CN109982982A - The manufacturing method of glass fibre glass composition, glass fibre and glass fibre - Google Patents

The manufacturing method of glass fibre glass composition, glass fibre and glass fibre Download PDF

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Publication number
CN109982982A
CN109982982A CN201780071995.2A CN201780071995A CN109982982A CN 109982982 A CN109982982 A CN 109982982A CN 201780071995 A CN201780071995 A CN 201780071995A CN 109982982 A CN109982982 A CN 109982982A
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glass
glass fibre
mass
tio
glass composition
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CN109982982B (en
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横田裕基
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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    • 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
    • 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
    • C03C13/001—Alkali-resistant fibres
    • C03C13/002—Alkali-resistant fibres containing zirconium
    • 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
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The object of the present invention is to provide the glass fibre glass compositions excellent with excellent alkali resistance and productivity.Glass fibre glass composition of the invention is characterized in that, is formed as glass, contains SiO in terms of the quality % of oxide conversion250%~65%, Al2O30%~5%, CaO 0%~10%, Na2O 10%~20%, K2O 0%~5%, ZrO2It more than 15% and is 20% or less, TiO20.1%~10%, B2O30.1%~10%.

Description

The manufacturing method of glass fibre glass composition, glass fibre and glass fibre
Technical field
The present invention relates to the glass fibre glass compositions of corrosion resistance excellent.In particular to be suitable as calcium silicate board, The reinforcing materials or battery interval part, asbestos substitute etc. such as GRC (glass fiber-reinforced concrete) require corrosion proof material Glass fibre glass composition.
Background technique
In the past, it as the reinforcing material of GRC, has used and has recorded such SiO in patent document 12-ZrO2-R2O (R Li, Any one in Na, K) system contains ZrO2Alkali-resistant glass fiber.
The glass fibre also serves as the corrosion resistant material of the reinforcing material of calcium silicate board, battery interval part etc..
GRC is glass fibre, cement, aggregate, intermixture and the water that specific length will be cut by using ejecting gun etc. Deng mixture spray to being configured to the structural material for building of plate in pattern.Even if it is required that being used for the glass fibre of GRC The intensity for meeting reliability is also able to maintain by many decades in concrete.
Glass fibre as described above is the bushing device using such as noble metal, by melten glass progressive forming, is spun Silk is simultaneously made obtained by threadiness.In addition, the structure of bushing has container shapes to be detained melten glass, in its bottom Multiple nozzles are equipped along vertical direction.By that will adjust, to spinning temperature, (viscosity of glass becomes about glass fibre 103The temperature of dPas, also referred to as forming temperature) nearby temperature melten glass from the nozzle of bushing bottom pull out at threadiness To shape.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Publication 49-40126 bulletin
Patent document 2: Japanese Unexamined Patent Application Publication 2009-513470 bulletin
Patent document 3: Japanese Patent Publication 57-16940 bulletin
Summary of the invention
Subject to be solved by the invention
Patent document 1 is disclosed from the viewpoint of improving alkali resistance, largely contains ZrO in glass composition2Glass Composition.But if largely contain ZrO2, then the spinning temperature of glass is got higher.If the spinning temperature of glass is high, noble metal system The damage of bushing device becomes to aggravate, and the replacement frequency of bushing is got higher, and the production cost of glass fibre is got higher.In addition, if a large amount of Contain ZrO2, then liquidus temperature rises, and the difference of spinning temperature and liquidus temperature is easy to become smaller.If spinning temperature and liquidus temperature it Difference is small, then at the nozzle of bushing bottom, glass is easy devitrification, there are problems that glass fibre is difficult to continuous production.
In addition, patent document 2 is disclosed by reducing ZrO2And contain a certain amount of TiO2And maintain the glass of alkali resistance Composition.But the glass spinning temperature for the glass fibre recorded in patent document 2 is also high.
In addition, patent document 3 is disclosed by reducing ZrO2And contain a certain amount of B2O3And reduce the glass of spinning temperature Glass composition.But the difference of the glass spinning temperature for the glass fibre recorded in patent document 3 and liquidus temperature is small, there are difficulties The problem of with continuous production.
Like this, it is difficult to obtain the glass fibre glass composition for having excellent alkali resistance and productivity excellent.
