A kind of high-performance glass fiber
CN108840574A (en) * 2018-09-21 2018-11-20 辽宁新洪源环保材料有限公司 A kind of 50,000 tons of spun yarn tank furnace glass compositions
CN109133654A (en) * 2018-09-21 2019-01-04 辽宁新洪源环保材料有限公司 A kind of high-performance perlite fiber and preparation method thereof

Also Published As

Publication number Publication date
CN112174537A (en) 2021-01-05

Similar Documents

Publication Publication Date Title
KR101758938B1 (en) Improved modulus, lithium free glass
JP2012531373A (en) High strength high elasticity glass fiber
KR102685011B1 (en) Glass fiber with low coefficient of thermal expansion
JP2014101270A (en) Glass composition for glass fiber, glass fiber and method of manufacturing glass fiber
CN104478223B (en) High-performance glass fibre
CN103086605A (en) Glass fiber
CN107216042A (en) A kind of high-modulus glass fiber composition and glass fibre
EP2676939A1 (en) Glass fibre composition free of boron and fluorine
CN101549958A (en) Composition for high-performance glass fiber
CN103964697A (en) Basalt fiber composition with high alkali resistance and application method of basalt fiber composition
JP2000247683A (en) Corrosion resistant glass fiber
CN112745031B (en) Low-thermal expansion coefficient high-strength glass fiber
CN108373268A (en) A kind of high-modulus glass fiber composition and glass fibre
WO2018123327A1 (en) Glass composition for glass fiber, glass fiber, and method for producing glass fiber
CN103332866A (en) Glass fiber
CN105948486A (en) Ultrathin glass and preparation method thereof
CN109133654B (en) High-performance perlite fiber and preparation method thereof
CN107056075A (en) Glass fiber compound and glass fibre
CN108840574B (en) Glass composition for 5 ten thousand ton spun yarn tank furnace
WO2016093212A1 (en) Glass composition for glass fiber, glass fiber, and method for producing glass fiber
CN109052971A (en) A kind of high-performance glass fiber composition and glass fibre being easy to large-scale production
WO2022088452A1 (en) Acid-resistant glass fiber composition, and acid-resistant glass fiber and preparation method therefor
CN111433166B (en) Glass fiber and method for producing same
JP2019112246A (en) Glass fiber and method for producing the same
CN108395109A (en) A kind of high-modulus glass fiber composition and glass fibre

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20959609

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20959609

Country of ref document: EP

Kind code of ref document: A1