JPH0729815B2 - Glass fiber - Google Patents
Glass fiberInfo
- Publication number
- JPH0729815B2 JPH0729815B2 JP62008557A JP855787A JPH0729815B2 JP H0729815 B2 JPH0729815 B2 JP H0729815B2 JP 62008557 A JP62008557 A JP 62008557A JP 855787 A JP855787 A JP 855787A JP H0729815 B2 JPH0729815 B2 JP H0729815B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- glass fiber
- fiber
- fibers
- elastic modulus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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
-
- 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
- C03C3/045—Silicon oxycarbide, oxynitride or oxycarbonitride glasses
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
- C03B2201/24—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with nitrogen, e.g. silicon oxy-nitride glasses
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Glass Compositions (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、ガラス繊維およびその製造方法に関する。さ
らに、詳しくは本発明はFRP、繊維補強セメントなどの
複合材料用の補強繊維として用いるに適した高弾性のガ
ラス繊維およびその製造方法に関する。TECHNICAL FIELD The present invention relates to a glass fiber and a method for producing the same. More specifically, the present invention relates to highly elastic glass fibers suitable for use as reinforcing fibers for composite materials such as FRP and fiber reinforced cement, and a method for producing the same.
従来の技術 近年、プラスチック、あるいはセメントなどの構造材を
強化する有力な手段として、これらの材料にガラス繊維
を混合する材料の複合化が進められている。このような
複合材料に用いられるガラス繊維には高い強度が求めら
れているが、従来はＥガラス、Ｓガラスを繊維化したも
のが広く用いられてきた。2. Description of the Related Art In recent years, as a powerful means for strengthening structural materials such as plastic or cement, compounding of glass fibers with these materials has been advanced. The glass fiber used for such a composite material is required to have high strength, but conventionally, glass fibers of E glass and S glass have been widely used.
一方、オキシナイトライドガラスは、酸化物ガラスの酸
素原子が窒素に置き換わった構造を有しており、窒素原
子の結合原子価が３であるところから従来のガラスに比
べ、高弾性率を有する。かかるオキシナイトライドガラ
ス弐の製造方法には、ゾル・ゲル法、熔融法、N2ガス吹
き込み法、多孔質ガラスのNH3ガス処理法などがある。On the other hand, oxynitride glass has a structure in which oxygen atoms of oxide glass are replaced with nitrogen, and the bond valence of nitrogen atoms is 3, so that it has a higher elastic modulus than conventional glasses. Examples of the method for producing such oxynitride glass include the sol-gel method, the melting method, the N 2 gas blowing method, and the NH 3 gas treatment method for porous glass.
しかしながら、その繊維化にあたっては、前記のうちゾ
ル・ゲル法を用いたものが存在するに過ぎない。However, in forming the fiber, only the one using the sol-gel method is available.
発明が解決しようとする問題点 従来、用いられている強化用ガラス繊維の強度はなお充
分でなく、弾性率についてはＥガラスで最大7500kg/mm2
であり、もっとも高い弾性率を有するImperial N−672
で12110kg/mm2に過ぎない。また高弾性を有するオキシ
ナイトライドガラス繊維にあっても、これまでゾル・ゲ
ル法により得られた繊維の弾性率は約8000kg/mm2と複合
材料の強化用ガラス繊維としてはなお充分とは言えな
い。Problems to be Solved by the Invention The strength of conventionally used reinforcing glass fiber is still insufficient, and the elastic modulus of E glass is 7500 kg / mm 2 at maximum.
And has the highest elastic modulus, Imperial N-672.
It is only 12110 kg / mm 2 . Even in oxynitride glass fiber having high elasticity, the elastic modulus of the fiber obtained by the sol-gel method up to now is about 8000 kg / mm 2, and it can be said that it is still sufficient as a glass fiber for reinforcing composite materials. Absent.
問題点を解決するための手段 本発明者らは、強化用繊維として優れた強度を有するガ
ラス繊維を得るべく種々検討を重ねた結果、材料として
オキシナイトライドガラスを用い、これを熔融法により
紡糸すれば、極めて高強度、高弾性のガラス繊維が得ら
れるとの知見を得、本発明を完成するに至った。Means for Solving the Problems As a result of various studies to obtain glass fibers having excellent strength as reinforcing fibers, the inventors have used oxynitride glass as a material and spun it by a melting method. Then, it was found that a glass fiber having extremely high strength and high elasticity can be obtained, and the present invention has been completed.
すなわち、本発明は、弾性率12500kg/mm2以上を有する
ガラス繊維およびその製造法を提供するものである。That is, the present invention provides a glass fiber having an elastic modulus of 12500 kg / mm 2 or more and a method for producing the same.
本発明のガラス繊維は、従来のガラス繊維では達成でき
なかった弾性率12500kg/mm2以上を得ることが可能とな
った。With the glass fiber of the present invention, it has become possible to obtain an elastic modulus of 12500 kg / mm 2 or more, which could not be achieved with conventional glass fibers.
