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    • 专利摘要:
    "internal combustion engine and method of manufacturing the same" means an internal combustion engine having an anodic oxidation coating formed on at least a portion of a wall surface facing a combustion chamber, where the anodic oxidation coating has voids and nanofores smaller than voids, at least part of the voids being sealed with a sealant derived by converting a sealing agent and at least a portion of the nanofores not being sealed.
    公开号:BR112014005733A2
    申请号:R112014005733
    申请日:2012-09-11
    公开日:2019-10-08
    发明作者:Kawaguchi Akio；Shimizu Fumio；Kosaka Hidemasa；Nishikawa Naoki；Yatsuduka Ryouta；Hijii Takumi；Wakisaka Yoshifumi
    申请人:Toyota Motor Co Ltd；
    IPC主号:
    专利说明:

    INTERNAL COMBUSTION ENGINE AND METHOD FOR MANUFACTURING THE SAME
    Fundamentals of the Invention
    Field of the Invention [001] The present invention relates to an internal combustion engine and a method of manufacturing it. The present invention relates in particular to an internal combustion engine of which the wall surface which faces a combustion chamber of an internal combustion engine is partially or fully provided with an anodic oxidation coating and a method of fabricating an internal combustion engine characterized by a method for the formation of anodic oxidation coating.
    Description of the Related Art [002] An internal combustion engine such as a gasoline engine or a diesel engine is basically configured from an engine block, cylinder head, and pistons. The combustion chamber is defined by an orifice surface of a cylinder block, a piston top incorporated into the orifice, a lower surface of a cylinder head and inlet and exhaust valve tops arranged within the cylinder head. Since a recent internal combustion engine needs to have low fuel consumption, it is important to reduce the loss of cooling. As one of the countermeasures for reducing cooling loss, a method of forming a ceramic thermal insulation coating on an internal wall of a combustion chamber can be cited.
    [003] However, the ceramics mentioned above generally have a low thermal conductivity and high heating capacity. When an internal wall of a combustion chamber is made of ceramic, due to a steady increase in surface temperature, an efficiency of entry is deteriorated and knocking (irregular combustion due to the confinement of heat within
    2/24 of a combustion chamber) is caused; accordingly, ceramics do not currently prevail as a material for lining an internal wall of a combustion chamber.
    [004] Thereafter, a thermal insulation coating formed on a combustion chamber wall surface is desirably formed from a material that not only produces heat resistance and thermal insulation property, but also low thermal conductivity and low heating capacity. That is, in order not to raise a wall temperature steadily, it is desirable that, in an entry step, the thermal insulation coating is low in heating capacity to reduce the wall temperature following an inlet air temperature . Additionally, in addition to the low thermal conductivity and low heating capacity, a coating is desirably formed from a material that can withstand the repeated stress of maximum combustion pressure and fuel injection pressure and thermal expansion and thermal shrinkage during combustion in a combustion chamber, and which is high in terms of adhesion with a base material such as a cylinder block.
    [005] A cylinder head in which on both the bottom surface of a cylinder head and the inner surface of a water jacket defined on the cylinder head, a coating of microporous silicone dioxide or aluminum oxide is formed by oxidation anodic is described in the publication of Japanese patent application No. 2003-113737 (JP 2003-113737 A). According to the cylinder head since a microporous coating is disposed on both the bottom surface of the head and an inner surface of the jacket, a surface area of the bottom surface of the head and the inner surface of the jacket is expanded by the coating, accordingly, the heat generated in the combustion chamber can be efficiently absorbed into it through the coating. On the surface
    3/24 inside the jacket, the heat absorbed inside can be efficiently released through the jacket into the cooling water. Accordingly, a cylinder head from which the temperature rise is suppressed and the material is either readily heated by heat absorption or readily cooled by the release of heat can be obtained.
    [006] Thus, when an anodic oxidation coating is formed on a wall surface that faces an internal combustion engine combustion chamber, an internal combustion engine that has low thermal conductivity and low heating capacity and is excellent in the thermal insulation property can be formed. In addition to these performances, the anodic oxidation coating is additionally required to have excellent temperature fluctuation characteristics. Here, temperature fluctuation characteristics are characteristics where while having a thermal insulation property, an anodic oxidation coating temperature follows a gas temperature inside a combustion chamber.
    [007] When the anodic oxidation coating is observed microscopically, there are many cracks on a surface thereof. Within the anodic oxidation coating, there are many defects that connect to the cracks. In general, many empty spaces that form these cracks and defects are present through a surface of the coating to the interior of the same. The present inventors have identified that these cracks and defects have a size in the range of about 1 to 10 pm.
