Patent Application
20120286195
The present invention is related to a heat conducting member and an adsorbent using burned plant materials; and more particularly, it is related to a heat conducting member such as plate type and paste type, and an adsorbent for toxic gas and toxic substance removal.
Patent Document 1 discloses the silicone rubber composition including silicone rubber, having thermally conductive and electrical insulation whose thermal conductivity of the forming body after vulcanization is 0.4 W/(m·K) or more and specific volume resistance value is 109 Ω·cm or more.
In addition, as disclosed by Non-Patent Document 1, the raw materials for activated carbon contained in gas adsorbent are divided roughly into carboniferous base (peat, lignite, brown coal, bituminous coal, etc.), woody base (coconut shell, wood, sawdust), and others (petroleum pitch, synthetic resin (polymer), various organic ashes, etc.). In the relation between the raw materials of activated carbon and the pore size distribution, the pore size distribution of coconut shell activated carbon is concentrated at a small pore size compared to carboniferous based activated carbon, and, it is a characteristic that there are few large pores concerning pore diameter. Therefore, coconut shell activated carbon is often used in gas phase adsorption for the molecules that size is small.
Even if it is same carboniferous base, when lignite and peat which are less-advanced coalification are used as raw materials, many mesoporous tend to be generated. Therefore, such activated carbon is used for adsorption in the liquid phase of the substance (coloration material and humic acid) of high molecular weight of large molecular size. The average pore size has been described as 3.54 nm with sawdust, 2.15 nm with coal, 1.97 nm with coal, 1.77 nm with coconut shell and 1.60 nm with synthetic polymer.
Patent Document 1: JPA2000-053864
Non-Patent Document 1: http://www.jpo.go.jp/shiryou/s_sonota/hyoujun_gijutsu/mizushori/1-9-1.pdf
However, the heat conductive member containing silicone rubber as shown in Patent Document 1 has a problem about a generating of siloxane gas causing the contact failure for switch and relay. Therefore, without using silicone rubber, the substitute which the thermal conductivity is equal to or better than conventional products has been requested.
In addition, the activated carbon as shown in Non-Patent Document 1 has 1.60 nm pore size on average, corresponding to a synthetic polymer even if the average pore size is small. Therefore, It is a difficulty in absorbing efficiently the substance which is several 10% smaller than the activated carbon. More specifically, for example, the molecular sizes of nitrogen, oxygen, and carbon dioxide are about 0.36 nm, about 0.34 nm, and about 0.33 nm respectively. So, the adsorption of these gases using the activated carbon which consists of existing raw materials is marginal.
On the other hand, in general, because most of things called activated carbon have a wide pore radius range of about 0.1 nm to about several 100 nm, it is unsuitable for adsorbing the substance of specific size efficiently. Therefore, the selection of raw materials and manufacturing conditions of activated carbon becomes a very important factor in the production of adsorbent.
The present invention is to provide the heat conducting material which does not need to use silicone rubber, and a heat conducting member using it, maintaining thermal conductivity equivalent to thermal conductivity of conventional products.
In addition, the present invention is to provide an adsorbent capable of adsorbing the substance of specific molecular size effectively by selecting the raw materials and manufacturing conditions of activated carbon suitably.
In order to solve the above problems, the heat conducting member of the present invention comprises a base material and a burned plant material containing in the base material, and is manufactured by controlling at least one the content ratio of the burned plant material to the base material, and the burning temperature of the burned plant material.
In addition, a heat conducting material of the present invention includes the above burned plant material.
As the burned plant material, a burned material such as soybean hulls, rapeseed meal, sesame meal, cotton seed meal, cotton hulls, soybean chaffs, or cacao husk can be used. As the base material, ethylene propylene diene monomer rubber, paint, or cement can be used.
According to the present invention, for example, in the case of each above plant, 0.4 [W/(m·K)] or more as the thermal conductivity can be obtained when the content ratio of each burned plant material to the base material is 200 phr, and the burning temperature is 900° C. or higher (phr: per hundred resin (rubber), by weight).
The adsorbent of the present invention comprises a burned plant material having a peak of the differential volume in specific pore radius value. The burned plant material is adjusted a burning temperature and a median diameter. The burned plant material is one of the burned materials of soybean hulls, rapeseed meal, sesame meal, cotton seed meal, cotton hulls, soybean chaffs, and cacao husk.
The adsorbent of the present invention can adsorb under controlling the pore radius value of the burned plant material by determining the burned temperature, etc. of the burned plant material in response to the substances to be adsorbed.
Referring to drawings, embodiments according to the present invention are described hereinafter.
This embodiment first produces a burned plant material by burning and carbonizing any of soybean hulls, rapeseed meal, cotton hulls, sesame meal, cotton seed meal, and cacao husk. Today, the production of food oil etc. from soybeans as a raw material results in causing a large amount of soybean hulls etc. Although most of those are reused as fodder for live stock or agricultural fertilizer, further usages have been sought. As a result of dedicated study from the aspect of ecology, as a way of further reusing soybean hulls etc., it was found that the burned material of soybean hulls etc. can be beneficially used as a heat conducting material and a heat conducting member.
In addition, as described later in EMBODIMENT 2, it was found that the burned material of soybean hulls etc. can be beneficially used not only as a heat conducting material and a heat conducting member but also as various adsorption material such as gas adsorption material.
The burned plant material is obtained by burning soybean hulls etc. in an inert gas atmosphere with nitrogen gas etc. or in a vacuum condition by using a carbonization apparatus such as holding furnace or rotary kiln, for example, at a temperature of approx. 900[° C.]. Then, the burned material of soybean hulls etc. is ground and then sieved with, for example, a 106 μm by 106 μm mesh. As a result, about 80% of the entire burned material of soybean hulls becomes 85 μm or below. In this case, the median diameter becomes, for example, approx. 30 μm to approx. 60 μm.
The median diameter was measured by a laser diffraction particle size analyzer, SALD-7000 etc. made by SHIMADZU Corporation. The heat conducting member of this embodiment use, for example, approx. 30 μm to approx. 60 μm as the median diameter for a burned material of soybean hulls etc., and approx. 1 μm as the minimum median diameter by those further selective pulverizing.
Pulverizing herein refers to a pulverization of a pre-pulverizing material to reduce its median diameter by about one decimal order. Therefore, it refers that a median diameter of 30 μm before pulverization is pulverized to 3 μm. However, pulverizing does not refer to exactly reducing the median diameter before pulverization by approx. one decimal order, and it also includes pulverizing to reduce the median diameter before pulverization to ⅕- 1/20. In this embodiment, the pulverization was carried out so that the median diameter after pulverization becomes 1 μm at the smallest.
Mixing a resol-type phenolic resin with raw soybean hulls allows improving the strength and carbon content of the burned material of soybean hulls. However, please note that said mixing itself is not essential for producing the heat conducting material and heat conducting member of this embodiment.
In
These electromagnetic shielding characteristics were obtained by using Shield Material Evaluator (TR17301A manufactured by Advantest Corporation) and Spectrum Analyzer (TR4172 manufactured by Advantest Corporation) at Yamagata Research Institute of Technology, Okitama Branch on 5 Jul. 2007.
