JPS58130164A - Boron-containing metal-containing resin - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to carbon-carbon composite materials, and more specifically, carbon fiber materials, thermosets**, boron-containing compounds, and reacting with boron-containing compounds to produce metal borides. Relating to composite materials made from refractory metals that can be The present invention also provides a! of the carbon-carbon composite material. Carbon impregnated with a thermosetting resin binder useful for relics! l#l fiber materials and methods of manufacturing such composite materials also keep 〇 filler such as graphite powder and #1 such as pitch or resin.
It is known that boron is used in the production of carbon materials such as graphite from materials that can be converted into lead. .

It is also known in the industry to use boron in the manufacture of carbon-carbon composite materials consisting of carbon fiber materials, such as graphite cloth, and thermosetting resins. Examples of this type of composite material are L@o C, Ehr@nr*I
eh U.S. Patent @, 3, 1, 7, No. 736 (/
(June 27, 2013) disclosed in the specification. This patent discloses that when a boron-containing compound is applied to a skin-impregnated carbon fiber material prior to carbonization of 8M, there is some improvement in oxidation resistance as well as interlaminar tensile strength. There is.

Rob@rt C, 8haff@r U.S. Patent No. 1
No. 083j - The specification states that boron-containing carbon-carbon composite materials have at least approximately 10% carbonization and graphitization properties. rO”c
The interlaminar tensile strength of the composite material is greatly improved if heated at K, and at such temperatures the unidirectional tensile strength of the carbon fiber material typically decreases substantially. It is disclosed that this is apparently due to the deterioration of the composite material brought about by the reaction with boron at high temperatures. According to this patent, #
A significant reduction in the tensile strength in the fiber direction of the R-fiber material is prevented by the use of a protective coating on the fibers.

The core coater material includes a thermoset material that remains flexible after exposure to curing temperatures. A coating is applied to the fibers and cured prior to the addition of the skin and boron-containing compounds. The resin and boron-containing compound can then be added to at least partially cure the resin. producing a laminate;
When the laminate is heated by a force Ω to a temperature sufficient to carbonize and at least partially graphitize **, the tensile strength in the fiber direction of the sNj carbon fiber material significantly decreases. It was found that the interlaminar tensile strength was greatly improved without the need for a barrier.
However, this barrier is insufficient to limit boron migration and ill
! When the solidification temperature exceeds 1 da S-°C, it is insufficient to preserve the anisotropy of the gold material. Above this cohesion temperature, boron at high degrees A exhibits such instability that either an isotropic composite is obtained or the composite becomes useless due to large fractures. A mixture containing a curable resin is obtained. This resin is such that it remains OTN even after death when exposed to curing temperatures. The metal can be in the form of particulate metal or fine fractional metal or both metals.

The metal can react with boron in the carbon ternary system at high temperatures. The carbon fiber material is coated with this mixture and the thermosetting resin is cured. The coated carbon fiber material is then re-impregnated with a second thermosetting II shield comprising a boron compound and optionally a refractory metal capable of reacting with the boron to form a metal boride within the coating. For the refractory metal, if present, the metal can be in the form of particulate gold lI4 or finely dispersed metal or both metals. The second thermoset 1M# is at least partially cured and then brought to a temperature sufficient to carbonize and lead sensitize the 0 thermoset W resin, leaving a laminate of fibrous materials. IA heat the laminate. The resulting carbon-carbon composite has better oxidation resistance, improved high temperature stability, and higher density compared to composites made without the presence of refractory metals within the thermoset 41 skin. has
Interlaminar tensile strength was improved.

According to the present invention, carbon fiber material is first coated with a flexible thermosetting resin that remains flexible even after hardening.
Thermosetting resins include refractory metals that can react with boron to form metal borides. The refractory metal can be finely dispersed within the resin (i.e., the refractory metal is an integral part of the resin's molecular structure) or the refractory metal can be a particulate metal; You can also use

Tungsten carbonyl and/or molybdenum
Incorporation of the refractory metal into the resin in the form of the reaction product of carnyl and pyrrolidine facilitates the production of thermosetting resins containing finely dispersed nine metals. Examples of such thermosetting resins include copolymers of furfuryl alcohol and polyester pre-4 remers, which are the reaction products of tungsten carnyl and/or molybdenum carnyl and pyrrolidine. It was reacted with a certain complex. Such;-rimer is Rob@rtC.