    [008] Additionally, within the anodic oxidation coating, in addition to the micro-order voids, many fine nano-order holes (nanofurts) are also present.
    [009] An anodic oxidation coating generally includes voids such as micro-order surface cracks and internal defects and many
    4/24 nano-order nanofits. It has been identified according to the present inventors that while micro-order voids must be sealed (embedded, obstructed) from the point of view of the coating resistance, many nanofurts must remain in the anodic oxidation coating in a state having pores nanosize from the point of view of temperature fluctuation characteristics.
    [010] Here, as a conventional technology that seals micro-order surface cracks (voids), a corrosion resistance surface treatment article and a production method of the same described in the publication of Japanese patent application No. 2005-298945 (JP 2005-298945 A) can be cited.
    [011] JP 2005-298945 A describes a technology where a silicon component derived from perhydropolysilazane or polycondensate of it is filled in the surface cracks for sealing purposes.
    [012] As described in JP 2005-298945 A, when surface cracks of relatively large size are sealed by filling with perhydropolysilazane, the sealed voids and coating strength can be improved. However, just by filling with perhydropolysilazane in an anodic oxidation coating, the nanofuros present in the coating are also sealed. Accordingly, it is difficult to form an excellent anodic oxidation coating on the temperature fluctuation characteristics.
    [013] The present invention provides an internal combustion engine that is provided with an anodic oxidation coating that has low thermal conductivity and low heating capacity, is excellent in thermal insulation properties, and is excellent in temperature fluctuation characteristics in a part or all of a wall surface that faces a combustion chamber, and a method of manufacturing the internal combustion engine
    5/24 tender.
    Summary of the Invention [014] An internal combustion engine according to a first embodiment of the present invention is an internal combustion engine having an anodic oxidation coating formed on at least one part of a wall surface that faces a gas chamber. combustion, where the anodic oxidation coating has smaller empty spaces and nanofurts than empty spaces; at least part of the voids being sealed with a sealant derived by converting a sealing agent; and at least a part of the nanofunctions not being sealed.
    [015] An internal combustion engine in the first modality has an anodic oxidation coating (or thermal insulation coating) in at least part of a combustion chamber. On the other hand, in an internal combustion engine in a first modality, different from a conventional anodic oxidation coating, at least part of the cracks present on a surface and defects present within it (both are microorder empty spaces) are sealed with a sealant derived by converting a sealing agent and, thus, a high strength coating is formed. Additionally, in an internal combustion engine in a first mode, at least part of many nanofurts (nano-size holes) present in the anodic oxidation coating is not sealed; accordingly, a coating having a structure where many micropores are contained is formed.
    [016] At least a portion of the voids are sealed with a sealant derived by converting a sealing agent means, in addition to a mode where all micro-order voids present in an anodic oxidation coating are sealed with a seal , a mode where only the nanofuros present more deeply than a defined depth from a
    6/24 surface layer of the anodic oxidation coating is not sealed. In addition, at least a part of the nano-holes is not sealed means, in addition to a mode in which all the nano-size holes present in the anodic oxidation coating are not sealed, a mode in which only the nano-holes present to a defined depth from a superficial layer of the anodic oxidation coating are not sealed. It can be said that a coating mode in which all micro-order voids are sealed with a seal and all nano-size holes are not sealed is desirable from the point of view of both the hardness of the anodic oxidation coating and the temperature fluctuation characteristics. However, empty spaces and nanofurls are micro-order or nano-order holes; according, in fact, a coating mode where only the empty spaces in a surface region are not sealed, or a coating mode where the empty spaces are not sealed with a sealant and nano-holes (part of all nano-holes) that are not are sealed are dispersed is obtained.
    [017] To seal the surface cracks and internal defects means to coat the sealing agent in micro-order size empty spaces to bury and obstruct with a sealant derived by converting the sealing agent. The sealing agent is a liquid coating containing an inorganic material, and the sealant is a substance derived by converting the coating material containing an inorganic material. According to the present inventors, it has been identified that a micro-order-sized void dimension that the anodic oxidation coating formed on a wall surface that faces an internal combustion engine combustion chamber has, is usually in the range of about 1 to 10 pm.
    [018] Nanofurts are not sealed means that in a way in which nanofurts have nanosize pores, their interior is not blocked
    7/24 with a sealant derived by converting a sealing agent. According to the present inventors, it has been identified that a pore size of nanofurts, which the anodic oxidation coating formed on a wall surface that faces a combustion chamber of an internal combustion engine has, is generally in the range of about 20 to 200 nm. The identification of the range from 1 to 10 pm and the range from 20 to 200 nm can be conducted in such a way that from the SEM image photography data and TEM image photography data of a cross section of the anodic oxidation coating, empty spaces and nano-holes in a defined area respectively are extracted and the maximum dimensions are measured, and the respective mean values are obtained to identify the size.