As seen in
Here, instead of the burned material of soybean hulls, when carbon black was used as the containing object to ethylene propylene diene monomer rubber, it was found that the flexibility of the heat conducting member is reduced by containing as much as 100 [phr] of carbon black against ethylene propylene diene monomer rubber.
And, I would not say that it is impossible to contain as much as 400 [phr] of carbon black against the rubber, but it will essentially be very difficult to achieve that. In contrast to this, in the case of the heat conducting member of this embodiment, as much as approx. 400 [phr] of the burned material of soybean hulls can be contained against the rubber.
The second point is that the heat conducting member of this embodiment can advantageously improve the electromagnetic shielding effectiveness significantly as a result of the increased content ratio of the burned material of soybean hulls against the base material. From a different view point, the heat conducting member of this embodiment is advantageously easy to control its electromagnetic shielding effectiveness by adjusting the content ratio of the burned material of soybean hulls against the base material.
As shown in
This value is a tremendous value considering that most of the generally commercially available electromagnetic shielding materials in the market have an electromagnetic shielding effectiveness within the range of 5 [dB] to 25 [dB]. Similarly, even if the content ratio of the burned material of soybean hulls is approx. 300 [phr], an electromagnetic shielding effectiveness of 20 [dB] or above has been maintained in the frequency band of 300 [MHz] and below.
First, paying attention to the frequency band of up to 500 [MHz], it is found that a measurement result with an electromagnetic shielding effectiveness similar to the chart in
However, the electromagnetic shielding effectiveness increases for most of the measuring objects up to the frequency band of around 800 [MHz]. Then the electromagnetic shielding effectiveness decreases again from approx. 900 [MHz] to approx. 1000 [MHz].
a)-
Rapeseed meal, sesame meal, cotton seed meal, cotton hulls and cacao husk were burned at a burning temperature of 900[° C.] and the obtained burned materials were ground and sieved with a 106 μm by 106 μm mesh, and thus the median diameters were respectively approx. 48 μm, approx. 61 μm, approx. 36 μm, approx. 34 μm and approx. 39 μm. Therefore, hereinafter, when the burning temperature of rapeseed meal etc. is clearly specified as 900[° C.], it means that the burned material of rapeseeds etc. has a median diameter of approx. 48 μm, etc.
First, as comparing
In addition, when the content ratio of burned plant material is 400 [phr], it is found that the electromagnetic shielding effectiveness exceeds 30 [dB] as the maximum value in all charts. Furthermore, it is also found that the electromagnetic shielding effectiveness shows a small peak in the frequency band of 700 [MHz]-1000 [MHz].
a)-
a) shows a chart in which the burning temperature stayed at 900[° C.] and then the burned material of soybean hulls was pulverized, while
As shown in
As shown in
As shown in
Furthermore, according to
Hereinafter, the heat conducting material and the heat conducting member of this embodiment are described in further detail.
Next, the burned soybean hulls are ground and sieved to obtain a burned material of soybean hulls with a median diameter of, for example, approx. 4 μm to approx. 80 μm (for example, 60 μm). In this way, first of all, a heat conduction material is produced. Subsequently, the heat conducting material and ethylene propylene diene monomer rubber are set in a kneading machine together with various additives and are then given a kneading process. Then, the kneaded material is given a molding process, and is then given a vulcanization process. In this way, the production of heat conducting member completes.
Here, the heat conducting member of this embodiment can be formed by using a metal mold with a required shaped etc. Therefore, even if an electronic substrate requiring heat conducting member mounted on an electronic appliance does not have a planer shape, a heat conducting member corresponding to the shape of the electronic substrate can be produced.
However, the heat conducting member of this embodiment also has a degree of freedom to process cutting and vending, etc. This point is also advantageous in the production of heat conducting member.
Today, due to space-saving inside the case of electronic appliance accompanied by the downsizing of electronic appliances in late years, there are problems such as a difficulty in using a heat conducting member, or necessity for a layout of electronic appliance considering the space allocation for a heat conducting member. Since the heat conducting member of this embodiment can be formed into a shape corresponding to the shape of the space inside electronic appliance, it also causes a secondary effect of not requiring a product layout etc. considering the space allocation for a heat conducting member.
The heat conducting member of this embodiment can be preferably used for electronic appliance, inspection apparatus for electronic appliance and building material, etc. That means, the heat conducting member of this embodiment can be provided for a communication terminal body such as a mobile phone and PDA (Personal Digital Assistant), etc., or can be mounted on an electronic substrate built in a communication terminal body, or can be provided for a so-called shield box, or can be provided for roof material, floor material or wall material, etc., or can be used for a part of work shoes and work clothes as an anti-static material due to its conductivity.
As a result of this, there are advantageous effects of making it possible to eliminate a cause for concern about adverse impact on human body from the electromagnetic waves generated from mobile phones etc. or power cables etc. around houses, to provide a light-weight shield box, and to provide work shoes etc. having anti-static capability.
More specifically, as shown in
In addition, as shown in
Next, the following measurements etc. have been carried out for “raw soybean hulls”, “burned material of soybean hulls (heat conducting material)”, and “heat conducting member”.
(1) Component analysis of the “raw soybean hulls” and “burned material of soybean hulls”, etc.
(2) Tissue observation of the “raw soybean hulls” and “burned material of soybean hulls”,
(3) Conductivity test for the “burned material of soybean hulls”,
(4) Regarding the “heat conducting member”, measurement of the surface resistivity by different burning temperatures or median diameters for the heat conducting member of the test object.
a) shows a chart indicating the result of the component analysis based on the ZAF quantitative analysis method for soybean hulls, rapeseed meal, sesame meal, cotton seed meal, cotton hulls, and cacao husk before burning.
The soybean hulls before burning shown in
Similar to the soybean hulls before burning, the rapeseed meal etc. before burning are composed of the carbon (C) component and oxygen (O) component roughly half-and-half. As seen in detail, it has been found that “C” shown in
In addition, as shown in
In addition, the oxygen (O) component in the soybean hulls after burning was decreased to nearly half by burning. Although others have been variously changed (ranging from that reduced to half to that increased by a factor of 5), any of the changes were within several % of the total. It has also been read that the rapeseed meal etc. after burning somewhat tends to increase the carbon (C) component and to reduce the oxygen (O) component just like the soybean hulls after burning. Regarding the measurement target elements, none of them showed a distinctive change in quantity except for “C” and “O” for all plants, just like the case of soybean hulls.
Regarding soybean hulls, when the burning temperature was set to 1500[° C.], “C” was increased to 75.25%, “H” was decreased to 0.51%, and “N” was decreased to 0.96%. Furthermore, regarding soybean hulls, when the burning temperature was set to 3000[° C.], “C” was increased to 99.92%, “H” was decreased to 0.00%, and “N” was decreased to 0.03%.
However, the results of the component analysis shown in
a) shows a chart indicating the result of the component analysis based on the organic micro-elemental analysis method corresponding to
As seen in
In contrast, since soybean hulls and cotton hulls have the common feature of being hulls, it is perceived that those charts are similar to each other. Specifically, it is perceived that “N” is relatively low while the increase rate in “C” before and after burning is relatively high. On the other hand, although a cacao husk has the common feature that “N” is relatively low, the increase rate in “C” before and after burning is relatively low. In addition, in terms of “C”, cotton hulls are the highest (approx. 83%), while sesame meal is the lowest (approx. 63%).
