JPS59144620A - Partially stabilized zirconia fiber - Google Patents
Partially stabilized zirconia fiberInfo
- Publication number
- JPS59144620A JPS59144620A JP1349183A JP1349183A JPS59144620A JP S59144620 A JPS59144620 A JP S59144620A JP 1349183 A JP1349183 A JP 1349183A JP 1349183 A JP1349183 A JP 1349183A JP S59144620 A JPS59144620 A JP S59144620A
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- zirconia
- stabilized zirconia
- fiber
- tetragonal
- 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.)
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- Inorganic Fibers (AREA)
Abstract
Description
【発明の詳細な説明】 本発明は部分安定化ジルコニア實藏維に関する。[Detailed description of the invention] The present invention relates to partially stabilized zirconia fibers.
ジルコニアセラミックは耐熱性、耐蝕性等において他の
セラミックの追随を許さないほど優れた性實を有する月
利である。しかし、ioo。Zirconia ceramic has excellent properties such as heat resistance and corrosion resistance that are unrivaled by other ceramics. But ioo.
〜1200℃付近で単斜晶−正方晶間の相転移が起きる
ため、ジルコニア単独組成(1000〜1200℃以下
の低温では単斜晶)のセラミックを作製することが困難
であったり、便用温度が限られたりして取扱いにくい材
料であった。Because the phase transition between monoclinic and tetragonal occurs at temperatures around ~1200°C, it is difficult to produce ceramics with a single composition of zirconia (monoclinic at low temperatures below 1000-1200°C), and It was a difficult material to handle due to limited availability.
ところが、ジルコニアにマグネシア、カルシア、希土類
・変化物等を糸加することによシ高温な定泪であるホタ
ル石型立方晶として前記相転移を防IFLようとする安
定化ジルコニアや、立方晶と単斜晶との混合物として前
記相転移を一部残しだ部分安定化ジルコニアが開発され
、相転移に伴う取扱いにくさがある稈度だ服されてさた
。However, by adding magnesia, calcia, rare earth elements, etc. to zirconia, stabilized zirconia and cubic crystals can be created that prevent the above phase transition from IFL as a fluorite-type cubic crystal which has a constant state of high temperature. Partially stabilized zirconia, which partially retains the phase transition described above, was developed as a mixture with monoclinic crystals, and the culm that is difficult to handle due to the phase transition has been overcome.
しかしながら、こうした安定化あるいは部外安定化ジル
コニアは上述したような化学組成及び結晶構イMを有す
るため、純ジルコニアが本来性すると予想される特性を
元分発+!ltl〜でいるとはi゛い引トいのが実情で
ある。However, since such stabilized or externally stabilized zirconia has the above-mentioned chemical composition and crystal structure M, it has properties that are expected to be inherent in pure zirconia. The reality is that it is very difficult to be ltl~.
一ノテ、ジルコニア賀、竜誰に関してもこれ捷で釜くの
提案がなされ、商品化も試みられてきだが、未7で良好
な繊維が寿らnていない。その原因としては上述した安
定化または部分安定化ジルコニアセラミックの開発にお
ける伎南的思;(IAをその蜂ま受は継いた形での提案
しかなされていないことを神げることができる。例えば
、(Jsp3992498では相転オ多の1涛市という
点にのみ層目し、安に化剤としてマグネシウム、カルシ
ウム、穐土顛化合物を加えるとtハう7〕こけて刃、1
Illの1晟購造についての検謄1はは(1−んどなさ
れていない。まグと、カルシア、イツトリア、ンリカを
加えて形成された立方晶ジルコニア(尼や安定化ジルコ
ニア)あるいは立方晶ジルコニアオ午沙な相として各i
l’、一部汁女定化ジルコニアからなる繊維(U S
p3311481 )や、マダイ、ンア、カルシアを角
んた立方晶安定化ジルコニア賀、成維(USP3322
865、・旨公昭45−9896)が知られているが、
従来からの安定化または?f15 O安定化ジルコニア
セラミックの考え万から脱却しているとはiい帷い。Proposals have been made to produce Ichinote, zirconia and dragon fibers using this method, and attempts have been made to commercialize them, but good fibers have not yet been produced. The reason for this is the above-mentioned Kinan thinking in the development of stabilized or partially stabilized zirconia ceramics (it can be said that proposals have only been made in the form of IA). For example, , (Jsp3992498 focuses only on the point that the phase change is 1, and adds magnesium, calcium, and a clay compound as a chemical agent.
Verification 1 for Ill's 1st year purchase is (1-1).Cubic zirconia (or stabilized zirconia) or cubic zirconia formed by adding mag, calcia, ittria, and nrica. Each i as a zirconia phase
l', fibers partially composed of zirconia (U.S.
p3311481), cubic stabilized zirconia with square sea bream, nua, and calcia
865, 1986-9896) is known,
Conventional stabilization or? It's amazing how far the idea of f15 O-stabilized zirconia ceramics has gone.
したがって、上述したようなジルコニア質憤=a +は
機械的外力に対して脆く、+繊維のま塘の状態で敗り扱
うことが困難てあった。Therefore, the above-mentioned zirconia fibers are brittle against external mechanical forces, and are difficult to handle when they are still in the form of fibers.