    [019] An internal combustion engine in a first mode can be any one for use in a gasoline engine and a diesel engine. The configuration is basically configured for an engine block, a cylinder head, and a piston. The combustion chamber is defined by an orifice surface of a cylinder block, a piston top embedded in the orifice, a lower surface of a cylinder head and inlet and exhaust valve tops arranged within the cylinder head.
    [020] The anodic oxidation coating can be formed on an entire wall surface facing the combustion chamber or on only part of it. In the case of the latter, a modality in which the anodic oxidation coating is formed only on a piston top or a valve top can be mentioned.
    [021] Additionally, examples of the base materials that make up a combustion chamber for an internal combustion engine include aluminum and alloys thereof, titanium and alloys thereof, and iron-based materials with additional anodically oxidized aluminum. An anodic oxidation coating formed on a wall surface that is configured from a base material
    8/24 aluminum or an alloy of the same becomes alumite. Not only in the case of a general aluminum alloy, but also in the case of a high strength aluminum alloy having a higher composition ratio of a copper component, a nickel component and a titanium component than above, a dimension the empty spaces that make up the surface cracks or internal defects tend to be larger. Accordingly, an improvement in coating strength when a sealing agent is coated in these voids and converted into a sealant becomes more noticeable.
    [022] According to a first internal combustion engine, between an anodic oxidation coating formed on at least part of a wall surface that faces a combustion chamber, at least a part of relatively large empty spaces in size micro-order seals are sealed with a sealant derived by converting a sealing agent, and at least a portion of the nano-order size nanofits is not sealed. Thus, an internal combustion engine that has an anodic oxidation coating that is excellent in thermal insulation property, high in mechanical resistance, and also excellent in temperature oscillation characteristics where an anodic oxidation coating surface temperature follows a gas temperature in a combustion chamber is obtained.
    [023] The sealant can be a substance basically made of silica.
    [024] As the sealing agent that forms the sealant, any type of polysiloxane, polysilazane and sodium silicate can be applied. A polysiloxane or polysilazane coating material that contains a normal temperature-curable inorganic substance that has a viscosity capable of smoothly permeating empty spaces in the anodic oxidation coating, which can be cured without applying high temperature treatment (sintering) and has a very high hardness of a seal obtained by curing can be applied.
    9/24 [025] A second embodiment of the present invention is a method for manufacturing an internal combustion engine where an anodic oxidation coating is formed on at least part of a wall surface that faces a combustion chamber includes : the sealing of a nanoform periphery, the anodic oxidation coating having smaller void spaces and nanofurts than the empty spaces within it; and the coating of a sealing agent in the voids to seal at least a part of the voids with a sealant derived by converting the sealing agent to form the anodic oxidation coating where at least a part of the nano-holes is not sealed.
    [026] In an anodic oxidation coating that faces an internal combustion engine combustion chamber, as a method of forming anodic oxidation coating in such a way that at least a portion of the micro-sized voids order is sealed and at least a part of the nano-order size nanofurts is not sealed, a periphery of nanofurts is sealed to form nanofurts that form an enclosed space.
    [027] The sealing treatment is a process where a nanoform surface wall is formed (by expanding a nanoform surface wall) to trap the nanosize pores within it. Examples of sealing treatments include modalities of the following plurality of treatment methods.
    [028] That is, a method in which an anodic oxidation coating is located in pressurized water vapor, a method where an anodic oxidation coating is immersed in boiling water, and a method in which an anodic oxidation coating is immersed in a solvent containing an inorganic substance or an organic substance can be cited.
    [029] In either method, a periphery of an initial nanoform ex
    10/24 pande and a coating formed by the expansion is formed inside the nanofuro, pores of nano size configuring a nanofuro are defined by an expanded coating to trap the pores. In a nano-hole state before the sealing step of a nanosize hole is not completely defined from a region outside of it and a nanosize pore shape is not retained. Accordingly, in a state as it is, a sealing agent coated in the second step described below invades the interior of the nanoform to seal with a sealant derived by converting it.
    [030] On the other hand, it has been found that according to the sealing step like this, empty spaces such as micro-order size surface cracks and internal defects cannot be sealed. As described above, sealing treatment is a process where a pore surface wall is completely defined from a region outside it (by expanding a pore surface wall to shrink an internal pore diameter). However, in a micro-order-sized empty space, a pore size is too large to form an expansion coating in order to completely define the entire surface of an empty space from outside it.