As individually seen, according to the component analysis based on the organic micro-elemental analysis method, the soybean hulls before burning had the carbon (C) component, hydrogen (H) component and nitrogen (N) component of respectively 39.98%, 6.11% and 1.50%. Thus, it has been found that the soybean hulls before burning are essentially rich in the carbon component. In addition, it is seen in
In contrast, according to the component analysis based on the organic micro-elemental analysis method, the soybean hulls after burning had the carbon (C) component, hydrogen (H) component and nitrogen (N) component of respectively 73.57%, 0.70% and 1.55%. Thus, it has been found that the carbon component has been increased by burning. In addition, it is seen in
In addition, according to the component analysis for the cacao husk, the results of the component analysis of cacao husk before burning had the carbon component, hydrogen component and nitrogen component of respectively approx. 43.60%, approx. 6.02% and approx. 2.78%. In contrast, the results of the component analysis of cacao husk after burning had the carbon component, hydrogen component and nitrogen component of respectively approx. 65.57%, approx. 1.12% and approx. 1.93%. Furthermore, the specific volume resistivity of the burned material of cacao husk was 4.06×10−2 Ω·cm.
As a summary of the above, according to the component analysis based on the organic micro-elemental analysis method, it is perceived that the plant material before burning, in general, is essentially rich in the carbon component and the carbon component after burning is increased by burning.
The outer skin of the raw soybean hull shown in
The inner skin of the raw soybean hull shown in
As far as this picture of the cross-section is seen, the cross-section of the raw soybean hull shown in
As in the overall shape, the outer skin of the burned material of soybean hull shown in
Although the inner skin of the burned material of soybean hull shown in
Although the cross-section of the burned material of soybean hull shown in
As shown in
As shown in
a) and
Interestingly, the burned material of soybean hulls has granular substances attached to the surface. Furthermore, these substances increase the number and the size as the burning temperature for the burned material of soybean hulls increases. It could not be specified that whether these substances were something like crystal growth, or something like carbon nanotubes, or otherwise neither of these, and this kind of phenomenon has not been confirmed in any other plants.
In addition, as seen in
The method employed was that, 1 g of the powdered “burned material of soybean hulls” as a measuring object was put in a cylindrical container with an inner diameter of approx. 25Φ, and a cylindrical brass with a diameter of approx 25Φ was aligned to the opening part of the above container, and then a press machine (MP-SC manufactured by Toyo Seiki Seisaku-Sho, Ltd.) was used to apply pressure to the burned material of soybean hulls by pressing via the brass from 0 [MPa] to 4 [MPa] or 5 [MPa] with an increment of 0.5 [MPa] so that the specific volume resistivity was measured by bringing the side part and bottom part of the brass into contact with a probe of a low resistivity meter (Loresta-GP MCP-T600 manufactured by DIA Instruments Co. Ltd.) while the burned material of soybean hulls was pressured.
When a cylindrical container with approx. 10Φ was used instead of the cylindrical container with approx. 25Φ, and a cylindrical brass with a diameter of approx. 10Φ was used instead of the cylindrical brass with a diameter of approx. 25Φ, and when the rest of the conditions were the same as above, an equivalent test result was obtained by the conductivity test.
According to the test result shown in
Furthermore, according to the test result of
According to
In fact, although there is exactly three times difference, for example, between the specific volume resistivity of 1.0×10−1 [Ω·cm] and the specific volume resistivity of 3.0×10−1 [Ω·cm], such a degree of exactness is not required in the measurement results of the specific volume resistivity as it is clearly known by those skilled in the art. Thus, since the specific volume resistivity of 1.0×10−1 [Ω·cm] and the specific volume resistivity 3.0×10−1 [Ω·cm] both are on the same order of “10−1”, those can be evaluated as equivalent to each other.
In addition, in view of the evaluation of
As a summary of the above, it is found that the burned plant material of this embodiment has a characteristic of increasing its conductivity by applying a pressure of, for example, 0.5 [MPa] or above.
As clearly seen in comparison with
Specifically, the specific volume resistivity of cotton hulls was 3.74×10−2 [Ω·cm], and the specific volume resistivity of sesame meal was 4.17×10−2 [Ω·cm], and the specific volume resistivity of rapeseed meal was 4.49×10−2 [Ω·cm], and the specific volume resistivity of cotton seed meal was 3.35×10−2 [Ω·cm], and the specific volume resistivity of cacao husk was 4.06×10−2 [Ω·cm].
First, as comparing the case that a holding furnace was chosen as the burning furnace and the burning temperature stayed at 900[° C.] (plotted with ∇) with the case that a rotary kiln was chosen as the burning furnace and the burning temperature stayed at 900[° C.] (plotted with □), there is not much difference in specific volume resistivity between those. Specifically, the specific volume resistivity of the chart plotted with ∇ is 4.68×10−2 [Ω·cm], while the specific volume resistivity of the chart plotted with □ is 9.60×10−2 [Ω·cm], and therefore, both are in common with being on the order of “10−2”. Thus, it can be said that the selection of the burning furnace for soybean hulls is most unlikely to affect the specific volume resistivity.
In contrast, when a rotary kiln was chosen as the burning furnace and the burning temperature was lowered to 700[° C.] (plotted with Δ), the specific volume resistivity was increased in comparison with the case of setting the burning temperature to 900[° C.] in a holding furnace (plotted with ∇). Thus, it can be said that the burning temperature for soybean hulls affects the specific volume resistivity.
Hence, the specific volume resistivity was measured further at different burning temperatures for soybean hulls. In addition, the specific volume resistivity was also measured for a pulverized burned material of soybean hulls.
As clearly seen in
The chart with the second highest specific volume resistivity is from the case that the burning temperature was set to 1500[° C.] and the burned material was pulverized (plotted with ◯). The reason for the high specific volume resistivity can be evaluated to be attributable to the relatively lower burning temperature. In addition, as comparing the case that the burning temperature was set to 1500[° C.] and the burned material was pulverized (plotted with ◯) with the case that the burning temperature was set to 1500[° C.] and the burned material was not pulverized (plotted with ∇), the pulverized burned material has a higher specific volume resistivity.
As described above, the same tendency is observed in the burned material at a burning temperature of 900[° C.], and is also observed in the burned material at a burning temperature of 3000[° C.] as explained below. Therefore, it can be said that the burned material of soybean hulls increases its specific volume resistivity when pulverized.
In addition, paying attention to the burning temperature, the burned material of soybean hulls by a burning temperature of 1500[° C.] (plotted with ∇) has a specific volume resistivity lower than that of the one by a burning temperature of 1100[° C.] (plotted with Δ), and further the one by a burning temperature of 3000[° C.] (dotted line, plotted with □) has an even lower specific volume resistivity, and thus it can be said that the specific volume resistivity decreases as the burning temperature increases. This relationship between burning temperature and specific volume resistivity also fits to the case of pulverizing the burned materials.