本発明は上記事゛晴に虚みてなされたものであり、oT
撓性で・・繊維としての取り扱いの容賜な部分安定化ジ
ルコニア質裁維を沸供しようとするものである。The present invention has been made in light of the above, and is
The aim is to provide partially stabilized zirconia fibers that are flexible and easy to handle as fibers.
本発明者らl/j、鷹維の化学組成及び微構造に着目し
て検討を市ねた結果、本発明をなすに至った。The present inventors conducted studies focusing on the chemical composition and microstructure of l/j and hawk fibers, and as a result, the present invention was completed.
すなわち、本発明の部分安定化ジルコニア質礒碓は、ジ
ルコニアの他にマグネシア、カルシア、チタニア、変化
インジウム及び希土頌元素情化物のうち少なくとも一棟
を下記の化学組成範四でキみ、かつ2μm以下の正方晶
結晶子を10重骨%以上有することを特徴とするもので
あるっ
一ヒ記゛つ化゛吻ノ化学絹、 rr’Q ・H+j、
11111rJ−4=# 中K 者マ、hる;佼化物の
貸体を100モル係としてモル俸で() 1 ご≦呈ヤ
ト、イ≦’0 ’= 1 4 、 0
.1:’Q Ca0S 12 。That is, the partially stabilized zirconia-based powder of the present invention contains, in addition to zirconia, at least one of magnesia, calcia, titania, modified indium, and rare earth oxides in the following chemical composition range 4, and The chemical silk described in the above is characterized by having 10% or more of tetragonal crystallites with a diameter of 2 μm or less, rr'Q ・H+j,
11111rJ-4=# Medium K person ma, hru; Assuming that the lending body of the compound is 100 moles, the molar salary is () 1 ≦ presentation yato, i ≦ '0' = 1 4, 0
.. 1:'Q Ca0S 12 .
0.05’; TiO2S 20 、 0.05SI
n203415 。0.05'; TiO2S 20 , 0.05SI
n203415.
0 ()5≦SC2Q3く、15 、 0.
05≦、Y2O3〈〜 4 。0 ()5≦SC2Q3ku, 15, 0.
05≦, Y2O3<~4.
005SLa−ro3;”=30 + 0.055
Ce02:525 +005≦、Pr60I Is
20 + 0.05<、Nd2O3’、y−15r
o、05″′−、Sm20s’l’;、15 +
0.05<、Eu203−15 +0.05−千’=
Gd 20sS、 1 5 ’+ 0.
05で’:’、 T +)、o 7 二〉 15 。005SLa-ro3;”=30+0.055
Ce02:525 +005≦, Pr60I Is
20 + 0.05<, Nd2O3', y-15r
o, 05″′−, Sm20s′l′;, 15 +
0.05<, Eu203-15 +0.05-1000'=
Gd 20sS, 1 5'+0.
05 ':', T +), o 7 2〉 15.
o、oa= D7203 S 15 + 0.05
’> Ho203m 15 +005て、Er203
≦−,15、o、os\ ’丁m2o3”、:’:’y
1 5 +0.05;i Yb20s S 1
5 、 0.05りLu2O3$ 15である。o, oa = D7203 S 15 + 0.05
'> Ho203m 15 +005, Er203
≦-, 15, o, os\ 'Cing m2o3', :':'y
1 5 +0.05;i Yb20s S 1
5, 0.05 riLu2O3$15.
!+:I″:来におけるジルコニアの部分安定化の沈木
的な栓えh−は、ホタルNi )Qj立方晶(安定化ジ
ルコニア)と甲斜晶(非安定化ジルコニア)との混合(
′ツとすることで鳥6・〃、から低温まで、11転移を
起こさないという性・tqを安定化ジルコニアに寿たせ
るとともに非安定化ジルコニアによって安定化ジルコニ
アのもつ欠点をある惺度改良しようとするものでりる。! +:I″:The sunken wood plug h- of partial stabilization of zirconia in the past is a mixture of firefly Ni)Qj cubic crystal (stabilized zirconia) and cholinic crystal (unstabilized zirconia) (
By making stabilized zirconia, we aim to extend the lifespan of stabilized zirconia by not causing the 11 transition from 6. It's something to do.
これに対して、本発明の部分’M’if−イヒジルコニ
ア買偵椎は室温で準安定な正方晶(℃必用的に青むもの
であり、この正方晶5時晶子は応力、ぜんめ〒、jrM
等の機械的外力によって室温における安定相である単斜
晶に転移する。したがって、(、iff来の部分安定化
ジルコニアが必須構成相としてホタル石型立方JAlk
沈むという考え方とは根本的VC黄なる。On the other hand, the part 'M'if-zirconia of the present invention is a metastable tetragonal crystal (°C) that necessarily turns blue at room temperature, and this tetragonal crystallite is caused by stress, jrM
It transforms into a monoclinic phase, which is a stable phase at room temperature, by an external mechanical force such as . Therefore, (, if partially stabilized zirconia is an essential constituent phase of the fluorite-type cubic JAlk
The idea of sinking is a fundamental VC problem.
、+発明の部分安定化ジルコニア買J((tにおいて、
嘴化物の化学組成&[′i、囲と一式維の微構造とを上
述したようにj現定したのはU下のような理由による。, + Partially stabilized zirconia purchase J ((t,
The chemical composition of the beak compound &['i, the surrounding area and the microstructure of the set of fibers were determined as described above for the reasons listed below.
