Patent Grant
11951547
This application is a U.S. National Stage of International Patent Application No. PCT/JP2018/039328, filed Oct. 23, 2018, which claims benefit of Japanese Patent Application No. 2017-209189, filed Oct. 30, 2017, and which applications are incorporated herein by reference. To the extent appropriate, a claim of priority is made to each of the above disclosed applications.
The present invention relates to a valve guide made of an iron-based sintered alloy and a method of producing the same.
In recent gasoline engines for automobiles, combustion efficiency has been improved by combining various technologies, such as downsizing, and direct injection and turbocharging, with intent to achieve low fuel consumption, low emission, and high output. The combustion efficiency has been improved by reducing various losses, and in particular, an exhaust loss having a high loss rate has attracted attention. As a technology for reducing the exhaust loss, high compression has been attempted. The high compression inevitably brings about an increase in temperature of an engine and entails a risk of the occurrence of abnormal combustion, such as knocking, and hence a measure to cool a combustion chamber is required. Particularly around an exhaust-side valve having a high ambient temperature, improvement in cooling is essential, and also a valve guide, which is responsible for a valve cooling function, is required to have a high valve cooling capacity.
As a valve guide material having a high valve cooling capacity, there is given, for example, a valve guide made of brass. However, the valve guide made of brass has problems in that its wear resistance is insufficient because the number of pores each having an oil retention property is small, and cost, such as processing cost, is also high as compared to the case of a valve guide made of an iron-based sintered alloy, which has hitherto been used. Therefore, there is proposed a technology for improving the valve cooling capacity and wear resistance of a valve guide made of a sintered alloy, which has lower cost than the valve guide made of brass (Patent Literatures 1 and 2).
For example, in Patent Literature 1, there is proposed a valve guide made of a sintered alloy which has a composition including, in terms of mass %, 10% to 90% of Cu, 0% to 10% of Cr, 0% to 6% of Mo, 0% to 8% of V, 0% to 8% of W, and 0.5% to 3% of C, with the balance being Fe and inevitable impurities and having a total content of Cr, Mo, V, and W of 2% or more and 16% or less, and which has a structure including an Fe-based alloy phase containing Fe as a main component, a Cu phase or a Cu-based alloy phase containing Cu as a main component, and a graphite phase. In addition, in Patent Literature 2, there is proposed a valve guide made of a sintered alloy formed of a sintered material in which iron-based alloy powder and copper-based alloy powder including 26 wt % to 30 wt % of Ni are mixed at a blending ratio in terms of weight of from 4:6 to 6:4.
The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a valve guide made of an iron-based sintered alloy excellent in wear resistance and thermal conductivity, and a method of producing the same.
The above-mentioned object is achieved by the following aspects of the present invention.
That is, according to one aspect of the present invention, there is provided a method of producing a valve guide made of an iron-based sintered alloy, the method including the steps of: molding raw material powder including diffusion-alloyed powder including core iron powder and Cu bonded to the core iron powder through diffusion to obtain a molded body; and sintering the molded body, to thereby produce a valve guide made of an iron-based sintered alloy.
According to one embodiment of the present invention, in the method of producing a valve guide made of an iron-based sintered alloy, it is preferred that: (1) the raw material powder have a content of a Cu component falling within a range of from 14 mass % to 40 mass %; and (2) a ratio of a Cu component derived from the diffusion-alloyed powder including core iron powder and Cu bonded to the core iron powder through diffusion with respect to the Cu component contained in the raw material powder be 45% or more.
According to another embodiment of the present invention, in the method of producing a valve guide made of an iron-based sintered alloy, it is preferred that the raw material powder include C powder and a solid lubricant.
According to another embodiment of the present invention, in the method of producing a valve guide made of an iron-based sintered alloy, it is preferred that a sintering temperature in the sintering step fall within a range of from 1,102° C. to 1,152° C.
According to another embodiment of the present invention, in the method of producing a valve guide made of an iron-based sintered alloy, it is preferred that a sintering time period in the sintering step fall within a range of from 10 minutes to 2 hours.
