JPS6065116A - Continuous inorganic yarn containing silicon, zirconium and carbon - Google Patents

Abstract

PURPOSE:The titled yarn useful for metals reinforced with fibers and fiber materials for plastic, etc., having improved mechanical strength, heat resistance, and oxidation resistance, having a new structure, comprising an amorphous substance consisting of Si, Zr, C, etc., or an agglomerate of fine crystalline particles of them. CONSTITUTION:The desired yarn comprising (A) an amorphous substance consisting of Si, Zr, C, and, optionally O, obtained by reacting a polycarbosilane having a main chain skeleton shown by the formula (R is H, lower alkyl, or phenyl), having 200-10,000 number-average molecular weight, with an organozirconium compound shown by the formula ZrX4(X is 1-20C alkoxy, phenoxy, or acetylacetoxy) under heating to give a polyzirconocarbosilane, spinning it, followed by making it infusible, or (B) an agglomerate comprising fine crystalline particles consisting of beta-SiC, ZrC, solid solution of beta-SiC and Zr, and ZrC1-x (0<X<1), having <=500Angstrom particle diameter (with the proviso that amorphous SiO2 and ZrO2 may exist around them), or (C) a mixed system of the amorphous substance A and the agglomerate of the fine crystalline particles B.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention mainly relates to St , Zr s C or Sl, Z
The present invention relates to a novel continuous inorganic fiber consisting of r, c, and o having extremely excellent performance.

The present inventors previously applied for a patent in JP-A-51-126.
No. 300, JP-A No. 51-139929, etc., polycarbosilane whose main skeleton components are silicon and carbon are spun into fibers, the spun fibers are made infusible, and then fired, so that mechanical A technique for obtaining silicon carbide continuous fiber (SIC continuous fiber) with good physical and thermal properties has been disclosed.

The present inventor then developed a novel copolymer consisting of a crosslinked polycarbosilane moiety and a polytitanosiloxane moiety, or a polycarbosilane whose main chain skeleton mainly consists of →31-CH2-)- structural units. and→Ti −0−)
- SI obtained by spinning a novel polytitanocarbosilane derived from titanium alkoxide as a bonding unit into fibers, making the resulting fibers infusible, and then firing them.
A patent application filed in 1983 claims that C-IC continuous fibers have even better mechanical properties than conventional SiC continuous fibers.
-80793 or Japanese Patent Application No. 55-29781.

In addition, the present inventor found that the main chain skeleton is mainly →5ICH! - A novel polyzirconocarbosilane derived from a polycarbosilane consisting of one structural unit and an organic zirconium compound represented by 7rX< (where X in the formula represents an alkoxy group, phenoxy group or acetylacetoxy group) and disclosed the invention relating to this new polyzirconocarbosilane and its manufacturing method in Japanese Patent Application No. 169443/1983. The present inventor further discovered that a continuous woven fabric mainly composed of 81C-ZrC is obtained by spinning the above novel polyzirconocarbosilane into fibers, making the resulting fibers infusible, and then firing them. ,
We discovered that it is a composite carbide with a unique structure that exhibits better mechanical properties and oxidation resistance at high temperatures than SiC fibers obtained from conventional polycarbosilane,
This has led to the present invention.

According to the invention, a continuous inorganic fiber consisting essentially of 31.7r and C1 optionally further O, wherein the fiber consists essentially of (1) St, Zr and C1 optionally further comprising 0 to 5- (2) substantially a solid solution of β-8tC, ZrC1β-8iC and ZrC, and each crystalline state with a grain size of 500A or less of ZrG (only -2 and 0<x<1) An aggregate consisting of ultrafine particles (however, amorphous sr ox and Zr0t may be present in the vicinity of these crystalline ultrafine particles), or (3) an aggregate consisting of the amorphous of (1) above and (2) above. ) A continuous inorganic fiber with a novel structure is provided, which is characterized by comprising a mixed system of crystalline ultrafine particle aggregates.

The method for producing the continuous inorganic fiber of the present invention described above mainly has the general formula -tS I -CH! →− − (However, R in the formula represents a hydrogen atom, a lower alkyl group, or a phenyl group) having a number average molecular weight of 200 to
10,000 polycarbosilane and an organic zirconium compound represented by the general formula % (where X in the formula represents an alkoxy group, phenoxy group, or acetylacetoxy group having 1 to 20 carbon atoms), In addition to a quantitative ratio such that the ratio of the total number of →31=CHt→- structural units of the carbosilane to the total number of →Zr-0 structural units of the organic zirconium compound is within the range of 2:1 to 200:1. , by heating reaction in an atmosphere inert to the reaction, at least a part of the silicon atoms of the polycarbosilane are bonded to the zirconium atoms of the organic zirconium compound via oxygen atoms, and the number average molecular weight is reduced. A first step of producing polyzirconocarbosilane of about 700 to 100,000, a second step of preparing and spinning a spinning dope of the polyzirconocarbosilane, and making the spun fiber invulnerable under tension or no tension. Substantially 81. characterized in that it consists of a third step and a fourth step of firing the infusible spun fibers in a vacuum or in an inert gas atmosphere at a temperature range of 800 to 1800°C. This is a method for producing continuous inorganic fibers made of Zr, C or 81 SZr , C,0 (hereinafter sometimes referred to as the method of the present invention).

The present invention will be explained in more detail below, but first the method of the present invention will be described.

The first step of the method of the present invention consists in using fibers with a number average molecular weight of about 700 as starting material for producing continuous inorganic fibers.
This is a process for producing polyzirconocarbosilane of ~100,000. The above-mentioned polyzirconocarbosilane and its manufacturing method are as mentioned above (the subject of Japanese Patent Application Laid-Open No. 11B54-169443 filed by the present applicant,
This is disclosed in detail in the specification of this patent application, but it can be summarized as follows.

Polyzirconocarbosilane, which is a starting material used in the method of the present invention, mainly has the general formula % (where R in formula 9 is a hydrogen atom or a lower alkyl group).