1ず、・・)夕化物の化学組成砲門は繊維の微構造と相
互に関ヰしており、上述した範囲を外れると1.″J雄
中に2μm以下の正方晶結晶子を10嘱丑チ以上形成す
ることができない。すなわち、繊維中のMyO,CaO
がそれぞれ01モル条未740辺1合及びTiO□、
工n20s +希土唄元素啼化物がそれぞれ0.05モ
ルチ未満の場合にはM&維中にIF方晶がほとんど形成
されず、小斜晶または早斜晶と立方晶が形成され易くな
る。一方、値維中の各酸化物がそれぞれ上述した上限値
を超えた」!清合にに[立方晶が主相として形成され橢
くなる。本発明は純ジルコニア、戎維を沈むものではな
い。1,...) The chemical composition of the evening sun is mutually related to the microstructure of the fiber, and if it falls outside the above range, 1. "It is not possible to form more than 10 square crystallites of 2 μm or less in the J male. In other words, MyO, CaO in the fiber
are respectively 01 mol 740 sides 1 go and TiO□,
When the amount of the n20s + rare earth element nitride is less than 0.05 molti, hardly any IF square is formed in the M&fiber, and minor or peroclinic and cubic crystals are likely to be formed. On the other hand, each oxide in the value fiber exceeded the upper limit mentioned above. During the synthesis, cubic crystals are formed as the main phase and the crystal becomes opaque. The present invention does not contain pure zirconia or fibers.
また、本発明の部外安定化ジルコニア買鐵維は正方晶結
晶子を必須構成相としてよみ、その大きさは轢造方法、
化学組成等の違いにより石十′になるが2μm以下でし
か存在しイ畳ない。これは・成碓中の正方晶結晶子ば゛
室温においては帖安定であり、安定な単斜晶より自由エ
イ、ルギーの旨い状態にあるため、そのエネルギー差ケ
界+ftiエネルギー等の形状塘因による形で1呆持し
なければならず、大きな塊で存在するよりも小さく分、
赦された状態で存在した方がエネルギー的にイイ利とな
るためである。In addition, the externally stabilized zirconia steel fiber of the present invention has tetragonal crystallites as an essential constituent phase, and the size of the crystallites is determined by the rolling method.
Due to differences in chemical composition, etc., it can become a stone, but it exists only at a thickness of less than 2 μm and is not a problem. This is because the tetragonal crystallites under formation are stable at room temperature and are in a state of free energy and energy that is better than stable monoclinic crystals, so shape factors such as the energy difference field + fti energy etc. It must be kept in the form of 1 part, smaller than in large chunks,
This is because it is more energetically advantageous to exist in a forgiven state.
咀に、こうした正方晶結晶子I″ii哉維中に10市ト
、1%以上よまれる必要があり、10市計φ未病になる
と実用的な取り扱いが困難となり、伶喘な腸1合には、
戒椎の形態をとどめず粉化してしまう。こうした現象は
、鷹維に機イ・71に的外力が加えられた際に準安定な
正方晶結晶子が安定な申結情へ転移して機械的外力を吸
収するわけであるが、正方晶がxo3.@:骨饅未満に
なると機械的外力を吸収しきれないだめであると考えら
れる。In the mouth, it is necessary for these tetragonal crystallites to be absorbed by 1% or more during the formation of these tetragonal crystallites. In case,
It turns into powder without retaining its form. This phenomenon is caused by the fact that when an external force is applied to the hawk fiber, the metastable tetragonal crystallite transforms into a stable crystallite and absorbs the external mechanical force. is xo3. @: It is considered that if it becomes less than bone mass, it cannot absorb the external mechanical force.
以上のように、機維の化学組成と微JM造とは本発明の
部分安定化ジルコニア質絨維を構成するうえで不可分の
関係にあり、どちらか一方たけ満たされたとしても可撓
性で取り扱いの容易な・・戒、1韮を得ることはで@な
い。As described above, the chemical composition of the fiber and the fine JM structure are inseparable in constructing the partially stabilized zirconia fiber of the present invention, and even if one or the other is satisfied, it will not be flexible. It is not possible to obtain one precept that is easy to handle.
なお、本発明において1.或絢中の正方晶は100・1
1でも全く冷し支えはない。このような正方晶がioo
*=%の儀維はJ敢智な意味で(d部分安定化とはいえ
ないが、本願においては便宜上部外安定化ジルコニア′
W 41 維と称する。In addition, in the present invention, 1. Or the tetragonal crystal in Ayana is 100.1
1 has no cooling support at all. Such a tetragonal crystal is ioo
* = % is in a simple sense (although it cannot be said to be partially stabilized, in this application, it is conveniently referred to as externally stabilized zirconia).
It is called W 41 fiber.
凍だ、本発明において繊維を構成する必須構成相である
正方晶結晶子以外の部分はjll定形、立方晶結晶子ま
たは単斜晶結晶子あるいはこれら三神のうち二(す1以
上のi、l1合した状態である。In the present invention, the parts other than tetragonal crystallites, which are essential constituent phases constituting the fiber, are regular shaped, cubic crystallites, monoclinic crystallites, or two of these three gods (i of 1 or more, It is in a state where 11 is combined.
寸だ、A lil+中のジルコニア分はその原料から由
来するハフニアを10モル矛梶を里まで沈んだもので、
(うってもテE% j糸−ヒi亨し支えない。The zirconia content in Alil+ is made up of 10 moles of hafnia derived from the raw material.