According to a first aspect of the present invention, there is provided a valve guide made of an iron-based sintered alloy, which is produced through the steps of: molding raw material powder including diffusion-alloyed powder including core iron powder and Cu bonded to the core iron powder through diffusion to obtain a molded body; and sintering the molded body.
According to one embodiment of the first aspect of the present invention, in the valve guide made of an iron-based sintered alloy, it is preferred that: (1) the raw material powder have a content of a Cu component falling within a range of from 14 mass % to 40 mass %; and (2) a ratio of a Cu component derived from the diffusion-alloyed powder including core iron powder and Cu bonded to the core iron powder through diffusion with respect to the Cu component contained in the raw material powder be 45% or more.
According to a second aspect of the present invention, there is provided a valve guide made of an iron-based sintered alloy, including 10 mass % to 40 mass % of Cu, having a structure including pores and a Cu phase, and having a pore area ratio of the pores of 3% or more and a Cu area ratio of the Cu phase of from 11% to 36%.
According to one embodiment of the first aspect and the second aspect of the present invention, it is preferred that the valve guide made of an iron-based sintered alloy include 12 mass % to 35 mass % of Cu.
According to another embodiment of the first aspect and the second aspect of the present invention, it is preferred that the valve guide made of an iron-based sintered alloy include 20 mass % to 30 mass % of Cu.
According to another embodiment of the first aspect and the second aspect of the present invention, it is preferred that the valve guide made of an iron-based sintered alloy have a Cu area ratio of from 13.1% to 33.8%.
According to another embodiment of the first aspect and the second aspect of the present invention, it is preferred that the valve guide made of an iron-based sintered alloy have a Cu area ratio of from 17% to 29%.
According to another embodiment of the first aspect and the second aspect of the present invention, it is preferred that the valve guide made of an iron-based sintered alloy have a pore area ratio of 3.6% or more.
According to another embodiment of the first aspect and the second aspect of the present invention, it is preferred that the valve guide made of an iron-based sintered alloy have a pore area ratio of 7.3% or more.
According to another embodiment of the first aspect and the second aspect of the present invention, it is preferred that the valve guide made of an iron-based sintered alloy have a pore area ratio of 15% or less.
According to the present invention, the valve guide made of an iron-based sintered alloy excellent in wear resistance and thermal conductivity, and the method of producing the same can be provided.
A method of producing a valve guide made of an iron-based sintered alloy (hereinafter sometimes abbreviated as “valve guide”) according to an embodiment of the present invention includes the steps of: molding raw material powder including diffusion-alloyed powder including core iron powder and Cu bonded to the core iron powder through diffusion (hereinafter sometimes referred to as “Cu partially diffusion-alloyed powder”) to obtain a molded body; and sintering the molded body. In this case, a Cu content in the Cu partially diffusion-alloyed powder is not particularly limited, but is preferably from 8 mass % to 45 mass %, preferably from 10 mass % to 30 mass %, particularly preferably 25 mass %±2 mass %. As the Cu partially diffusion-alloyed powder, for example, Cu partially diffusion-alloyed powder having a Cu content of 25 mass % or Cu partially diffusion-alloyed powder having a Cu content of about 10 mass % may be used.
In the raw material powder, C powder and a solid lubricant are preferably used in addition to the Cu partially diffusion-alloyed powder, and a lubricant used at the time of forming the molded body with a mold is more preferably incorporated. The solid lubricant is not particularly limited, and any known solid lubricant may be utilized. An example thereof may be MoS2. In addition, a mold release agent is not particularly limited, and any known mold release agent may be utilized. An example thereof may be zinc stearate. In addition, the Cu partially diffusion-alloyed powder is used as a main supply source for a Fe component and a Cu component in the raw material powder, but in order to adjust a Cu content in the valve guide to a desired value, Fe powder, Fe-based alloy powder, Cu powder, or Cu-based alloy powder may also be used in combination as required. In addition, other than the above-mentioned powders, powder containing, as a main component, another metal element, a non-metal element, or a compound (e.g., an oxide, a carbide, a carbonate, or an alloy) containing each of these elements may also be used in combination. Examples of the powder containing such element as a main component include powders containing Ca, Zn, Ni, Cr, V, W, and the like as main components.