The present invention has been made in view of the above-described circumstances, it is intended that providing has excellent alkali resistance and productivity Excellent glass fibre glass composition.
The method used for solving the problem
Present inventor has performed further investigation as a result, it has been found that: about glass fibre glass composition, if containing one ZrO more than quantitative2Glass composition in contain TiO2And B2O3As essential component, then can significantly reduce liquidus temperature and The spinning temperature of glass is not improved, can significantly increase the spinning temperature of glass and the difference of liquidus temperature.And it is further discovered that: Due to containing a certain amount of above ZrO2, therefore, even if addition TiO2And B2O3Acid resistance, alkali resistance, water resistance will not be made At substantially influencing.
That is, glass fibre glass composition of the invention is characterized in that, formed as glass, with oxide conversion Quality % meter contains SiO250~65%, Al2O30~5%, CaO 0~10%, Na2O10~20%, K2O0~5%, ZrO2It is super It crosses 15% and is 20% or less, TiO20.1~10%, B2O30.1~10%.
, it is surprising that containing the ZrO more than a certain amount of2Glass composition in, by containing B2O3And TiO2This two Person, it is believed that the crystallization comprising Na, Zr, Si becomes eutectiform state with the crystallization comprising K, Zr, Si, and liquidus temperature significantly drops It is low.As a result, glass fibre of the invention glass composition has excellent alkali resistance, and the spinning temperature and liquid of glass Phase temperature difference is big, and productivity is excellent.
The spinning temperature of glass fibre of the invention glass composition and the difference of liquidus temperature are preferably 115 DEG C or more. It should be noted that " spinning temperature " refers to that the viscosity of glass becomes 103The temperature of dPas.Thereby, it is possible to productivity is made Excellent glass fibre glass composition.
In glass fibre glass composition of the invention, in terms of the mass ratio of oxide conversion, B2O3/TiO2Value it is excellent It is selected as 0.01~95.Thereby, it is possible to the difference of spinning temperature and liquidus temperature with excellent alkali resistance and glass is made more Greatly, the excellent glass fibre glass composition of productivity.
In glass fibre glass composition of the invention, B2O3+TiO2Content be preferably 1~20 mass %.Herein, “B2O3+TiO2" refer to B2O3With TiO2Total amount.Thereby, it is possible to more reliably be made with excellent alkali resistance and glass The glass fibre glass composition that the difference of spinning temperature and liquidus temperature is bigger, productivity is excellent.
In glass fibre glass composition of the invention, B2O3Content be preferably 0.5~7.8 mass %.As a result, can Spinning temperature, liquidus temperature are enough reduced, the excellent glass fibre glass composition of alkali resistance can be made.
In glass fibre glass composition of the invention, Li2The content of O is preferably 0~0.2 mass %.Thereby, it is possible to Reduce production cost.
In glass fibre glass composition of the invention, Na2O+K2The content of O is preferably 10~20%.Herein, " Na2O +K2O " refers to Na2O and K2The total amount of O.Thereby, it is possible to reduce the viscosity of glass, meltbility can be made, have excellent formability glass Glass fiber glass composition.
In glass fibre glass composition of the invention, spinning temperature is preferably 1270 DEG C or less.Thereby, it is possible to low Temperature is lower to carry out fibrosis, therefore can reduce melting cost, additionally it is possible to realize the long lifetime of the fibrosis equipments such as bushing, therefore It can reduce production cost.
In glass fibre glass composition of the invention, liquidus temperature is preferably 1150 DEG C or less.It is easy to carry out as a result, Spinning, therefore the excellent glass fibre glass composition of productivity can be made.
Glass fibre glass composition of the invention is in the NaOH aqueous solution 100ml of 10 mass %, 80 DEG C, 90 hours Under conditions of the rate of mass reduction of glass when being impregnated be preferably 4% or less.It should be noted that evaluation has used classification At specific gravity × 1 mass parts glass of 300~500 μm of granularity.It is easy to get as a result, as composite woods such as calcium silicate board, GRC The glass fibre of the reinforcing material high reliablity of material.
Glass fibre glass composition of the invention is in the HCL aqueous solution 100ml of 10 mass %, 80 DEG C, 90 hours Under conditions of the rate of mass reduction of glass when being impregnated be preferably 4% or less.It should be noted that evaluation has used classification At specific gravity × 1 mass parts glass of 300~500 μm of granularity.It is easy to get as a result, as the corrosion resistances material such as battery interval part Expect the glass fibre of high reliablity.
