• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    The present invention provides a carbon-carbon composite material consisting of a matrix carbon and a fibrous reinforcing carbon, said matrix carbon consisting substantially of optically anisotropic carbon and said fibrous reinforcing carbon consisting substantially of optically isotropic carbon, and said matrix carbon and fibrous reinforcing carbon forming an interface without an intervening third material, wherein said composite material has a fracture surface showing a uniform vitreous light reflection, and a method for the preparation thereof. The composite material has a high flexural strength and a very low gas permeability and is useful as a molding material in the fields of high temperature chemistry, the atomic energy industry and medicine.
    公开号:SU791253A3
    申请号:SU782665906
    申请日:1978-09-08
    公开日:1980-12-23
    发明作者:Мацуи Хиронори
    申请人:Канебо Лтд (Фирма)；
    IPC主号:
    专利说明:

    It is impossible to avoid the formation inside the previous product in the burning stage of various stresses (e.g. shrinkage, tension, discharge), resulting in scaly-shaped bulges, which are called shells or cracks, on the surface of the material. Naturally, in this case the yield of the final product is is insignificant. For the same reasons, such a carbon-carbon composite material is formed, in which the fibrous carbon and the carbon matrix loosely adhere to each other and form a noticeable border of the section, therefore the resulting composite material has a sufficiently high gas permeability.
    Closest to the proposed technical solution is a method for producing a carbon-carbon composite material, comprising mixing 20-150 parts by weight. phenolic resin with 100 weight.h. organic fibers based on phenolic resin, heat-treated from room temperature to in an oxidizing atmosphere and further up to 600 ° C in an inert atmosphere, molding the mixture and subsequent carbonization to 800-1000 ° C in an inert medium with a carbonization rate of B-TO S / h 2 .
    The disadvantage of this method is that it does not provide the material with a sufficiently high flexural strength, gas impermeability and reflective properties.
    The purpose of the invention is to increase the flexural strength and gas tightness and ensure the reflective properties of the material.
    This goal is achieved by using as a phenolic resin a cutting phenol-formaldehyde resin, which is mixed with novolac fibers with a content of 4-12% by weight of methylol groups heat-treated from 250 ° C to 500 ° C in an inert atmosphere.
    The fibrous reinforcing carbon is 30-90% by weight, preferably 50-80% by weight, based on the weight of the carbon-carbon composition, and the remainder is essentially amorphous matrix carbon, which is optically anisotropic.
    Fibrous reinforced carbon and matrix carbon fly around substantially the same density, which is about 1.42 l, 6i g / cm, in a preferred embodiment, 1.48-1.58 g / cm} Thus, a composite material of the uRlerod-carbon type can have a density of about 1.42-1.61 g / cm, in a preferred embodiment, 1.48-1.58 g / s
    A carbon-carbon type material is extremely high in purity and, in general, contains 94% by weight, in a preferred embodiment, 96% by weight, and sometimes 98% by weight with carbon.
    An advantage of the invention is the fact that despite the fact that this material consists of a fibrous reinforcing
    Q carbon and carbon matrix, its surface fracture has a uniform ability to reflect light.
    This material has a high bending strength of at least 9 kg / mm, in preferred
    5 option is not less than 10.5 kg / mm in the most preferred embodiment 11.514, 0 kg / mm, as well as high density and very low gas permeability. For example, its permeability
    0 with respect to gaseous helium is generally not more than 10 cm / s, preferably no more than 1 (G cmr, most preferably no more than 10 cm / s.
    5 Despite its high density, the material has a high toughness, which is usually at least 2.5 kg-cm / cm, preferably at least
    .. 3.5 kg-cm / cm in the most preferred embodiment 4.0-10.0 kg-cm / cm. The material has a high hardness, which is determined by measuring the Vicker hardness, comprising at least 350 kg / mm,
    in the preferred embodiment, at least 800 kg / mm, in the most preferred embodiment, at least 1000 kg / mm
    Material conductivity
    0 is slightly lower than that of conventional carbon products or graphite. In general, it has a resistivity of 10 ohms / cm, preferably 10-1 cm ohms / cm, most preferably 1 {-10 ohms / cm. The thermal conductivity of the composition is 1-40 kcal / MCh ° C, in particular from 2 to 10 kcal / m-h C.
    The material has excellent thermal stability and can withstand in general tempo. temperatures to about, and usually temperatures to about, in
     the presence of air. It also has very good chemical resistance and is not affected by exposure. most organic and inorganic chemicals
    0 (the latter fact was established as a result of tests for chemical resistance using a large number of chemicals). Cured Novolacs,
    5 which are used in accordance
    With the proposed method as a starting material, it can be obtained by extruding a melt of a novolac resin and. curing the resulting Novolac fibers with aldehyde.
    Bulk resin is a fusible thermoplastic resin that has not been heat treated and is formed by the reaction (polycondensation) of phenol and aldehyde when heated, usually in the presence of an acidic catalyst. Novolac resins having an average molecular weight of about 500-2000, in particular 7001500, are used.
    The phenols used to produce novolac resins are the most common phenol and cresol. But you can also use other phenols. Examples of such 1 | enols are phenol, ortho-cresol, Aetha-cresol, para-cresol, 2, 3-xylenl, 2,5-xylenol, 2,4-xylenol, 2,6-xylenol, 3,4-xylenol , 3,5-xyl nol, ortho-ethylphenol, 1 years-ethylphenol. Para-ethylphenol, para-phenylphenol, para-tertiary butylphenol, noipa - tertiary amylphenol, bisphenol A, res .cin, and also mixtures of two or more of the listed phenols.