The raw material powder obtained by mixing the component powders is filled into a mold, and compressed under pressure with a forming press or the like. Thus, the molded body is obtained. The density of the molded body may be set to, for example, from about 6.55 g/cm3 to about 7.15 g/cm3. Next, the molded body is subjected to degreasing treatment as required, and is then sintered within a temperature range above the melting point of Cu (1,085° C.), for example, within a range of from 1,102° C. to 1,152° C. An atmosphere at the time of sintering may be a vacuum atmosphere or an atmosphere of a non-oxidizing gas, such as a nitrogen gas. At this time, a sintering time period is preferably from 10 minutes to 2 hours, more preferably from 15 minutes to 1 hour, still more preferably from 20 minutes to 40 minutes. Moreover, the molded body after the sintering is subjected to cutting work or the like. Thus, a valve guide having a predetermined shape is obtained.
In the method of producing a valve guide according to this embodiment, it is preferred that: (1) the raw material powder have a content of a Cu component falling within a range of from 14 mass % to 40 mass %; and (2) a ratio of a Cu component derived from the Cu partially diffusion-alloyed powder with respect to the Cu component contained in the raw material powder be 45% or more. In this case, the valve guide can be significantly improved in wear resistance while ensuring comparable thermal conductivity as compared to a valve guide produced by using only Fe powder and Cu powder as supply sources for the Fe component and the Cu component in the raw material powder, respectively.
When (1) the raw material powder has a content of a Cu component of 14 mass % or more, and (2) the ratio of a Cu component derived from the Cu partially diffusion-alloyed powder with respect to the Cu component contained in the raw material powder is 45% or more, the degree of improvement in wear resistance is easily increased as compared to the case of the valve guide produced by using only Fe powder and Cu powder as supply sources for the Fe component and the Cu component in the raw material powder, respectively. In addition, while absolute wear resistance tends to be reduced more as (1) the raw material powder has a higher content of the Cu component, when the content of the Cu component is 40 mass % or less, wear resistance at a practical level is easily ensured.
In addition, when (2) the ratio of the Cu component derived from the Cu partially diffusion-alloyed powder with respect to the Cu component contained in the raw material powder is 45% or more, Cu can be dispersed more uniformly in a matrix as compared to the case of the valve guide produced by using only Fe powder and Cu powder as supply sources for the Fe component and the Cu component in the raw material powder, respectively, and as a result, the wear resistance is more easily improved.
Herein, (1) the content of the Cu component in the raw material powder is more preferably from 20 mass % to 40 mass %, still more preferably from 23 mass % to 37 mass %. In addition, (2) the ratio of the Cu component derived from the Cu partially diffusion-alloyed powder with respect to the Cu component contained in the raw material powder is preferably 50% or more, more preferably 56% or more, still more preferably 80% or more, particularly preferably 100%. Even when the blending ratio of the Cu partially diffusion-alloyed powder in the raw material powder is set to 55 mass % or more as an alternative condition to the condition (2) to be combined with the condition (1), the same effects as in the case of combining the conditions (1) and (2) can be exhibited. In this case, the blending ratio of the Cu partially diffusion-alloyed powder in the raw material powder is preferably 80 mass % or more, more preferably 90 mass % or more.
Next, a valve guide according to an embodiment of the present invention is described.
A valve guide according to a first embodiment of the present invention has a feature in that the valve guide is produced by utilizing the method of producing a valve guide according to the above-mentioned embodiment of the present invention. With this, a valve guide having comparable or higher performance in terms of wear resistance and thermal conductivity as compared to a valve guide produced by the related-art method of producing a valve guide can be provided. In particular, when (1) the raw material powder has a content of a Cu component falling within a range of from 14 mass % to 40 mass %, and (2) the ratio of the Cu component derived from the Cu partially diffusion-alloyed powder with respect to the Cu component contained in the raw material powder is 45% or more, the valve guide can be significantly improved in wear resistance while ensuring comparable thermal conductivity as compared to a valve guide produced by using only Fe powder and Cu powder as supply sources for the Fe component and the Cu component in the raw material powder, respectively.