本発明ガラス繊維の材料としてはオキシナイトライドガ
ラスが用いられる。オキシナイトライドガラスの組成と
しては、Ca−Si−Al−Ｏ−Ｎ、Na−Ca−Si−Ｏ−Ｎ、La
−Si−Al−Ｏ−Ｎ、Na−Ｂ−Si−Ｏ−Ｎ、Mg−Si−Al−
Ｏ−Ｎ、Si−Al−Ｏ−Ｎ、Ｙ−Al−Si−Ｏ−N Na−Ｂ−
Al−Ｐ−Ｏ−Ｎなどが挙げられる。Oxynitride glass is used as the material of the glass fiber of the present invention. The composition of oxynitride glass includes Ca-Si-Al-O-N, Na-Ca-Si-O-N, and La.
-Si-Al-O-N, Na-B-Si-O-N, Mg-Si-Al-
ON, Si-Al-ON, Y-Al-Si-ON Na-B-
Al-P-O-N etc. are mentioned.
このような組成のオキシナイトライドガラスを得るに
は、金属酸化物に金属窒化物を加え、高温で熔融する。To obtain an oxynitride glass having such a composition, a metal nitride is added to a metal oxide and melted at a high temperature.
金属酸化物の例としては、SiO2、CaO、MgO、SrO、Na
2O、K2O、La2O3、Y2O3、ZrO2、TiO2、Na2O、K2O、B2O3
などが挙げられる。Examples of metal oxides include SiO 2 , CaO, MgO, SrO, Na
2 O, K 2 O, La 2 O 3 , Y 2 O 3 , ZrO 2 , TiO 2 , Na 2 O, K 2 O, B 2 O 3
And so on.
また、金属窒化物の例としては、Si3N4、AlNなどが用い
られる。Moreover, as an example of the metal nitride, Si 3 N 4 , AlN, or the like is used.
つぎに、これら混合物を熔融するには、電気炉、イメー
ジ炉などの加熱炉を用い、窒素雰囲気下、温度1400〜19
00℃、昇温速度10〜800℃/minにて処理する。Next, in order to melt these mixtures, a heating furnace such as an electric furnace or an image furnace is used, and the temperature is 1400 to 19 in a nitrogen atmosphere.
Process at 00 ℃, heating rate 10-800 ℃ / min.
得られたガラスを窒素雰囲気下、温度1100〜1600℃にて
加熱、熔融し、紡糸速度20〜3000m/minにて紡糸して連
続繊維を得る。The obtained glass is heated and melted at a temperature of 1100 to 1600 ° C. under a nitrogen atmosphere, and spun at a spinning speed of 20 to 3000 m / min to obtain continuous fibers.
得られたガラス繊維の弾性率は、12500〜18000g/mm2、
引っ張り強度70〜500kg/mm2である。The elastic modulus of the obtained glass fiber is 12500 to 18000 g / mm 2 ,
Tensile strength is 70 to 500 kg / mm 2 .
ガラス繊維の繊維径は、５〜150μｍであるのが好まし
い。繊維径がこれより小さいと、紡糸が固難であり、一
方、これを越えると強度が極端に低下し好ましくない。The fiber diameter of the glass fiber is preferably 5 to 150 μm. If the fiber diameter is smaller than this, spinning is difficult to harden, while if it exceeds this, the strength is extremely lowered, which is not preferable.
ガラス繊維の窒素含有率は、１〜13.5重量％であるのが
好ましい。窒素含有率が、１重量％未満であると、窒素
添加の効果がなく、13.5重量％を越えると結晶化し好ま
しくない。The nitrogen content of the glass fiber is preferably 1 to 13.5% by weight. If the nitrogen content is less than 1% by weight, the effect of nitrogen addition is not obtained, and if it exceeds 13.5% by weight, crystallization is not preferable.
窒素含有率の調整は、窒化物原料の添加割合により行な
う。The nitrogen content is adjusted by the addition ratio of the nitride raw material.
作用 本発明により極めて高弾性のガラス繊維が得られる。Effect The present invention provides glass fibers with extremely high elasticity.
実施例 つぎに、実施例により本発明をさらに具体的に説明す
る。EXAMPLES Next, the present invention will be described more specifically by way of examples.