Next, when measuring the specific volume resistivity of the burned material of soybean hulls, some parameters were changed. The pressure condition was the same at 0.5 [MPa].
(2) Change in the Median Diameter of the Burned Material of Soybean Hulls
The median diameter of the burned material of soybean hulls was changed to approx. 15 μm and to approx. 30 μm by the previously-mentioned sieving followed by grinding etc. However, those values of the specific volume resistivity are both around approx. 10−1.0 [Ω·cm] showing no significant difference.
In contrast, when the median diameter of the burned material of soybean hulls was changed to approx. 4 μm and to approx. 8 μm by the previously-mentioned sieving followed by grinding etc., the specific volume resistivity slightly increased to around approx. 10−0.7-0.8 [Ω·cm]. In the case of these values, it is speculated that it is due to almost no columnar or net-like structure in the cell layer that is unique to soybean hulls in spite of the change in the median diameter of the burned material of soybean hulls.
(3) Change in the Burning Temperature for Soybean Hulls
When the burning temperature for soybean hulls was changed, an interesting measurement result was obtained. More specifically, the burning temperature for soybean hulls was changed to approx. 500[° C.], approx. 700[° C.], approx. 1100[° C.] and approx. 1500[° C.]. The measuring object was prepared at a phenol resin impregnation rate of 25 [wt. %] for raw soybean hulls and under the pressure condition of 5 [MPa] for the burned material of soybean hulls.
In contrast, when the burning temperature for soybean hulls becomes approx. 1100[° C.] or above, it is found that there is not much change in the specific volume resistivity. It can be considered that this is due to almost no change in the carbon content and other component contents in the burned material of soybean hulls.
In particular, a larger change is seen where the burning temperature for soybean hulls is between approx. 500[° C.] and approx. 700[° C.]. It can be considered that this is due to a large change in the carbon content in the burned material of soybean hulls. When the burning temperature for soybean hulls was approx. 1500[° C.], the specific volume resistivity was as very small as approx. 10−1.5 [Ω·cm].
As a summary of the above, it is found that the heat conducting member of this embodiment has a characteristic of increasing its conductivity when the burning temperature for soybean hulls is, for example, 700[° C.] or above.
(4) Other Changes
In addition to changing either the median diameter of the burned material of soybean hulls or the burning temperature for soybean hulls, the content ratio of the burned material of soybean hulls against ethylene propylene diene monomer rubber was changed.
As shown in
In contrast, when the burning temperature was relatively low such as the burning temperature for soybean hulls of 600[° C.], the specific volume resistivity still decreased as the content ratio of the burned material of soybean hulls increased, however said fall in the specific volume resistivity was more linear in comparison with the case of the relatively higher burning temperature for soybean hulls. Thus, no abrupt fall was observed unlike in the case of the burning temperature for soybean hulls of 900[° C.] etc.
Therefore, the reason for different measurement results depending on a relatively high or low burning temperature for soybean hulls is considered as follows: That is, organic components with insulation properties essentially exist inside soybean hulls, and when the burning temperature for soybean hulls is relatively low, it is considered that those largely remain without carbonization or pyrolysis in comparison with the case of the relatively high burning temperature for soybean hulls.
It is considered that the reason why the case of the burning temperatures of soybean hulls of 900[° C.] and the case of 1500[° C.] show almost the same measurement result is that there is no significant change in the component constitution of soybean hulls, that is, the carbon content when the burning temperature is 900[° C.] or above.
First, in the case of the burned material of soybean hulls that was burned at 3000[° C.], when the content ratio of the burned material of soybean hulls is 0 [phr], the measurement result is almost the same as the case of the burned material of soybean hulls that was burned at 900[° C.].
However, in the case of the burned material of soybean hulls that was burned at 3000[° C.], when the content ratio of the burned material of soybean hulls is 150 [phr] and 400 [phr], it is confirmed that the specific volume resistivity is about 3.0×103 [Ω·cm] and 80×10−1 [Ω·cm] respectively.
According to the measurement result shown in
In addition, according the measurement result shown in
Furthermore, according to the measurement result shown in
b) shows measurement results of the specific volume resistivity at the median diameter of the burned material of soybean hulls of 2 μm, 10 μm and 60 μm respectively. The lateral axis and vertical axis of
As shown in
Here, the cluster is formed by the burned materials of soybean hulls linking with each other and forming a current pathway. Therefore, when it is hard for clusters to be formed, it is hard for electrical current to flow. Corresponding to the increased content ratio of the burned material of soybean hulls, the specific volume resistivity gently decreases, making it easy for electrical current to flow. In contrast, when an excess amount of clusters have been formed, the specific volume resistivity abruptly falls even if the content ratio of the burned material of soybean hulls is low.
As a summary of the above, it is found that the heat conducting material of this embodiment has a characteristic of increasing its conductivity when the median diameter of the burned material of soybean hulls is, for example, 10 μm or above.
As shown in
a) shows a chart indicating the measurement results of the “surface resistivity” by different burning temperatures for obtaining the heat conducting member of the test object. The lateral axis and vertical axis of
According to the measurement results shown in
b) shows a chart indicating the measurement results of the “surface resistivity” by different median diameters of the burned material of soybean hulls regarding the heat conducting material of the test object. The lateral axis and vertical axis of
According to the measurement results shown in
c) shows a chart indicating the measurement results of the “surface resistivity” by different content ratio of the burned material of soybean hulls against rubber. The lateral axis and vertical axis of
According to the measurement results shown in
As a summary of the above, it is found that the heat conducting material of this embodiment has a characteristic of increasing its conductivity by setting the content ratio of the burned material of soybean hulls against rubber to 200 [phr] or above, and increasing the burning temperature, and increasing the grain size.
a)-
In
a) and
c) and
e) and
g) and
a) and
From the above consideration, it can be said that it has a characteristic of increasing the conductivity when the content ratio of the burned material of the plant against rubber is set to 200 [phr] or above, which is just like the case of the burned material of soybean hulls.
Regarding only to the respective burned materials of soybean hulls, rapeseed meal, sesame meal and cotton seed meal and cotton hulls, when the content ratio of the burned plant material against rubber is set to 200 [phr] or above, it is found that the surface resistivity significantly decreases in all cases in contrast to the case that said content ratio is set to 150 [phr] or below. In addition, when said content ratio is 200 [phr] or above, each specific volume resistivity significantly decreases in contrast to the case that said content ratio is set to 150 [phr] or below.
a)-
In
a) and
First, as the charts are compared with each other, it is found that both specific volume resistivity and surface resistivity decrease as the burning temperature increases as described above. In addition, as the measurement results are compared with each other, it is also found that both specific volume resistivity and surface resistivity decrease not only as the burning temperature increases but also as the content ratio of the burned material of soybean hulls against rubber increases.
Here, Samples 1-4 with the following conditions were prepared. The prepared samples were as follows:
Sample 1: Thickness of the heat conducting member of 2.5 [mm], Content ratio of the burned material of soybean hulls against rubber of 300 [phr]
Sample 2: Thickness of the heat conducting member of 2.5 [mm], Content ratio of the burned material of soybean hulls against rubber of 400 [phr]
Sample 3: Thickness of the heat conducting member of 5.0 [mm], Content ratio of the burned material of soybean hulls against rubber of 300 [phr]
Sample 4: Thickness of the heat conducting member of 5.0 [mm], Content ratio of the burned material of soybean hulls against rubber of 400 [phr]
All of Samples 1-4 were prepared under the following conditions:
Burning temperature for soybean hulls to obtain heat conducting material: 900[° C.]