Glass fibre of the invention is characterized in that it includes above-mentioned glass fibre glass compositions.
The manufacturing method of glass fibre of the invention is characterized in that, raw materials batch is melted with glass melting furnace Melt, resulting melten glass is continuously extracted out from bushing and be configured to threadiness, the raw materials batch is according to as glass Glass composition becomes SiO in terms of the quality % that oxide converts250~65%, Al2O30~5%, CaO 0~10%, Na2O 10 ~20%, K2O 0~5%, ZrO2It more than 15% and is 20% or less, TiO20.1~10%, B2O30.1~10% mode Obtained by allotment.
The manufacturing method of glass fibre of the invention is preferably become with the difference of the spinning temperature of gained glass and liquidus temperature 115 DEG C or more of mode deploys raw materials batch.
It is preferable to use the B in terms of the mass ratio by weight of oxide for the manufacturing method of glass fibre of the invention2O3/ TiO2Value as 0.01~95 mode deploy obtained by raw materials batch.
Thereby, it is possible to further increase the difference of the spinning temperature of glass and liquidus temperature without rising melting temperature, because This can be improved productivity.
Specific embodiment
Hereinafter, being illustrated for glass fibre of the invention with glass composition.It should be noted that as long as no spy It does not record, then in the explanation containing range of each ingredient, % expression refers to quality %.
SiO2It is to form the main component of glass skeleton structure, and improve the acid proof ingredient of glass.SiO2Content be It 50~65%, is preferably 55~60%, more preferably 57~60%.If SiO2Content it is very few, then glass mechanical strength hold It easily reduces, and the acid resistance of glass reduces.If SiO2Content it is excessive, then the viscosity of glass is got higher, needed for the melting of glass Energy increases.In addition, the damage of noble metal bushing becomes to aggravate, replacement frequency is got higher, and production cost is got higher.In turn, glass Alkali resistance reduce.
Al2O3It is the chemical durability for improving glass, the ingredient of mechanical strength.On the other hand, Al2O3It is also to improve glass The ingredient of viscosity.Al2O3Content be 0~5%, preferably 0~3%, more preferably 0~1%.If Al2O3Content it is excessive, Then the viscosity of glass is got higher, and energy needed for the melting of glass increases.
CaO is the ingredient for reducing glass viscosity.The content of CaO be 0~10%, preferably 0~5%, more preferably 0~ It 4%, is more preferably 0~3%.If the content of CaO is excessive, it is easy that the knot comprising Zr, Si, Na, Ca is precipitated in glass The liquidus temperature of crystalline substance, glass is got higher, and the difference of spinning temperature and liquidus temperature becomes smaller, and productivity reduces.
Na as alkali metal oxide2O and K2O be reduce glass viscosity, improve glass meltbility or formability at Point.On the other hand, alkali metal oxide is excessively largely containing the ingredient for reducing glass water resistance sometimes.Na2O+K2The amount of O is 10 It~20%, is preferably 10~18%, more preferably 12~18%, further preferably 15~17%.If Na2O+K2The amount mistake of O Few, then the viscosity of glass is got higher, and energy needed for the melting of glass increases.In addition, the damage of noble metal bushing becomes to aggravate, Replacement frequency is got higher, and production cost is got higher.If Na2O+K2The amount of O is excessive, then the water resistance of glass reduces.
Na2O is to reduce glass viscosity, improve the meltbility of glass or the ingredient of formability.Na2The content of O be 10~ It 20%, is preferably 10~18%, more preferably 12~18%, most preferably 12~17%.If Na2The content of O is very few, then glass Viscosity get higher, energy needed for the melting of glass increase.In addition, the damage of noble metal bushing becomes to aggravate, replacement frequency It gets higher, production cost is got higher.If Na2The content of O is excessive, then the liquidus temperature of glass is got higher, spinning temperature and liquidus temperature it Difference becomes smaller, and productivity reduces.In addition, the water resistance of glass reduces.