    [031] In the first step, as described above, many nanofurts of a size in the range of about 20 to 200 nm are formed (defined) in an anodic oxidation coating.
    [032] In the second step, a sealing agent is coated in micro-order-sized voids and a sealant derived by converting the sealing agent seals at least part of the voids. In this way, an anodic oxidation coating where at least part of the nanofurts is not sealed can be formed.
    [033] Here, examples of sealing agents include, as described above, polysiloxane and polysilazane. This is because when these are used, a high temperature heat treatment (sintering) can be eliminated, the sealing agent can be relatively easily permeated inside the empty micro-size spaces, and, after curing, a hard body ( for example, silica glass) with high hardness is formed and the strength of an anodic oxidation coating can be improved.
    [034] Additionally, a method of coating a sealing agent is not particularly restricted. However, a method in which an anodic oxidation coating is immersed in a sealing agent, a method in which a sealing agent is sprayed on a surface of an anodic oxidation coating, a sheet coating method, a method of rotary coating, and a brush coating method can be applied.
    [035] Since a nanoform surface is sealed in the first stage, a coated sealing agent in the second stage is prevented from invading the nanofunctions. As a result, an internal combustion engine having an anodic oxidation coating excellent in temperature fluctuation characteristics in at least a part of the combustion chamber can be manufactured.
    [036] According to the present inventors, it is estimated that, with a turbocharged injection diesel engine for passenger vehicles, for example, in the number of revolutions of 2100 rpm, and in a better point of fuel consumption corresponding to the pressure effective mean of 1.6 MPa, the maximum improvement in fuel consumption of 5% can be obtained. A 5% improvement in fuel consumption is a value that is not covered by the measurement error when measuring, but a value that can clearly be seen as a significant difference. Additionally, simultaneously with the improvement in fuel consumption, it is also estimated that an exhaust gas temperature rises by about 15 ° C due to thermal insulation. An increase in the exhaust gas temperature is efficient to shorten the heating time of
    12/24 a NO X reduction catalyst immediately after starting on a real machine and a value where an NO X reduction rate is improved and the NO X reduction achieved can be achieved.
    [037] On the other hand, a cooling test (rapid cooling test) that is conducted when evaluating the temperature oscillation characteristics of an anodic oxidation coating is conducted as follows. That is, with a test piece on one side from which an anodic oxidation coating is formed, while continuing with heating on the other side (a side on which the anodic oxidation coating is not formed) with a temperature jet stream predetermined high temperature, a cooling air of a predetermined temperature is sprayed from a front side of a test piece (a side on which the anodic oxidation coating is formed) to reduce a front temperature of the test piece, a temperature of the same is measured, a cooling curve of a coating surface temperature and a time is prepared, in this way, a rate of temperature reduction is evaluated. The rate of temperature reduction is evaluated as a reduction time of 40 ° C by reading the time required to reduce a coating surface temperature by 40 ° C from a graph.
    [038] A plurality of test pieces are subjected to a rapid cooling test, the temperature reduction time of 40 ° C of each of the test pieces is measured, and an approximate curve of a plurality of representations defined by a rate of improvement of fuel consumption and temperature reduction time of 40 ° C is obtained.
    [039] Then, when a temperature reduction time value of 40 ° C corresponding to the 5% fuel consumption improvement rate is read, it is identified as being 45 m-sec. by the present inventors. The shorter the temperature reduction time of 40 C, the lower the thermal conductivity and
    13/24 the heat capacity of a coating, and greater effect to improve fuel consumption.
    [040] According to an internal combustion engine and a method for manufacturing it in the mode of the present invention, when nano-size holes present within an anodic oxidation coating that is formed on a wall surface that faces a combustion chamber are sealed, many of the nanofurts are rendered non-permeable by a sealing agent and at least a part of nanofurts are not sealed, so when a sealing agent is coated in relatively large empty spaces of at least part empty spaces is sealed with a sealant derived by converting the sealing agent. Thus, an internal combustion engine that has an anodic oxidation coating that is excellent in thermal insulation property, strong in mechanical resistance and excellent in temperature oscillation characteristics on at least part of or all of a wall surface that faces a combustion chamber can be manufactured.
