JPH07166475A - Alumina yarn stuck with sizing agent - Google Patents
Alumina yarn stuck with sizing agentInfo
- Publication number
- JPH07166475A JPH07166475A JP31338793A JP31338793A JPH07166475A JP H07166475 A JPH07166475 A JP H07166475A JP 31338793 A JP31338793 A JP 31338793A JP 31338793 A JP31338793 A JP 31338793A JP H07166475 A JPH07166475 A JP H07166475A
- Authority
- JP
- Japan
- Prior art keywords
- sizing agent
- alumina
- fiber
- yarn
- weight
- 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.)
- Pending
Links
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は糊剤を付着したアルミナ
質繊維に関するものである。更に詳細にはアルミナ質繊
維の織布、不織布、組紐等を製造するのに好適な繊維を
得るための糊剤付着アルミナ質繊維に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alumina fiber to which a sizing agent is attached. More specifically, the present invention relates to a sizing agent-adhered aluminous fiber for obtaining a fiber suitable for producing a woven fabric, a non-woven fabric, a braid and the like of an aluminous fiber.
【０００２】[0002]
【従来の技術】アルミナ質繊維は耐熱性があり、軽量で
高強度、高弾性を有し、織布や組紐状として耐熱性分野
等で使用されている。しかし、アルミナ質繊維は伸度が
小さく脆い為にその取扱い中に折れやすく、毛羽も発生
しやすい。そこでこれらのアルミナ質繊維による織布や
組紐等の製造中及び製造後の性能を改良しやすくする為
に、各種糊剤を被覆することが行われている。2. Description of the Related Art Alumina fibers have heat resistance, are lightweight, have high strength and high elasticity, and are used in the heat resistance field as woven fabrics or braids. However, since the alumina fiber has a small elongation and is brittle, it easily breaks during its handling and fluff easily occurs. Therefore, in order to make it easier to improve the performance of the woven fabric, braid, and the like made of these alumina fibers during and after the production, various sizing agents are coated.
【０００３】この糊剤としては、各種のエポキシ樹脂や
ポリビニルアルコール等からなるものが知られている。
例えば特開平３−７６８７２号公報には高純度アルミナ
長繊維を製織するに際し、エポキシ系樹脂を糊付けする
方法が提案されており、特開昭６１−８１４０３号公報
と特開昭５９−６６５７６号公報にはポリビニルアルコ
ール系糊剤及び糊付け方法が提案されている。As the sizing agent, those made of various epoxy resins, polyvinyl alcohol, etc. are known.
For example, Japanese Unexamined Patent Publication (Kokai) No. 3-76872 proposes a method of gluing an epoxy resin when weaving high-purity alumina long fibers, and is disclosed in Japanese Unexamined Patent Publication Nos. 61-81403 and 59-66576. Has proposed a polyvinyl alcohol-based sizing agent and a sizing method.
【０００４】[0004]
【発明が解決しようとする課題】特開平３−７６８７２
号公報で示されているエポキシ樹脂で糊付けされたアル
ミナ質繊維は、繊維と樹脂マトリックスとの接着性を向
上させる目的には適しているが、織布や組紐等にする為
には、繊維の摩擦が十分に小さいものではなく耐擦過性
が不充分で、織布や組紐等を製造中の繊維の切断や毛羽
を少なくする上で未だ改良の余地がある。[Patent Document 1] Japanese Unexamined Patent Publication No. 3-76872
Alumina fibers glued with an epoxy resin shown in Japanese Patent Publication are suitable for the purpose of improving the adhesiveness between the fibers and the resin matrix, but in order to make a woven cloth or a braid, the fibers of Since the friction is not sufficiently small and the abrasion resistance is insufficient, there is still room for improvement in cutting fibers and reducing fluff during the production of woven fabrics, braids and the like.