K2O is the ingredient that the meltbility of glass, formability are improved by reducing the viscosity of glass.K2The content of O be 0~ 5%, it is preferably 0~3%, is most preferably 0~2%.If K2The content of O is excessive, then the water resistance of glass reduces.In addition, raw material Batch is easy to absorb moisture, the aggregation (so-called " agglomerate ") of raw material powder easy to form.If forming the poly- of raw material powder Collective, then the dissolubility deterioration of raw materials batch, is easy the undissolved zirconium oxide of residual, therefore not preferably in glass fibre.
Li2O is that liquidus temperature is greatly reduced and adding on a small quantity, the difference for increasing spinning temperature and liquidus temperature, improves The ingredient of productivity.But Li2The cost of material of O is high, therefore, if Li2Excessively then the production cost increases for the content of O.In turn, with The increase in demand of lithium battery, lithium raw material supply shortage risk get higher, therefore, if Li2The content of O is excessive, then there is nothing Method ensures to produce the risk of required lithium raw material.Thus, Li2The content of O is preferably 0~0.2%, from the viewpoint of cost and supply It sets out, is preferably free of Li2O.Herein, " Li is free of2O ", which refers to, does not contain Li actively as glass composition2The meaning of O, however not excluded that no Evitable impurity.More specifically, the content comprising impurity, which refers to, is calculated as 0.01% or less with quality %.In this way, hold The problems such as easily avoiding raw material supply uneasy, raw material cost surging.
ZrO2It is the alkali resistance for improving glass, the ingredient of acid resistance and water resistance.ZrO2Content be more than 15% and for 20% It below, is preferably 15.5~19.5%, more preferably 16~19%, further preferably 16.5~18.5%, most preferably 17 ~18%.If ZrO2Content it is very few, then the alkali resistance of glass fibre glass composition reduces, as a result, cannot achieve pair Durability required by GRC.If ZrO2Content it is excessive, then the liquidus temperature of glass is got higher, spinning temperature and liquidus temperature it Difference becomes smaller, and productivity reduces.
TiO2It is the water resistance and alkali resistance for improving glass, and the ingredient for reducing spinning temperature, liquidus temperature being greatly reduced. TiO2Content be 0.1~10%, preferably 1~9%, more preferably 2~8%.If TiO2Content it is very few, then glass is resistance to Aqueous and alkali resistance reduces, and spinning temperature rises, production cost is got higher.If TiO2Content it is excessive, then be easy in glass Being precipitated includes TiO2Crystallization, liquidus temperature is substantially increased.As a result, the difference of spinning temperature and liquidus temperature becomes smaller, productivity It reduces.
B2O3It is the ingredient for reducing spinning temperature, liquidus temperature being greatly reduced.B2O3Content be 0.1~10%, preferably 1~9%, it is more preferably 1~7.8%.If B2O3Content it is very few, then spinning temperature rise, the difference of spinning temperature and liquidus temperature Become smaller, productivity reduces.In addition, if B2O3Content it is excessive, then glass alkali resistance reduce.
In glass fibre glass composition of the invention, contain B2O3And TiO2As essential component.This is because: such as It is upper described, containing the ZrO more than a certain amount of2Glass composition in, by containing B2O3And TiO2The two, it is believed that packet Crystallization containing Na, Zr, Si becomes eutectiform state with the crystallization comprising K, Zr, Si, and liquidus temperature significantly reduces.B2O3/TiO2Value Index as the index and management glass alkali resistance that determine eutectic point is important.B2O3/TiO2Value be 0.01~95, it is excellent It is selected as 0.02~92, more preferably 0.05~90, further preferably 0.10~85, particularly preferably 0.12~80.If B2O3/ TiO2Value it is too small, then liquidus temperature rise, productivity reduce.In addition, if B2O3/TiO2Value it is excessive, then alkali resistance reduce.
In order to more reliably obtain B2O3With TiO2Interaction, containing B2O3And TiO2When, preferably by B2O3With TiO2 Total amount limit to a certain range.Thereby, it is possible to significantly reduce liquidus temperature, productivity is improved.Therefore, B2O3+TiO2Value be 1~20%, preferably 2~19%, 3~18%, further preferably 4~18%, 5~17%, 6~16%, 6.5 are more preferably ~15%, 7~13% are particularly preferably.If B2O3+TiO2Value it is too small, then spinning temperature is got higher with liquidus temperature, productivity drop It is low.If B2O3+TiO2Value it is excessive, then the production cost increases.