(It doesn't support it even if it goes up.)
本発明の部分安定化ジルコニア′w ”+& :+jj
;を製造する方法としては、いわゆる熱分1lVt法が
・ぺしている。このノミ法は(+) ij]紡性枯稠溶
液(紡糸液)の調製、(11)乾式紡糸、(iii)熱
分I・a、Ov)結晶化執処「′11八を成A:r桿と
するものである。この方法は曳糸性の1憂れた紡糸液の
]j司シ;にが容易であり、イυノ糸;/んも従来技術
をその井ま1史うことかでさ、熱り11(により戒准中
に做・tHlなIE方晶ジルコニアを容弓に形成できる
点で・11刈である。1ツ、下、−上述した各丁桿につ
いてaq: in+に説明する。Partially stabilized zirconia of the present invention ′w ”+& :+jj
The so-called thermal 11Vt method is used as a method for producing . This chisel method includes (+) ij] Preparation of spinning solution (spinning solution), (11) Dry spinning, (iii) Heat component I・a, Ov) Crystallization process "'118" A: This method is easy to remove the spinning solution, which has poor spinnability, and also incorporates conventional technology. By the way, it is 11 years old in that it is possible to form the IE square zirconia into the bow during the precepts. 1, bottom - Regarding each of the above-mentioned bows: aq: I will explain to in+.
(1)用紡性枯(周温1夜(l−1:り下のようにして
調理される。(1) Cooked in the same manner as in the 1 night (1-1) period.
すなわち、水あるい(伐有機溶媒に少なくともジルコニ
ウム化合物及びV+y、 Ca、 ’ri 、 Inあ
るいは席上4、l’1元素の化合物等を混合、溶解し、
′政すればθ、゛3縮哲コ作して71力糸b]能々粘川
二に調整し、司紡性枯稠溶液(紡糸液)とする。That is, by mixing and dissolving at least a zirconium compound and a compound of V + y, Ca, 'ri, In or 4, 1' elements in water or organic solvent,
If the process is carried out, θ is prepared, ゛3 fibers are made, 71 fibers b] are adjusted to 2,000 ml, and a spinning solution (spinning solution) is obtained.
前記S機浴媒としては溶買の棹類に応じてアルコール、
ケトン、アミド系のもの等が1史用される。As the S bath medium, alcohol,
Ketones, amide types, etc. have been used for some time.
まだ、r+’lJ凸己ジルコニウム化合物としては(イ
)塩身塩、硝・う塩、四鳴化ジルコニウム等の無機ジル
コニウム化合物、あるいは(ロ)酢・唆塩、シュウ浚塩
、テトラベンジルジルコニウム等の有機ジルコニウム化
合物を挙げることができ、これらのうち少なくとも一種
が使用される。However, as r+'lJ convex zirconium compounds, (a) inorganic zirconium compounds such as salt salts, nitrate salts, zirconium tetrachloride, and (b) vinegar salts, salt salts, tetrabenzyl zirconium, etc. Organic zirconium compounds can be mentioned, and at least one of these is used.
また、前記Mグ+Ca+Ti、Inあるいは希土類元素
の化合物等としてはり(lI機化合物でも有機化合物で
もよく、これらのうち少なくとも一紳が1史用される。Further, the compound of Mg + Ca + Ti, In or rare earth elements may be an organic compound or an organic compound, and at least one of these is used.
こうした溶液に曳糸性及び溶液の安定性を向上させるた
めに塩酸、(IdC酸等の無磯峙、ギ酸、咋−嘩、乳愼
寺の有機□・・夕、有機高分子化合物、アルコール、イ
J+!j、ケトン、エーテル、エステル、if! 1I
jj酸、界面活性剤等を114゛目′添加してもよい。In order to improve the spinnability and stability of the solution, hydrochloric acid, (IdC acid, etc.), formic acid, organic acid, organic polymer compound, alcohol, i J+!j, ketone, ether, ester, if! 1I
Acid, surfactant, etc. may be added at the 114th point.
寸だ、この溶液にzr、 ”7+Ca+Ti+丁nある
い(は希土類元累寺の酸化物または水酸化物の粉末を0
口えてもよい。これら粉末の伯晶子径は2μrn Jン
、下であることが噴ましく1.史に気相法、聰分解法、
共沈法等で造られるサブミクロン粒子であることが望ま
し7い。特に、ジルコニア粉末(ri無定形あるいは低
温型市万晶に結晶化したサブミクロン粒子であることが
Stしい。In this solution, add a powder of oxide or hydroxide of rare earth oxide or hydroxide to this solution.
You can talk. The crystallite diameter of these powders is likely to be less than 2 μrn J. The history includes the gas phase method, the Satoshi decomposition method,
Preferably, the particles are submicron particles produced by a coprecipitation method or the like. In particular, zirconia powder (amorphous or low-temperature crystallized submicron particles) is preferred.