【０００５】特開昭６１−８１４０３号公報で示されて
いる、末端に反応性の硅素基を含有するポリビニルアル
コール系重合体を糊剤として使用したものは、織布や組
紐等を製造後に糊剤を水洗により容易に除去し得るもの
の、処理コストの比較的低い空気中での加熱除去方法
（以下、ヒートクリーニングと表現する）では充分に除
去できない。加えて、この糊剤はアルミナ質繊維の柔軟
性の改良に寄与しない。Japanese Patent Laid-Open No. 61-81403, which uses a polyvinyl alcohol-based polymer having a reactive silicon group at its end as a sizing agent, is used as a sizing agent after manufacturing a woven fabric, braid or the like. Although the agent can be easily removed by washing with water, it cannot be sufficiently removed by a heat removal method in air (hereinafter referred to as heat cleaning), which has a relatively low treatment cost. In addition, this sizing agent does not contribute to improving the flexibility of the alumina fiber.
【０００６】また、特開昭５９−６６５７６号公報に示
されているポリビニルアルコールと特定範囲の平均重合
度を有するポリエチレングリコール及びエマルジョン型
ワックスよりなる糊剤をアルミナ質繊維表面に糊付けし
たものは、繊維に柔軟性や集束性が付与され、繊維相互
或いは繊維と他の固体との摩擦が小さく、繊維の毛羽だ
ちや損傷の改良効果は見られるもののヒートクリーニン
グ性が不良であるとの欠点を有する。[0006] Further, the one in which a sizing agent composed of polyvinyl alcohol, polyethylene glycol having an average degree of polymerization in a specific range and emulsion type wax, as disclosed in JP-A-59-66576, is glued on the surface of an alumina fiber is The fibers have flexibility and bundling property, and the friction between the fibers or between the fibers and other solids is small, and although the effect of improving the fluffing and damage of the fibers can be seen, the heat cleaning property is poor. .
【０００７】そこで、本発明者等はアルミナ質繊維より
織布や組紐等を製造するに際し、繊維に適度の柔軟性と
集束性を付与し、繊維相互或いは繊維と他の固体との摩
擦が小さく、毛羽立ちや繊維損傷が少なく、かつ製造後
の織布や組紐より糊剤の加熱除去、即ちヒートクリーニ
ング性に優れたアルミナ質繊維を得ることを目的とし鋭
意検討した結果、本発明を完成するに至った。Therefore, the present inventors, when producing woven fabrics, braids and the like from alumina fibers, impart appropriate flexibility and bundling property to the fibers, and reduce friction between fibers or between fibers and other solids. The present invention has been completed as a result of diligent studies for the purpose of obtaining an alumina fiber excellent in heat cleaning property, that is, fluffing and fiber damage are small, and a sizing agent is removed by heating from a woven fabric or braid after production. I arrived.
【０００８】[0008]
【課題を解決するための手段】即ち、本発明はアルミナ
質繊維に対し、ケン化度約７０〜約９０モル％、平均重
合度約３００〜約１５００のポリビニルアルコール約１
０〜約５０重量％、平均重合度約７００〜約２５００の
ポリエチレングリコール約５０〜約９０重量％よりなる
糊剤を約１〜約１２重量％付着してなる糊剤付着アルミ
ナ質繊維を提供するにある。SUMMARY OF THE INVENTION That is, according to the present invention, about 1 to about 1 mol of polyvinyl alcohol having a saponification degree of about 70 to about 90 mol% and an average degree of polymerization of about 300 to about 1500 relative to an alumina fiber.
Provided is a sizing agent-adhered alumina fiber having a sizing agent comprising 0 to about 50% by weight and polyethylene glycol having an average degree of polymerization of about 700 to about 2500 of about 50 to about 90% by weight. It is in.
【０００９】以下、本発明を更に詳細にのべる。本発明
に於いて用いられるアルミナ質繊維とは、１本の直径が
約３〜約２０μｍ、長さ約１ｍｍ以上のものが約１００
〜約１００００本程度からなり、アルミナの含有量が約
６０重量％以上のものである。中でも１本の直径が約５
〜約１５μｍ、連続長繊維のものが約５００〜約６００
０本程度からなり、引張強度、弾性率はそれぞれ約１５
０Kg／mm2 以上、約１２ｔ／mm2 以上の値を有するもの
が好ましい。上記のアルミナ質繊維は、例えば特公昭５
１−１２７３６号公報、特公昭５１−１３７６８号公報
等に記載された方法で製造することができる。The present invention will be described in more detail below. The alumina fiber used in the present invention has a diameter of about 3 to about 20 μm and a length of about 1 mm or more of about 100.