    The most convenient aldehyde used in the polycondensation reaction with phenols is formaldehyde, but monoaldehydes and dialdehydes can also be used, such as paraformaldehyde, hexamethylenetetramine, furfurol, glutaraldehyde, adipoaldehyde and imidazole.
    The acid catalyst used in the Novolac resin formation reaction may be any known organic or inorganic acid, for example, hydrochloric, nitric, sulfuric, phosphoric, formic acid, p-toluene sulfonic acid, acetic acid or phthalic acid.
    Various methods for producing fibers from novolac resins are also known. Novolac fibers can be obtained, for example, using a method that involves heating a novolac resin in an inert gas atmosphere, such as carbon dioxide or nitrogen, in order to produce a fluid melt, and extruding or sucking the melt into an inert cooling medium such as air, nitrogen or water, through a die, having nozzles of the required size, in order to cool and solidify the fiber.
    In accordance with this method, no more than 30 wt.% Are allowed, in a preferred embodiment, no more than 15 wt.%, In terms of
    on the weight of Novolac resin, other thermoplastic resins - from which fibers can be obtained, such as polyamides, polyurethane, polyesters or polyolefins.
    The uncured fibers thus obtained are further cured. The curing step is carried out using known methods. For example, novolac fibers are heated to 90-105 ° C in a water solution containing an acid catalyst and aldehyde. Or uncured novolac fibers undergo a preliminary curing step, which is carried out at
    5 help heating them to about 70-105 C in an aqueous solution containing an acidic catalyst and aldehyde, and then the pre-cured novolac fibers are heated in a water solution containing the alkaline catalyst and aldehyde to about 70-95 ° C. Examples of suitable aldehydes and acid catalysts that are used for curing novolac fibers are aldehydes and catalysts that are used in the preparation of novolac resins. Examples of alkaline catalysts are sodium hydroxide, potassium oxide, calcium oxide, oxide
    0 barium, lithium oxide, magnesium oxide, strontium oxide, ammonia, dimethylamine, methylamine and hexamethylenetetramine. Ammonia and hexamethylenetetramine are preferably used.
    five
    The content of hydroxymethyl in cured novolac fibers thus obtained is not a decisive factor, but cured novolac fibers can usually
    0 contain hydroxymethyl groups of at least 3.5 weight-. %, in the preferred embodiment, 4-12 wt.%, in the most preferred embodiment, 5-10 wt.%. It has been established that when using 5 trusted novolac fibers with a reduced percentage of oxymethyl groups, even when the content of oxymethyl groups decreases as a result post heat cured
    0 novolac fiber, hydroxymethyl groups, remaining on the surface of the novolac fiber after heat treatment, can effectively interact with phenolic resins,
    5, which are used as a matrix, to form a single dense carbon-carbon composition in which the fibrous reinforcing carbon and matrix carbon form an interface that does not contain a third material, while significantly increasing the yield of the carbon-carbon composition.
    In order to ensure that the oxymethyl groups in the cured novolac fiber are within the given limits, the concentrations of the acidic or alkaline catalyst and aldehyde in the curing bath and / or the reaction time can be directly controlled. The corresponding concentration of the catalyst is 10-20 wt.%, And the corresponding aldehyde concentration is 18 wt.%. In a preferred embodiment, the reaction time is 315 hours.
    The cured novolac fibers thus obtained are further heat treated. Thermal treatment should, in general, be carried out without tension using known heating devices, such as an electric furnace or an infrared induction furnace at a temperature of 250 - less than 500 ° C, in a preferred embodiment, 270440 ° C, most preferred, 280-350 ° C. Thermal treatment should be carried out in a non-oxidizing gas atmosphere. Thermal treatment in an atmosphere of oxidizing gaseous gas does not allow obtaining a carbon-hydrocarbon-type composition having the listed properties. The term non-oxidizing atmosphere means an atmosphere from which air is substantially removed, or an atmosphere of inert gas such as nitrogen, carbon dioxide, carbon monoxide, argon, helium.
    In the heat treatment process of the cured Novolac fiber, the rate of temperature rise from room temperature to the heat treatment temperature is not a decisive factor. In general, the temperature can be raised at a rate of 0.5–50 s per minute, preferably 1.0–20 ° C per minute.
    The heat treatment time depends on the heat treatment temperature. It is small at higher temperatures, and at lower temperatures longer. In general, the heat treatment time is 5180 minutes, preferably 15-120 minutes.
    In order to obtain particularly favorable results, it is important to adjust the heat treatment process so that in the infrared absorption spectrum for novolac fibers after heat treatment, the ratio) 6CX) absorption intensity with a given wavelength {0770 absorption peak region 740-770 cm which corresponds to the adjacent hydrogen atom on the benzene ring, the absorption intensity with a given wavelength (D -, (joo) in the peak area of 1600 cm, which corresponds to the benzene ring, changed in the range of 0.05-0.40, a clear version of 0.10-0.35, and in the most preferred embodiment, 0.150, 30.
    The absorption intensity ratio is a measure of the degree of growth of three-dimensional chemical bonds in a novolac fiber as a result of heat treatment. It is indisputable that when conducting heat treatment of novolac fiber in such a way that the ratio is in the range of 0.05-0.40, the matrix carbon is optically anisotropic, and the reinforcement carbon is optically isotropic. At the same time, due to the presence of the remaining hydroxymethyl groups, the matrix carbon and the reinforcing carbon form an interface that does not contain a third material. Due to this, the fracture surface of the composition has a uniform ability to reflect light. The resulting carbon-carbon type composition possesses a number of significant properties, for example, high bending strength and low gas permeability.