Glass fibre of the invention may include with glass composition in addition to mentioned component (SiO2、Al2O3、CaO、Na2O、 K2O、Li2O、ZrO2、TiO2And B2O3) except ingredient.Wherein, it is expected that the content according to mentioned component becomes 98% in the total amount Adjust composition above, particularly as 99% or more mode.The reason is that holding when the total amount of these ingredients is less than 98% Following unfavorable condition easily occurs: leading to alkali resistance, acid resistance, water resistance drop because of being mixed into for ingredient not of the same race not intentionally added It is low, the difference of characteristic reduction or spinning temperature and liquidus temperature as product becomes smaller, and productivity reduces etc..
It, can be respectively containing such as H to 0.1% as the ingredient other than mentioned component2、CO2、CO、H2O、He、 Ne、Ar、N2Etc. micro constitutents.Furthermore, it is possible to be added to the precious metal elements such as Pt, Rh, Au of 500ppm into glass.
In addition, in order to improve alkali resistance, acid resistance, water resistance, liquidus temperature, can calculate in the total amount containing to 2% MgO、SrO、BaO、ZnO、P2O5、Fe2O3、Cr2O3、Sb2O3、SO3、MnO、SnO2、CeO2、Cl2、La2O3、WO3、Nb2O5、Y2O3 Deng.
For glass fibre glass composition of the invention, by the specific gravity for the granularity for being classified to 300~500 μm × Glass when being impregnated under conditions of the glass of 1 weight point is in the NaOH aqueous solution 100ml of 10 mass %, 80 DEG C, 90 hours The weight reduction rates of glass be 4% or less, preferably 3.9% or less, more preferably 3.8% or less, further preferably 3.6% with Under, particularly preferably 3% or less.If the glass weight slip based on the alkaline resistance test is more, it is used as calcium silicate board, GRC The reliability of the reinforcing material of equal composite materials is lower.
For glass fibre glass composition of the invention, by the specific gravity for the granularity for being classified to 300~500 μm × Glass of the glass of 1 weight point in the HCL aqueous solution 100ml of 10 mass %, when being impregnated under conditions of 80 DEG C, 90 hours Weight reduction rates are 4% or less, are preferably 3% or less, are more preferably 2% or less, are more preferably 1.5% or less, especially Preferably 1% or less.If the glass weight slip based on the acid resisting test is more, as corrosion resistances materials such as battery interval parts The reliability of material reduces.
For glass fibre glass composition of the invention, as Water Resistance Test, using based on JIS R3502 (1995) method measurement alkali soluble output be 0.40mg or less, preferably 0.35mg or less, further preferably 0.30mg with Under, particularly preferably less than 0.30mg.If alkali soluble output is more, alkali composition is dissolved out from glass in autoclave process, and glass is easy Deterioration.
The spinning temperature of glass fibre glass composition of the invention be 1270 DEG C or less, be preferably 1265 DEG C or less, Further preferably 1260 DEG C or less, particularly preferably 1250 DEG C or less.If spinning temperature is excessively high, need to carry out at high temperature Therefore spinning not only melts cost and gets higher, the damage of noble metal bushing also becomes to aggravate, and replacement frequency is got higher, production cost It gets higher.
The liquidus temperature of glass fibre glass composition of the invention be 1150 DEG C or less, be preferably 1140 DEG C or less, Further preferably 1130 DEG C or less, particularly preferably 1120 DEG C or less.If liquidus temperature is excessively high, it is easy devitrification, productivity It reduces.
The spinning temperature of glass fibre glass composition of the invention and the difference of liquidus temperature are 115 DEG C or more, preferably It is 120 DEG C or more, more preferably 130 DEG C or more, further preferably 140 DEG C or more, particularly preferably 150 DEG C or more.If spinning Silk temperature and the difference of liquidus temperature are small, then productivity reduces.
Then, by taking direct fusion method (DM method) as an example, the method that illustrates to manufacture glass fibre of the present invention.It needs to illustrate It is that the present invention is not limited to following methods, can also be leaked using the fiber glass material that for example will be shaped to marble-like Panel assembly carries out remelted and spinning so-called indirect forming process (MM method: marble fusion method).This method is suitble to a small amount of more product The production of kind.