.About.10000, and the alumina content is about 60% by weight or more. Above all, the diameter of one is about 5
~ About 15μm, about 500 ~ 600 about continuous filaments
It consists of about 0 pieces, and the tensile strength and elastic modulus are each about 15
Those having a value of 0 kg / mm 2 or more and about 12 t / mm 2 or more are preferable. The above-mentioned alumina fiber is, for example, Japanese Patent Publication Sho 5
It can be produced by the method described in Japanese Patent Publication No. 12-13736, Japanese Patent Publication No. 51-13768, or the like.
【００１０】本発明に於いて用いられるポリビニルアル
コールはケン化度約７０〜約９０モル％、平均重合度約
３００〜約１５００のものである。ケン化度が約７０モ
ル％未満の場合は水に溶け難く、成膜した時の膜強度が
弱くなりすぎ不適当である。約９０モル％を越える場合
は膜強度が強く、硬くなってしまう為、糊付け処理され
た繊維束は柔軟性に欠け、目的を達成することができな
い。平均重合度が約３００未満の時は成膜性に欠け、且
つ膜強度も弱く不適である。約１５００を越える場合
は、水に対する溶解性が悪くなると共に処理繊維束の柔
軟性に欠ける。The polyvinyl alcohol used in the present invention has a saponification degree of about 70 to about 90 mol% and an average degree of polymerization of about 300 to about 1500. When the saponification degree is less than about 70 mol%, it is difficult to dissolve in water, and the film strength when formed is too weak, which is unsuitable. If it exceeds about 90 mol%, the film strength becomes strong and the film becomes hard, so that the fiber bundle subjected to the gluing treatment lacks flexibility, and the purpose cannot be achieved. When the average degree of polymerization is less than about 300, the film formability is insufficient and the film strength is weak, which is not suitable. When it exceeds about 1500, the solubility in water becomes poor and the treated fiber bundle lacks flexibility.
【００１１】本発明に於いて用いられるポリエチレング
リコールは平均重合度約７００〜約２５００である。平
均重合度が約７００未満の場合は、織布や組紐等を製造
した後のヒートクリーニング性に劣り、一部炭素が繊維
に残留しやすく悪影響を与える。約２５００を越えると
水への溶解度が減少し、融点も高くなり取扱い難くな
る。The polyethylene glycol used in the present invention has an average degree of polymerization of about 700 to about 2500. When the average degree of polymerization is less than about 700, the heat cleaning property after producing a woven fabric, a braid, etc. is poor, and some carbon is likely to remain in the fiber, which has an adverse effect. If it exceeds about 2,500, the solubility in water decreases, the melting point becomes high, and it becomes difficult to handle.
【００１２】これらポリビニルアルコールとポリエチレ
ングリコールの配合割合は、それぞれ約１０〜約５０重
量％、約５０〜約９０重量％の範囲であり、好ましくは
約１５〜約３５重量％、約６５〜約８５重量％の範囲で
ある。この範囲を越えた場合は、糊剤処理されたアルミ
ナ質繊維束の柔軟性が失われ、硬く脆くなり折れやすく
なって織布や組紐等に使用できない、繊維束表面の粘着
性が増し織機にかからない或いは生産速度が落ちる等の
問題が発生する。The blending ratio of these polyvinyl alcohol and polyethylene glycol is in the range of about 10 to about 50% by weight and about 50 to about 90% by weight, preferably about 15 to about 35% by weight and about 65 to about 85% by weight. It is in the range of% by weight. If it exceeds this range, the flexibility of the sizing agent-treated alumina fiber bundle is lost, it becomes hard and brittle, and it easily breaks, and it cannot be used for woven fabrics or braids. There is a problem that it does not occur or the production speed decreases.