    It has been established that when preparing a carbon-carbon composition in accordance with the proposed method using hardened novolac fibers without heat treatment (for which the ratio is usually about 0, 5; the matrix carbon and reinforcing carbon are optically isotropic and are integral. probably occurs because the matrix and the reinforcing fiber have the same shrinkage during carbonization.
    If a carbon-carbon composition is prepared in accordance with the inventive method using hardened novolac fibers that have been heat treated at a temperature of 500 ° C so that the ratio is less than 0.05, then the reinforcing fibrous carbon gives only a slight shrinkage. In this case, stresses result from differences in shrinkage of the fiber and the matrix. This leads to local graphitization (graphitization — under the effect of stresses), with the formation of voids even in the matrix. This increases the gas permeability of the final product.
    If the cured novolac fibers are heat treated in such a way that the ratio is contained in the described area, some stress arises in the matrix due to
    the fact that she and the reinforcing carbon begin to shrink at different temperatures (of course, the matrix begins to shrink earlier). But when heated to a temperature of 80 ° C or more, the matrix is not graphitized due to the fact that it and reinforcing fiber carbon have substantially the same shrinkage. In accordance with this, the matrix will be optically anisotropic. As a result, the degree of three-dimensional chemical bonds in heat-treated fibers increases (fiber strength increases). At the same time, the matrix and reinforcing fibrous carbon enter into adhesion by activating certain groups, a typical example of which is the oxymethyl group that remains on the fibers after heat treatment. This leads to the formation of a carbon-carbon composition having the properties described.
    After heat treatment, said fibers should have a fiber length of not less than 0.4 shl, preferably not less than 1.0 mm. The fiber diameter is not a decisive factor, but some advantages can be achieved if the fiber diameter varies in the range of 5-60 microns, preferably 10-40 microns. Thus, the heat-treated fiber has a length / diameter ratio of at least 40, preferably at least 100.
    You can use heat-treated fibers in the form of short fibers, and in the form of long fibers. Pre; various types of materials are made from them: sheets, woven material, knitted material, non-woven material, chopped threads or staple. In a preferred embodiment, the fibers are used in the form of a woven fabric, a nonwoven fabric or a staple.
    The phenolic resin, which is used in combination with thermally treated novolac fibers, is a precondensate obtained by reacting phenol with an aldehyde in the presence of an acid or alkaline catalyst. In general, the phenolic resin contains self-curing resins having a molecular weight of up to about 600, as well as a large percentage of oxymethyl groups, and is formed by reaction in the presence of an alkaline catalyst, as well as thermoplastic novolac resins having a molecular weight of 300- 2000, in which phenol is bound mainly through methylene bonds and which are formed as a result of the reaction of phenol with aldehyde in the presence of jII of an acidic catalyst. In the preferred embodiment, resols are used.
    Heat-treated pillow fibers and phenolic resin are blended to form a resinous composition containing heat-treated fibers dispersed in a phenolic resin matrix. Heat treated blending
    O fibers with phenolic resin is carried out by known methods. For example, if the phenolic resin is a liquid, it is converted to a structure consisting of fibers. If the phenolic resin is a solid material, it is sprayed with a thin layer and then mixed with fibers using a kneader, hot rollers, etc.
    The ratio in which the heat-treated fibers and the phenolic resin matrix are mixed can vary widely, depending, for example, on the shape of the heat-treated novolacs.
    5 fibers, the content of hydroxymethyl groups in these fibers before heat treatment, the intensity ratio of absorption in the infrared spectrum, as well as the type of phenol
    0 resin. The content of thermally treated fibers is generally from 30 to 90% by weight, preferably from 40 to 85% by weight, most preferably from 50 to 80% by weight.
    5 in terms of the weight of the resinous composition. Alternatively, the phenolic resin may be contained in an amount of 10-70% by weight, in a preferred embodiment, 15-60% by weight, in a most preferred embodiment, 20-50% by weight
    0 in terms of the solids content of the excellent phenolic resin, in turn, based on the weight of the resinous composition.
    The amount of phenolic resin that
    5 must be mixed in this process, it can be determined by curing the phenolic resin and calculating the ratio of the weight of the phenolic resin before: curing to the weight of the cured resin.
    0 phenolic resin. Further, the solids content of the solidified phenolic resin is multiplied by the calculated ratio.
    If necessary, resinous
    5, the composition may contain other additives, such as furan-type resins, epoxy resin, a mixture of vinyl polymer and divinyl compound, a urea resin, an unsaturated polyester resin, melamine resin,
    0 resin from pitch or oil, in small quantities, for example, not more than 20 wt.% Based on the weight of the phenolic resin. The resinous composition thus obtained is profiled with
    five
    The goal is to give it the necessary shape, for example, a sheet, rod, cylinder, block, film, ball or crumb. It is important at this stage to make a shaped product larger than necessary. Actually, since the product shrinks at subsequent stages of heating and heat treatment. The profiling operation can be carried out using well-known VAP (fiber-reinforced plastic) profiling methods, for example, using a mold, sequential deposition of layers, a spraying method, a fiber winding method, a molding method using a centrifuge, a poltrusion method, a pre-mixing method, a preforming method and a cross method reeling. Of all these methods, methods comprising pressure molding are used in the preferred embodiment.
    The resinous composition, after giving it the desired shape, can solidify under normal conditions or under pressure, which is preferably 10-300 kg / cm.