A polycarbosilane having a main chain skeleton represented by the following formula (or a phenyl group) and having a number average molecular weight of 200 to 10.000; group or acetylacetoxy group)
A polyzirconocarbosilane having a number average molecular weight of 00 to 100,000 and derived from an organic zirconium compound represented by:

At least a part of the silicon atoms of the polyzirconocarbosilane are bonded to zirconium atoms via oxygen atoms, and ÷8l in the polyzirconocarbosilane
-OR, a polymer in which the ratio of the total number of structural units of 10 to the total number of structural units of +Zr-0÷ is within the range of 2:1 to 200:1. Further, such polymers include monofunctional polymers, difunctional polymers, trifunctional polymers, and tetrafunctional polymers as shown in the figure.

10- (Monofunctional polymer) (Difunctional polymer) RHRH l 1 1 I To ~81-0 ~ ~ ~ To 81-0 ~1 1
1 1 0HOH 1 X-Zr-X X-Zr-X 1 〜〜〜8l-ON%A〜〜〜〜81-0〜〜〜〜〜8
1-0- -81-0- 1 1 1 1 1()i RH (However, R and X have the same meanings as above) Furthermore, the polyzirconocarbosilane used in the present invention is and the organic zirconium compound, +8l-0) of polycarbobilane! , ÷ to the total number of structural units of +Zr-0÷ of the organic zirconium compound is in the range of 2:1 to 200:1, and in an atmosphere inert to one reaction. It is obtained by a heating reaction.

The polycarbosilane used in the first technology has a number average molecular weight of 200 to 10,000 and has the general formula % (wherein R in formula 2 is a hydrogen atom or a lower alkyl group).

My father is mourning the bead chain skeleton represented by (representing a phenyl group). In addition to the side chain described above, a hydroxyl group may be bonded to the silicon atom of the terminal group of the polycarbosilane.

The method for producing polycarbosilane itself is well known.

Polycarbosilane a used as a starting material in the present invention can be produced by such known methods.

For example, a method of thermally polymerizing monosilane t directly, e,
Fr1tz; Angew, Ohem,, F9,
65γ (196)) and a, Fr1tZ at a
l; Aav, InOrg, Ohem.

Radlochem, 7, 349 (196
5) Disclosed by. There is also a method of manufacturing polycarbosilane by once converting monosilane into polysilane and then polymerizing it.
It is disclosed in Japanese Patent Application Laid-open No. 74000, Japanese Patent Application Laid-Open No. 52-112700, and Japanese Patent Application Laid-Open No. 54-61299. The polycarbosilane used in the present invention is a linear, network-like, or block-like polymer whose ball chain skeleton has substantially +8l -OH,÷ structural units.

In the first step, the organic zirconium compound used as another starting material is represented by the general formula (X in formula 1 represents an alkoxy group having 1 to 20 carbon atoms, a phenoxy group, or an acetylacetoxy group). The compound can be produced by a commonly used synthetic method.

-11-' In the first step of the method of the present invention, the above-mentioned polycarbosilane and an organic zirconium compound are used.

In addition to the quantitative ratio such that the specific gravity of the total number of structural units of ÷8l-OH, 10 of the polycarbosilane to the total number of structural units of ÷Zr-0+ of the organic zirconium compound is within the range of 2:1 to 200:l, and heating. React to produce an electrolyte. This reaction results in structural units divided by 8 in the main clavicular tract of polycarbosilane.
In a part of 1-OH, 10, one of *1+KiyoshiR bonded to the silicon atom is detached.

The silicon atom is bonded to the zirconium atom of the organic zirconium compound through all the oxygen atoms.

The novel polyzirconocarbosilane produced in the first step of the process of the invention has a number average molecular weight of about '700 to 100,
000, and 2 usually 50-400℃
It is a thermoplastic substance that melts in a bath when heated to a temperature of 100 mL, and is soluble in solvents such as n-hexane, benzene, toluene, xylene, and tetrahydrofuran.

In the second step of the production method of the present invention, the polyzirconocarbosilane obtained in the first step is heated and melted to prepare a spinning stock solution, and in some cases, this is passed through once to remove microgels, impurities, etc. Substances that are harmful during spinning are removed, and the resulting material is spun using commonly used synthetic fiber spinning equipment. The temperature of the spinning dope during spinning varies depending on the softening temperature of the polyzirconocarbosilane raw material.
A range of m degrees from 0 to 400° C. is advantageous. In the spinning device.

If necessary, the spinning tube is evacuated, and the atmosphere inside the spinning tube is changed to air, inert gas, hot air, or heated inert gas.

By increasing the winding speed after creating an atmosphere of at least -a1 selected from steam and ammonia gas, it is possible to form fibers with a suitable diameter. The spinning speed in the melt spinning varies depending on the average molecular weight, molecular weight distribution, and molecular structure of the raw material polyzirconocarbosilane, but good results can be obtained in the range of 50 to 5 ooom/min.

In step @2 of the manufacturing method of the present invention, in addition to the above-mentioned #melt spinning, the polyzirconocarbosilane obtained in the above-mentioned 1st step is mixed with one another, such as benzene, toluene, xylene or other polyzirconocarbosilane. Dissolve it in a solvent that can dissolve it.

He prepares a spinning stock solution and, in some cases, passes it through kF' to remove macrogels, impurities, and other harmful substances during spinning.The spinning stock solution is then spun using a dry spinning method using a commonly used synthetic fiber spinning device to increase the winding speed. By increasing the size, you can obtain the desired thin fiber gold.

In these spinning steps, if necessary, a spinning tube is installed in the spinning device, and the atmosphere inside the tube is changed to a saturated vapor atmosphere of at least one of the above solvents, air, and an inert gas. Atmosphere mixed with at least one gas selected from the following, or air, inert gas,
Assimilation of the spun fibers in the spinning tube can be controlled by providing an atmosphere of hot air, hot inert gas, steam, ammonia gas, hydrocarbon gas, or organosilicon compound gas.

Next, in step 31 of the present invention, the spun fibers are subjected to tension or no tension in an oxidizing atmosphere for 50 minutes.
The spun fibers are rendered infusible by low-temperature heating in the temperature range of ~400C for several minutes to 30 hours. The purpose of this low-temperature heating is to form a thin oxide film on the surface of the spun fibers.
This is to protect the spun fibers with the oxide film so that they do not melt in the firing process described later. pi7i due to the oxide film
The yarn fibers do not melt during the post-process firing, and even if they come into contact with adjacent fibers, they do not adhere.