【００１３】本発明に於いて、必要に応じて滑り性を改
良する為に周知のワックス類を添加したり、界面活性
剤、制電剤、酸化防止剤等を単独或いは２種以上で添加
してもよく、本発明の必須成分（糊剤）に対してこれら
の添加成分の合計が約５〜約３０重量％の範囲で使用し
てもよい。In the present invention, well-known waxes may be added as necessary to improve the slipperiness, or a surfactant, an antistatic agent, an antioxidant, etc. may be added alone or in combination of two or more. Alternatively, the total amount of these additional components may be in the range of about 5 to about 30% by weight with respect to the essential component (paste agent) of the present invention.
【００１４】これら糊剤のアルミナ質繊維束に対する付
着量は約１〜約１２重量％、好ましくは約３〜約１０重
量％である。付着量が１重量％未満の場合は糊剤の繊維
集束性が悪くなり、繊維束のバラケ、単繊維切れや繊維
束の切断を生じやすい。付着量が約１２重量％を越える
と屈曲強さが低下し、ヒートクリーニング性も不良とな
る。The amount of these sizing agents attached to the alumina fiber bundle is about 1 to about 12% by weight, preferably about 3 to about 10% by weight. When the adhesion amount is less than 1% by weight, the sizing agent has a poor fiber-bunching property, and the fiber bundle is likely to be scattered, and the single fiber or the fiber bundle may be cut. If the adhered amount exceeds about 12% by weight, the flexural strength decreases and the heat cleaning property becomes poor.
【００１５】アルミナ質繊維への該糊剤の付着方法は、
該糊剤を水溶液又は水エマルジョン液として使用する。
該糊剤の水溶液又は水エマルジョン液のアルミナ質繊維
への付着は、浸漬法、ローラー転写接触法、スプレー法
等の周知の方法によって行われる。The method of attaching the sizing agent to the alumina fiber is as follows.
The sizing agent is used as an aqueous solution or a water emulsion solution.
Adhesion of the aqueous solution or water emulsion solution of the sizing agent to the alumina fibers is performed by a known method such as a dipping method, a roller transfer contact method, or a spray method.
【００１６】アルミナ質繊維に付着された該糊剤は次い
で乾燥される。乾燥方法は特に限定されるものではな
く、例えば約１００℃〜約２００℃の熱風乾燥、或いは
熱ローラー上等での乾燥等、周知の方法によって行えば
よい。アルミナ質繊維に対する該糊剤の付着は、一般的
には、糊剤構成成分を混合後繊維表面に付着させるが、
必要により構成成分の一種を単独で付着させ乾燥させて
から別の成分を単独で付着させて乾燥させてもよいし、
付着、乾燥を複数回に分割、実施してもよい。The sizing agent attached to the aluminous fibers is then dried. The drying method is not particularly limited, and may be performed by a known method such as hot air drying at about 100 ° C. to about 200 ° C. or drying on a hot roller. Adhesion of the sizing agent to the alumina fiber is generally performed by adhering the sizing agent constituents to the fiber surface after mixing,
If necessary, one of the constituents may be adhered alone and dried, and then another constituent may be adhered alone and dried,
The adhesion and drying may be performed by dividing it into plural times.
【００１７】該糊剤のアルミナ質繊維への付着量の調節
は、該糊剤の水溶液、水エマルジョン液の濃度、繊維に
付与された張力や浸漬した後の液の絞り程度によって行
う。つまり、該糊剤の付着量は、水溶液やエマルジョン
液中の糊剤の濃度が高く、繊維に付与された張力が低く
液の絞り程度が小さいほど大きくなり、糊剤の濃度が低
く繊維に付与された張力が高く液の絞り程度が大きいほ
ど小さくなる。The amount of the sizing agent attached to the alumina fibers is controlled by the concentration of the sizing agent in the aqueous solution or the water emulsion solution, the tension applied to the fibers, and the degree of squeezing of the liquid after immersion. In other words, the amount of the sizing agent attached increases as the concentration of the sizing agent in the aqueous solution or emulsion liquid is high, the tension applied to the fiber is low, and the degree of squeezing of the liquid is small. The higher the applied tension and the larger the degree of contraction of the liquid, the smaller the tension.