Median diameter of the burned material of soybean hulls: 60 μm
According to
In addition, it is found that Samples 2, 4 having a higher content ratio of the burned material of soybean hulls against rubber (plotted with (, (in the figure) shows a less electromagnetic wave absorption than Samples 1, 3 having a lower content ratio of the burned material of soybean hulls against rubber (plotted with (, (in the figure) do.
Regarding
Sample 5: Burning temperature for soybean hulls to obtain heat conducting material: 600[° C.]
Sample 6: Burning temperature for soybean hulls to obtain heat conducting material: 900[° C.] (Sample 1)
Sample 7: Burning temperature for soybean hulls to obtain heat conducting material: 1500[° C.]
All of Samples 5-7 were prepared under the following conditions:
Median diameter of the burned material of soybean hulls: 60 μm
Thickness of heat conducting member: 2.5 [mm]
Content ratio of the burned material of soybean hulls against rubber: 300 [phr]
According to
In contrast, it is found that Sample 5 (plotted with Δ in the figure) increases the electromagnetic wave absorption as the frequency increases. In contrast, it is found that Sample 6 (plotted with ◯ in the figure) reduces the electromagnetic wave absorption as the frequency increases.
Regarding
Sample 8: Thickness of heat conducting member: 0.5 [mm]
Sample 9: Thickness of heat conducting member: 1.0 [mm]
Sample 10: Thickness of heat conducting member: 1.5 [mm]
Sample 11: Thickness of heat conducting member: 2.0 [mm] (Sample 4)
Sample 12: Thickness of heat conducting member: 5.0 [mm] (Sample 3)
All of Samples 8-12 were prepared under the following conditions:
Burning temperature for soybean hulls to obtain heat conducting material: 900[° C.]
Median diameter of the burned material of soybean hulls: 60 μm
Content ratio of the burned material of soybean hulls against rubber: 300 [phr]
According to
The electromagnetic wave absorption characteristics shown in
According to
According to the enlarged view of
Here, paying attention to the burned material of soybean hulls with the content ratio of 400 [phr], the electromagnetic wave absorber of this embodiment has an electromagnetic wave shielding effect of 40 [dB] at the frequency band of around 50 [MHz] as shown in
According to
In contrast, when the thickness of the heat conducting member is 5.0 [mm], the electromagnetic wave absorption is relatively high at any point in the frequency band up to 3000 [MHz]. In addition, when the thickness of the heat conducting member is 2.5 [mm], the electromagnetic wave absorption increases around over 1200 [MHz].
Here, according to this test result, the electromagnetic wave absorption with the thickness of the heat conducting member of 2.5 [mm] is somewhat different from the one with the thickness of the heat conducting member of 5.0 [mm] in the frequency band of 2400 [MHz] and above.
However, it is worth noting that when the thickness of the heat conducting member is 5.0 [mm], the absorption characteristic of about −4 [dB] has been obtained at the frequency of 50 [MHz] and the absorption characteristic of about maximum −5 [dB] has been obtained in the frequency band of 2000 [MHz]-2500 [MHz].
a)-
a) shows electromagnetic wave absorption characteristics of the heat conducting member with a thickness of 2.5 [mm], wherein the burned material of rapeseed meal was burned at a burning temperature of 900[° C.], and
c) shows electromagnetic wave absorption characteristics of the heat conducting member with a thickness of 2.5 [mm], wherein the burned material of cotton seed meal was burned at a burning temperature of 900[° C.], and
e) shows electromagnetic wave absorption characteristics of the heat conducting member with a thickness of 2.5 [mm], wherein the burned material of sesame meal was burned at a burning temperature of 900[° C.], and
g) shows electromagnetic wave absorption characteristics of the heat conducting member with a thickness of 2.5 [mm], wherein the burned material of cotton hulls was burned at a burning temperature of 900[° C.], and
Whenever the burned material of any one of plants such as rapeseed meal is used, when the thickness of the heat conducting member is 2.5 [mm], the absorption characteristic of about maximum −5 [dB] has been obtained in the frequency band of 3000 [MHz] and below, and when 5.0 [mm], the absorption characteristic of about maximum −8 [dB] has been obtained.
Although it has not been determined (regarding sesame meal, we could not carry out a measurement for the case containing 300 [phr] of the burned material against rubber) it may be said that the burned material of any one of plants such as rapeseed meal has an effective frequency absorption characteristic in the frequency band of 2000 [MHz]-3000 [MHz] when containing 300 [phr] against rubber.
a) shows electromagnetic wave absorption characteristics of the heat conducting member with a thickness of 2.5 [mm], wherein the burned material was burned at 900[° C.] and was then pulverized, and
c) shows electromagnetic wave absorption characteristics of the heat conducting member with a thickness of 2.5 [mm], wherein the burning temperature was at 1500[° C.], and
e) shows electromagnetic wave absorption characteristics of the heat conducting member with a thickness of 2.5 [mm] according to soybean hulls, wherein the burning temperature was at 3000[° C.], and
First, it was confirmed from all of the measurement results of
In addition, as comparing
Based on the above, in order to obtain an heat conducting material preferably used at, for example, around 2500 [MHz], it is understood that:
(1) the conditions may be the burning temperature for the burned material of soybean hulls of 1500[° C.], the thickness of the heat conducting member of 5 [mm], the content of the burned material of soybean hulls against rubber of 200 [phr], and not applying pulverization for the burned material of soybean hulls.
(2) the conditions may be the burning temperature for the burned material of soybean hulls of 900[° C.], the thickness of the heat conducting member of 5 [mm], the content of the burned material of soybean hulls against rubber of 300 [phr]-400 [phr], and applying pulverization for the burned material of soybean hulls.
As shown in
In addition, there also seems to be association between the content ratio of the burned material of soybean hulls against ethylene propylene diene monomer rubber and the absorption itself. That is, as the content ratio of the burned material of soybean hulls against ethylene propylene diene monomer rubber increases, the electromagnetic wave absorption increases except for the cases that the content ratio of the burned material of soybean hulls against ethylene propylene diene monomer rubber is set to 50 [phr] and 100 [phr].
However, when the content ratio of the burned material of soybean hulls is 50 [phr] and 100 [phr] in the sample, the absorption characteristic cannot be obtained. In
As shown in
a)-
a) shows electromagnetic wave absorption characteristics of the heat conducting member formed from the burned material of rapeseed meal.
First, looking at
Although it has not been determined (regarding the cotton seed meal shown in
a) shows electromagnetic wave absorption characteristics of the burned material of soybean hulls that was burned at a burning temperature of 900[° C.] and was then pulverized.