    The curing of the shaped resinous composition can be carried out in accordance with known methods for curing the phenolic resins, usually by heating. If the matrix phenolic resin is a resole resin, the composition is simply heated to 110-180 ° C, preferably up to 130-1 ° C. These temperatures are maintained for approximately 0.15-24 hours, and curing agents are not used. If the matrix phenolic resin is a novolac resin, during the connection the thermally treated novolac fibers or fiber structure consisting of the fibers with the novolac resin are fed at least 1 equivalent, preferably 1.1-2.0 equivalents, for an equivalent amount of novolac resin, formaldehyde or a compound from which formaldehyde is formed under curing conditions, such as hexam tilentetramin, paraformaldehyde, trioxane, tetraoxane or imidazole and then in the presence of a curing agent profiled resinous composition is heated to 110-180 C in the preferred embodiment to 13C 1bOs which is maintained for 0 h.
    The profiled and cured resinous composition is then naked to a carbonation temperature which is at least 800 ° C, preferably at least, most preferably at least 1200 ° C, in an atmosphere free of oxidizing agents, i.e. under reduced pressure or in an inert gas atmosphere such as nitrogen, carbon dioxide, carbon monoxide, argon or helium. There is no upper limit for the firing temperature, but for the sake of equipment maintenance and for economic reasons, temperatures up to 3500 ° C are sufficient.
    According to the proposed method, at the heating stage, at least in the temperature range from 200 to 500 ° C, the temperature rise rate S is not more than 60 ° C / h, in the preferred embodiment, not more than 40s / h, in the most preferred embodiment, not more than 20 ° C / h. In the area of x. temperatures below 200 ° C and higher heating can be carried out at the indicated speed or at high speeds.
    At a temperature of about 200 ° C, oxygen-containing compounds, such as H.O., HCHO, CO, and / a begin to scorch from the profiled resinous composition. At temperatures above 500 ° C, hydrogen evolution is observed.
    In addition, in the temperature range 200-500 ° C, the hydroxymethyl groups remaining on the novolac fibers after heat treatment can chemically react in various ways with reactive residues (for example, the oxymethyl group) in a matrix of cured phenolic resin, thereby reducing deformation and as a result, the resin composition is a single unit. The resulting composition is then carbonized at a high temperature. Accordingly, in this temperature range, it is necessary to carefully control the rate of temperature rise, the heating rate should not exceed 60 ° C / h. If the rate is greater than 60 ° C / h, the resinous composition is carbonized without reducing deformations and the rate of chemical reactions is reduced. As a result, flakes or cracks form on the surface of the resulting carbon-carbon compositions. In addition, the composition has low strength, and the yield of the product also decreases.
    The heating of the profiled and cured resinous composition can be carried out by known methods, for example in an individual furnace, a continuous furnace, in an electric furnace or a continuous tunnel furnace at specified firing temperatures for a period
    5 less than 0.15 h, in general, 1-72 h.
    The carbonized carbon-type composition is further cooled to a temperature below about and removed from the furnace.
    In this way, it is easy to obtain carbon-carbon compositions of different shapes and sizes, and a high product yield is provided. In addition, there are opportunities for lightening the firing time and the cost of the product.
    The determination of the content of hydroxymethyl groups in the cured novolac fiber is as follows.
    Getting a calibration curve.
    Novolac resin, which does not contain hydroxymethyl groups (i.e. in which there is no absorption in the region of 995, characteristic of the oxymethyl group, in the infrared absorption spectrum obtained by the method containing potassium bromide tablets) and having an average molecular weight of 1000 (intrinsic viscosity 1 is 0.076) is uniformly mixed with a resol having a known content of hydroxymethyl groups. The infrared absorption spectrum of the mixture obtained is determined using potassium bromide tablet. Using an analytical method in order to separate the superimposed absorption peaks, the absorption intensity% in the region 995 (absorption peak characteristic of the oxymethyl group) and the absorption intensity O (, OQ
    in the region of 1600 cm (absorption peak characteristic of benzene), and then the ratio of absorption intensities Dggj is calculated
    The process described is then repeated, but the number of resole (i.e., the content of hydroxymethyl groups) varies.
    The ratio of the absorption intensities and the total content of hydroxymethyl groups in the mixture are used to plot the graph, which is the calibration curve. .
    Determination of the content of hydroxymethyl groups in the cured novolac fibers.
    A sample of the cured Novolac fiber is finely ground and its infrared absorption spectrum is determined using potassium bromide tablet. According to the described method, the absorption intensity OQ55 / bfboo- is determined. The ratio of the absorption intensities is compared with the previously obtained calibration curve and the content of oximethyl groups corresponding to this ratio of absorption intensities is read. The value obtained is the content of hydroxymethyl groups in the sample.
    The ratio of the absorption intensities in the infrared spectrum of a thermally treated novolac fiber is determined by the following method.
    A sample of the thermally treated Novolac fiber is finely crushed and its infrared spectrum is determined with the help of a Brog-potassium potassium tablet. Using an analytical method to separate the superimposed peaks from the spectrum: the absorption intensity of the absorption peak is determined in the region of 740-770 cm characteristic of adjoining, hydrogen atoms on the benzene ring, and the absorption intensity of the absorption peak of 1600
    benzene ring. The ratio of absorbance values is then calculated.
    77 o
    The yield in the burning step is determined by the amount of the carbon-carbon type composition obtained, expressed as a percentage based on the amount (100) of the preceding material that was loaded into the burning kiln.
    five
    To determine the optical properties of a carbon-carbon composition.
    The cross section of the sample composition is examined using a polarization microscope.