【００１８】[0018]
【発明の効果】以上詳述した本発明の糊剤付着アルミナ
質繊維は、従来法に比較しヒートクリーニング性に優れ
ると共に、得られた繊維に適度な集束性、柔軟性、平滑
性を付与するので高い屈曲強さと耐擦過性を有する。従
って、該処理後の繊維を用い織布や組紐等を製造する際
に繊維の毛羽が発生し難く、損傷が少ないので加工時に
於ける繊維の切断が少なくなり、高品質の織布や組紐等
の加工品を高生産性、低コストで製造でき、その産業上
の価値は頗る大である。EFFECTS OF THE INVENTION The sizing agent-adhered alumina fiber of the present invention, which has been described in detail above, is superior in heat cleaning property to the conventional method and imparts appropriate sizing property, flexibility and smoothness to the obtained fiber. Therefore, it has high bending strength and scratch resistance. Therefore, when the woven fabric, braid, etc. are produced using the treated fiber, fiber fluff is less likely to occur, and damage is less, resulting in less fiber breakage during processing, and high quality woven fabric, braid, etc. Can be processed with high productivity and low cost, and its industrial value is enormous.
【００１９】[0019]
【実施例】以下、本発明を実施例により更に具体的に説
明するが、本発明はこれら実施例により限定されるもの
ではない。尚、本発明方法に於いて糊剤付着アルミナ質
繊維の評価は以下の方法により測定した。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, in the method of the present invention, the evaluation of the sizing agent-adhered alumina fiber was measured by the following method.
【００２０】屈曲強さ；表面が平滑な直径０．５ｍｍの
金属棒に繊維を３６０度屈曲させて引っ掛け、引張速度
８０ｍｍ／分で引っ張った時の繊維が破断する強度。Flexural strength: Strength at which the fiber breaks when the fiber is bent 360 degrees on a metal rod having a smooth surface and a diameter of 0.5 mm to be hooked and pulled at a pulling speed of 80 mm / min.
【００２１】耐擦過性；２００ｇの張力で引っ張った繊
維の上に、１００ｇの張力で引っ張った繊維を１３５度
の折り曲げ角度で９０度に交叉させた状態で、該繊維を
１００ｍｍ／秒の速度で３５０ｍｍのストロークで６０
回往復運動させた後の毛羽立ちの少ないものから○、
△、×で評価した。Scratch resistance: A fiber pulled by a tension of 200 g and a fiber pulled by a tension of 100 g are crossed at 90 ° at a bending angle of 135 °, and the fiber is fed at a speed of 100 mm / sec. 60 with a 350 mm stroke
From the one with less fluff after reciprocating motion ○,
It was evaluated by Δ and ×.
【００２２】集束性；直径２０ｍｍのガラス管の中に繊
維の一端を固定し、固定した側から乾燥した空気を２Kg
／cm2 の圧力で４分間流通した後、繊維の広がり状態を
広がりの少ないものから○、△、×で評価した。Convergence: One end of the fiber is fixed in a glass tube having a diameter of 20 mm, and 2 kg of dry air is supplied from the fixed side.
After flowing for 4 minutes at a pressure of / cm 2 , the spreading condition of the fibers was evaluated by ○, Δ, and × from the one with less spreading.
【００２３】ヒートクリーニング性；糊剤を付着させた
アルミナ質繊維束１ｍ長を、空気中で６００℃×１時
間、７００℃×１時間それぞれ加熱したものについて、
黒色物が全く見られないものを○、１〜４個見られるも
のを△、５個以上見られるものを×で評価した。Heat-cleaning property: Aluminous fiber bundles 1 m long to which a sizing agent is attached are heated in air at 600 ° C. × 1 hour and 700 ° C. × 1 hour, respectively,
The case where no black matter was observed at all was evaluated as ◯, the case where 1 to 4 pieces were observed was evaluated as Δ, and the case where 5 or more pieces were observed was evaluated as x.