The atmosphere for the low temperature heating is air, ozone, i! I! Basic.

An oxidizing gas atmosphere selected from chlorine gas, bromine gas, and ammonia gas or 2 or more gases is preferable, and even if low-temperature heating in the gas atmosphere is performed at 50°C or less, the spun fibers will not be oxidized. unable to form a membrane,
At temperatures above 400CB, oxidation progresses too much, so 50~
Good results in the temperature range of 400°C are better than 70i. The time for the low-temperature heating is related to the temperature, and is suitably in the range of several minutes to 30 hours.

In addition to the above-mentioned oxidizing gas atmosphere, KM is used as a low-temperature heating atmosphere.
Aqueous solutions of nO, K@Or@01, H2O, and other inorganic peroxides can also be used, in which case the temperature is preferably in the range of room temperature to 90°C, at 0.5° to 5°C for 1 hour. A time range is preferred.

However, the polyzirconocarbosilane obtained in the first step of the method of the present invention has a different molecular weight distribution depending on the synthesis conditions9.
．． The softening temperature may vary depending on the amount of low molecular weight compounds.
Temperatures may drop below 0°C. In this case, the softening temperature of the copolymer can be adjusted to at least 50'C by reducing the amount of low molecular weight compounds by various methods as described below. Even if polyzirconocarbosilane with a softening temperature of 50C or less is spun into fibers, the shape of the fibers will not be lost if the spun fibers are heated at a low temperature in an oxidizing atmosphere in the temperature range of 50 to 400C to make them infusible. This is because there are times when you may be exposed. That is, if a polyzirconocarbosilane having a softening point of about 50'C or less is obtained in the first step, the il step is followed by an additional step if necessary before the second step.
In step t-m, low molecular weight compounds in the polyzirconocarbosilane obtained in the step are removed. A typical method for carrying out this addition process is to use a low molecular weight compound such as methanol or ethyl alcohol in the polyzirconocarbosilane obtained in the first step. Extract with a solvent such as alcohol or acetone, and the softening temperature is approximately 5.
The polyzirconocarbosilane has a temperature of 0'C or higher, or the polyzirconocarbosilane is heated at a temperature of 500°C or lower under reduced pressure or in an inert gas atmosphere to remove low molecular weight compounds by distillation and soften it. This is a method for producing polyzirconocarbosilane with a temperature of 500 or higher. In this addition step, it is not preferable to distill in an oxidizing atmosphere containing sudden air or oxygen gas because the polyzirconocarbosilane will be oxidized and decomposed or gelled. In addition, if the heating temperature is 500°C or higher, the polyzirconocarbosilane will tend to decompose, so the heating temperature should be 500°C or higher.
Is it necessary to set it below 00?

In the third step of the present invention, in addition to the method of heating at low temperature in an oxidizing atmosphere to make it infusible, the spun fibers are further heated under tension or non-tension in an oxidizing atmosphere or a non-oxidizing atmosphere. Depending on the situation, it can be made infusible by low-temperature heating and then r=irradiation or electron beam irradiation. This 7
1%1i! Alternatively, the purpose of electron beam irradiation is to further polymerize the polyzirconocarbosilane that forms the spun fibers, so that the polyzirconocarbosilane decomposes without softening and the spun fibers melt in the firing process described later. This is to prevent the fiber from losing its shape.

The above-mentioned infusibility due to γ-ray or electron beam irradiation.

It can be carried out in a non-oxidizing atmosphere such as an inert gas or a true tube.
It can be done at room temperature. The r-ray or -son beam irradiation can be carried out in an oxidizing gas atmosphere of one or more selected from air, ozone, oxygen, chlorine gas, bromine gas, and ammonia gas, and further, if necessary If so, a thin oxide film can be formed on the upper surface of the spinning edge by heating in a temperature range of 50 to 200 DEG C., and this can be achieved in a shorter time than in the case of untreated purple.

When the polyzirconocarbosilane obtained in the first step is rendered infusible by this r-ray, irradiation, or electron beam irradiation, it is sufficient that it is solid at room temperature.

If a viscous fluid product is obtained, the low molecular weight compounds in the polyzirconocarbosilane must be removed by extraction with the aforementioned solvent or distillation, and the polyzirconocarbosilane must be made solid at room temperature. .

If the infusibility is carried out under no tension, the spun fibers will shrink and take on a wavy shape, but this can sometimes be corrected in the subsequent firing step.

Tension is not necessarily required, but if tension is applied, the tension should be large enough to at least prevent the spun fibers from becoming wavy even if they shrink during infusibility. Good results can be obtained by applying a tension chamber in the range of 1 to 500 t/Ij.

Even if a tension below 1f/IjJa is applied, it is not possible to apply a tension that will not cause the rim to sag, and when a tension r above 500F is applied, the tension becomes large fIII#&
may break, so the tension is preferably in the range of 1 to 50027-.

21- The spun fibers subjected to the unification treatment in the third step of the present invention are
Its tensile strength and elongation are very high, which is a great advantage for producing continuous fibers. In other words, in the conventional method of producing 810 m fibers from polycarbosilane, when polycarbosilane is spun and made infusible, its tensile strength generally cannot exceed 1.0 gy7- and its elongation rate is 2% or less. On the other hand, 9 For example, according to the method of the present invention described in Actual Sub-Example 1 below, the tensile strength of the infusible fiber is 5.0 and the V-elongation is 13.0%.

In addition, the infusible yarn of the present invention is easy to store and handle, and it is possible to reduce yarn breakage during firing in the subsequent process, which is advantageous in increasing yield.

Next, in step 4 of the present invention, the infusible fibers are fired at a temperature range of 800 to 1800°C.

Mainly 81. zr, O or 81. Zr, O, O
A continuous inorganic fiber consisting of

The calcination is carried out at 800 mA or below in an inert gas atmosphere.
~1800 C i? ii It is carried out under tension or no tension in the 1 degree range. The polyzirconocarbosilane that is entirely formed in the spun fiber 22 during this firing releases easily volatile components through a heat chamber condensation reaction and a thermal decomposition reaction. Volatilization of easily volatile components is greatest in the temperature range of 500 to 700°C, which causes the spun fibers to shrink and bend;
Applying tension during heating is particularly advantageous in preventing this bending.