以上のように調製された溶液の枯;には組成あるいは柄
糸法によって異なるが、お2むね0.1〜10000ボ
イズの節回が望ましい。一般的に、溶液の粘度は紡糸す
る歳、1准がi%続、1維の場合には高めに、短1載維
の場合には低めにした方が紡糸操作が容颯となる。この
場合、口j粘性粘稠溶液中の結晶化熱処理後に潜られる
固形分箸は必ずしも多くなくともよく、むしろ紡糸特性
を重視する方が望ましい。The drying time of the solution prepared as described above varies depending on the composition or patterning method, but it is desirable that the number of voids be approximately 0.1 to 10,000. In general, the spinning operation will be more convenient if the viscosity of the solution is set higher in the case of spinning, i% continuous, 1 fiber, and lower in the case of short 1 fiber. In this case, it is not necessarily necessary that the amount of solid content absorbed into the viscous solution after the crystallization heat treatment is large, but rather it is preferable to emphasize the spinning properties.
(11)以上のように調製された”J紡性枯稠溶液(紡
糸液)は乾式紡糸により前・枢体である連続贋維または
知磯維に紡糸される。(11) The J-spinning dry solution (spinning solution) prepared as described above is spun into continuous fake fibers or Chiiso fibers, which are front and center fibers, by dry spinning.
++!!続繊維全繊維する場合には例えば従来からの巻
き取り法が用いられる。この巻き取り法は先端部が0.
05〜0.5 +a程度の径を有する紡糸、ノズルが取
付けられた容器内に紡糸液を入れ、圧縮ガスあるいはギ
アポンプ等を用いて紡糸液を下方に押し出して温湿凝が
N)4整されたイ囲気中で紡糸液の細流を形成し、溶媒
を揮散させながら回転している円筒ドラム上に落下させ
て円筒ドラムに連続線維を巻き取るものである。++! ! For example, a conventional winding method may be used to form a continuous fiber. In this winding method, the tip is 0.
The spinning solution is put into a container equipped with a spinning nozzle having a diameter of about 05 to 0.5 +a, and the spinning solution is pushed downward using compressed gas or a gear pump to achieve warm and wet coagulation (N)4. A thin stream of the spinning solution is formed in the surrounding air, and the spinning solution is dropped onto a rotating cylindrical drum while evaporating the solvent, and the continuous fiber is wound around the cylindrical drum.
また、巻き取り法に限らず、上述した如く温湿度の調整
された雰囲気中に押し出された細流を糸道で収束させ、
その下方に配置された回転円筒ドラムで一旦受け、更に
その下方に配[4゛された互いに反対方向に回転してい
る2個の円筒ドラムの間を通して連続繊維を延伸し、こ
の鐵維束を逆行方向に対して左右にゅっくシ振動しなが
ら進んでいるベルトコンベア上に捕畷する方法でもよい
。また、上記延伸操作は回転ドラムによらず、層流が形
rriされているエア流によっても行なうことができる
。In addition to the winding method, as mentioned above, it is possible to converge the trickle pushed out into an atmosphere with controlled temperature and humidity in the thread path,
The continuous fibers are once received by a rotating cylindrical drum placed below the iron fibers, and then drawn between two cylindrical drums placed below the iron fibers rotating in opposite directions. It is also possible to collect the rice on a belt conveyor that moves while vibrating left and right in the reverse direction. Further, the above-mentioned stretching operation can be performed not by using a rotating drum but also by using a laminar air flow.
このようにして紡糸された連続誠維の鷹維径は1〜10
0/Imとなる。The diameter of the continuous fiber spun in this way is 1 to 10.
0/Im.
一方、短、哉維は上記連続べ維を適当な長さに切断する
ことにより造ることができるが、例えば以Fのような方
法によっても造ることができる。On the other hand, short and long fibers can be made by cutting the above-mentioned continuous fibers into appropriate lengths, but they can also be made by, for example, the method described below.
すなわち、周IJ1」にいくっがの0.1〜1鶴匝の細
孔を治する回転円筒内に紡糸液を入れ、この円筒を高球
回転させ、遠心力により紡糸液を#tll孔から温湿度
の調整された雰囲気中に噴出させて短シ蔵堆を造ること
ができる。この隙、回転円筒の外周にエアジェツトを形
成し、紡糸液の+IN出益を吹き11ヲげせげ鷹雉イ・
絆のより小さい短傭維を造ることができる。That is, the spinning solution is put into a rotating cylinder that cures a pore of 0.1 to 1 tll in circumference IJ1, and this cylinder is rotated at a high pitch, and the centrifugal force causes the spinning solution to be heated through the #tll hole. It is possible to create a short-term storage tank by ejecting it into a humidity-controlled atmosphere. During this gap, an air jet is formed on the outer periphery of the rotating cylinder, and the +IN output of the spinning solution is blown out.
You can create short mercenary fibers with smaller bonds.
徳だ、連傍、1載44tを造るi奈と同情に温湿度のi
νI4幣された゛外囲気中で形成された紡糸液のI別離
をエアジェツトで吹き飛ばすことによっても短禮^・碩
を造ることができる。It's a virtue, I'm sorry for the temperature and humidity, and I'm sorry for making 44 tons in 1 listing.
It is also possible to create a short-cut fabric by blowing away the separation of the spinning solution formed in the surrounding air with an air jet.
このようにして造られた短繊維は、%続載、イトとlt
l・ゆして曳碓径が〜1分小さく、約0.5〜100μ
+71となる。The short fibers produced in this way are
l・The diameter of the spool is ~1 minute smaller, about 0.5~100μ
It becomes +71.