【００２４】実施例１〜３、比較例１〜８ ケン化度８８モル％、各種平均重合度のポリビニルアル
コール２０重量％を熱水中に溶解し、それに各種平均重
合度のポリエチレングリコール７０重量％、エマルジョ
ンタイプワックス１０重量％を加え水溶性液を得た。こ
の水溶性液中にアルミナ質繊維束（住友化学工業株式会
社製、アルテックス−アルミナ分８５重量％、シリカ分
１５重量％、径１５μｍ、引張強度１８０Kg／mm2 、引
張弾性率２００００Kg／mm2 、単繊維数約１０００本）
を浸漬し、取り出して１３０℃で揮発分を乾燥し表１に
示す対繊維糊剤付着量のものを得た。性能評価結果を表
１に示す。Examples 1 to 3 and Comparative Examples 1 to 8 20% by weight of polyvinyl alcohol having a saponification degree of 88 mol% and various average degrees of polymerization are dissolved in hot water, and 70% by weight of polyethylene glycol having various average degrees of polymerization is dissolved therein. Then, 10% by weight of the emulsion type wax was added to obtain an aqueous solution. In this water-soluble liquid, an alumina fiber bundle (manufactured by Sumitomo Chemical Co., Ltd., Altex-alumina content 85% by weight, silica content 15% by weight, diameter 15 μm, tensile strength 180 kg / mm 2 , tensile elastic modulus 20000 kg / mm 2 , About 1000 single fibers)
Was dipped, taken out and dried at 130 ° C. to remove the volatile matter, to obtain the one shown in Table 1 with the amount of the fiber sizing agent attached. The performance evaluation results are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
Claims (1)
０モル％、平均重合度３００〜１５００のポリビニルア
ルコール１０〜５０重量％、平均重合度７００〜２５０
０のポリエチレングリコール５０〜９０重量％よりなる
糊剤を１〜１２重量％付着してなる糊剤付着アルミナ質
繊維。1. A saponification degree of 70 to 9 with respect to an alumina fiber.
0 mol%, polyvinyl alcohol having an average degree of polymerization of 300 to 1500 10 to 50% by weight, average degree of polymerization of 700 to 250
A sizing agent-adhered alumina fiber having a sizing agent consisting of 50 to 90% by weight of polyethylene glycol of 0 attached to 1 to 12% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31338793A JPH07166475A (en) | 1993-12-14 | 1993-12-14 | Alumina yarn stuck with sizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31338793A JPH07166475A (en) | 1993-12-14 | 1993-12-14 | Alumina yarn stuck with sizing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07166475A true JPH07166475A (en) | 1995-06-27 |
Family
ID=18040658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31338793A Pending JPH07166475A (en) | 1993-12-14 | 1993-12-14 | Alumina yarn stuck with sizing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07166475A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009522461A (en) * | 2005-12-30 | 2009-06-11 | スリーエム イノベイティブ プロパティズ カンパニー | Ceramic oxide fiber |
| CN106884328A (en) * | 2017-03-24 | 2017-06-23 | 武汉龙图新材料科技有限公司 | A kind of alumina fibre sizing agent and preparation method thereof |
| CN106894238A (en) * | 2017-03-24 | 2017-06-27 | 武汉龙图新材料科技有限公司 | A kind of silicon carbide fibre sizing agent and preparation method thereof |
| CN106948176A (en) * | 2017-03-24 | 2017-07-14 | 武汉龙图新材料科技有限公司 | A kind of silicon nitride fiber sizing agent and preparation method thereof |
-
1993
- 1993-12-14 JP JP31338793A patent/JPH07166475A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009522461A (en) * | 2005-12-30 | 2009-06-11 | スリーエム イノベイティブ プロパティズ カンパニー | Ceramic oxide fiber |
| EP1969173A4 (en) * | 2005-12-30 | 2015-07-08 | 3M Innovative Properties Co | Ceramic oxide fibers |
| CN106884328A (en) * | 2017-03-24 | 2017-06-23 | 武汉龙图新材料科技有限公司 | A kind of alumina fibre sizing agent and preparation method thereof |
| CN106894238A (en) * | 2017-03-24 | 2017-06-27 | 武汉龙图新材料科技有限公司 | A kind of silicon carbide fibre sizing agent and preparation method thereof |
| CN106948176A (en) * | 2017-03-24 | 2017-07-14 | 武汉龙图新材料科技有限公司 | A kind of silicon nitride fiber sizing agent and preparation method thereof |
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