In contrast to the case of rapeseed meal etc. shown in
For example, large electromagnetic wave absorption was obtained at the content of 300 [phr] in the case of the burning temperature of 900[° C.] as shown in
From
According to
However, the electromagnetic wave absorption increases as the thickness of the heat conducting member increases, and as the content ratio of the burned material of soybean hulls against low density polyethylene increases. Therefore, when low density polyethylene is used as the base material, it is preferred to increase the content ratio itself of the burned material of soybean hulls in terms of the electromagnetic wave absorption.
What can be said from the charts shown in
As explained above, it is observed that the heat conducting member of this embodiment not only has the anti-charge function and anti-static function, but also has a shielding function. In addition, these functions can be tailored to various applications by changing the production conditions for the burned plant material of soybean hulls etc.
In other words, the heat conducting member of this embodiment can be tailored to various applications by adjusting the content ratio of the burned material of soybean hulls against a base material, the median diameter of the burned material of soybean hulls, the burning temperature for obtaining the burned material of soybean hulls. Consequently, the heat conducting member of this embodiment can be used as, for example, conductive filler to the plastic and rubber used in electronic appliances.
Regarding the burned material of soybean hulls according to this embodiment, the following tests and measurements have been carried out. Here, regarding the burned material of soybean hulls, although those with the median diameter of approx. 30 μm and those with the median diameter of approx. 60 μm were used to carry out several tests and measurements, this range of differences in median diameter did not indicate any differences in the test results and measurement results.
(1) Regarding the burned material of soybean hulls according to this embodiment, the physical properties such as bulk specific gravity, BET specific surface area, and crystallite size were measured.
(2) Regarding the burned material of soybean hulls according to this embodiment, whether or not it can be blended with a base material other than ethylene propylene diene monomer rubber, and if possible to blend, the content ratio of said burned material against the rubber were measured.
First, the following measurement results were obtained regarding the physical properties.
As comparing those burned at respective burning temperatures of 900[° C.], 1500[° C.] and 3000[° C.] with each other, it is found that the BET specific surface area varies depending on the burning temperature.
For example, JPA2005-336017 discloses a porous carbon material with a bulk specific gravity of 0.6-1.2 g/cm3. When comparing the above measurement results with those in this publication, the burned material of soybean hulls according to this embodiment has a lower value in the bulk specific gravity. Here, the bulk specific gravity of the burned material of soybean hulls according to this embodiment has been measured in conformity to JIS K-1474.
JPA2007-191389 discloses carbonaceous or graphitic particles for electrodes of non-aqueous secondary battery that have a median diameter of 5-50 μm and a BET specific surface area of 25 m2/g or below.
JPA2005-222933 discloses carbonaceous particles that have a crystallite size of over 100 nm as a negative-electrode material for lithium battery. When comparing the above measurement results with those in this publication, the burned material of soybean hulls according to this embodiment has a smaller crystallite size, and thus it is evaluated as low-crystalline carbon.
If it explains additionally, the bulk specific gravity of rapeseed meal, sesame meal, cotton seed meal, cotton hulls and cacao husk were approx. 0.6 g/ml to 0.9 g/ml, approx. 0.7 g/ml to 0.9 g/ml, approx. 0.6 g/ml to 0.9 g/ml, approx. 0.3 g/ml to 0.5 g/ml, and approx. 0.3 g/ml to 0.5 g/ml respectively. Therefore, the kinds of hulls (soybean hulls, cotton hulls and cacao husk) are a relatively bulky.
Next, the measurement results of whether or not being able to blend with a base material other than ethylene propylene diene monomer rubber, and if possible to blend, the content ratio of said burned material against the rubber were found as follows.
Here, No. 191-TM TEST MIXING ROLL manufactured by Yasuda Seiki Seisakusho Ltd. was used as an open roll (biaxial kneading machine), and TOYO SEIKI mini TEST PRESS 10 was used as a molding process machine (compacting machine).
For comparison, in addition to the burned material of soybean hulls according to this embodiment, (1) coconut shell activated carbon (granular SHIRASAGI WH2C8/32SS Lot No. M957 manufactured by Japan EnviroChemicals. Ltd.), and (2) carbon black (SUNBLACK285, Lot No. 8BFS6 manufactured by ASAHI CARBON CO., LTD.) were used.
For the base material other than ethylene propylene diene monomer rubber, (a) isoprene (IR-2200 manufactured by Kraton JSR Elastomers K.K.), and (b) polyvinyl chloride resin (ZEST1000Z, Lot No. C60211 manufactured by Shin Daiichi Enbi K.K.) were used.
In addition, regarding coconut shell activated carbon and carbon black, whether or not it can be blended with ethylene propylene diene monomer rubber was also checked.
Blending the burned material of soybean hulls according to this embodiment with a base material was the same as explained above with reference to
Subsequently, the molding process machine was used to process molding for the base material that had been blended with the burned material of soybean hulls according to this embodiment or others under the pressure of 20 [MPa] for 5 minutes at the temperature of 100[° C.].
Hence, regarding the resultant products, the measurement results of whether or not being able to blend with the base material, and if possible to blend, the content ratio of said burned material against the rubber were found as follows.
1. Regarding the burned material of soybean hulls according to this embodiment,
(1) In the case that isoprene was used as the base material, the content ratio was found to be as much as approx. 600 [phr].
(2) In the case that polyvinyl chloride resin was used as the base material, the content ratio was found to be as much as approx. 350 [phr].
2. Regarding coconut shell activated carbon,
(1) In the case that isoprene was used as the base material, the content ratio was found to be approx. 150 [phr]. However, it was not possible to knead in to 200 [phr] or more.
(2) In the case that ethylene propylene diene monomer rubber was used as the base material, the content ratio was found to be approx. 150 [phr]. However, in this case, when this compressed compact was curved, it caused a crack. Moreover, it was not possible to knead in to 200 [phr] or more.
3. Regarding carbon black,
(1) In the case that isoprene was used as the base material, the content ratio was found to be approx. 100 [phr]. However, in this case, when this compressed compact was curved, it caused a crack. Moreover, it was not possible to knead in to 150 [phr] or more.
(2) In the case that ethylene propylene diene monomer rubber was used as the base material, the content ratio was found to be approx. 100 [phr]. However, in this case, when this compressed compact was curved, it caused a crack. Moreover, it was not possible to knead in to 150 [phr] or more.
As a summary, in contrast to the burned material of soybean hulls according to this embodiment, even though “coconut shell activated carbon” that is in common in terms of being plant-derived carbide and being porous structure was used, a large amount of blending with the base material such as the one obtained by the burned material of soybean hulls according to this embodiment was not recognized. So any one of the burning temperature for the burned material of soybean hulls according to this embodiment, the carbon content attributable thereto, and a lager number of reactive functional residues is possibly contributing to the increased content ratio against the base material.
In the case of petroleum-pitch-derived carbon black, it was found that not only containing the amount of 100 [phr] for ethylene propylene diene monomer rubber causes a reduced flexibility, but also containing the amount of 100 [phr] for isoprene causes a reduced flexibility.
It was confirmed that the burned material of soybean hulls according to this embodiment was able to be blended with a base material even if silicon rubber was used as the base material. When reproducibility tests were selectively carried out for various test results etc. explained in this embodiment, it was confirmed that all of them were reproducible. In addition, the burned material of soybean hulls according to this embodiment may be blended with not only rubber but also paint, cement, etc. as a base material. Therefore, for example, the burned material of soybean hulls may be used as a paint containing a heat conducting member for a roof material etc., or also may be used as cement containing a heat conducting member at the time of construction of collective housing.