    0
    The flexural strength of a carbon-carbon type composition is measured by modifying method 31S K6911.
    The impact strength of a carbon-carbon composition is determined by such
    5 way.
    With the help of the Charpy Dynamic Impact Tester, the total impact energy that was spent when the test sample of the composition was broken was determined. Impact strength is calculated at
    Assist in dividing the total impact energy by the cross-sectional area at the fracture of the test specimen.
    The gas permeability of a carbon-to-carbon composition is measured using a method for calculating the pressure change using a gaseous helium substantially using an ASTM D-1434 device. Examples 1-5 show logarithms of gas permeability values (cm / s).
    To determine the density, the sample is finely ground and its density is measured by the ascent method.
    five
    The thermal stability of a carbon-carbon composition is measured at the temperature at which the sample begins to lose weight. The sample is contained in a body device in which the temperature rises at a rate of 5 s / min in air.
    The hardness of a carbon-carbon composition is measured by the Vickers method using a solid-5 micro sensor under a load of 500 kg.
    To determine the X-ray diffraction pattern for a carbon-carbon composition, the sample is sprayed using a tungsten disk-type sprayer, and the X-ray diffraction pattern is examined using a diffractometer; the radiation source is CuKd, and nickel is used as the filter.
    The electrical resistivity of a carbon-carbon composition is measured by measuring the voltage drop in accordance with Л IS Р-7202
    The percentages in the examples are by weight.
    Example 1. In a Florentine vessel with a capacity of 10 liters load 6.5 kg of phenol, 3.4 kg of 44% formaldehyde solution and 20 g of oxalic acid; with stirring, the temperature is raised from 20 ° C to 100 s for 5 h. The mixture is maintained at this temperature for 1. h, and then the heating is continued under reduced pressure (20 mm Hg), while for 3 h raise to 180 ° C so as to remove water, unreacted materials and compounds with a low boiling point. The resulting Novolac resin has an average molecular weight of 1000 and a melting point of 125 ° C.
    The Novolac resin is heated to 148 ° C and extruded through a spinneret j containing 120 nozzles with a diameter of 0.20 mm at a speed of 700 m / min. This forms uncured fibers having a weight number of 1.85 denier and a tensile strength of 0.25 kg / m and an elongation ratio of 16%. Next, the fibers are immersed in an aqueous solution at a temperature of 28 ° C, containing 17.5 wt.% Hydrochloric acid and 14.5 wt.% Formaldehyde, and then over 2 hours the temperature of the aqueous solution gradually rises to 98 ° C. At a temperature of 98 ° C, the fibers of the rye are filled in for 2 hours, resulting in cured fibers having a degree of curing (weight gain) of 10%. Hardened novolac fibers contain oxymethyl groups in the amount of 4.5%.
    The cured novolac fibers without tension are heated from room temperature to each of the temperatures listed in Table. 1a, at a rate of 150 s / h under nitrogen and heat treatment at each temperature is continued for 1 hour. The resin resin is cured and then re-fired. This cycle is repeated four times.
    The tensile strength and infrared absorption intensity (rjo / Offoo) of the heat-treated novolac fiber are determined; the results are summarized in Table 16. 1 Heat-treated fibers are cut into pieces with a length of 6 mm and treated with a beater in order to increase their degree of dispersion. The cut fibers are mixed with a cutting resin having a gelation time of 100 s at 140 ° C, using a mixing machine, in such a way that the fiber content is equal to the value given in table. 16. Each of the resinous compositions thus obtained is air-dried, then in an oven, and finally under vacuum; the composition is then weighed. The compositions are rectangular formable. The material is placed in a mold heated to 150 ° C and profiled so as to obtain a workpiece having a width of 20 mm, a thickness of 10 mm and a length of 120 mm.
    The billet is heated in a stream of argon from room temperature to 120 ° C at a rate from 30 ° C to 500 ° C at a rate of 20 ° C / h, from 500 ° C to 1000 ° C at a speed of 80 ° C / h, and then fired at 1000 ° C for 5 hours.
    The optical properties, gas permeability, flexural strength, impact toughness and density of the resulting carbon-carbon compositions are determined in accordance with the above methods, and the fracture surfaces of the specimens are examined using a conventional microscope.
    Table la
    Table 16
    3 According to the proposed method 4 Compare. 5 On the proposed method 6-7 On the proposed method
    And 9CravIt is difficult to get a pre-security BEI prIIzotrop10Po Anisone way to propose a way out
    9.6 7.0. 1.5710.05
    -7 08,82,21,57 ± 0,05 011,5 ОЗ, 51,57 + 0.05 08,32,31,57 ± 0,05 012,73,01,57 ± 0,05 13,2 4.7 1, 05 11.9 6.6 1.57 ± 0.05 0 no azts, 57tO, 05
    14.- there is
    If heat treatment of cured novolac fibers is used, temperatures below 250 ° C are used, the resulting product is most likely a glassy carbon body than a carbon-carbon composition. Although this product has excellent gas impermeability, its flexural and impact strength are not satisfactory at all. If the heat treatment of cured novolac fibers uses a 500 ° C and higher temperature tag, then the resulting product can even distinguish the matrix and carbon reinforcing with the naked eye; The product has a high gas permeability.
    If the content of thermally treated Novolac fibers in the resinous composition is less than 30%, then reinforcement cannot be achieved, so the strength of the product is very low. If this content exceeds 90%, then it is difficult to mold the blank itself, and in this case its density is insufficient.