8haff@r US Pat. ! Other thermosetting remers containing 0-bonded metals are shown and can be used in the present invention, such as tungsten carbonyl and/or molybdenum carbonyl.
Complex and mono which are reaction products of nil and pyrrolidine! −
The 9-rimer produced by reaction with the gleamer and the gleamer is described in Rob@rt C, 5haffer, U.S. Patent I.
II No. 3, 42 (filed on 3rd day of 2013)
After application, the resin is diluted with a suitable solvent, such as dimethylformamide, to reduce the solid content to, for example, fi, 7096. Carbon fiber materials that can be used in practicing the present invention can include carbon materials that are in the form of fibers or filaments or other shapes. For example, carbon cloth maku includes fabrics such as lead cloth. As used herein, the term "carbon" is intended to include carbon in all its forms, including goocarbons; The first coatender of resin is, in addition to finely dispersed resistance II & @ Iso! Particulate refractory metals having a particle size of ~0μ include niobium, mental, titanium (as titanium dioxide), molybdenum, and tungsten, etc.Refractory metals include boron and A ternary system (one that converts into a stable boride in the resin) can be used. Preferably, about 5θ to 90% of the total content of refractory metals in the resin is particulate metal, and the remainder is finely dispersed metal. It is metal.

Applying and curing the first oJgIa coating to the carbon fiber material using a suitable technique Seven of the methods that may be used include applying the first oJgIa coating to the carbon fiber material in an fc open container containing the coating material. Excess coating material is removed by soaking the material and then pulling the carbon fiber material through a pressure roll, after which the fibrous material is suspended in air at ambient temperature to allow some of the solvent in the coated puffer material to evaporate. This dries the coated material. The carbon fiber material is then heated in an air circulation furnace by Km<
The coating material is cured to advance polymerization of the resin and to remove the solvent. The solids content of the thermosetting coating material is adjusted to provide a cured coating containing about 5 to -00 tons of carbon-wire material.

After applying the carbon fiber coated material, the second S
Re-impregnate with curable resin. This resin is partially cured or BR#. This resin is t
qIllll thermosetting 1M resin and glue;
Further, as described above, the material may or may not contain appropriate components of a finely dispersed heat-resistant metal, a particulate heat-resistant metal, or both metals. This am also
It contains a boron compound*, and the amount of boron is preferably balanced on a molecular basis with the amount of metal present throughout the system. The boron-containing compound is preferably amorphous boron. Impregnation and curing may be accomplished by any suitable method, such as by dipping into an open vessel containing a thermoset resin containing the crumpled carbon fI & sinter layer material boron and optionally a refractory metal. Excess material is removed by drawing the carbon fiber material under pressure rolls, and the material is then dried by hanging it in air at ambient temperature to evaporate some of the solvent contained in the resin. . The dried carbon fiber material is then treated to at least partially cure the thermosetting resin, such as by placing the dried carbon fiber material in a circulating air oven to promote polymerization of the resin.

The amount of amorphous boron to be added to the AI fat is K115 so that the amorphous boron consists of about λ to 100% of the volume of the laminate.

The amount of metal contained in the boron-containing thermosetting resin and the boron-containing thermosetting resin is due to the chemical chemistry necessary to combine with the boron present. Preferably, it is present in excess. Preferably, N#n
about 75 to 100 of the total metal content is present in the first q-containing thermoset resin coating and the balance is present in the second thermoset resin coating.

The resulting laminate is then integrated, reinforced with a #M resin matrix, and further cured. According to one method of doing this, the logging is carried out at high pressure and i%lji for a sufficient time to impart a relatively high degree of fiber-resin i-trix to the laminate. and placed in an electrically heated corrugated brace mold for a sufficient period of time to render the log material adequately self-supporting to maintain its shape and dimensions throughout subsequent processing. .

The laminate is then carbonized and preferably at least partially graphitized. This is, for example, 23 ℃ to -tqo℃
temperature and about 35 to about λ//Kf/2” (soo to 3
This is done by heating under a pressure of 000p*1). Carbonization and graphitization methods that can be used are:
Truly Rlchard J, Lars@nhiro's US patent issue #lI vote tt! ,, ttri issue (March 10, 7275
(Application date) Written in the specification. The method described in the US patent application of Lars@n et al.
The M resin composite material is first shaped by molding and at least partially precured.