(:ii)以上のように作製された前駆体繊維を充分乾
燥して残余の溶媒を除去した後、ジルコニア繊維とする
ため、vD熱により前駆体鷹維中の化合物を分解体数せ
しめる。(:ii) After sufficiently drying the precursor fiber produced as described above to remove the remaining solvent, the compound in the precursor fiber is decomposed by VD heat to obtain a zirconia fiber.
上記分解温j貌は化合物、焼成雰囲気によって異なるが
、酸化性ず囲気、例えば空気、炭酸ガスあるいは水蒸気
(加水分解性゛イ囲気でもある)中においては、酢・酸
化合物は約400℃、塩素化合物は約600℃で熱処理
される。一般的な11向として有機化合物の場合は分解
温度が低く、前轍化合物の場合は分解濡髪が高い。また
、有機化合物を沈む前駆体繊維を非酸化性疼囲気、例え
ば窒素、アルゴン、ヘリウム、水素、アンモニアあるい
は−1化炭素中で加熱すると、炭素を陰むジルコニア′
政漬我維がイ外ら才する。The above decomposition temperature varies depending on the compound and the firing atmosphere, but in a non-oxidizing atmosphere such as air, carbon dioxide gas, or water vapor (also a hydrolyzable atmosphere), vinegar and acid compounds will react at about 400°C and chlorine. The compound is heat treated at about 600°C. In general, the decomposition temperature is low in the case of organic compounds, and the decomposition temperature is high in the case of front-rut compounds. In addition, heating the precursor fibers containing organic compounds in a non-oxidizing atmosphere, such as nitrogen, argon, helium, hydrogen, ammonia, or -carbon monoxide, produces carbon-containing zirconia'.
Masazuke Gawei is talented outside the country.
ここ1での工程を経たジルコニア質鷹維はX線回折によ
る分析でばnlf定形もしくは結晶形の判然としないブ
ロードなピークを示すW IJfである。When analyzed by X-ray diffraction, the zirconia fibers subjected to the step 1 are WIJf, which shows a broad peak with no distinct nlf or crystalline shape.
Gy) 史に熱処理を施すことにより2μat D)下
の正方晶結晶子を10重岐チ以上言む部分安定化ジルコ
ニアn、1、戒維を寿ることができる。By applying heat treatment to Gy), the tetragonal crystallites under 2μat D) can be made into partially stabilized zirconia with more than 10 folds.
この結晶化熱処理は上記(iii)の熱処理に引き続き
、同じ炉内で行なうことがでさる場合もあるが、良好な
繊維を得るためには上記(iii)の力;1熱条件とは
、温斐、昇温速1貌、雰円]気寺が異なる場合が多く、
一旦熱分解炉から繊維を取出して別の結晶化専用の炉に
移し替えて熱処理を行なう方が望ましい。In some cases, this crystallization heat treatment can be performed in the same furnace following the heat treatment in (iii) above, but in order to obtain good fibers, the power and heat conditions in (iii) above are [hi, temperature rise rate 1 aspect, atmosphere circle] Qi temples are often different,
It is preferable to once take out the fibers from the pyrolysis furnace and transfer them to another furnace dedicated to crystallization for heat treatment.
こうした結晶化熱処理としては例1えば、(イ)低温熱
処理法あるいは(ロ)高温熱処理法を皐けることができ
る。As such a crystallization heat treatment, for example, (a) a low-temperature heat treatment method or (b) a high-temperature heat treatment method can be used.
(イ)の低温熱処理法は、熱分:11イを終えた無定形
状態の;、戒維を低偶で加熱し、低部jl、す、 jf
、方晶を形成するものである。この」;11合、結晶と
して最?JJに生じる低温型面方晶が中斜晶や立方晶へ
転移して10屯1着係木71;うとなるのをl≦ノテ1
卜するため、熱処理が過度とならないように注意する。The low-temperature heat treatment method of (a) heats the amorphous fiber after heat content 11a at a low temperature, and then heats the fiber at a low temperature to form the lower parts jl, s, jf.
, which forms a square crystal. This'; 11 go, the best as a crystal? The low-temperature hexagonal crystals that occur in JJ are transformed into mesoclinic and cubic crystals, resulting in 10 tons of crystals.
Therefore, be careful not to apply excessive heat treatment.
仲)の高篇ト処哩ば、熱分解を終えたjll(定形状態
の遺′411°を立方晶が安定な温υり領域(例えけZ
r0293モル条、CaO7モル条の組成を有する成層
の」υ1合、1900 ’Cり上の高17g、 −)に
おいて充分加熱した後、急冷して、・或に全体を高温型
立方晶として凍結し、更に正方晶が安定な温度頌滅でエ
ージングして正方晶結晶子が10重置逅以上になるよう
にするものである。上述した急冷とエージングd1、嘔
妃まで膚、冷、した後、正方晶が安定な湿度′唄I成捷
で書加熱してエージングする手法でもよいし、正方晶が
安定な温度類(戒で急冷をエトめ、エージングする手法
でもよい。When the high-density structure of Z
After heating sufficiently at a height of 17g, -) above 1900'C for a stratified layer having a composition of 0293 mol of r0 and 7 mol of CaO, it was rapidly cooled and/or the whole was frozen as a high-temperature cubic crystal. Furthermore, the tetragonal crystal is aged by stable temperature oxidation so that the number of tetragonal crystallites becomes 10 or more. After the above-mentioned rapid cooling and aging d1, the skin may be cooled down to a certain temperature, and then aged by heating at a humidity level where the tetragonal crystals are stable, or at a temperature range where the tetragonal crystals are stable. An aging method may be used instead of rapid cooling.