    From experiments 5-8, it is not possible to notice any relationship between the fiber content and the density of the resulting carbon-carbon composition; Matrix carbon and carbon reinforcing cannot be distinguished from each other using a conventional microscope. It follows that the densities of the matrix and the reinforcement part are essentially the same.
    Compositions such as carbon-carbon from experiments 3,5,8 and 10-12 have a carbon content of 97-98 wt.%. X-ray diffraction analysis showed that they have a wide diffraction profile with a deflection angle of 26®. In addition, they do not possess a separate profile with two peaks with deviation angles during diffraction in
    Continued table. sixteen.
    -3 12.4 13.4 1.53 ± p, 05
    5 areas 42-46 ° and, therefore, these compositions are entirely composed of amorphous carbon.
    Example 2. The resin used in Example 1 is processed under the same conditions. The resulting uncured novolac fibers are immersed in an aqueous solution of hydrochloric acid and formaldehyde in various proportions indicated in
    5 tab. 2a, the ratio of fiber to aqueous solution being maintained at a level of 1:20 and heated to a temperature of 97 ° C for 3 hours. The fibers are maintained at 96-98 0 for 7-20 hours. The treated fibers of ttJ are watered with water, immersed in an aqueous solution containing 1% ammonia and 55% methanol and treated at 60 minutes,
    5 are washed with water and dried. The content of hydroxymethyl groups in the resulting fiber is determined.
    The resulting cured novolac fibers are heated without tension in a stream of gaseous nitrogen from room temperature to 350 ° C with a shelf of 150 H / h and kept at that temperature for 1 hour. Then, the tensile strengths of the resulting fibers are determined.
    In accordance with the same method as in Example 1, of these thermally treated novolac fibers, various carbon-carbon compositions are prepared, the content of volokots in which is 53 wt.%.
    After the burning stage of the composition, the la surface of which was formed
    5, flakes or cracks are removed, and for the remaining compositions, the yield, optical properties, gas impermeability, bending strengths and toughness are determined.
    68
    Isotropic
    Anisotropic
    The fracture surfaces of these carbon-carbon compositions have a uniform ability to reflect light, and if these fracture surfaces are examined using a conventional microscope, it is impossible to distinguish the matrix carbon and fibrous reinforcing carbon from each other, since both these carbonaceous materials form a single whole.
    It was found that these carbon-carbon type compositions contain 97-98% carbon, an X-ray analysis of these compositions showed that they consist entirely of amorphous carbon.
    Example 3. About (; vergentine & novolac fibers obtained in the same way as in example 1 are heated without tension in a stream of nitrogen
    Table 2a
    Table 26 about
    11.3
    -6
    5.9
    from room temperature to 300 ° C at a rate of h; the fibers are maintained at this temperature for 2.5 hours so as to obtain fibers having an absorption intensity ratio in the infrared spectrum of 0.26.
    The resulting thermally treated fibers are cut into 6 mm long pieces and mixed using a hot roller with a molding novolac resin (in the form of granules) having an average molecular weight of 540 and containing 3% hexamethylene tetramine in such a way that the mixture contains 55% thermally treated fibers. Using the resulting resinous composition, the same
    in the manner that Example 1 prepares a preform.
    Further, the billet is heated in a stream of nitrogen from room temperature to 200 ° C at a rate of 70 ° C / h, then 200-500 C at speeds indicated in Table 3, and 500-1200 s at a rate of 100 ° C / h ; roasting at 1200 ° C continues for 1 hour.
    Outputs, gas permeability, flexural strength, and carbon content in these carbon-carbon compositions are listed in the table. 3.
    Table 3
    20
    60 97
    100
    100 . 62
    -ten
    -eight
    -7
    13.4
    12.7
    5.8
    98.1
    98.3
    98.1
    The cross section of these three carbon-carbon compositions obtained has a uniform ability to reflect light. An examination of the cross sections using a conventional microscope shows that there are cracks in the product from experiment 3, which were formed between the carbon of the matrix 8 X 6 X 1 X 9 X 1 X
    in carbon reinforcing, as well as in the carbon matrix itself, but such cracks are completely absent in the other two products from experiments,
    1 and 2. The optical properties of the products from experiments 1 to 2 are investigated with a fipH using a polarization microscope.
    The matrix carbon is found to be optically anisotropic, and the reinforcing carbon is optically isotropic.
    o X-ray diffraction analysis of two compositions from experiments 1 and
    2 showed that they consist essentially of amorphous carbon.
    Example 4 Thermally treated novolac fibers, prepared in accordance with Example 3, are immersed in a methanol solution of the same resole resin that was used in Example 1, are extracted.
    0 from solution and dried to remove methanol. In this way, a tow is obtained consisting of thermally treated novolac fibers whose surface is coated with a resol resin. From the tow cut off
    The 5 piece is 80 mm long and is placed in a form with a length of 80 mm, a thickness of 4 mm and a width of 10 mm, with the fibers in the form arranged in the longitudinal direction. As a result, the mold is formed under pressure at 150 ° C with a fiber content of 48.5%.
    The preform is further heated in the same atmosphere as used in Example 1, to each of the firing temperatures shown in Table 4, with the same rate of temperature rise as in Example 1; the workpiece is held at each
    0 firing temperature for 3 hours. Thus, five carbon-carbon compositions are obtained.
    Resistance to penetration, resistivity, thermal
    5 stability and elementary analysis of each of these compositions.