The magnitude of the tension at this time may be at least as large as being able to at least prevent the fibers from forming a wavy shape even if they contract during the heating process, but practically 0.001
Good results can be obtained by applying a tension in the range of ~5 KF/-, and even if a tension of O,0O1F4/- or less is applied, it is not possible to apply a tension that does not cause the fiber metal to sag.
If a tension of 5Q/- or more is applied, the tension may be too large and the fibers may break.
It is preferable to apply a tension in the range of /-. Note that the firing is performed under different atmospheres and temperatures.

A multi-stage firing method in which heating conditions such as time are changed can also be used.

The fibers obtained through the above steps include β-810,
ZrO, β-810 and zro (7) solid solution and Zr
In addition to 0l-x (tad 0 x x 1), graphite, free carbon, 8102 or ZrO□ can be used as 1f1. Depending on the purpose of use, it may be necessary to eliminate these. Therefore, if necessary, the fibers may be treated with sulfuric acid, nitric acid, or a mixed diamic acid of sulfuric acid and nitric acid.

Mixed acid of nitric acid and hydrochloric acid, sulfuric acid acidic solution of potassium chromate, sulfuric acid acidic solution of potassium permanganate.

The above-mentioned graphite is incorporated into the fired fiber by immersion in hydrofluoric acid, a mixed acid of hydrofluoric acid and nitric acid, a mixed acid of hydrofluoric acid and sulfuric acid, or the like.

free carbon, 810. Alternatively, it is possible to dissolve ZrO2. Other methods include N, OH.

Borax, Na200g, K2O0g I K2
00g/Na2003.

Na2804, KNO2, Na0j, xaLos
l No20g, K2O03/KNO34 slang l
l11! 11 salt can be used to elute the 8102, and phosphoric acid can also be used to elute the free carbon.

In addition, the above-mentioned free carbon is obtained by using fibers that have been fired in the 4 steps of 18 times at a temperature of 1000° C. or higher, and then using oxygen gas.

It can be removed by heating preferably at a temperature in the range of 800 to 1600° C. in an atmosphere of at least one selected from the group consisting of carbon dioxide, ozone, hydrogen gas, water vapor, and 00 gas. Even if the above-mentioned calcination is performed at a temperature of 800°C or lower, free carbon cannot be removed by light;
If the temperature exceeds 0°C, the reaction between the composite carbide and the atmospheric gas becomes significant, which is not preferable. If the firing temperature is low, the firing time in the above atmosphere will take a long time, and if the firing temperature is high, it will take a short time, but if anything, firing at a low temperature for a relatively long time will produce a composite carbide. Good results can be obtained because the amount of reaction products produced with the atmospheric gas is small.

Although it is not necessarily necessary to apply tension to the de-recovered raw material, by applying tension in the range of 0.001 to 1oOKf/- and firing at a high temperature, slow-onset inorganic fiber gold with reduced bending and easy strength can be obtained. can be O,0O1
Even if a tension of less than h/- is applied, there is no effect (,1,00
Even if a tension of Kg/j or more is applied, the effect will not change, so the tension to be applied is preferably in the range of 0.001 to 100 hours/-.

25- The polyzirconocarbosilane produced in the first step of the present invention is spun in the second step, and the spun fibers made infusible in the 3' step are mineralized from about 700°C in the heating process of the fourth step. It is estimated that the mineralization becomes intense and almost complete at about 800 U. Therefore, it is necessary to carry out the fourth step at a firing temperature of 800°C or higher, and the upper limit is 1800°C to obtain excellent fiber strength, and preferably 1000 to 1500°C.

Next, two continuous inorganic fibers of the present invention will be explained.

The continuous inorganic fiber of the present invention has a substantially 81. Zr, O or 8
1. It is an inorganic fiber consisting of Zr, o, O, and the above-mentioned first
It is manufactured by the method of the present invention consisting of steps to the fourth step, and depending mainly on the firing temperature in the fourth step, the structure of the #& fiber can be as shown in (A) to (0) below. Changes as shown.

(A) When the firing temperature is relatively low, substantially amorphous inorganic fibers are obtained;

Depending on the manufacturing conditions adopted in the 4th process from the 1st process to tJl, the raw material is 81. Consisting of Zr, O or 26
-81, Zr, c, or 0. Generally speaking, if conditions are selected in the first to fourth steps such that substantially no oxygen remains in the fiber obtained after firing in the fourth step, an amorphous material consisting mainly of 81°Zr and O will be produced. Quality generates and vice versa.

If conditions are selected in the first to fourth steps such that oxygen tends to remain in the fiber after firing, the final result will be 81°Zr, O, O.
An amorphous substance consisting of for example.

In producing polyzirconocarbosilane in the first step, the amount of organic zirconium compound used is relatively large relative to the amount of polycarbosilane used.

The more easily the fibers are oxidized in the infusibility treatment in the third step (for example, by increasing the heating temperature in an oxidizing atmosphere), the more likely oxygen will remain in the fibers after firing. Also m
In the fourth step, oxygen is more easily removed when firing is performed in a mineral vacuum than in a stream of an inert gas such as nitrogen, so that oxygen is less likely to remain in the fiber after firing.

For example, in Example 3, which will be described later, in the first step, polycarbosilane and zirconium tetraisogloboxoxide were mixed at l:1.
Polyzirconocarbosilane is produced from a mixture with a weight ratio of 9 to 9, in the third step the spun fibers are infusible by heating to 110° C. in air, and in the fourth step they are heated to 1000° C. in an argon stream. Firing was carried out at a relatively low temperature of 81°C. Zr.

It is a fiber consisting essentially of an amorphous substance consisting of 0.0. On the other hand, in Actual Example 5 described later, the weight ratio of polycarbosilane to zirconium tetraphenoxide in the 1 ml process was 1.
5.4:l, and the inorganic fiber obtained due to the relatively small amount of organic zirconium compound used is 81
．． It is a fiber consisting essentially of an amorphous material consisting of Zr and O.

(B) When the firing temperature is high, each crystalline ultrafine particle aggregate of β-810, ZrO, a solid solution of β-810 and ZrO, and Zr0x-x (where O < X < Inorganic fibers consisting essentially of the body are obtained.