Firstly, containing SiO in terms of the quality % by weight of oxide250~65%, Al2O30~5%, CaO 0~ 10%, Na2O 10~20%, K2O 0~5%, ZrO2It more than 15% and is 20% or less, TiO20.1~10%, B2O30.1~ The mode of 10% glass deploys glass raw material.It should be noted that glass can be used in part or all of glass raw material Piece.The content of each ingredient has been stated according to above-mentioned such the reasons why setting, has been omitted the description herein.
Then, the raw materials batch of allotment is put into glass melting furnace, carries out vitrifying, melts, homogenizes.Melting Temperature is suitably for 1400~1600 DEG C or so.
Then, melten glass is subjected to spinning and is configured to glass fibre.If being described in detail, by melten glass supply to Bushing.The melten glass supplied to bushing is continuously extracted into filiform from the multiple bushing nozzles for being set to its bottom surface.To such The monofilament of extraction is coated with various inorganic agents, and every fixed radical carries out boundling, thus obtains glass fibre.
So shaped glass fibre of the invention is processed to chopped strand, yarn, rove etc., and for various use On the way.
In addition, chopped strand refers to: glass fibre made of glass monofilament boundling (harness) is cut into specific length and The product obtained.Yarn refers to product obtained by harness twisting.Rove refer to by more zygonemas of harness and be wound into it is cylindric and The product obtained.
Embodiment
Hereinafter, based on embodiment, the present invention will be described in detail.The embodiment of the present invention (No.1~8) and ratio is shown respectively in table 1 Compared with example No.9.
[table 1]
Each sample of table makes as follows.
Firstly, weighing the various glass raw materials such as natural material, chemical conversion raw material simultaneously in the way of becoming the glass in table and form Mixing makes raw materials batch.Then, which is put into platinum-rhodium alloy crucible, in indirect heating electric furnace It is interior to be heated 5 hours with 1550 DEG C, obtain melten glass.In addition, the melten glass of homogeneous in order to obtain, when heated using heat-resisting Property stirring rod, melten glass is stirred multiple.Then, gained melten glass is flowed out to fire resistance mold, is configured to plate After glass, slow cooling processing is carried out in leer (than 1013High 30~50 DEG C of the temperature of temperature when dPas heats 30 minutes Afterwards, annealing point~strain point temperature region is cooled down with 1 DEG C/min).For resulting each sample, spinning temperature is measured Degree, liquidus temperature, acid resistance, alkali resistance, alkali soluble output.
The measurement of spinning temperature carries out as follows.Firstly, above-mentioned plate glass sample is broken into size appropriate, with as far as possible The mode for not bringing bubble into is put into oxidation aluminum cup.Then, it by oxidation aluminum cup heating, is made and melts liquid status, benefit The glass viscosity at multiple temperature is found out with platinum ball czochralski method.Thereafter, viscograph is made by the multiple measured values of gained, and passed through Its interpolation, which calculates, becomes 103Temperature when dPas.
The measurement of liquidus temperature carries out as follows.Firstly, above-mentioned plate glass sample is crushed, by granularity adjust to 300~500 μm of range is filled with the state with bulk density appropriate in the container of fire resistance.Then, by the fire resisting Property container is put into in the temperature gradient furnace for the indirect heating type that maximum temperature is set as to 1350 DEG C and standing, in air atmosphere The middle heating operation for carrying out 16 hours.Thereafter, test body is taken out together with fire resistance container from temperature gradient furnace, be cooled to After room temperature, liquidus temperature is determined using polarization microscope.
The difference of spinning temperature and liquidus temperature is calculated by the value of the two.
Acid resistance measures as follows.Firstly, above-mentioned plate glass sample is crushed, by 300~500 μm of granularity of diameter Glass accurate weighing specific gravity × 1 mass parts, be then immersed in 10 mass %HCl solution 100ml, at 80 DEG C, 90 hours Under the conditions of vibrated.Thereafter, the rate of mass reduction of glass specimen is measured.The value is smaller, then acid resistance is more excellent.
Alkali resistance measures as follows.Firstly, above-mentioned plate glass sample is crushed, by 300~500 μm of granularity of diameter Glass precision weighing specific gravity × 1 mass parts, be then immersed in 10 mass %NaOH solution 100ml, at 80 DEG C, 90 hours Under the conditions of vibrated.Thereafter, the rate of mass reduction of glass specimen is measured.The value is smaller, then alkali resistance is more excellent.
