JPH07505831A - Diamond-carbon material and its manufacturing method - 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] Diamond-carbon material and method for producing the same The present invention relates to the chemistry of carbon, and Carbon is a cubic modified carbon, roentgen-amorphous diamond-carbon materials, including carbon in the ous) phase and crystalline carbon phases; Regarding the manufacturing method.

Charcoal under conditions that allow condensed carbon explosion products to be preserved. When detonating an oxygen-deficient explosive substance that contains carbon atoms, a carbon structure with many defects is formed. Ultra-high reactivity and ultra-fine particle-like properties. A dispersed carbon-containing powder is produced. Practical application as a modifier in composite materials It is the range of these properties that defines the area of interest.

The properties of carbon-containing materials produced using explosive forces are known from numerous publications. .

1 publication, Yokan Nomura and Kazurou Kawamura, Carbon.

Volume 22, No. 2. Pages 189-191 (1984) describes the Some properties of the soot produced by the explosion of trinitrotoluene in a It is listed. (Elemental composition not reported). From the data of electronic microscopy, This sample consists of 5 to IO, which are randomly dispersed to prevent the formation of graphite phase. The radiographically amorphous phase of non-diamond carbon is composed of particles in a non-planar carbon layer. Mainly includes. When examined using photographic methods, it was found that it was just a very wide reflection (002) of carbon. existence was shown. Carbon particles are non-spherical and resemble soot particles formed during the explosion process. Distinguished from children.

Another theoretical research publication, Van Th1ef, M. & Rec. F, H, J.

Appl, Phys, 62. pp, 1761-1767 (1987) considers some properties of the carbon formed by the explosion of trinitrotoluene are doing. As a basis for calculations, this author states that the carbon formed under these conditions is It is characterized by an energy excess of 1 to 2 kca11 moles compared to graphite. I'm making assumptions. Proceeding from these data, the carbon particles produced in the explosion are 10 It was assumed that it should have a size on the order of nm.

As the closest prior art (prototype), N, Ray Greiner, D, S .

Ph1llips, J, D, Johnson & Fred Volk Nature vol, 333.2nd.

June 1988. pp. 440-442. This document is based on atmospheric temperature. , with a composition of 60/40% trinitrotoluene and RDX under an argon atmosphere. Discloses some properties of carbon obtained from the explosion products of explosive materials made from are doing. From these data, the condensation products of the explosion are diamond and non-diamond. Contains Yamond-transformed carbon.

The crystalline and X-ray amorphous carbon phase is a tightly packed spheroid with a diameter of approximately 7 nm. It is made of a curved strip with a thickness of about 4 nm. This non-diamond-shaped carbon is , the interplanar spacing of completely amorphous graphite and randomly unoriented graphite is 0. Characterized by an X-ray pattern with a typical reflection (002) of 35 nm.

A tightly packed spheroid of diamond-carbon phase with a diameter of approximately 7 nm. For electron diffraction In the method study, the following set of interplanar reflections were recorded. That is, d=0. 2058, (1,1266, 0,1075, 0,884, 0 and 0.636 nm , these are diamond reflective surfaces (111), (220), (311), (40 0) and (440).

Several of the prior art materials mentioned above have found industrial use.

The present invention provides a set of properties suitable for use as a component of composite materials with improved properties. A technical task that provides a diamond-carbon material with a diamond-like structure and a method for its production. based on the topic.

For this purpose, the die according to the invention contains carbon, hydrogen, nitrogen and oxygen in the following mass %: Yamond - achieved by carbon material.

Cubic modified carbon 30-75% X-ray amorphous carbon phase: 10-15% crystalline modified carbon, remainder The amount ratio (mass%) of the elements is Carbon 84.0-89.0 Hydrogen 0.3-1. 1 Nitrogen 3.1-4.3 Oxygen 2.0-7.1 Nonflammable impurities 2.0-5.0 And the surface is methyl, carbonyl, lactone, aldehyde, ether and quinone. It has a group.

The products of the invention are characterized in that they contain oxygen in a closed volume in a medium that is inert to carbon. Manufactured by detonation of missing explosives, detonation production It is synthesized at a cooling rate of 200 to 600 degrees/minute.