However, depending on the manufacturing conditions adopted in the first to fourth steps, amorphous 810. and Zr01 may be present. For example, the inorganic fiber described in Actual Example (1-11) below is prepared by heating the infusible yarn obtained in Example (1-1) at 1700°C.
The inorganic fiber of this working example (1-1) is an inorganic fiber consisting of an aggregate of each of the above-mentioned crystalline ultrafine particles.

The reason why fibers with the above structure can be obtained when the firing temperature is high is as follows. The fiber obtained after the infusibility treatment in the third step is 1M, and although a thin oxide film is formed on the shaft surface, most of the fiber is made of the polyzirconocarbosilane used as the starting material. Such infusible threads are mineralized by the firing process in the fourth step, but at a stage where the firing temperature is relatively low, the substances produced from the second process are mineralized (as described in the previous section (A), Mainly 8
1゜Zr, O father is 81. It is amorphous and consists of Zr, 0,0, and crystalline ultrafine particles have not yet been produced. However, if the firing temperature increases further.

β-
810, ZrO, solid solution of β-810 and ZrO and 2
9- ZrO1+g (however, O<X<1) is converted into an aggregate consisting of crystalline ultrafine particles, and if the firing temperature is high enough, substantially all of the amorphous particles are converted into the above-mentioned It is converted into a crystalline ultrafine particle aggregate.

In this conversion to crystalline ultrafine particle aggregates, amorphous is king.81. When consisting of Zr, 0,
An aggregate consisting essentially of crystalline ultrafine particles of β-810, ZrO, a solid solution of β-810 and ZrO, and Zr01-x is produced. However, amorphous is king as 81.
In the case of Zr, O, and O, amorphous 810. and Zr01 (two).

(0) If the calcination temperature is relatively high, but does not reach the point where the conversion from amorphous to crystalline ultrafine particle aggregates is completed, the above-mentioned Xji(A) A*-free fiber is obtained which is a mixed system of such amorphous material and a crystalline ultrafine particle aggregate as described in the previous section (B). As is clear from the explanation given in the previous section (B), amorphous is mainly 81. When consisting of Zr, 0, this amorphous, β-810, and ZrO.

-a〇- A mixed system consisting of a solid solution of β-810 and ZrO, and each crystalline ultrafine particle aggregate of Zr01-H is generated. On the other hand, amorphous materials are mainly st, Zr, O,.

In this case, this amorphous and the amorphous 810! formed in the vicinity of each crystalline ultrafine particle. A mixed system with a crystalline ultrafine particle aggregate having Zr01 is produced.

As mentioned above, the continuous inorganic fiber of the present invention contains various I
i! 11s exists, and the fibers of each of these embodiments have structures as shown in the following types (A-1) to (o-2)m.

(A-1) 凰: Continuous inorganic fibers are substantially (281.Z
It is substantially composed of amorphous material consisting of r and 0.

(A-2) fl! : Continuous inorganic fibers are substantially 8
1. Zr.

It is substantially composed of amorphous material consisting of 0 and 0.

Type (B-1): Continuous inorganic fiber is substantially β-810
゜ZrO, solid solution of β-810 and ZrO and Zr0l
-x (provided that O<X<1> is substantially composed of an aggregate of crystalline ultrafine particles having a particle size of 500λ or less.

Type (B-2): Continuous inorganic fiber is substantially β-810
゜ZrO, solid solution of β-810 and ZrO and zrcl
-x (where O<J<1), the particle size is substantially composed of an aggregate of Igjx ultrafine particles having a particle size of 500λ or less.

At this time, amorphous 81 particles are present near these crystalline ultrafine particles.
0. and Zr01 are present.

(o-1) type: continuous inorganic fibers are substantially si, zr
and 0, and substantially β-810°Zr
Solid solution of O, β-810 and ZrO and Zr0x-x (
However, it is composed of a mixed system of aggregates of crystalline ultrafine particles having a particle size of 500λ or less where 0(a=(1)).

(0-2) type: Continuous inorganic fibers are substantially 81. Zr
.

Amorphous consisting of 0 and 0 and substantially β-810°Z
rO, solid solution of β-810 and ZrO and ZrOx+)
i (provided that o(z(1)) is composed of a mixed system of aggregates of crystalline ultrafine particles with a particle size of 500 microns or less.

At this time, amorphous 81 particles are present near these crystalline ultrafine particles.
0! and Zr01 are present. To summarize 1 or more, 9 In the continuous inorganic fiber manufacturing method consisting of the striped I step to the #$4 step specified in the present invention, the conditions of the first step to the number step are appropriately selected, and the fourth step is performed. When substantially no oxygen remains in the inorganic fibers obtained after firing and the firing temperature is relatively low, the above (A-1)! A fiber with the structure can be obtained, and if the firing temperature is raised sufficiently (
A fiber with a structure of B-1) is obtained, and at an intermediate firing temperature, a fiber with a structure of (0-1) is obtained. On the other hand, if conditions are selected such that oxygen tends to remain in the inorganic fibers obtained after firing, and the firing temperature is relatively low, # (A-2)
If the firing temperature is set high enough, fibers with a (B-2) type structure can be obtained, and at an intermediate firing temperature, fibers with a (0-2) type structure can be obtained. .

Surprisingly, the continuous inorganic fiber of the present invention is e(A-1)!
Or, even in the case of a predominantly amorphous structure such as (A-2), it has extremely good strength and thermal properties, but in general.

In the case of a structure 33- consisting of a mixed system of amorphous and crystalline ultrafine particle aggregates such as the (O-X) type or (o-2) type, the strength properties and other properties are the best. be. The reason for this is thought to be that the contribution of the amorphous and the contribution of the crystalline ultrafine particle aggregate to these properties cooperate with each other, resulting in a synergistic effect.

The crystalline ultrafine particles present in the continuous inorganic fibers of the (B-1) type, (B-'2) type, (C-1) type or (0-2) type structure of the present invention are β-810 , ZrO.

It can be confirmed from the X-ray diffraction pattern of the fiber that the fiber is composed of a composite carbide consisting of an isosolute of β-810 and ZrO and Zr0x-x (0<Z<1). (1) in Figure 1 is an example of actual power (1-1) described later.
It is an X-ray powder diffraction pattern of the continuous inorganic fiber of the present invention having the (B-1) type structure described in E.