In addition, it is preferred that the valve guide according to the first embodiment of the present invention include 10 mass % to 40 mass % of Cu, have a structure including pores and a Cu phase, and have a pore area ratio of the pores of 3% or more and a Cu area ratio of the Cu phase of from 11% to 36%.
When the Cu content is 10 mass % or more, and the Cu area ratio is 11% or more, additionally excellent thermal conductivity is easily obtained. In addition, when the Cu content is 40 mass % or less, and the Cu area ratio is 36% or less, the pore area ratio of 3% or more is easily obtained. In addition, when the pore area ratio is 3% or more, the valve guide can ensure a sufficient oil retention property, and hence easily achieves excellent wear resistance. In this case, the valve guide has excellent thermal conductivity, and hence is suppressed in increase in temperature, and thus has a high valve cooling capacity. As a result, heat dissipation from a valve is promoted, and an increase in temperature of the valve can be suppressed. This enables suppression of wear of the valve, and can contribute to reduction in engine abnormal combustion, such as knocking.
In the valve guide according to the first embodiment of the present invention, a thermal conductivity at 400° C. can be controlled to fall within a range of from about 28 W/m·K to about 60 W/m·K by mainly selecting the Cu content and the Cu area ratio. From the viewpoint of the valve cooling capacity, the thermal conductivity is preferably from 40 W/m·K to 60 W/m·K, more preferably from 50 W/m·K to 60 W/m·K, and from the viewpoint of satisfactorily balancing the valve cooling capacity and other characteristics, is still more preferably from 50 W/m·K to 55 W/m·K.
When the Cu content is 40 mass % or less, also production cost is easily reduced. The Cu content is preferably more than 10 mass % and 40 mass % or less, more preferably from 12 mass % to 35 mass %, still more preferably from 20 mass % to 30 mass %, particularly preferably from 23 mass % to 27 mass %.
In addition, the Cu area ratio is preferably from 13.1% to 33.8%, more preferably from 17% to 29%.
In addition, the pore area ratio is preferably 3.6% or more, more preferably 7.3% or more. The upper limit value of the pore area ratio is not particularly limited, but from the viewpoint of ensuring the strength of the valve guide, is preferably 15% or less, more preferably 12% or less, still more preferably 11.5% or less. With this, the valve guide can be prevented from escaping from a cylinder block after the valve guide is pressed into the cylinder block.
While the valve guide according to the first embodiment of the present invention has a composition including at least Cu, Fe, and inevitable impurities, a metal element other than Cu and Fe and a non-metal element may be further incorporated therein. Examples of such elements may include C, Mo, S, Ca, Zn, Ni, Cr, V, and W, and the kind and content of the element may be appropriately selected as required. However, it is known that Ni forms an all proportional solid solution with Cu, and hence the thermal conductivity is remarkably reduced owing to the formation of the solid solution of Ni with Cu (for example, paragraph 0015 of Patent Literature 1). That is, Ni inhibits an increase in thermal conductivity, and hence it is preferred that the valve guide of this embodiment be free of Ni.
In addition, Cr, Mo, V, and W cause an increase in cost. Therefore, it is preferred that the valve guide of this embodiment be basically free of Cr, Mo, V, and W, or have extremely small contents of these elements. However, of those elements, it is preferred to use Mo in a small amount in the valve guide of this embodiment from the viewpoint of improving the wear resistance and processability.
C is an element which strengthens an iron base material of a sintered body to increase strength and hardness, but when C is included in an excess amount, cementite is liable to be formed in the base material. Therefore, when C is used, a C content is preferably from 0.8 mass % to 1.2 mass %. In addition, as a mold release agent at the time of molding, for example, zinc stearate may be used. The other metal elements listed above may each be included in a matrix in the form of a sulfide (e.g., MoS2) or a carbonate, other than a metal.