Commonly used for detonating compositions are: That is, Trinitrotoluene/RDX (Octogen, analogue of RDX) 50150-7 0/30° The material of the present invention has a unit surface (unit 5 surface) of 218 to 60 00m2/g, a black powder with a specific gravity of 2.2-2.8g/Cm' and a moisture content of 4.0%. Ru. The specific gravity of this sample is determined by the proportion of nonflammable impurities. Non-flammable products of the invention The proportion of pure substances is 2.0 to 5.0%. This non-flammable impurity is magnetite, iron Contains alpha transformation and ferric carbide. From data from gamma resonance spectroscopy , the following distribution in the spectrum is seen. That is, the alpha iron wire is 29 ~43%, magnetite lines make up 36-48%, and ferric (ferric carbide) The ion line (represented by diiron) constitutes 16-27%. According to elemental analysis , the product contains 84.0 to 89.0 carbon, 0.3 to 1.1 hydrogen on a mass % basis , 3, 1 to 4.3 nitrogen, 2. Contains 0-7.1% oxygen (depending on the difference). ( This elemental composition was determined using the quasi-combustion method of organic chemistry).

Nitrogen and carbon distribution data were obtained using X-ray photoelectron spectroscopy. In the original sample and the following relationship between oxygen and carbon, nitrogen and carbon atoms, namely 0/C = 0.03 It was found that a relationship of 0 to 0.040 and N/C = 0.01 to 0.03 exists. Ta. After etching the surface with argon ions, these relationships are as follows: That is, O/C=0.017-0.020, N/C=0.001-0.0005 It had changed like that. This is due to the presence of oxygen- and nitrogen-containing groups on the surface of the particles. It shows. The low molecular weight components of the substances of the present invention are dissolved in non-polar solvents (carbon tetrachloride, Separation was achieved by extraction with tel, n-hexane and benzene). of the total mass Both fractions vary within the range of 0.36-1.13% and are a mixture of organic compounds. T From the R spectroscopy data, OH, NHSCH2-1CH3-1CH- and -C The presence of functional groups such as -O-C- groups was revealed. These compounds are detoxifying It is the product of the condensation of stable fragments of molecules by nation waves.

Information on superficial deafness was obtained using the following method.

Based on data from gas chromatography analysis, when heated at 673 in vacuum for 2 hours , the following gases are separated. That is, methane 0.03-0. 47cm’/g , hydrogen 0.　03～0. 30 cm3/g, carbon dioxide 0.　02〜0. 8 4cm3/g, oxygen 0.00-0.05cm'/g, nitrogen 0.　20~], 8 3 cm'/g is separated. The total gas separation is 0. 36-2. 98 am ”/g.

These data indicate that the surface of the claimed product is methyl (methane is separated). separation of carboxyl (Co) and carboxyl (Co) groups is detected. vinegar.

Based on gas data from samples at temperatures between 573 and 773, a large number of gases Therefore, the activation energy is calculated as - 103.6 KJ 1 mole for carbon oxide, 1 mole of diacid Carbon is 23.4KJ1 mole, nitrogen is 22.5KJ1 mole, methane is 47 ．． It was 6KJ1 mole.

The obtained activation energy value suggests that the generated gas may have been adsorbed on the surface. This indicates that it was formed by the detachment of a group that was chemically bonded to the surface.

According to a review of polarographic data, quinones, lactones, carbonyls, Aldehyde and ether groups were present in all samples. However, the product according to the invention There are many methyl groups in it (because of this, this substance is characterized by water-repellent properties. This means that Second, it contains non-polar components such as rubbers, polymers, oils, etc. Determine the scope of use of materials in composite materials. Both chemical treatments affect the surface properties of materials. and the potential for use in one or more composite materials.

The distribution of carbon forms in the materials of the invention can be determined using X-ray photoelectron spectroscopy (XPES). I know it by using it.

From the XPE5 data, (Juls is a wide asymmetric peak with a half-width of 4.1 eV) After the argon ion attack, this is sandwiched between 2.5 eV and the graph This is a typical form of coal or finely dispersed coal. The surface charge is equal to 0 and the electric charge This is a characteristic of air conductors.

The spectral volume is represented by the non-diamond carbon and diamond carbon phases, Diamond carbon appears to be distributed as particles.

Phase composition information of the materials of the invention was obtained using methods of X-ray analysis.

The X-ray pattern of the sample studied shows three lines associated with carbon in the diamond phase. , the reflection of carbon 002 related to the X-ray amorphous phase of carbon and d = 0.418 m The presence of this phase is defined by the synthesis conditions. (the maximum of the latter The presence of width occurs after partial oxidation of the substance by oxygen in the air or oxidizing components of the acid. particularly clearly indicated. ) The distribution of particles of the material was found by the method of small angle scattering. When following a curve, grains The size distribution of offspring is characterized by one maximum in the region of 40-50A. these From the data, the carbon layer is not divided by particle size.

From the study of the behavior of samples heated in an air atmosphere, it was found that the maximum value was between 683 and 773K. One broad exotherm is observed on the DTA curve, indicating a very high degree of homogeneity of the material. suggest Separates carbon into non-diamond and diamond forms without destroying the material It turns out that this is impossible.