    The results are shown in table 4. Table 4 10 10 ° 10 10 10
    Using a conventional microscope (those sections of each of the carbon-carbon compositions (experiments 2-5) that are perpendicular and parallel to the direction of the fibers are examined. As a result, it was found that matrix carbon and carbon reinforcing cannot be distinguished from each other). carbon types, there is no interface.In addition, both sections are examined using a polarization microscope to determine the optical properties of each of these carbon-carbon compositions. This leads to the conclusion that carbon the matrix is optically anisotropic, while the reinforcement carbon is optically isotropic.
    Example 5. A mixture containing 113 g (1.20 mol) of phenol, 30 g (1.00 mol) of formaldehyde and 1 g of oxalic acid is heated from room temperature to a speed of 30 ° C / h. The resulting novolac resin is hereinafter referred to as a resin (N-1).
    N-1 resin is maintained for 1 hour, resulting in the formation of a novolac resin (N-2).
    Resin N-2 is heated to 180 ° C to form a Novolac resin (N-3).
    N-3 resin is maintained at 180 ° C for 1 hour, resulting in the formation of a Novolac resin (N-4).
    N-4 resin is maintained at 180 ° C and a pressure of 50 mmHg. for 3 hours in order to obtain a Novolac resin (N-5).
    N-5 resin was held at a pressure of 10 mm Hg. for 3 hours
    the purpose of obtaining Novolac resin (N-6).
    N-6 resin is maintained at a pressure of 5 mm Hg. for 3 hours to obtain a Novolac resin (N-7).
    N-7 resin is maintained at a pressure of 5 mm Hg. for 20 hours to obtain a Novolac resin (N-8).
    N-8 resin is maintained at 190 and a pressure of 10 mm Hg. in order to obtain Novolac resin (N-9).
    The average molecular weight of the resulting novolac resins is determined; the results are shown in Table 5.
    Each of the obtained Novolac resins is melted and, under optimal conditions for each resin, is extruded at a pressure of 50 cm HdO using a die with a nozzle with a diameter of 0.20 mm. This results in uncured novolac fibers. The maximum winding speed (m / min) and the number of fiber breaks within 10 minutes at the same winding speed are measured. The results are shown in table.5.
    Uncured novolac fibers are cured at a temperature of 97 ° C for 7 hours in an aqueous solution containing 17.5% hydrochloric acid and 14.0% formaldehyde, resulting in cured fibers. The strength of these fibers is measured and the results are shown in Table 5.
    It has been found that cured novolac fibers obtained from. Novolac resins 1-9, contain hydroxymethyl groups from 6 to 7 wt.%.
    Table 5.
    Honest, and cured novolac fibers obtained from resins 4-7, have sufficient strength.
    The obtained Novolac fibers are heated without tension in a stream of nitrogen gas from room temperature to 300 ° C at a speed of 15 and kept at this temperature for 1.0 hour. The nine thermally treated novolac fibers obtained have a ratio of absorption intensities in the infrared spectrum with a given wavelength D p, in the region of 0.300, 32.
    Heat-treated novolac fibers are cut into 10 mm long pieces and from them a preform is prepared containing 50% by weight of fibers, which is then burned, as was done in Example 1.
    The yield, flexural strength and gas permeability of the resulting carbon-carbon compositions are determined; the values obtained are collected in Table 6.
    Table b
    In the study of the fracture surface of the resulting carbon-carbon compositions with Proceed to table 5
    It is noted that the matrix carbon and the reinforcing carbon do not differ between each other. When studying the optical properties of the compositions obtained, it was found that the matrix carbon is optically anisotropic, and the reinforcing carbon is optical isotropic.
    The carbon content of these carbon-carbon compositions is 97-98%.
    EXAMPLE 6 The thermally treated novolac fibers obtained in Example 5 from Novolac resin N-6 are cut into pieces of a length of 70 mm and yarns with a twist of 13.9 tons / inch are prepared from them. From the yarns obtained, weavers tweed having a basis weight of 300 g / m. The fabric has a tensile strength of 33 kg / 25 mm in the direction of the base fabric and 26 kg / 25 mm in the direction of weft.
    The woven material is immersed in a methanol solution of resole resin having a gelation time at 110 s, and then dried for the purpose of obtaining a preform with a fiber content of 50%. Fifteen blanks are molded with a forming press and then solidified.
    The material obtained is baked in the same way as in example 1, in order to obtain a carbon-carbon composition having a thickness of 2.8 mm, a bending strength of 13.0 kg / mm, a gas permeability of 10 cm / s, a Vickers hardness of 1,100 kg / cm and the carbon content is 98.0%.
    As a result of studying its optical properties, it was found that the matrix carbon is optically anisotropic, and the reinforcing carbon is optically isotropic.
    The resulting carbon-carbon composition is used as an anode and subjected to electrolytic trapping in a 50% aqueous solution of sulfuric acid at a current density of 500 mA / cm for 0.7 h. A platinum plate is used as the cathode, which is larger than the ano dimensions. Yes.
    The surface of the composition is examined using a scanning electron microscope before etching and after etching. After etching, the matrix portion of the composition can be distinguished from the fibrous reinforced portion, since the etching degree of the matrix portion is greater than the etching degree of the fibrous reinforcing portion.
    The weight of the composition before etching and after etching is determined. The resistance to electrolytic etching for a given composition, calculated by the formula (weight after etching / weight before etching) x 100, is 87%.
    For the purpose of comparison, a preliminary preparation is prepared: the mixture obtained by adding 1% by weight of aniline sulfate to furfuryl alcohol is coated using a multi-layer coating method (whereby the coating-cure cycle is repeated several times to obtain a thin coating). The resulting material is calcined in accordance with the described method in order to obtain a vitreous carbon product having essentially the same shape as the carbon-carbon composition described.