Furthermore, each test was selectively carried out by setting the median diameter of the burned material of soybean hulls according to this embodiment to 30 μm. As explained with reference to
Next, the heat conducting members formed from the burned material of cacao husk (heat conducting material) is described. In addition, the various following measurements were carried out under similar conditions to those for the burned material of raw soybean hulls and soybean hulls, etc. as stated above.
First, according to the component analysis (organic micro-elemental analysis method) for raw cacao husk, the carbon component, hydrogen component and nitrogen component were approx. 43.60%, approx. 6.02% and approx. 2.78% respectively. In contrast, according to the component analysis (organic micro-elemental analysis method) for burned material of cacao husk, the carbon component, hydrogen component and nitrogen component were approx. 65.57%, approx. 1.12% and approx. 1.93% respectively. In addition, the volume specific resistivity of the burned material of cacao husk was 0.0406 Ω·cm.
As shown in
Interestingly, as shown in
From
A form like the spiral is not confirmed in soybean hulls, rapeseed meal, sesame meal, cotton seed meal, cotton hulls and soybean chaffs as stated above. Therefore, such a form has a high possibility of being peculiar to a cacao husk.
In
Next, the measurement result of thermal conductivity of the heat conducting member of this embodiment is explained. Thermal conductivity measurement was performed under the temperature of 25° C. to each sample mentioned later. The measuring method of thermal conductivity was made into the hot wire method, and was carried out in accordance with JIS standard R2616.
The measurement of thermal conductivity of a sample was carried out in the state where eight heat conducting members of size with 100 mm (length)×50 mm (width)×2.5 mm (thickness) were made to laminate (2.0 mm (thickness)×10 laminations was adopted only for the measurement of sample A and for the measurement of 150 phr regarding sample D). Moreover, the quick thermal conductivity meter QTM-500 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) was used as measuring device. And, the measurement of thermal conductivity was carried out on the accuracy conditions from which the numerical value of less than ±5% of the thermal conductivity standard value of standard sample mentioned later is acquired.
First, the thermal conductivities of standard samples were the firing polyethylene (PE), silicon rubber, and quartz glass of respectively 0.036 [W/(m·K)], 0.238 [W/(m·K)], and 1.42 [W/(m·K)].
The thermal conductivities of carbon black (CB1, 2) were 0.377 [W/(m·K)] and 0.418 [W/(m·K)] respectively. The content ratios of the carbon black (CB1, 2) against the base material were 100 phr respectively. In addition, the thermal conductivity of base material was slightly 0.211 [W/(m·K)].
Sample A is a heat conducting member which burned the soybean hulls at the temperature of approx. 900° C., and is not pulverized. The heat conducting member uses the heat conducting material which has approx. 30 μm median diameters. The thermal conductivities in the case that the content ratios of Sample A against the base material were 100 phr, 200 phr and 400 phr respectively were 0.342 [W/(m·K)], 0.446 [W/(m·K)] and 0.651 [W/(m·K)] respectively.
Sample B is a heat conducting member which burned the soybean hulls at the temperature of approx. 900° C., and is pulverized. The heat conducting member uses the heat conducting material which has approx. 5 μm median diameters. The thermal conductivities in the case that the content ratios of Sample B against the base material were 100 phr, 150 phr, 200 phr, 300 phr and 400 phr respectively were 0.334 [W/(m·K)], 0.391 [W/(m·K)], 0.436 [W/(m·K)], 0.518 [W/(m·K)] and 0.587 [W/(m·K)] respectively.
Sample C is a heat conducting member which burned the soybean hulls at the temperature of approx. 1500° C., and is not pulverized. The heat conducting member uses the heat conducting material which has approx. 30 μm median diameters. The thermal conductivities in the case that the content ratios of Sample C against the base material were 100 phr, 200 phr and 300 phr respectively were 0.498 [W/(m·K)], 0.769 [W/(m·K)] and 1.030 [W/(m·K)] respectively.
Sample D is a heat conducting member which burned the soybean hulls at the temperature of approx. 3000° C., and is not pulverized. The heat conducting member uses the heat conducting material which has approx. 30 μm median diameters. The thermal conductivities in the case that the content ratios of Sample D against the base material were 150 phr and 400 phr respectively were 1.100 [W/(m·K)] and 3.610 [W/(m·K)] respectively.
Sample N is a heat conducting member which burned the rapeseed meal at the temperature of approx. 900° C., and is not pulverized. The heat conducting member uses the heat conducting material which has approx. 48 μm median diameters. The thermal conductivities in the case that the content ratios of Sample N against the base material were 100 phr, 200 phr and 400 phr respectively were 0.344 [W/(m·K)], 0.460 [W/(m·K)] and 0.654 [W/(m·K)] respectively.
Sample M is a heat conducting member which burned the cotton seed meal at the temperature of approx. 900° C., and is not pulverized. The heat conducting member uses the heat conducting material which has approx. 36 μm median diameters. The thermal conductivities in the case that the content ratios of Sample M against the base material were 100 phr, 200 phr and 400 phr respectively were 0.348 [W/(m·K)], 0.482 [W/(m·K)] and 0.683 [W/(m·K)] respectively.
Sample G is a heat conducting member which burned the sesame meal at the temperature of approx. 900° C., and is not pulverized. The heat conducting member uses the heat conducting material which has approx. 61 μm median diameters. The thermal conductivities in the case that the content ratios of Sample G against the base material were 100 phr, 200 phr and 400 phr respectively were 0.345 [W/(m·K)], 0.471 [W/(m·K)] and 0.665 [W/(m·K)] respectively.
Sample CT is a heat conducting member which burned the cotton hulls at the temperature of approx. 900° C., and is not pulverized. The heat conducting member uses the heat conducting material which has approx. 34 μm median diameters. The thermal conductivities in the case that the content ratios of Sample CT against the base material were 100 phr, 200 phr and 400 phr respectively were 0.361 [W/(m·K)], 0.495 [W/(m·K)] and 0.705 [W/(m·K)] respectively.
Sample CA is a heat conducting member which burned the cacao husk at the temperature of approx. 900° C., and is not pulverized. The heat conducting member uses the heat conducting material which has approx. 39 μm median diameters. The thermal conductivities in the case that the content ratios of Sample CA against the base material were 100 phr, 200 phr and 400 phr respectively were 0.355 [W/(m·K)], 0.483 [W/(m·K)] and 0.692 [W/(m·K)] respectively.
First, when comparing the thermal conductivity of base material and the thermal conductivity of each sample, it can be found that the thermal conductivity of each sample is high. Therefore, it can be found that containing the heat conducting material of this embodiment against the base material is better in respect of thermal conductivity rather than using only base material as a heat conducting member.
The thermal conductivity in the case that the content ratio of Sample A against the base material is 100 phr has no great difference compared to each of comparative examples. It seems due to the fact that the carbon content against the base material is close. In addition, although the thermal conductivity in the case that the content ratio of Sample A against the base material is 200 phr can be evaluated as slightly better compared to each of comparative examples, the significant increase cannot be confirmed. On the other hand, the thermal conductivity in the case that the content ratio of Sample A against the base material is 400 phr increased to more than 1.5 times compared to each of comparative examples.