Based on the studies carried out, the material according to the invention can be considered to have the following particle structure: Ru. A central diamond core is surrounded by an X-ray amorphous phase of carbon.

The X-ray amorphous carbon phase in contact with the nucleus passes through the X-ray amorphous carbon phase and the carbon Contains the radiographically amorphous phase of diamond up to the crystalline phase. The surface group is crystalline carbon Found on the surface of the phase.

The diamond-carbon material of the present invention is exposed to acid in a closed space in a medium inert to carbon. 20 depleted explosives in a conventional blasting chamber Detonate the detonation product at a cooling rate of 0 to 6000 degrees/min. manufactured by

The explosion temperature of composition T/RDX 60/70 is 3500-4000K (also in the calculation method) ) and after the explosion the product is cooled to 350K.

If a cooling rate of the order of 7000 degrees/min is adopted, under these conditions the carbon phase It will be produced containing 70-80% by weight of cubic phase (diamond). deer However, in order to implement such cooling conditions, the volume of the explosion chamber must be It must be approximately one million times larger than the charge volume of the projectile. In other words, composition T/RD In the detonation of a 1 kg charge of X 60/40 explosive, an explosive chime of approximately 500 m” economical due to chamber requirements, high product loss levels, and low yields. It is not a good idea both physically and technically.

Conversely, if the cooling rate is lower than 200 degrees/min, the interaction between carbon dioxide and water vapor Accordingly, the products of the claimed invention have time to react with them; For this reason, it completely changes to co.

Therefore, it is technically feasible and the need for a limited composition of carbon phase and surface groups. It is necessary to provide a cooling rate that makes it possible to obtain a suitable relationship. these are In both cases, the materials produced can be used as components of highly efficient composite materials. made possible.

− The gas cooling rate is determined by the explosion volume and explosion chamber volume using different gas release conditions. Adjusted by changing the product.

example As a first step, the need for gas explosion products to preserve the diamond-carbon material is Trinitrotoluene and RDX in a 60/40 ratio to form the required atmosphere. A charge containing 0.65 kg of explosive was detonated in a 3 m3 explosion chamber. Next A similar charge of explosives was detonated inside the chamber. The explosion products expand and heat After reaching equilibrium, for 40 seconds through a supersonic Laval nozzle with a cross section of 15 mm. It was allowed to flow out from the chamber. Heat exchange with chamber walls and work done by gas Therefore, the cooling rate of the mixture was 304 degrees/min.

The condensate formed was captured in a cyclone and analyzed without any additional cleaning.

Analysis of the powder gave the following data: The black powder has the following elemental composition, viz. 83.9% carbon, 1.1% hydrogen, 8. 1% oxygen, 3.3% nitrogen and It had this composition. The content of nonflammable impurity components was 3.5%.

From the X-ray measurement data, the product has three phases, namely 50% cubic modification (da diamond) carbon, 20% X-ray amorphous carbon, and 30% crystalline carbon. It was becoming.

The composition of oxygen-containing functional groups on the surface was measured by polarography.

Carboxyl, quinone, lactone, ether, and aldehyde groups are was identified. The methyl group was identified from the composition of the gas generated during heating (meth (due to the occurrence of problems).

Other examples of implementing processes within the scope of the claimed method are shown in Table 1. child The table contains the claims for graphical correlations with the properties of the manufactured product. Comparative examples carried out under different method conditions than those described are also included.

Table 1 Cooling rate (17 minutes) Analysis results 7.000 (comparative example with cooling rate exceeding the maximum value) Production amount (output): 8.　O% elemental composition: Nonflammable impurities 7. 0 Phase composition: Cubic crystal modified carbon 7゜ Crystalline carbon 10 Composition of surface groups: dimethyl, carboxyl 6, '000 (comparative example at maximum cooling rate) ) Generation amount = 7.8 Elemental composition: Nonflammable impurities 4. 0 Table 1 (continued) Cooling rate (17 minutes) Analysis results Phase composition: Cubic modified carbon 55 X-ray amorphous carbon 15 Crystalline carbon 30 Composition of surface groups: methyl, carboxyl, 3.000 Production amount = 7.2 Elemental composition/ Nonflammable impurities 3.5 Phase composition: Cubic crystal modified carbon 45 X-ray amorphous carbon 15 Crystalline carbon 40 Composition of surface groups: methyl, carboxyl, quinone, lactone, ether, aldehyde Table 1 (continued) 304 Production amount: 4.2 Elemental composition: Nonflammable impurities 3.5 Phase composition: Cubic modified carbon 35 X-ray amorphous carbon 15 Crystalline carbon 50 Composition of surface groups: methyl, carboxyl, 200 (comparative example at minimum cooling rate) Production amount: 3.3 Elemental composition: Nonflammable impurities 3.0 Table 1 (continued) Yo Mal! (1’f/e) etff, Ii! -Noshi111 Phase composition: Cubic modified carbon 30 X-ray amorphous carbon 15 Crystalline carbon 55 Composition of surface groups, methyl, carboxyl, 100 (Ji small value at a cooling rate of Comparative example) Generation l: 0.8 Elemental composition: Nonflammable impurities 1000 Phase composition: Cubic modified carbon 5 X-ray amorphous carbon 45 Crystalline carbon 50 Composition of surface groups: carboxyl and aldehyde Table 1 (continued) 60 (Comparative example with cooling rate below the minimum value) No condensed phase observed The diamond-carbon material of the present invention enhances the physical, mechanical and performance properties of rubber. It is proposed to be used as an additive in composite materials and as a component of composite materials. in this way , for example, when 1 to 3% of the substance according to the invention is added to highly compounded rubber, the abrasion resistance increases to 1. It increases by 2 to 1.4 times, and for low compound rubber it is 21. ．． Increase by 5 times. Residue The quality index remains constant. Performed in a pilot batch of commercial rubber articles Bench tests have shown that components made from highly compounded rubber, such as bushings and sirens, Items such as to-blocks have a rated life of 1.3. ,.