実施例１ SiO225gおよび、CaOの原料であるCaCo370gを混合し、空
気中1500℃で２時間熔融した。混合物を冷却後、ボール
ミルを用いて約10μｍに粉砕し、Si3N413gを加え、窒化
ホウ素ルツボを用い、窒素中1750℃で30分熔融し、オキ
シナイトライドガラスを得た。得られたガラスを第１図
に示す紡糸装置内に配置した窒化ホウ素ルツボ１に入
れ、周囲を断熱材２により保温した円筒状のカーボン発
熱体３を用いて、窒素雰囲気下、1380℃にて加熱、紡糸
しワインダ４に巻取った。紡糸速度60m/minにて、直径
的30μｍの連続繊維を得た。得られたガラス繊維の引っ
張り弾性率は、13700kg/mm2であった。Example 1 25 g of SiO 2 and 70 g of CaCo 3 which is a raw material of CaO were mixed and melted in air at 1500 ° C. for 2 hours. After cooling the mixture, it was ground to about 10 μm using a ball mill, 13 g of Si 3 N 4 was added, and the mixture was melted in nitrogen at 1750 ° C. for 30 minutes using a boron nitride crucible to obtain an oxynitride glass. The obtained glass was placed in a boron nitride crucible 1 arranged in the spinning device shown in FIG. 1, and a cylindrical carbon heating element 3 having its periphery kept warm by a heat insulating material 2 was used at 1380 ° C. in a nitrogen atmosphere. It was heated, spun, and wound on a winder 4. Continuous fibers having a diameter of 30 μm were obtained at a spinning speed of 60 m / min. The tensile modulus of elasticity of the obtained glass fiber was 13700 kg / mm 2 .
実施例２ オキシナイトライドガラスの原料としてSiO224g、AlO35
g、CaCo368.5g、Si3N415gを用い、紡糸温度を1415℃し
た以外は前記実施例１と同様にして紡糸を行ない連続ガ
ラス繊維を得た。紡糸速度80m/minにて、直径的25μｍ
の繊維を得た。得られたガラス繊維の引っ張り弾性率は
15500kg/mm2であった。Example 2 As a raw material for oxynitride glass, SiO 2 24 g and AlO 3 5
Spinning was performed in the same manner as in Example 1 except that g, CaCo 3 68.5 g, and Si 3 N 4 15 g were used and the spinning temperature was 1415 ° C. to obtain a continuous glass fiber. 25 μm in diameter at a spinning speed of 80 m / min
Fibers were obtained. The tensile modulus of elasticity of the obtained glass fiber is
It was 15500 kg / mm 2 .
実施例３〜５ つぎの第１表に示す組成および条件により実施例１と同
様にしてガラス繊維を得た。Examples 3 to 5 Glass fibers were obtained in the same manner as in Example 1 with the compositions and conditions shown in Table 1 below.
発明の効果 本発明のガラス繊維は、従来のガラス繊維では達成でき
なかった弾性率12500kg/mm2以上を得ることが可能とな
った。したがって、各種プラスチック、セメント用の強
化用繊維として極めて優れている。 EFFECTS OF THE INVENTION The glass fiber of the present invention can obtain an elastic modulus of 12500 kg / mm 2 or more, which cannot be achieved by the conventional glass fiber. Therefore, it is extremely excellent as a reinforcing fiber for various plastics and cement.
第１図は、本発明ガラス繊維の製造に用いる紡糸装置の
断面図である。 図中の主な符号はつぎのとおりである。 1:ルツボ、2:断熱材、3:発熱体。FIG. 1 is a sectional view of a spinning device used for producing the glass fiber of the present invention. The main symbols in the figure are as follows. 1: Crucible, 2: Insulation, 3: Heating element.
Claims (2)
維。1. A glass fiber having an elastic modulus of 12500 Kg / mm 2 or more.
項のガラス繊維。2. The first (1), wherein the fiber diameter is 5 to 150 μm.
Section glass fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62008557A JPH0729815B2 (en) | 1987-01-16 | 1987-01-16 | Glass fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62008557A JPH0729815B2 (en) | 1987-01-16 | 1987-01-16 | Glass fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63176340A JPS63176340A (en) | 1988-07-20 |
| JPH0729815B2 true JPH0729815B2 (en) | 1995-04-05 |
Family
ID=11696407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62008557A Expired - Lifetime JPH0729815B2 (en) | 1987-01-16 | 1987-01-16 | Glass fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0729815B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019003464A1 (en) | 2017-06-29 | 2019-01-03 | 日本板硝子株式会社 | Glass composition and glass product using same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0293105B1 (en) * | 1987-05-28 | 1993-04-21 | Shimadzu Corporation | Oxynitride glass and fibers thereof |
| RU2018491C1 (en) * | 1992-03-12 | 1994-08-30 | Виктор Федорович КИБОЛ | Method for production of basalt fibers |
| JP3425701B2 (en) * | 1993-10-14 | 2003-07-14 | 株式会社島津製作所 | Nitrogen-containing glass, its production method and glass fiber |
| CN114671621B (en) * | 2022-04-02 | 2023-09-19 | 陕西理工大学 | Method for preparing microcrystalline glass fiber by utilizing blast furnace slag powder and microcrystalline glass fiber |
-
1987
- 1987-01-16 JP JP62008557A patent/JPH0729815B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019003464A1 (en) | 2017-06-29 | 2019-01-03 | 日本板硝子株式会社 | Glass composition and glass product using same |
| EP4276079A2 (en) | 2017-06-29 | 2023-11-15 | Nippon Sheet Glass Co., Ltd. | Glass composition and glass product using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63176340A (en) | 1988-07-20 |
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