    Brief Description of the Drawings [041] Characteristics, advantages and technical and industrial significance of the illustrative modalities of the invention will be described below with reference to the attached drawings, in which numerical references denote similar elements, and where:
    [042] Figure 1 is a vertical cross-sectional view that simulates a state before the application of a treatment of empty spaces and nanofurts in an anodic oxidation coating formed on a wall surface that faces a combustion chamber of an engine internal combustion relating to an embodiment of the present invention;
    [043] Figure 2 is an enlarged diagram of part II of figure 1;
    [044] Figures 3A and 3B are schematic diagrams explaining sequence
    14/24 a sealing step of a method for manufacturing an internal combustion engine referring to a modality of the present invention;
    [045] Figure 4 is a schematic diagram for describing a step of forming an anodic oxidation coating, and is a diagram for describing the anodic oxidation coating formed according to a method of manufacturing an internal combustion engine of the present embodiment of the present invention;
    [046] Figure 5 is a vertical cross-sectional view that simulates an internal combustion engine that is formed by applying a manufacturing method of the present modality to an anodic oxidation coating formed on a totality of a wall surface that is facing a combustion chamber;
    [047] Figure 6A is a schematic diagram to describe a contour of a test piece, and figure 6B is a diagram illustrating a cooling curve based on the cooling test result and a 40 ° C reduction time derived from there;
    [048] Figure 7 is a diagram illustrating a correlation graph of a rate of improvement of fuel consumption and the reduction time of 40 ° C in the cooling test;
    [049] Figure 8 is a diagram illustrating experimental results from which the temperature fluctuation characteristics and the mechanical resistance of an anodic oxidation coating are obtained; and [050] Figure 9A is a SEM image photograph illustrating a state in which micro-order-sized hollows configuring surface cracks and internal defects are sealed with a sealing agent, and Figure 9B is a photograph of SEM image illustrating nanofurts.
    Detailed Description of the Modalities
    15/24 [051] In what follows, with reference to the drawings, the modalities of an internal combustion engine of the present invention and a method of manufacturing it will be described. An illustrative example illustrates a way in which an anodic oxidation coating is formed on the entire wall surface that faces an internal combustion engine combustion chamber. However, a mode in which an anodic oxidation coating is formed only on part of a wall surface that faces a combustion chamber so that only a piston top or a valve top can be used.
    [052] Figures 1 to 4 illustrate in that order flowcharts of a method of manufacturing an internal combustion engine. More specifically, figure 1 is a vertical cross-sectional view that simulates a state before applying a treatment to empty spaces and nanofurts, figure 2 is an enlarged diagram of part II of figure 1, figures 3A and 3B are, in that order, schematic diagrams to explain a sealing step of a method for the manufacture of an internal combustion engine of the present embodiment, and figure 4 is a schematic diagram to describe a step of forming an anodic oxidation coating and a diagram for describe the anodic oxidation coating formed according to a method of manufacturing an internal combustion engine of the present embodiment.
    [053] First, an anodic oxidation step is applied to a wall surface that faces an internal combustion engine combustion chamber not shown to form an anodic oxidation coating. That is, an internal combustion engine is basically configured from a cylinder block, a cylinder head, and pistons. The combustion chamber is defined by an orifice surface of a cylinder block, a piston top incorporated into the orifice, an underside surface of a cylinder head and valid tops
    16/24 inlet and exhaust valve arranged inside the cylinder head. The anodic oxidation coating is formed on an entire wall surface that faces a combustion chamber.
    [054] Additionally, examples of base materials that configure a combustion chamber for an internal combustion engine include aluminum and alloys thereof, titanium and alloys thereof, and iron-based materials with additional anodically oxidized aluminum. An anodic oxidation coating formed on a wall surface that is configured from an aluminum-based material or an alloy thereof becomes alumite.
    [055] As illustrated in figure 1, when an anodic oxidation coating 1 formed on a surface of an aluminum-based material B that forms a wall surface of a combustion chamber is observed microscopically, on a surface of the same , many 1a cracks are present. Within the anodic oxidation coating 1, many defects that remain in cracks 1a are present. In general, many voids that form these cracks 1a and defects 1b are present through a coating surface to the interior of the same.
    [056] Cracks 1a and defects 1b have a microorder size in the range of about 1 to 10 pm. Not only in the case of aluminum alloys in general, but also in the case of high strength aluminum alloys where the composition ratios of the copper component, nickel component and titanium component are greater than above, a dimension of the voids that configure the surface cracks and internal defects tends to be greater.
    [057] Additionally, inside the anodic oxidation coating 1, as illustrated in figure 2, in addition to surface cracks 1a and internal defects 1b of the micro-order void spaces, also many holes of nanorodem size (nanofurls) 1c are gifts. A pore size of nanofurts is ge
    17/24 in the range of about 20 to 200 nm.