The composite material is then placed in an induction furnace where S3 is applied to substantially decompose the a#I, which is rapid but without delamination or other damage to the composite material. Heat at a temperature of about 1000° C. (1000”?) at a temperature of 30° C. until the composite material is substantially beam-like and 90° C. (300° C.). F) Continue heating at a second rate at a temperature above 500 ft. The composite material is then maintained at an elevated temperature, typically above about 1000 ft (zooo ya), while at the same time not applying high pressure. Continuous processing requires sequential processing steps performed in a relatively short space and at different locations or using different equipment. Without any
A very dense ll5 honey product is produced that has virtually all of the IR signature composition.

71 due to the combination of refractory metal and boron in the composite material.
III Metal borides are generated behind the scenes of thermal processing.

Metal borides are considerably more stable at high temperatures than boron carbide. Thus, boron migration is limited, and the sum of Both the borosilicate and the metal present in the 0'awI product prevent attack of the fibers by gK and prevent fiber deterioration. The synergistic effects on the interlaminar tensile strength of the carbon-carbon composite material are coupled.

The following examples illustrate the invention.

Examples/30 weight resin (Ahaffor U.S. Patent Nos. Q, O)
resin produced according to the method of Example 1 described in the specification) and granular niobium (-3
A pulverized product was prepared containing 100% of the particle size of mesh. The graphite fabric was immersed in an open container filled with grinding material.

The solids content of the mill was adjusted to produce a coating consisting of approximately 5 parts by weight of fabric. The fabric was pulled through pressure rolls to remove excess coating and hung to dry in air at ambient temperature. It is then placed in a circulating air oven at a temperature of about /A joc(,?,2!roF) f) for about 60 minutes at a temperature of tKMi.
I put down the fabric.

This temperature treatment cured the resin sufficiently to prevent intermixing with the resin of the second coating.

Next, ahaffor's U.S. Patent No. θZari, Hirot
The coated fabric is immersed in an open container holding a pulverized product consisting of a resin T7, a pulverized graphite fiber, and amorphous boron prepared in accordance with the example described in the specification. , further impregnated.

Sufficient amount of milling material was added to coat approximately 1-0 weight percent of the original weight of the fabric. The fabric was drawn between pressure rolls to remove excess resin and hung to dry in air at ambient temperature. After that, about /6j'C (jJj'F
)F) ffi&, approximately 30 molecules) between.

The fabric was placed in an air circulation oven (1) and then the temperature was raised to about -〇joc (daoocv) for about 70 minutes. This temperature treatment allowed the resin to proceed to stage B. Then, the impregnated fabric was cut into pieces with selected dimensions and shape;
It was laid-up into the desired shape. The laminate is integrated, reinforced, and approximately 70'fJ/3'' (
1000psi) k Z and J t toc (06
The matrix material was further cured in an electrically heated step-dissipation mold for approximately 16 hours at 0F). It has been found that the length of time required for curing depends on various factors including the wall thickness and shape of the product. When removed from the press, the product had high fiber-matrix adhesion. The product was made properly self-supporting to maintain its shape and dimensions throughout further processing steps.

Next, induction heating is applied to approximately -t70oc (approximately 300a).
F') in a device heated to a temperature of about 7θ to about /4! O
kl//cfIR” (1000-2000psi
), the laminate was fully carbonized, further compacted and graphitic MK. This process completed the transformation of the resin matrix, the advanced graphite crystallinity and the formation of metal borides within the matrix. When the tensile strength in the direction was measured, it was as follows.

X-ray diffraction of sample / shows highly graphitic a,3z
A graphitic peak of X was shown, indicating that boron promoted graphitization.

In addition, xll analysis revealed that NbC, NbB2 and δ-WB
However, B4C was not found. These results indicate that the reaction between boron and the metal present is complete and that the molecular distance traveled by boron is large when high temperatures and pressures are applied.

EXAMPLE A carbon-carbon composite material was prepared by combining as described in Example. However, without using 1 grain of niobium, it is 3/4 c.
A high coalescence temperature of 'cC4L coo'y' was not used. This composite material contained only finely divided (dispersed) tungsten and excess boron on a molecular basis, and did not contain any particulate metals.

This composite material is 6? 3 kg/cII4” (9!
It was found that it had a tensile strength in the direction of f) and an interlaminar tensile strength of /7/yu/cllIHakoda3kopal). This glabellar tensile strength is 5haff@r U.S. Patent No. 4I, /4da, 60/
This was a significant improvement over the carbon-carbon composites described in that patent, ie, composites that did not contain refractory metals. However, a bereavement carbon-carbon composite material made in the same manner at a high coalescence temperature of 710C (JCooo'r) and containing only finely dispersed tungsten is only l za/J/
, m" (ko5t3p field weight) in the fiber direction and glabellar tensile strength of /4.2 IKg/lnr" (kojO/psi). These results indicate a decrease in tensile strength in the fiber direction, resulting in an isotropic composite.