A valve guide according to a second embodiment of the present invention has features of including 10 mass % to 40 mass % of Cu, having a structure including pores and a Cu phase, and having a pore area ratio of the pores of 3% or more and a Cu area ratio of the Cu phase of from 11% to 36%. Other configurations of the valve guide according to the second embodiment of the present invention may be the same as in the valve guide according to the first embodiment of the present invention. In addition, the valve guide according to the second embodiment of the present invention may be produced by the method of producing a valve guide according to the above-mentioned embodiment of the present invention, but may be produced by any other production method.
The valve guides according to the first and second embodiments of the present invention may each be utilized as a valve guide for an intake valve or a valve guide for an exhaust valve of an internal combustion engine, but are each preferably used as the valve guide for an exhaust valve.
Now, the present invention is described by way of Experimental Examples, but the present invention is not limited only to the following Experimental Examples.
1. Production of Valve Guide
For producing each of valve guides of Experimental Examples, powders listed below were appropriately combined and used as raw material powder. The particle diameter (a particle diameter in a region having a relatively high frequency in a particle size distribution) of each component powder used as the raw material powder is as described below.
<Fe and Cu Components>
Cu partially diffusion-alloyed powder (Cu content: 25 mass %): a range of from 106 μm to 150 μm
Cu partially diffusion-alloyed powder (Cu content: 10 mass %)
Fe powder: a range of from 106 μm to 150 μm
Cu powder: 45 μm or less
<Components other than Fe and Cu>
C powder: 50 μm or less
Other powders (e.g., a solid lubricant and a mold release agent)
The raw material powder was prepared by mixing the component powders so as to give a blend composition as shown in Table 1. Next, the raw material powder was compressed under pressure to obtain a molded body in the form of a circular pipe measuring 10.5 mm in outer diameter, 5.0 mm in inner diameter, and 45.5 mm in length. During the compression under pressure, a molding pressure was appropriately selected. Thus, the density of the molded body was adjusted as shown in Table 2. Next, the molded body was sintered in a nitrogen gas atmosphere at a temperature of 1,127° C. for 30 minutes to obtain a sintered body. Then, the sintered body was subjected to cutting work. Thus, a valve guide measuring 10.3 mm in outer diameter, 5.5 mm in inner diameter, and 43.5 mm in length was obtained. The Cu content and the C content in each of the valve guides of Experimental Examples are shown in Table 2. The “Cu content in valve guide” shown in Table 2 is a value corresponding to the “Content of Cu component in raw material powder” shown in Table 1.
2. Measurement of Density
The density of the molded body before sintering treatment was measured in accordance with JIS Z 2501. The results are shown in Table 2.
3. Measurement of Pore Area Ratio
A cross section obtained by cutting the valve guide in a direction perpendicular to an axial direction was photographed with a laser microscope (HYBIRD L3 manufactured by Lasertec Corporation) at a magnification of 20 times. Next, the obtained image data was subjected to binarization treatment to determine the ratio of the area of pores with respect to the total area of the observation field. Thus, a pore area ratio was determined. The results are shown in Table 2.
4. Measurement of Cu Area Ratio
Photographing was performed in the same manner as in the measurement of the pore area ratio, and the image data of a cross section of the valve guide was subjected to binarization treatment. At this time, brightness at the time of photographing was changed from that in the measurement of the pore area ratio so that a Cu phase and a portion other than the Cu phase were able to be distinguished from each other at the time of binarization treatment. Then, the ratio of the area of the Cu phase with respect to the total area of the observation field was determined based on the image data subjected to the binarization treatment. Thus, a Cu area ratio was determined. The results are shown in Table 2.
5. Measurement of Thermal Conductivity
The thermal conductivity of the valve guide was measured by a laser flash method. The thermal conductivity was measured for a disc-shaped test piece (diameter: 10 mm, thickness: 2 mm) produced on the same production conditions as the valve guide of each Experimental Example with a vertical thermodilatometer (model DL-7000) manufactured by Shinku-riko Inc. (current company name: Advance Riko, Inc.). The thermal conductivity was measured for a time period from the start of laser irradiation until heat was transferred to a back surface of the test piece, and was calculated based on the thickness of the test piece. The results are shown in Table 2.