    [058] A method of manufacturing an internal combustion engine in the present embodiment includes the treatment step to improve the performance of an anodic oxidation coating formed on a wall surface that faces a combustion chamber of a combustion engine internal. In the present embodiment, the anodic oxidation coating is formed in such a way that at least part of the cracks 1a and defects 1b of the micro-order size empty space (that is, all of them or that is present in the range of one surface layer to a defined depth of a coating 1) is sealed and at least part of the nanoform size nano-order 1c (that is, a totality of them or what is present in the range of a surface layer to an even depth greater than the defined depth of a coating 1) are not sealed. As a first step in the fabrication method, a periphery of the nanofurts 1c is sealed to form a nanofunction that forms a closed space.
    [059] The sealing step is a step where a surface wall of the nano-hole is formed (the surface wall of the nano-hole is expanded to shrink an inner diameter of a nano-hole) to trap a nano-sized pore within it. In this way, a sealing agent that is coated in the second step is prevented from invading the interior of the nanofuro and sealing it.
    [060] Like the sealing step, a method in which an anodic oxidation coating is located in pressurized water vapor, a method where an anodic oxidation coating is immersed in boiling water, or a method in which an anodic oxidation coating is immersed in a solvent containing an inorganic substance or an organic substance can be cited.
    [061] According to a method in which an anodic oxidation coating is located in pressurized water vapor, an element of khan formation
    18/24 combustion chamber, which is supplied with a pressure-impermeable container and sealed by water vapor flowing from 3 to 5 atmospheric pressures in the container for 20 to 30 minutes.
    [062] According to a method in which an anodic oxidation coating is immersed in boiling water, after completely washing the combustion chamber forming parts supplied with an anodic oxidation coating, the parts are immersed in a bath of pure water water heated to 95 to 100 ° C (pH; 5.5 to 6.5) for 30 minutes to seal.
    [063] According to a method in which an anodic oxidation coating is immersed in a solvent containing an inorganic substance or an organic substance, parts of the combustion chamber's formation are immersed in a water bath of nickel acetate or acetate of cobalt and the water bath is maintained at 95 ° C or more for 10 to 20 minutes.
    [064] When an anodic oxidation coating is placed in water vapor or a high temperature water bath, as shown in figure 3A, a coating on the periphery of a nanocore 1c expands (bubble-shaped) in a direction from the inside of the nanofuro 1c (direction X1), and finally, as illustrated in figure 3B, by a coating 1c formed by expansion, a nano size (nanofuro 1c ') is defined in a state in which a liquid cannot invade from outside. According to the first stage, many nanofurts 1c 'having a size in the range of about 20 to 200 nm are formed (defined) in the anodic oxidation coating.
    [065] Then, as a second step, as illustrated in figure 4, a sealing agent 2 is coated on cracks 1a and defects 1b of micro-order-sized voids to seal at least a portion of the voids. In this way, an anodic oxidation coating 10, where at least part of the nanofurts 1c 'in a state in which a liquid cannot invade due to the re
    19/24 expanded clothing 1c unsealed, is formed.
    [066] Here, examples of sealing agent coating methods 2 include a method where an anodic oxidation coating is immersed in a container where a sealing agent 2 is accommodated, a method of spraying a sealing agent 2 into a surface of an anodic oxidation coating, a blade coating method, a rotary coating method and a brush coating method.
    [067] As the sealing agent 2, polysiloxane and polysilazane can be cited. This is because their use can eliminate a high temperature heat treatment (sintering), the sealing agent can be relatively easily permeated within the micro-size cracks 1a and defects 1b, and, after curing, a hard body such as high hardness silica glass is formed to improve the strength of an anodic oxidation coating 10.
    [068] Since a nanofunction surface is sealed in the first stage, a coated sealing agent in the second stage is prevented from invading the nanofunction. As a result, an internal combustion engine provided with an excellent anodic oxidation coating in terms of temperature oscillation characteristics in at least part of a combustion chamber thereof can be produced.
    [069] Figure 5 simulates an internal combustion engine that is provided with an anodic oxidation coating on the entire wall surface that faces the combustion chamber according to the manufacturing method.
    [070] An internal combustion engine N illustrated in figure 5 is, for example, a diesel engine. The internal combustion engine N includes approximately a cylinder block SB that has a cooling water jacket J inside it, a cylinder head SH arranged in the cylinder block SB, a KP inlet port and an HV exhaust port that are freely attached
    20/24 for openings where the KP inlet port and the HP exhaust port face an NS combustion chamber, and an OS piston freely formed from a lower opening in the cylinder block SB. The present invention can be applied to a gasoline engine.
    [071] The respective constituent parts configuring the internal combustion engine N are all formed of aluminum or an alloy thereof (including high strength aluminum alloy).