このような結晶化熱処理は・・+ψ化性、メ¥嘴化性の
い−1−れの体間気中でも行なうことができる。Such crystallization heat treatment can also be carried out in interbody air with +ψ-forming properties and metal-forming properties.
しだがって、熱分JII午後の炭素を嵜む無定形のジル
コニア゛L勺・裁維を史に非1化性め2囲気中で結晶化
熱処理して炭、シフを才み、かつ2μm以下の正方晶結
晶子を炭素を除いて1011以上キむ部分安定化ジルコ
ニア禎繊唯を・詩造することもできる。この際炭素は餓
定形状態で存在することが望ましい。Therefore, the amorphous zirconia crystal containing the carbon of the JII heat treatment was heat-treated to crystallize it in two atmospheres to make it non-monalized, and then the charcoal and Schiff were formed. It is also possible to produce partially stabilized zirconia with the following tetragonal crystallites of 1011 or more, excluding carbon. At this time, it is desirable that carbon exists in a starved state.
以下、本発明の実施例を旨、明する。Examples of the present invention will be explained below.
実施例1〜13及び比較例1〜14
まず、丁記第1表及び’4%’ 2表に示す原利物′d
を用い、水を溶媒として同表に示す粘度を・■する7防
糸液から前庄体繊1推である連れ11日(捷だは鉋偵イ
ボ:を1リドたっここで、連続・哉楡:はFffitJ
記紡糸液全IG径0.1・1illの円形ノズル10本
を有する紡糸1]金から吐出させて細θiL全形成し、
溶媒である水を蒸発させながら、直径18rν)&の円
1暦)ドラムに巻@取ることによりイ外られたものであ
る。才だ、短く・准は一ヒ記4続滅堆を卦る[1)1合
と同様に形成された荀糸欣の、他流をエアジノエトで吹
き昧ばすことにより得られたものである。Examples 1 to 13 and Comparative Examples 1 to 14 First, the original interest 'd shown in Table 1 and '4%' Table 2
Using water as a solvent, the viscosity shown in the same table is obtained by using 7 thread-proofing liquids and 1 layer of 11 days (11 days). Elm: FffitJ
Spinning liquid having 10 circular nozzles with a total IG diameter of 0.1 1ill 1] Discharged from gold to form a fine θiL,
It was removed by winding it around a drum with a diameter of 18 rν and 1 calendar year while evaporating the water, which was a solvent. The word ``Saida,'' short, and ``juni'' means ``Ichihiki 4 Gokumetsudan.''[1] It was obtained by blowing away the other stream of Xun Shixin, which was formed in the same way as the 1st Go, with Airjinoet.
つづいて、E記各前駆体眞−41:を充分に1.I雇t
sした後、同表に示す雰囲気、温度でφツノ〜分1・(
イを行なった。史に1.結晶化活部t“1!を行ないジ
ルコニア′n鷹准を得た。Subsequently, each precursor Shin-41 described in E was added to a sufficient amount of 1. I hire t
After s, φhorn ~ min 1・(
I did this. History 1. A crystallization active part t"1! was carried out to obtain zirconia 'n takata.
傷られた各ジルコニア・丙虜椎についてし・イ[俤、代
案組成、微構造、正方晶結晶子の大きさ及び:’Q E
li、のL& リ扱い状況について、胸べ、下記さ!3
飛救び;P、 4ジモに示す。For each damaged zirconia vertebra, the following information is given: Alternative composition, microstructure, tetragonal crystallite size and:
Regarding the handling situation of li, L & li, see below! 3
Flying rescue; P, shown in 4 Jimo.
上記第4衣から)す]らかなように比較例1〜14のジ
ルコニア賀(或維のうち、比1咬例3及び12について
はその化学組成は本発明の軛しI:l内であるが、正方
晶が含まれておらず、−またそれ以外のものについては
、いずれもその化学九1]成が本発明の4+1シv11
外であるうえに正方晶が10中4′i/)未t4である
。このため比較例1〜14のジルコニア賀1.戒7碓は
いずれも脆く、憧端な局舎には粉化するものもあり、1
.lil!椎としての敗り扱いVよノド常に困・2ff
jで、うった。The chemical composition of Comparative Examples 1 to 14 for Comparative Examples 3 and 12 is within the range I:l of the present invention. However, if tetragonal crystals are not included, and for all other crystals, the composition is the 4+1 system of the present invention.
In addition to being outside, the tetragonal crystal is 4'i/) not t4 in 10. For this reason, the zirconia of Comparative Examples 1 to 14 is 1. All precepts are fragile, and there are some that turn into powder at the end of the admiration, and 1
.. lil! Treated as a loser V, my throat is always in trouble, 2ff
I sang it in j.
これに対して、上記第3表から明らかなように′I7施
1りIJ l〜13のジルコニア’Iji 、奴肘1j
6丁りいずれも”J I’j’i−性で容すに破断しな
かった。On the other hand, as is clear from Table 3 above, zirconia 'Iji',
All 6 pieces were "JI'j'i-resistant" and did not break at all.