6. Measurement of Wear Amount
A valve (stem outer diameter: 5.48 mm, material: corresponding to SUH 35) was inserted into a hole of the valve guide. Next, while a lower end surface of the valve was heated with a gas burner so that the temperature of an outer peripheral surface of the valve guide on a lower end side (combustion chamber side) was 300° C., a vicinity of a middle portion of the valve guide in an axial direction was water cooled, and further, a pressing load of 70 N was applied to a side surface of the valve on a lower end side in a direction perpendicular to an axial direction of the valve. In addition, a lubricating oil (engine oil: corresponding to 0W-20) was dropped at 0.4 cc/hr from an upper end side of the valve guide. Under the state, the valve was reciprocated at 3,000 times/min for 4 hours while a stem rotation number was set to 0. Air was adopted as a test atmosphere. After the completion of the test, the inner diameters of the valve guide on the upper end side, in the middle portion, and on the lower end side in a direction parallel to the direction in which the pressing load was applied were measured. Based on change amounts in inner diameters of the valve guide on the upper end side, in the middle portion, and on the lower end side before and after the test, wear amounts at the respective positions were measured. Then, the average value of the wear amounts at these three positions was determined. The results are shown in Table 2.
7. Measurement of Hardness
As the hardness of a valve seat, a test piece after sintering was measured with a Rockwell hardness machine (model HR-100) manufactured by Mitutoyo Corporation. The hardness was measured at four positions for each test piece, and the average value thereof was determined.
8. Changes in Various Physical Property Values and Characteristic Values with Respect to Cu Content
Graphs for showing changes in various physical property values and characteristic values with respect to a Cu content created based on Table 1 and Table 2 are shown in
From
In addition, with reference to
Meanwhile, with reference to
Of Experimental Examples shown in Table 1 and Table 2,
Herein, of Experimental Examples A1 to A4, Experimental Examples A2 to A4 correspond to the condition (1) of having a Cu content falling within a range of from 14 mass % to 40 mass %. Moreover, when Experimental Examples A2 to A4 are compared to Experimental Examples B2 to B4 corresponding thereto in terms of Cu content, Experimental Examples A2 to A4 each have a feature of being produced by using the Cu partially diffusion-alloyed powder as main raw material powder, and (2) each have a ratio of the Cu component derived from the Cu partially diffusion-alloyed powder with respect to the Cu component contained in the raw material powder of 45% or more. That is, the valve guides each produced under the conditions satisfying the above-mentioned conditions (1) and (2) can be significantly improved in wear resistance while ensuring comparable thermal conductivity as compared to the valve guides each produced by using only the Fe powder and the Cu powder as supply sources for the Fe component and the Cu component in the raw material powder, respectively.
From the graph shown in
9. Observation of Cu Partially Diffusion-Alloyed Powder with Electron Microscope
10. Sectional Observation of Molded Body Before Sintering
In addition, of the six images shown in
While Experimental Example A3 and Experimental Example B3 shown in
Moreover, it is presumed that the result shown in
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-209189 | Oct 2017 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2018/039328 | 10/23/2018 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2019/087863 | 5/9/2019 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4011077 | Kaufman | Mar 1977 | A |