    [072] In an NS combustion layer defined by the respective constituent parts of an internal combustion engine N, on the wall surfaces where the respective constituent parts face an NS combustion layer (cylinder orifice surface SB ', bottom surface cylinder head SH ', piston top PS', valve tops KV and HV), an anodic oxidation coating 10 is formed.
    Cooling Test and Similar Results [073] The present inventors prepared a plurality of types of test pieces by forming an anodic oxidation coating under the condition illustrated in Table 2 for a base material having a component composition (alloy of aluminum (AC8A)) shown in table 1 below, conducted a cooling test to evaluate the temperature oscillation characteristics of the anodic oxidation coating, simultaneously conducted the resistance test and additionally conducted an experiment to obtain the relationship between the characteristics of temperature fluctuation and the anodic oxidation coating resistance.
    Table 1
    Component Ass Si Mg Zn Faith Mn Ni You Al aluminum alloy (AC8A) (% by mass) 0.99 12.3 0.98 0.11 0.29 <0.01 1.27 <0.01 balance
    21/24
    Table 2
    electrolyte solution liquid temperature (° C) current density (mA / cm 2 ) treatment time (minutes) average coating thickness (pm) 20% sulfuric acid 0 90 60 180
    [074] After the formation of an anodic oxidation coating, a sealing agent contains polysiloxane or polysilazane as a major component and isopropyl alcohol, alcohol, xylene, or dibutyl ether as a solvent.
    [075] An overview of the cooling test is as illustrated below. As illustrated in figure 6A, with a TP test piece only on one side from which an anodic oxidation coating is formed, the other side (one side that is not provided with the anodic oxidation coating) is heated (Heating in the drawing) by spraying at a high temperature of 750 ° C to stabilize the entire TP test piece at about 250 C, a nozzle from which a jet at room temperature flows in advance at a predetermined flow rate and is moved by a linear motor forward ( a surface provided with the anodic oxidation coating) of a TP test piece to initiate cooling (to provide the cooling air (Air in the drawing) of 25 ° C and the high temperature jet on the other side is continued at that point) . A surface temperature of the anodic oxidation coating of a TP test piece is measured with a radiation thermometer present outside it, a temperature reduction during cooling is measured, and a cooling curve illustrated in figure 6B is prepared. The cooling test is a test method that simulates a step of entering an internal wall of a combustion chamber and evaluates a cooling rate of a surface of a heated thermal insulation coating. In the case of a thermal insulation coating having low thermal conductivity and low heating capacity, the cooling rate tends to be faster.
    [076] From the prepared cooling curve, a time required for
    22/24 that a temperature drops by 40 ° C is read to evaluate the thermal characteristics of a coating such as the reduction time of 40 ° C.
    [077] On the other hand, according to the present inventors, as a value that can clearly verify the improvement of the fuel consumption rate without burying as a measurement error after the experiment, it can shorten the heating time of a reduction catalyst of NO X due to an increase in an exhaust gas temperature and can reduce NO X , 5% of the fuel consumption improvement rate is considered a target value achieved by the performance of an anodic oxidation coating configuring a chamber combustion of an internal combustion engine of the present modality. Here, in figure 7 a correlation graph of the rate of improvement of fuel consumption identified by the present inventors and the reduction time to 40 ° C in the cooling test is illustrated.
    [078] From figure 7, the reduction time to 40 ° C corresponding to 5% of the fuel consumption improvement rate in the cooling test is identified as 45 msec .; accordingly, 45 msec. or less can be considered an indicator showing excellent temperature fluctuation characteristics.
    [079] On the other hand, the mechanical strength is assessed by applying a micro Vickers hardness test. A part to be evaluated is configured for a central part of a cross section of an anodic oxidation coating and a weight is set to 0.025 kg.
    [080] The test results are illustrated in Table 3 below and in Figure 8.
    Table 3
    main component of the sealing agent sealing condition hardness HV0.025 reduction time to 40 ° C (msec) seal treatment coating thickness (um)
    23/24
    example 1 polysiloxane keep for 30 minutes or more in pure boiling water 5 400 42.5 example 2 polysilazane 5 500 42.5 comparative example 1 without sealing agent - 150 42 comparative example 2 polysiloxane none 5 500 46 comparative example 3 polysilazane 5 600 46 comparative example 4 without sealing agent - 150 42
    [081] In figure 8, a graph of the correlation of the hardness-reduction time to 40 ° C of an aluminum alloy, which was identified by the present inventors is illustrated. A region A in figure 8 where the rate of improvement of fuel consumption is 45 msec. or less and the Vickers hardness: HV0.025 is 300 or more can be considered an excellent region in terms of temperature oscillation characteristics as well as in hardness (this region is a region showing more excellent performance than aluminum alloy). Both examples 1 and 2 are found to be within region A.