Indicate that the alkali soluble output of water resistance utilizes the method based on JIS R3502 (1995) to be measured.The value is smaller, then Water resistance is more excellent.
Can be defined by table 1: the spinning temperature of No.1~8 as embodiment is 1270 DEG C or less, spinning temperature and liquid Phase temperature difference is 115 DEG C or more, is that 4% or less, alkali soluble goes out as the rate of mass reduction of alkali resistance or acid proof index Amount is 0.40mg or less.
In contrast, as the difference of the spinning temperature of the No.9 of comparative example and liquidus temperature less than 115 DEG C, it is difficult to stable Production.
Industrial availability
Glass fibre of the invention is suitable as the corrosion resistant materials such as the reinforcing material of calcium silicate board, battery interval part.

Claims (16)

1. a kind of glass fibre glass composition, which is characterized in that formed as glass, in terms of the quality % of oxide conversion Contain SiO250%~65%, Al2O30%~5%, CaO 0%~10%, Na2O 10%~20%, K2O 0%~5%, ZrO2It more than 15% and is 20% or less, TiO20.1%~10%, B2O30.1%~10%.
2. glass fibre glass composition according to claim 1, which is characterized in that spinning temperature and liquidus temperature it Difference is 115 DEG C or more.
3. glass fibre glass composition according to claim 1 or 2, which is characterized in that the matter to be converted with oxide Amount is than meter, B2O3/TiO2Value be 0.01~95.
4. glass fibre glass composition described in any one of claim 1 to 3, which is characterized in that B2O3+TiO2 Content be 1 mass of mass %~20 %.
5. glass fibre glass composition according to any one of claims 1 to 4, which is characterized in that B2O3Content For 0.5 mass of mass %~7.8 %.
6. glass fibre glass composition according to any one of claims 1 to 5, which is characterized in that Li2The content of O For 0 mass of mass %~0.2 %.
7. glass fibre glass composition described according to claim 1~any one of 6, which is characterized in that Na2O+K2O's Content is 10 mass of mass %~20 %.
8. glass fibre glass composition according to any one of claims 1 to 7, which is characterized in that spinning temperature It is 1270 DEG C or less.
9. glass fibre glass composition described according to claim 1~any one of 8, which is characterized in that liquidus temperature It is 1150 DEG C or less.
10. glass fibre glass composition described according to claim 1~any one of 9, which is characterized in that be based on JIS The alkali soluble output of R3502 is 0.30mg or less.
11. glass fibre glass composition described according to claim 1~any one of 10, which is characterized in that in 10 matter Measure in the NaOH aqueous solution 100ml of %, 80 DEG C, the rate of mass reduction of glass when being impregnated under conditions of 90 hours be 4% Below.
12. glass fibre glass composition described according to claim 1~any one of 11, which is characterized in that in 10 matter Measure in the HCL aqueous solution 100ml of %, 80 DEG C, the rate of mass reduction of glass when being impregnated under conditions of 90 hours be 4% with Under.
13. a kind of glass fibre, which is characterized in that it includes the glass fibre of any one of claim 1~12 glass groups Close object.
14. a kind of manufacturing method of glass fibre, which is characterized in that raw materials batch is melted with glass melting furnace, it will Resulting melten glass is continuously extracted out from bushing and is configured to threadiness,
The raw materials batch is to become SiO in terms of the quality % formed by weight of oxide as glass250%~65%, Al2O30%~5%, CaO 0%~10%, Na2O 10%~20%, K2O 0%~5%, ZrO2It more than 15% and is 20% Below, TiO20.1%~10%, B2O3Obtained by 0.1%~10% mode is deployed.
15. the manufacturing method of glass fibre according to claim 14, which is characterized in that with the spinning temperature of resulting glass The mode that the difference of degree and liquidus temperature reaches 115 DEG C or more deploys raw materials batch.
16. the manufacturing method of glass fibre according to claim 14 or 15, which is characterized in that it is used according to aoxidize The B of the mass ratio meter of object conversion2O3/TiO2Value as 0.01~95 mode deploy obtained by raw materials batch.
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CN112679096A (en) * 2020-12-31 2021-04-20 山东天舜环保科技有限公司 High-performance colored glass fiber and preparation method thereof
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