2.0 times more durable, and the tire is 1.0 times longer than its rated life. Shown to be 3 times more durable .

0.0% of the substance of the present invention. When added to lubricating oil in an amount of 1%, the following changes occur: It will be done.

Br0f-0,15 60KhVGS steel roller torpedo rubbing against bronze block From the revitalization wear test, it was found that the oil temperature decreased by 50 degrees and the friction coefficient was 0. 6 to 0°15 (other data shows a decrease of 1.5 to 1.8 times). This increases the wear time of the friction set by a factor of 2 to 10, and This allows the load on the friction unit to increase by a factor of 1.5 to 7. Substance of the invention to 100-type oil. When added in an amount of 1%, the friction coefficient is reduced to one-tenth. I will be lowering it.

Commercial trials have yielded the following results: i.e. car diesel Lubricating oil savings in the engine reached 25% (;; fuel consumption decreased by 8%. When used in a car's carburetor engine, fuel consumption is reduced by 2-3%, and the engine The running-in time (reduced by 1/2 to 3/3).

When the material of the present invention is combined with polytetrafluoroethylene (PTFE), Table 2 As can be seen, the performance characteristics of the material (substantially increased).

Table 2 Material Compressive modulus Friction coefficient Relative abrasion resistance PTFE 4.2±0.1 0 ．． 21 1 (4; RiteY lafluoroethylene) PTFE 12.2±0.5 0.32 25+20% Coke (20% in F4 ) PTFE 4.9±0.2 0.21 68-51V 坏>@95%-１１--- −−−−−−−−Sliding support of radio engineering industry articles and seal of compressor 1 Nong's commercial testing demonstrated the high performance properties of the composite material.

international search report Continuation of front page (72) Inventor Petrov, Evgeny Anatolyevich Russian Federation, 659 302.　Piisku, Uritsupribitkova, Day, 2/1. Kvar Chira 8 (72) Inventor Sakovich, Gennady Viktorovich Russian Federation, 6593 22.　Biysk, Ulitsaradescheva, Day, 2/2. Kvarchira 35 (72) Inventor Komarov, Vitaly Fedorovich Russian Federation, 65932 2. Biysk, Ulitsaradescheva, Day, 2/2. Kvar Chira 21 (72) Inventor Klimov, Anatoly Valentinovich Russian Federation, 65 9302. Biysk, Ulitsa Prvitkova, Day, 2/1. Kvarchira 6 (72) Inventor Kosilev, Nikolai Vladimirovich Russian Federation, 659 302. Biysk, Ulitsa Prvitkova, Day, 2. Kvarchira

Claims (2)

[Claims] 1. A diamond-carbon material containing carbon, hydrogen, nitrogen and oxygen, 30-75% by mass of cubic modified carbon X-ray amorphous phase of carbon: 10-15% by mass of carbon with quartz crystal change , and the amount ratio of the above elements is Carbon 84-89% by mass Hydrogen 0.3-1.1% by mass Nitrogen 3.1-4.3% by mass Oxygen 2.0-7.1% by mass Nonflammable impurities 2.0-5.0% by mass methyl, carboxyl, quinone, lactone, ether, aldehyde on the surface. A diamond-carbon material characterized by containing a carbon functional group. 2. Oxygen-deficient explosives in a closed space in a medium inert to carbon The diamond-carbon according to claim 1, comprising detonating the diamond-carbon. A method for producing a substance, the detonation product at a rate of 200 to 6000 degrees/min. A method characterized by performing synthesis at a cooling rate.