    [082] Both examples 1 and 2 are provided with an anodic oxidation coating where the micro-order-sized hollow spaces, which form cracks and defects, are sealed with a sealing agent and many nanofurts are not sealed. Thus, it is verified that both examples 1 and 2 have the same hardness and temperature oscillation characteristics as those of the aluminum alloy material.
    [083] The present inventors took SEM images of a surface and the interior of an anodic oxidation coating of example 1, additionally obtained SEM images of the interior by increasing magnification and observed a state of sealing of surface cracks and internal defects with an agent of sealing and a state of nanofuros. The respective SEM image photographs are
    24/24 illustrated in figures 9A and 9B.
    [084] From figure 9A, it can be confirmed that a sealing agent fills the surface cracks and internal defects of an anodic oxidation coating and the void spaces of it are sealed with a sealant derived by converting the sealing agent.
    [085] On the other hand, from figure 9B, it can be confirmed that a nanoform within the anodic oxidation coating is provided with an expansion coating on the periphery of the same (white part of the nanofunction surface) and nanosize pores are gifts.
    权利要求:
    Claims (7)
    [1]
    1. Internal combustion engine having an anodic oxidation coating (10) formed on at least part of a wall surface that faces a combustion chamber, CHARACTERIZED by the fact that:
    the anodic oxidation coating has empty spaces (1a, 1b) and nanofurts (1c) smaller than the empty spaces;
    at least part of the voids being sealed with a sealant derived by converting a sealing agent (2); and at least a part of the nanofunctions not being sealed.
    [2]
    2. Internal combustion engine, according to claim 1, CHARACTERIZED by the fact that the seal is a substance basically made of silica.
    [3]
    3. Internal combustion engine, according to claim 1 or 2, CHARACTERIZED by the fact that the sealing agent is any one of polysiloxane or polysilazane.
    [4]
    4. Method of manufacturing an internal combustion engine in which an anodic oxidation coating (10) is formed on at least part of a wall surface that faces a combustion chamber, FEATURED for comprising:
    a sealing of a nanoform periphery (1c), the anodic oxidation coating having voids (1a, 1b) and nanofurts smaller than the voids within it; and a coating of a sealing agent (2) in the voids and sealing at least a part of the voids with a sealant derived by converting the sealing agent to form an anodic oxidation coating, in which at least a part of the nanofores unsealed.
    [5]
    5. Method, according to claim 4, CHARACTERIZED by the fact that the
    2/2 sealant is a substance basically made of silica.
    [6]
    6. Method, according to claim 4 or 5, CHARACTERIZED by the fact that the sealing agent is any one of polysiloxane or polysilazane.
    [7]
    7. Method according to any of claims 4 to 6, CHARACTERIZED in that the seal is any one of a method where the anodic oxidation coating is located in pressurized water vapor, a method where an anodic oxidation coating is immersed in boiling water and a method where an anodic oxidation coating is immersed in a solvent containing an inorganic substance or an organic substance.
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    同族专利:
    公开号 | 公开日
    CN103842560A|2014-06-04|
    DE112012003783B8|2015-11-19|
    WO2013038249A3|2013-08-01|
    JP2013060620A|2013-04-04|
    JP5642640B2|2014-12-17|
    DE112012003783T5|2014-06-18|
    US20140245994A1|2014-09-04|
    DE112012003783B4|2015-09-24|
    RU2014109053A|2015-10-20|
    ZA201402661B|2015-06-24|
    WO2013038249A2|2013-03-21|
    RU2583496C2|2016-05-10|
    US9359946B2|2016-06-07|
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    法律状态:
    2019-10-15| B15I| Others concerning applications: loss of priority|Free format text: PERDA DA PRIORIDADE JP 2011-198812, DE 12/09/2011, POR AUSENCIA DE CUMPRIMENTO DA EXIGENCIA PUBLICADA NA RPI NO 2534, DE 30/07/2019. |
    2019-10-22| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE AS 6A E 7A ANUIDADES. |
    2020-02-11| B08K| Patent lapsed as no evidence of payment of the annual fee has been furnished to inpi [chapter 8.11 patent gazette]|Free format text: EM VIRTUDE DO ARQUIVAMENTO PUBLICADO NA RPI 2546 DE 22-10-2019 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDO O ARQUIVAMENTO DO PEDIDO DE PATENTE, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |
    2021-10-05| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011198812A|JP5642640B2|2011-09-12|2011-09-12|Internal combustion engine and manufacturing method thereof|
    PCT/IB2012/001750|WO2013038249A2|2011-09-12|2012-09-11|Internal combustion engine and method for manufacturing the same|
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