In the X-ray diffraction pattern of (1), m 2tl =
β-810 (ill) diffraction line at 35.8°, 2d
= 60.2° (two β-810 (220) diffraction lines and 2θ = 72.1' the (311') H-diffraction line of β-810, and 2θ = 33.0) the (111) diffraction line of ZrO line, (200”) diffraction line of ZrO at 20=39.1°,
(220) diffraction line of ZrO at 2θ=56.3°, 2#=
(311) diffraction line of 34-ZiO at 67.0° and 2θ = 10.6°E
The (222) diffraction line of ZrO is included, and the second noteworthy point is that each diffraction line of ZrO is different from that of conventional ZrO.
The difference is that the ZrO has a different lattice constant from that of conventional ZrO.

The data of the above X-ray diffraction pattern is based on a book in which the crystalline ultrafine particles present in the continuous inorganic fiber of the present invention mainly consist of β-810 and ZrO, and β-810 and ZrO are in solid solution. and zro, -x (where O<, Z!<
1) indicates that it is a composite carbide containing a part of it.

81. consisting of crystalline ultrafine particles of a specific composite carbide as described above. Zr and O-containing continuous inorganic fibers are novel fibers that have not been known until now. However, the fact that the crystalline ultrafine particles are composed of such composite carbides has the advantage of imparting highly desirable and excellent performance to the 81° Zr and 0 M continuous inorganic fibers of the present invention. It is something that brings. That is, ZrO is /-8
compared to 10.

Mechanical strength such as bending strength, tensile strength, and pressure resistance is
Also, due to its high melting point, it has excellent heat resistance.

81. of the present invention. In Zr and 0-word continuous inorganic wire miscellaneous, Z
This is because both rO and β-810 coexist in an intimate state in the fiber of the present invention, as is clear from the fact that both rO and β-810 are partially dissolved.

The favorable properties of ZrO become significantly volatile.

Thus, 81. of the present invention. The continuous inorganic fiber containing Zr and O-miya has better mechanical strength characteristics and heat resistance than the conventional fiber made only of β-810.

Further, the crystalline fine particles made of the composite carbide present in the continuous inorganic fiber of the present invention are ultrafine particles having an average particle size of 500λ or less. For example, the fiber with the (o-i) type structure described in Example (1-1) described below (firing temperature 1i 1300 ° C.
) The average particle size of the crystalline ultrafine particles is about 801, and that of the fiber (B-1) type structure described in Example (1-1) (firing temperature 1700°C) is about 160". Something has been revealed from the XMTJI diffraction sheet.

Generally, in the continuous inorganic fiber of the present invention, the average crystal grain size in the fiber increases as the firing temperature during production increases.

One of the reasons why the continuous inorganic fiber of the present invention has extremely high strength is thought to be that it is made up of ultrafine crystals. Because the crystals are dispersed through the grains, they are difficult to deform; because the crystals are ultrafine particles, there is no room for the dislocations necessary for deformation to exist in the grains; and because the grain size is very small, the apparent surface of the grains The tensile force becomes abnormally large, the resistance to deformation is large, and the surface of the fiber is smooth and has no unevenness, so there is no cause of decrease in strength due to concentration of stress on uneven parts. 1st class C2. Conceivable.

In general, fibers with a (0-1) type or fi (0-2) type structure obtained when the firing temperature is intermediate are better.

Rather, it is obtained when the firing temperature K is very low (B-1)
The strength properties are superior to fibers of type Ia and (B-2)W, mainly due to the lower firing temperature and smaller average grain size. It is thought that this is because of this.

The elemental ratio according to the chemical analysis of the continuous inorganic fiber of the present invention is x
t* for table wa Lte, general d, 81: 30-60iZ
r: 0.5-40%, 0:25-40%, O: 0.01
~20%.

As is clear from the above, if manufacturing conditions are selected such that oxygen tends to remain in the continuous inorganic fiber of the present invention obtained after the firing step, inorganic fiber containing up to 20% of oxygen by weight can be obtained.

Fibers of type (A-2), (B-2) and (o-2) are fibers containing a substantial amount of oxygen; ) The fibers with the structure of Mi& are 8
1. It has been found from X@ diffraction that it is mainly composed of an amorphous material consisting of Zr, O, and 0.

In a fiber with a B-2 type structure, the crystalline ultrafine particles have substantially C281. It is made of a composite carbide consisting of Zr and 0, and it is clear from the results of X-ray diffraction that oxygen atoms are not involved in the formation of crystalline ultrafine particles. In this case, oxygen atoms are some 8
1 and Zr to form an amorphous 810. and Zr01
This is thought to be present in the vicinity of the crystalline ultrafine particles of the composite carbide, for example in the gaps between the crystal particles.

The continuous inorganic fiber of the present invention has 1 mechanical strength and heat resistance.

Excellent oxidation resistance. It is a fiber with a new structure, and has better wetting with metals and alloys than carbon fiber.
In addition, it has low reactivity with metals and alloys, and is suitable for fiber-reinforced metals, plastics, and rubber fiber materials, fibrous heating elements, fireproof woven fabrics, acid-resistant diaphragms, nuclear reactor materials as reinforcement fibers, aircraft structural materials, Can be used for bridges, building materials, fusion reactor materials, rocket materials, @ light bodies, abrasive cloth, wire ropes, ocean development materials, golf shaft materials, ski stock materials, tennis racket materials, fishing rods, shoe sole materials, etc. can.

The present invention will be explained below by way of practical examples.

Reference Example 1 2.5 t of anhydrous xylene and 40 of sodium were placed in a 5 t three-loaf flask, heated to the boiling point of xylene under a nitrogen gas stream, and 1 t of dimethyldichlorosilane was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was heated under reflux for 10 hours to form a precipitate. This precipitate was filtered and washed first with methanol and then with water.

42 of white powder polydimethylsilane was obtained.

On the other hand #9 phenylchlorosilane 759t and boric acid 12
4F in n-butyl ether under a nitrous gas atmosphere.

The resulting white resinous material was heated at a temperature of 100 to 120°C and further heated in vacuum at 400°C for 1 hour to obtain 53 of polyborodiphenylsiloxane.