| 5631431 | Andersson | May 1997 | A |
| 6632263 | Nigarura | Oct 2003 | B1 |
| 20040112173 | Maulik | Jun 2004 | A1 |
| 20040131492 | Kawakami et al. | Jul 2004 | A1 |
| 20050040358 | Chikahata et al. | Feb 2005 | A1 |
| 20060032328 | Chikahata et al. | Feb 2006 | A1 |
| 20060099079 | Kawase et al. | May 2006 | A1 |
| 20060198752 | Kawase | Sep 2006 | A1 |
| 20110146448 | Fujitsuka et al. | Jun 2011 | A1 |
| 20120177528 | Takayama | Jul 2012 | A1 |
| 20130084203 | Fukae et al. | Apr 2013 | A1 |
| 20150285300 | Ito | Oct 2015 | A1 |
| 20150322828 | Kohler et al. | Nov 2015 | A1 |
| 20160160700 | Takahashi | Jun 2016 | A1 |
| 20170259340 | Takashita et al. | Sep 2017 | A1 |
| 20170298790 | Kohler et al. | Oct 2017 | A1 |
| 20180056394 | Yashiro et al. | Mar 2018 | A1 |
| 20180193911 | Kobayashi et al. | Jul 2018 | A1 |
| 20190055986 | Komatsubara et al. | Feb 2019 | A1 |
| Number | Date | Country |
|---|---|---|
| 1488006 | Apr 2004 | CN |
| 101772389 | Jul 2010 | CN |
| 101775521 | Jul 2010 | CN |
| 101786166 | Jul 2010 | CN |
| 102921941 | Feb 2013 | CN |
| 103882325 | Jun 2014 | CN |
| 103898416 | Jul 2014 | CN |
| 104073722 | Oct 2014 | CN |
| 104428500 | Mar 2015 | CN |
| 104907554 | Sep 2015 | CN |
| 105263653 | Jan 2016 | CN |
| 105695872 | Jun 2016 | CN |
| 107000052 | Aug 2017 | CN |
| 1370704 | Dec 2003 | EP |
| 2023184 | Oct 1982 | GB |
| 2429464 | Feb 2007 | GB |
| 51-149107 | Dec 1976 | JP |
| 6-066117 | Mar 1994 | JP |
| H06-66117 | Mar 1994 | JP |
| 11-323512 | Nov 1999 | JP |
| 2002-069599 | Mar 2002 | JP |
| 5658804 | Jan 2015 | JP |
| 2015-25169 | Feb 2015 | JP |
| 2017-150596 | Aug 2017 | JP |
| 10-2004-0030358 | Apr 2004 | KR |
| 20050088353 | Sep 2005 | KR |
| 10-2006-0050208 | May 2006 | KR |
| 10-2011-0073291 | Jun 2011 | KR |
| 10-2013-0035912 | Apr 2013 | KR |
| 02059388 | Aug 2002 | WO |
| 2009113821 | Sep 2009 | WO |
| 2015012249 | Jan 2015 | WO |
| 2016148137 | Sep 2016 | WO |
| 2017043094 | Mar 2017 | WO |
| Entry |
|---|
| Ramakrishnan, P. “Automotive applications of powder metallurgy.” 2013. Indian institute of Technology. Woodhead publishing. p. 493-519. (Year: 2013). |
| “Graphite powder”. American Elements. 2016. wayback machine: http://web.archive.org/web/20160420195155/https://www.americanelements.com/graphite-powder-7782-42-5 (Year: 2016). |
| International Search Report and Written Opinion for PCT/JP2018/039328, dated Dec. 25, 2018. |
| Office Action for Japanese Patent Application No. 2018-555692, dated Jan. 8, 2019. |
| Decision to Grant a Patent for Japanese Patent Application No. 2018-555692, dated Mar. 19, 2019. |
| Office Action for Chinese Patent Application No. 201880047375.X, dated Sep. 3, 2020. |
| Communication pursuant to Article 94(3) for European Patent Application No. 18872685.5, dated Nov. 2, 2020. |
| Office Action for Korean Patent Application No. 10-2020-7000579, dated Apr. 28, 2020. |
| Office Action for Chinese Patent Application No. 201880047375.X, dated May 8, 2020. |
| Search Report for European Patent Application No. 18872685.5, dated Apr. 14, 2020. |
| Communication pursuant to Article 94(3) EPC for European Patent Application No. 18872685.5, dated Jun. 1, 2021. |
| Office Action for Indian Patent Application No. 201927054775, dated Mar. 31, 2021. |
| Office Action for Corresponding Brazilian Patent Application No. BR112020002233-0 dated Jul. 17, 2022. (4 pages). |
| Office Action for Brazilian Patent Application No. 11 2020 002233-0 (dated Nov. 25, 2022). |
| Number | Date | Country | |
|---|---|---|---|
| 20200165945 A1 | May 2020 | US |