    The resulting vitreous carbon product has a gas permeability of 10, but the flexural strength is only 7 kg / mm.
    If the resulting glassy carbon product is electrolytically etched under the conditions described, there is no difference in the degree of etching of certain areas: the product is etched uniformly.
    The electrolytic resistance of the vitreous carbon product, calculated by the same method as that for the carbon-carbon composition, is 69%.
    P r and m p 7 (comparative). This example shows that cured novolac fibers, which are heat treated in an atmosphere containing an oxidizing agent, are not suitable for use as a fibrous reinforcing carbon.
    The cured novolac fibers obtained in the same manner as in Example 1 are heated in an atmosphere containing oxidizing agents: 3% by volume of nitrogen dioxide (NO). The temperature rises from room temperature to 1.5 ° C / min. It was found that the treated fibers have low strength, only 0.93 g / deg. °
    The treated fibers are cut into pieces of a length of 70 mm and are spun from them. However, the process itself
    It is very labor intensive since these fibers are very fragile,
    The fibers are cut into 3 mm long pieces and a sheet is made from them using a conventional (wet) sheet preparation method using a resol resin as a binding agent; the resulting paper-like sheet has a basis weight of 100 g / m (resonant resin content is 10%) . The paper-like sheet is then impregnated with the molten resole resin, which has a gel time at a temperature of 140 s, so that the fiber content in the obtained material is BW%; the material is pressed to compress it. Further, the pressed material is flattened out at a pressure of 30 kg / cm for 30 minutes, and then
    0 solidifies; a preform is obtained, having a thickness of 3 mm.
    The preform is fired in the same way that
    5 in Example 1-, resulting in a carbon-carbon composition. The product yield is 87%.
    The fracture surface of the resulting carbon-carbon composition does not have a uniform
    reflection of light; in addition, the matrix and fibrous reinforced carbon can be very easily distinguished from each other even with the naked eye. The composition has a fracture strength of 8.3 kg / mm & and gas permeability.
    Example 8 (comparative). This comparative example shows that heat treated
    0 rezol fibers are not suitable for use as a fibrous reinforcing material.
    Getting resole fibers. 94 g (1 mol) of phenol, 39 g
    E (1.3 mol) of formaldehyde and 0.85 g (0.05 mol) of ammonia are mixed, c and heated to. By varying the heating time, we obtain several resole resins. Each of these
    The Q resole resins undergo a melt-stretch operation. As a result, it was found that these resins are very poorly treated. this stage and the output (weight of the obtained fiber), the weight of the resin used (xUO) in most cases "was O.
    Two resole resins, which had relatively good stretching properties, were further subjected to the study of their optimum conditions for stretching. Each of the two resins for this was forced through a die with a nozzle with a diameter of 0.2 mm and the pressure during extrusion was
    In this case, in Table 7, the drawing temperatures and maximum drawing rates were established, at which it was possible to obtain resole fibers, at least in small quantities.
    When both types of resole resins are heated to 150 ° C, which is then maintained for 30 minutes, they melt. Therefore, when the fibers are first processed in a 20% aqueous solution of hydrochloric acid at 90 ° C, short cured reaeol fibers are formed. The various properties of rezol fibers from which P9 radiation of these cured resole fibers can be found, the behavior of resole resins during drawing, the conditions of drawing, and the properties of cured rezol fibers are given in Table 7.
    T a b l and c a 7
    Behavior during stretching
    At 90 ° C, the solution for pulling the yarns has a low viscosity
    At 95 ° C, stretching is possible for 8 s.
    At 115 ° C, the solution is covered with foam and turns into a gel.
    At 95 ° C, a gel is formed after 10 minutes
    Max. Exhaust speed, m / min
    The property- diameter of the fiber wa.
    Getting a carbon-carbon composition,
    The cured rezol fibers obtained from resin P-1 and having higher strength than the fibers obtained from resin P-2 are heat-treated in the same way as in example 2 and cut into 6 mm long pieces, mixed by means of a mixing machine rezol resin having sreda150
    200
    The scientific research institute has a molecular weight of 220 and a gel time at a temperature of 140 ° C with a temperature such that the fiber content is%. Further, the mixture is shaped and cured in the same manner as in Example 1, in order to obtain a precursor material having a width of 25 mm, a thickness of 3 mm and a length of 70 gm.
    The pre-material is calcined in the same manner as
    In example 1, in order to obtain a carbon-carbon composition.
    The output of the carbon-carbon composition is below 10%. When examining the surface of a fracture of a carbon-carbon composition using a conventional microscope, it was found that it contains pores of matrix carbon and carbon reinforcing material are not a single whole and can be easily distinguished.
    The carbon-carbon composition has a gas permeability, bending strength of 5.5 kg / cm. Consequently, the resulting carbon-carbon coltoxica is significantly different in its properties from the proposed composition, which has high bending strength and low permeability.
    权利要求:
    Claims (2)
    [1]
    1. US patent 3814642, cl. 156-60, 1974.
    [2]
    2. Patent. Great Britain 134669, cl. C 1 A, 1974 (drototype).
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    同族专利:
    公开号 | 公开日
    JPS5441913A|1979-04-03|
    GB2003845A|1979-03-21|
    FR2402631A1|1979-04-06|
    GB2003845B|1982-07-21|
    FR2402631B1|1980-11-21|
    DE2839167C2|1986-02-13|
    DE2839167A1|1979-03-15|
    US4198382A|1980-04-15|
    JPS5727057B2|1982-06-08|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP10907877A|JPS5727057B2|1977-09-09|1977-09-09|
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