Next, the above polyborodiphenylsiloxane 8.2'/f was added and mixed to the above polydimethylsilane 2502, and the mixture was heated for 35 minutes under a nitrogen stream in a 2t quartz tube equipped with a reflux tube.
The mixture was heated to 0° C. and polymerized for 6 hours to obtain polycarbosilane. After cooling at room temperature, add xylene and take out as a solution.
The xylene was evaporated and concentrated at 320° C. for 1 hour under a nitrogen stream to obtain 140 tons of solid.

Reference Example 2 100 f of tetramethylsilane was weighed out and reacted with fluorine at 0°C for 24 hours in a nitrogen atmosphere using a recyclable flow system to obtain polycarbosilane. After cooling at room temperature, normal hexane was added to obtain a solution, which was filtered to remove insoluble materials.

Evaporate normal hexane and heat at 180°C for 1 hour.

Concentration under reduced pressure of 5aawH7 gave 14f sticky material.

Reference Example 3 250 tons of polydimethylsilane obtained in Reference Example 1 was placed in an autoclave under an argon atmosphere.

Polycarbosilane was obtained by heating and polymerizing at 470° C. under about 100 atm for 14 hours. After cooling at room temperature, add normal hexane to take out as a solution, evaporate normal hexane, concentrate at 280 ° C. for 1 hour under reduced pressure of 1 auaBp, and treat the obtained solid with acetone to remove low molecular weight substances. Polymer 6091 was obtained.

Actual example 1 9 polycarbosilane obtained in reference example 1 40. Of and 41
- Weigh out 5.4 tons of tetrakisacetylacetonatosirconium, add 20% of ethanol and 300% of xylene to this mixture to make a mixed solution consisting of a homogeneous phase, and i!
A reflux reaction was carried out at 60° C. with stirring for 2 hours under a gas atmosphere. After the reflux reaction was completed, the mixture was further heated to distill off ethanol and xylene, and then polymerization was carried out at 285° C. for 30 minutes to obtain polyzirconocarbosilane. This polyzirconocarbosilane was heated and melted at 270°C using a spinning device, and then spun at 300 m/min through a 300 μm spinneret.
The fibers were obtained by melt spinning in air at a spinning speed of . This fiber was heated in air under no tension at a rate of 15 C/hour from room temperature and held at 110° C. for 1 hour to make it infusible.

The tensile strength of this infusible yarn is 5.0 Kf/J, and the elongation rate is 1.
It was 3.0chi.

Next, this infusible yarn was fired under two different conditions as shown in (1) and (1) below.

(1): Infusible thread in graphene airflow (100cc/mtn
), the temperature was raised to 1300℃ under no tension at 13B#,
It was fired by holding it at 1300°C for 1 hour. The diameter of the obtained continuous inorganic fiber 42-fiber is approximately 13μ, the tensile strength is 2F OKg/-, and the elasticity is approximately 13μ.
The sex rate is 13. It was Otm/-. The X-ray powder diffraction measurement of this fiber is shown in FIG. 1 (1). In (1) of Figure i1, each broad diffraction line of β-810 and each broad diffraction line of ZrO are observed, although the intensity is small [However, 20 of each diffraction line of ZrO is higher than that of conventional ZrO. From the results of chemical analysis, the fiber obtained under the firing conditions of Example (1-1) is a fiber with a structure of front H pi(0-1)ffi. I found out something. Furthermore, it was found by X-ray analysis that the average particle diameter of the crystalline ultrafine particles present in the fibers was about 80.

(I): Infusible yarn in nitrogen stream (100 CC/min
) under no tension to 1'700℃ in 17 hours.
It was held at 00C for 1 hour and fired. X of the obtained fiber
Line powder diffraction measurements are shown in Figure 1 (1). 1st (β-810 and ZrO which are sharp and strong in illusion)
(However, 20 of each diffraction line of ZrO is shifted to the high angle side).

From the results of chemical analysis of fibers with and, this real example (1-
The fibers obtained under the firing conditions of B-1
) It was found that the fiber had a type structure. In addition, the average particle size of the crystalline ultrafine particles present in the fiber is approximately 160X.
It was found by X-ray diffraction that

Example 2 Polycarbosilane 40 obtained in Reference Example 1. Or and 31.5 tons of zirconium tetrabutoxide were weighed out.

Xylene 400- was added to this mixture to form a mixed solution consisting of a homogeneous phase under an argon gas atmosphere.

The reaction was heated to reflux with stirring at 130° C. for 1 hour.

After the reflux reaction is complete, what is the temperature? After raising the temperature to 1-250°C to distill off the solvent xylene, polymerization was carried out at 250°C for 1 hour to obtain polyzirconocarbosilane. This polyzirconocarbosilane is produced using a spinning device ~230%
200 m/m from 250 μm by heating and melting at ℃
The fibers were obtained by melt spinning in air at a spinning speed of in. This fiber was heated in air at a rate of 7°C/hour from room temperature while applying a tension of 50t/-, and then heated to 155°C by 3°C.
It was kept for a while to make it infusible. The tensile strength of this infusible thread is 5
．． 5 Kg/mj, and the elongation rate was 17.0 yen.

Next, this infusible thread was placed in a vacuum (3X 10-'auwH
7), the temperature was raised to 1200°C in 6 hours under no tension, and 12
It was held at 00°C for 3 hours and fired. The diameter of the obtained continuous inorganic fibers was about 20μ, and the tensile strength was 200-/d.

The elastic modulus was '70.0 ta/-. From the results of X-ray powder diffraction measurement and chemical analysis, it was found that the fibers obtained here had the above-mentioned (0-2) type structure.

Actual power example 3 The polymer obtained in Reference Example 1 was heated at 3300 for 3 hours.

Polycarbosilane 40 obtained by concentrating under a nitrogen stream,
Of Tozirconium Tetraisogloboxide 75.3
f was weighed out, 500 - of benzene was added to this mixture to obtain a mixed solution consisting of a homogeneous phase, and a reflux reaction was carried out with stirring at 70° C. for 5 hours under an argon gas atmosphere. After the reflux reaction was completed, the mixture was further heated to distill off benzene, and then
Polymerization was performed at 200° C. for 2 hours to obtain polyzirconocarbosilane. This poly-45-zirconocarbosilane was mixed with benzene to prepare a spinning stock solution. 300 m/min from the base of Am
Fibers were obtained by dry spinning at a spinning speed of . This fiber was heated in air under no tension at a heating rate of 15 C/hour from room temperature and held at 110° C. for 0.5 hour to make it infusible. The tensile strength of this infusible yarn was 4.7 Kg/d, and the elongation rate was 12.0%.