なお、上記刈〃1目例及び比I咬例において、Nd2O
3り上の分子F+(r−有する冷土知元素?゛砂化j肉
についてはNd2O,(実Jq例10及び比′I佼例1
1〕、Sm203(実施例13 ) r ErtOs
(比較例12)、Yb20s (実、Qfli例11
及び比較例13)を用いた」4.0合について代表的に
記載したが、Nd2O3以上の分子用を有する他の希土
類元素酸化についても記載したものと同様な結果となる
ことが確認された。In addition, in the above-mentioned 1-bite case and 1-bite case, Nd2O
3. Molecule F+(r-) on the cold earth element? ゛For sanded meat, Nd2O, (actual Jq example 10 and ratio 'I case 1
1], Sm203 (Example 13) r ErtOs
(Comparative Example 12), Yb20s (actual, Qfli Example 11
4.0 using Comparative Example 13) was representatively described, but it was confirmed that the same results as those described were obtained for other rare earth element oxidations having molecules of Nd2O3 or more.
以上詳述した如く本発明によれば用恍性で偵維としての
取り狙いの容易な部分安定化ジルコニアで’i 鐵M@
を雰供できるものである。As detailed above, according to the present invention, partially stabilized zirconia is used which is flexible and easy to use as a reconnaissance weapon.
It can provide an atmosphere.
Claims (1)
をモルチで 0.14− MgO’; 14 、 0.15 Ca
O$ 1 :2 +0.05≦’ri02520
、 0.05:< In203515 。 0.05%5c203≦15 、 0.05SY20
,54 。 0.0!5’5Laz031”=30 + 0.0
5SCeO2425+005≦P r6o I + ≦
20 + 0.05’−5,≧ト丁d 20
3二≦−015。 0.0558m?0sS15 、 0.05Sgu20
3≦15゜0.05≦c62o、≦15 、 0.05
”;Tb4O7$ 15 。 0.0≦DY20+1≦15.0.05≦IJo203
≦15゜0.05j−Fjr20sS15 + 0.
053Tmz○3≦15゜0.05SYbzOsSL5
、 0.05SLuzOsS15のlji IJlで
沈み、かつ2μmn以下の正方晶結晶子をIO重叶チ」
9上有することを特徴とする部分安定化ジルコニア賀繊
維。[Claims] Z
O$ 1:2 +0.05≦'ri02520
, 0.05:<In203515. 0.05%5c203≦15, 0.05SY20
, 54. 0.0!5'5Laz031"=30+0.0
5SCeO2425+005≦P r6o I + ≦
20 + 0.05'-5, ≧ d 20
32≦−015. 0.0558m? 0sS15, 0.05Sgu20
3≦15゜0.05≦c62o, ≦15, 0.05
";Tb4O7$15.0.0≦DY20+1≦15.0.05≦IJo203
≦15°0.05j-Fjr20sS15 + 0.
053Tmz○3≦15゜0.05SYbzOsSL5
, 0.05SLuzOsS15 lji IJl sinks, and tetragonal crystallites of 2 μm or less are IO double-layered.
Partially stabilized zirconia fiber characterized by having 9 or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1349183A JPS59144620A (en) | 1983-01-29 | 1983-01-29 | Partially stabilized zirconia fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1349183A JPS59144620A (en) | 1983-01-29 | 1983-01-29 | Partially stabilized zirconia fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59144620A true JPS59144620A (en) | 1984-08-18 |
JPS646287B2 JPS646287B2 (en) | 1989-02-02 |
Family
ID=11834581
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1349183A Granted JPS59144620A (en) | 1983-01-29 | 1983-01-29 | Partially stabilized zirconia fiber |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59144620A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102943320A (en) * | 2012-10-24 | 2013-02-27 | 长春理工大学 | Erbium doped yttrium trifluoride upconversion luminescence hollow nanometer fiber preparation method |
CN102965762A (en) * | 2012-10-24 | 2013-03-13 | 长春理工大学 | Method for preparing Er-Yb co-blended yttrium fluoride up-conversion luminescence hollow nanofibers |
JP2015094055A (en) * | 2013-11-14 | 2015-05-18 | 独立行政法人物質・材料研究機構 | Zirconia continuous fiber and method for producing the same |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5127686A (en) * | 1974-08-05 | 1976-03-08 | Hitachi Ltd | |
JPS5319424A (en) * | 1976-08-04 | 1978-02-22 | Atomic Energy Authority Uk | Method and apparatus for producing fiber |
-
1983
- 1983-01-29 JP JP1349183A patent/JPS59144620A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5127686A (en) * | 1974-08-05 | 1976-03-08 | Hitachi Ltd | |
JPS5319424A (en) * | 1976-08-04 | 1978-02-22 | Atomic Energy Authority Uk | Method and apparatus for producing fiber |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102943320A (en) * | 2012-10-24 | 2013-02-27 | 长春理工大学 | Erbium doped yttrium trifluoride upconversion luminescence hollow nanometer fiber preparation method |
CN102965762A (en) * | 2012-10-24 | 2013-03-13 | 长春理工大学 | Method for preparing Er-Yb co-blended yttrium fluoride up-conversion luminescence hollow nanofibers |
JP2015094055A (en) * | 2013-11-14 | 2015-05-18 | 独立行政法人物質・材料研究機構 | Zirconia continuous fiber and method for producing the same |
Also Published As
Publication number | Publication date |
---|---|
JPS646287B2 (en) | 1989-02-02 |
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