Example 3 A carbon-carbon composite material containing not only finely dispersed tungsten but also particulate refractory metal was prepared in order to keep the fiber identity and anisotropy of the composite constant.
Manufactured as described.

The particulate metal was added to the barrier placed on the fibers to intercept the migrating boron. This additional metal protected the fibers, resulting in a stable composite. The metal is tantalum.

Titanium, molybdenum and tungsten as titanium dioxide were used in place of niobium in Example/. The high consolidating temperature used to make each composite material was approximately 1710C.

The interlaminar tensile strength and fiber direction tensile strength were measured and found to be as follows.

It can be seen that the addition of particulate metal protected the fibers and resulted in a stable composite material. The tensile strength in the fiber direction for each of the above samples was approximately 3/6°C (μmoocF>
Composites manufactured at high consolidation temperatures of about -g'yioc (SOO°F), although lower than composites containing only finely dispersed tungsten. This was considerably higher than that of composite materials containing only finely dispersed tungsten.

Analysis of the data obtained from the composites of Examples /, - and J shows that these composites have changed fiber volume. The obtained value was compared to 404 for standard composite material.
To normalize to the standard horizontal line volume (which could be expected to have), we give the following chart.

High temperature cohesion temperature Ko3/Aoc Kot71%
Kozakutsu ℃ (lI200 oF) C! r200'
F) C! r200'F) Additive metal * *
Tie2 * 2g710C, 2g7/oc 217/'t without adding particulate metal
217/'10(rxoo OI') (
zsoo a1') (sxoo'?) Czx
oo 0r) Nb Mo
W Tall93ke/lx”
On 7/3/lx"773kv'ca"
#27kt/lx? (riθ/jps i) (
10/lI/psi) (10 de? Jpsi)
(Si14) si) The fiber m of the above chart is approximately 217
/ QC (r, 100 oF) for example in the case of titanium dioxide, molybdenum and tungsten systems, is actually better compared to the case of finely dispersed systems at about 3/l, °C (00 oF'). It shows that it is protected.

Thus, it is clear that the fibers in the composite from the finely dispersed metal alone (boron) will be protected as long as the temperature does not exceed the temperature of 100 ml, and that this protection will not be applied to the metal-free flexible furfuryl resin, i.e. 5haff. @r US Patent No.'
1. It can be seen that this is superior to the resin disclosed in No./441-, I, 0/.

Composites made without metal granules exhibit a lower density than composites made with metal granules;
The use of finely dispersed metallic 14kK fibers provides significant weight savings. However, the intended use of metal granules is at higher cohesive temperatures, such as 24! fJ'
It is necessary to protect the fibers when using temperatures higher than C.

Claims (3)

[Claims] (1) A first portion surrounding the carbon fibers, including a flexible thermosetting fat coating containing a refractory metal capable of reacting with boron to produce a metal boride amount; a carbon fiber material impregnated with a thermosetting resin binder comprising a second portion coated over the first portion of the sill, the second portion comprising a thermosetting resin containing a compound. (2) A carbon-carbon composite material comprising multiple layers of carbon fiber material within a carbon matrix containing a metal boride, wherein the M resin matrix reacts with boron to form a metal boride. A first portion of a thermosetting resin surrounding the fibers, including a 9-coat thermosetting resin coating containing a heat-resistant metal capable of forming q1i as a main component, and a boron compound, furfuryl alcohol, Thermosetting 11J containing copolymer with polyester graymer! 1 and in which a polyester prepolymer has been reacted with a complex which is the reaction product of tungsten galyl and/or molybdenum caryl and pyrrolidine, and a second portion coated on the first portion. (3) A flexible thermosetting resin that remains flexible even after hardening and contains a heat-resistant metal that can react with boron to produce a metal boride. BI! Applying a coating of a thermosetting resin to a plain fiber material, curing the flexible thermosetting resin, and coating the carbon fiber material with a second thermosetting resin containing a boron compound. impregnating and at least partially curing the second fI & curable resin Bvt, assembling several layers of charcoal material to leave a laminate, and applying a temperature sufficient to carbonize the thermoset resin. 9f, a method for producing a carbon-carbon composite material comprising the step of heating a product in step 0