Next, this infusible thread was placed in an argon stream (100 CC/mi
n) while applying a tension of 50 f/-.

The temperature was raised to 1000°C over 5 hours, and the temperature was maintained at 1000°C for 1 hour to perform firing. The diameter of the obtained continuous inorganic fibers was 16μ, the tensile strength was 190 Kg/d, and the elastic modulus was 12.
-/- I was disappointed. The fibers obtained here.

From the results of X-ray powder diffraction measurement and chemical analysis, the above (A
-2) It was found that the fibers had a type structure.

Actual phase side number Polycarbosilane obtained in Reference Example 2 40. Of and 14.32 ml of tetrakis acetylacetonatosilconium were weighed out, 60 ml of ethanol and 300 m of xylene were added to this mixture to form a mixed solution consisting of a homogeneous phase, and the mixture was heated at 60°C for 8 hours under a nitrogen gas atmosphere. The reflux reaction was carried out while stirring. After the reflux reaction was completed, the ethanol and xylene were distilled off by further heating, and then heated at 250°C for 3
Time polymerization was performed to obtain polyzirconocarbosilane. Using a spinning device, this polyzirconocarbosilane was
Melt by heating to ℃ and 650 m/m from a 250 μm cap.
The fibers were obtained by melt spinning in air at a spinning speed of in. This fiber was irradiated with rm in air at 50℃ under no tension.
1.5 a xlOγ) Infusible round. This infusible yarn had a tensile strength of 6.0 and an f/-1 elongation of 18.1 inches.

Next, this infusible thread was placed in a nitrogen stream (100 CC/min).
) while applying a tension of 50 f/- at 1300 C.
The temperature was raised to 1300° C. over 13 hours, and the temperature was maintained at 1300° C. for 1 hour to perform firing. The diameter of the obtained continuous inorganic fiber was 9μ, the tensile strength was 320 Kf/-, and the elastic modulus was 21 taa/j. From the results of X-ray powder diffraction measurement and chemical analysis, it was found that the fibers obtained here had the above-mentioned (0-2) type structure.

Actual sister example 5 Polycarbosilane obtained in reference example 3 40. Of, 2.6 t of zirconium tetraphenoxide and 'i1+In were added to this mixture, 200 - of xylene was added to make a mixed solution consisting of a homogeneous phase, and the mixture was heated at 130°C in an argon gas atmosphere for 2
The reflux reaction was carried out while stirring for hours.

After the reflux reaction was completed, the mixture was further heated to distill off xylene, and then polymerized at 300° C. for 30 minutes to obtain polyzirconocarbosilane. This polyzirconocarbosilane is dissolved in toluene to create a spinning stock solution.

Fibers were obtained by dry spinning using a 300 μm spinneret at a spinning speed of 200 m/min. This fiber is 5
30 from room temperature in air while applying a tension of 0t/-
The temperature was increased at a temperature increase rate of 110° C./hour and held at 110° C. for 0.5 hours to make it infusible. The tensile strength of this infusible thread is 4.8
kg/d, and the elongation rate was 13.0%.

Next, this infusible thread is mixed with carbon monoxide and hydrogen (00:N, = 1
-:4 (molar ratio)] The temperature was raised to 1000° C. in 5 hours under no tension in an air flow (100 CC/min).

Firing was performed by holding at 1000° C. for 1 hour. This fired yarn was further heated to 800°C in air for 2 hours.

The yarn was held at 800° C. for 0.5 hours to remove excess carbon from the fired yarn. The diameter of the obtained continuous inorganic fiber is 20μ, the tensile strength is 195Kg/-, and the elastic modulus is 9. It was Otm/j. From the results of X-ray powder diffraction measurement and chemical analysis, the fiber obtained here was found to be a fiber having the structure of (A-1) 凰.

[Brief explanation of the drawing]

FIG. 1 is an X-ray powder cross-section diagram of a continuous inorganic fiber. Patent applicant Special Inorganic Materials Research Institute 49- sickle

Claims (1)

[Scope of Claims] 1. A continuous inorganic fiber consisting essentially of (1) Si, Zr and C1 optionally further consisting of O. or (2) substantially a solid solution of β-8I C, Zr C, β-3iC and ZrC and Z r C1-)L (where Q<
X < 1) amorphous SIOt and Zr0t may exist in the vicinity of each crystalline ultrafine particle with a grain size of 5008 or less), or (3) the amorphous of (1) above. A novel continuous inorganic fiber containing silicon, zirconium, and carbon, comprising: 2. The fiber according to claim 1, wherein the continuous inorganic fiber consists essentially of an amorphous material consisting essentially of Sl, Zr and C. 3. Claim 1 in which the continuous inorganic fiber consists essentially of an amorphous material consisting essentially of Si, Zr, C and 0.
Fibers as described in Section. 4. The continuous inorganic fiber is substantially β-8i C, ZrC1
The fiber according to claim 1, which consists essentially of an aggregate of crystalline ultrafine particles of a solid solution of β-8IC and ZrC and ZrC1-E (where 0<x<1) having a particle size of 5008 or less. . 5. The continuous inorganic fiber is substantially β-src. Solid solution of ZrC, β-81C and ZrC and Zr01
-X, (provided that the grain size of 0 The fiber according to claim 1, wherein O* and Z "0!" are present. 6. The continuous inorganic fiber has an amorphous material consisting essentially of 3i, zr and C, and an amorphous material consisting essentially of β- 8i C1zr c
, a solid solution of β-8IC and ZrC, and a mixed system of aggregates of crystalline ultrafine particles of ZrC1-x (where 0<x<1) having a particle size of 5008 or less, according to claim 1. fiber. 7. The continuous inorganic fiber substantially contains 81, Zr, C
and 0, and substantially β-8IC1zr
c, solid solution of β-8IC and ZrC and ZrCI--
L (However, it consists of a mixed system of aggregates of crystalline ultrafine particles with a grain size of 0<x<1> of 5008 or less, and in this case, amorphous 5iOt and Zr
O! The fiber according to claim 1, wherein the fiber is present.