Next, when the thermal conductivity of Sample A and the thermal conductivity of Sample N, M, G, CT, and CA are contrasted, it can be found that the same tendency is seen generally. That is, in the case that the content ratio of heat conducting material regarding each of these samples against the base material is same, it can be found that the thermal conductivity shows the same value. And, in the case that the content ratio of heat conducting material regarding each of these samples against the base material is increased, it can be found that the thermal conductivity also increases.
Next, when Sample A and Sample B are contrasted, Sample B using small median diameter has become loose slightly of the increasing trend in thermal conductivity Therefore, it is considered that the step of “pulverizing” is better to delete to increase the thermal conductivity.
Next, when Sample A and Sample C are contrasted, it can be found that the thermal conductivity increases with the increasing the burning temperature at the time of producing heat conducting material. For Sample C, when the content ratio of heat conducting material against the base material is only 100 phr, the thermal conductivity of approx. 0.5 [W/(m·K)] can be confirmed.
Similarly, when Sample A and Sample D are contrasted, it can be found that the thermal conductivity increases with the increasing the burning temperature at the time of producing heat conducting material. For Sample D, when the content ratio of heat conducting material against the base material is only 150 phr, the thermal conductivity of approx. 1.1 [W/(m·K)] can be confirmed. In addition, surprisingly, for Sample D, in the case that the content ratio of heat conducting material against the base material is 400 phr, the thermal conductivity of approx. 17 times to the thermal conductivity of the base material can be obtained.
Here, why such measurement result was obtained is considered. First, carbon itself has a heat transfer property. When substances having heat transfer property are in close to each other, a heat bridge is formed. The carbon content of the heat conducting material of this embodiment is high, so a heat bridge is easy to be formed. It is consider that the heat conducting material of this embodiment is excellent in thermal conductivity, so as to contain the heat conducting member.
Sample E is produced under the same process as Sample D, after not less than one year has passed since the produce of Sample D. That is, Sample E, as well as Sample D, is a heat conducting member produced by a non pulverizing burned material of soybean hulls burned at the temperature of approx. 3000° C. The heat conducting material using the heat conducting member has approx. 30 μm median diameters.
The thermal conductivities were measured, when the content ratios of Sample E against the base material were 100 phr, 150 phr, 200 phr, 300 phr and 400 phr respectively.
The thermal conductivity in the case that the content ratio of Sample E against the base material was 100 phr was 0.765 [W/(m·K)]. It can be found that the above figure is lower than the thermal conductivity in the case that the content ratio of Sample E against the base material was 150 phr.
In addition, the thermal conductivity in the case that the content ratio of Sample E against the base material was 150 phr was 1.10 [W/(m·K)] which was same figure as the thermal conductivity in the case that the content ratio of Sample D as shown in
Therefore, it can be found that the heat conducting member of this embodiment has high reproducibility about thermal conductivity. When added, the burned material of soybean hulls according to sample D and sample E were same results not only thermal conductivity but also physical properties, component analysis, etc.
In addition, the thermal conductivity in the case that the content ratios of Sample E against the base material were 200 phr and 300 phr respectively were 1.680 [W/(m·K)] and 2.860 [W/(m·K)] respectively.
In addition, as apparent from
Next, an adsorbent of Embodiment 2 according to the present invention is described. The inventors of the present invention found out that the burned plant material produced by the method described in Embodiment 1 had an adsorption action as described below.
First, the performance of the burned plant material is explained. In the burned material of soybean hulls which is a burned plant material, the sample weight is 1.1463 [g], the relative pressure range of BET-plot is 0.01 to 0.15, the measurement area is 440.5 [m2], the BET specific surface area is 384.3 [m2/g], the pore volume Vp is 0.1756 [cm3/g], the average pore radius rm is 9.14 [Å], the mode pore radius at the time of adsorption is 4.42 [Å], when the burning temperature is set to 900[° C.].
In addition, in case that the burning temperature is set to 1500[° C.] or 3000[° C.], the sample weight is 0.5637 [g] or 7.7389 [g], the measurement area is 29.4 [m2] or 38.1 [m2], the BET specific surface area is 52.2 [m2/g] or 4.92 [m2/g] respectively.
It should be noted that the burned material of soybean hulls at least shows a sole sharp peak in the differential volume at a specific pore radius that is rarely seen in the burned materials of other plants in consideration of the verification results for the burned material of soybean hulls that was burned at a temperature of 1500[° C.] or 3000[° C.] as described below.
Normally, the burned materials of other plants excluding burned material of soybean hulls, etc. rarely show a single sharp peak at a specific pore radius in the differential volume, and rather the chart of the pore size distribution curve results in broad, or several peaks appear in the chart of the pore size distribution curve.
The pore size of the burned material of soybean hulls burned at a temperature of 900[° C.] as shown
Here, the differential volume also shows a peak at a specific pore radius. The pore size of the burned material of soybean hulls burned at a temperature of 1500[° C.] showed a less sharp peak in the differential volume at a pore radius of approx. 8.29 Å, but the peak was still somewhat sharp. However, the pore distribution has become wider in the range of about 30 Å. See the chart in
As described above, it is found that the burned material of soybean hulls has a very rare characteristic of showing a peak in the differential volume at a specific pore radius regardless of the burning temperature.
Next, an adsorbent using each burned material of cotton seed meal, cacao husk, rapeseed meal, sesame meal and cotton hulls is as follows.
Table 1 is a showing the weight (g), the relative pressure range of BET-plot, the measurement area (m2), the specific surface area (m2/g), the pore volume Vp (cm3/g), the average pore radius rm [Å], the mode pore radius at the time of adsorption [Å] of each of these burned materials. In addition, each burned material is made into the burning temperatures of about 900° C.
The measurement techniques such as a pore radius explained in Specification are performed under the following conditions.
As measurement apparatus, Sorptmatic 1990 manufactured by Thermo Finnigan, Inc. is adopted.
As a pretreating method, the measuring object was dried under reduced pressure for about 6 hours at approx. 200° C. and cooled down, then, the measuring sample was weighed and degassed under reduced pressure for about 6 hours on condition of approx. 1×10−3 (Pa) and below at approx. 200° C. in predetermined burette.
As a measuring method of surface area, the nitrogen gas adsorption method (a constant volume method, an adsorption process, a helium gas blank method) was adopted.
As the analysis method, BET multipoint method was adopted.
The relative pressure range was set to 0.05-0.35 (burned material of cotton seed meal, burned material of cacao husk, burned material of rapeseed meal, and burned material of sesame meal) and 0.01-0.15 (burned material of cotton hulls).
As a measuring method of pore size distribution, the nitrogen gas adsorption method (a constant volume method, an adsorption process, a helium gas blank method) was adopted.
As the analysis method, Dollimore/Heal method was adopted.
The pore volume was the value that the relative pressure corresponded to P/P0=0.97 in the adsorption process.
As shown in Table 1, although the average pore radius is various by each burned material, an important aspect of the present invention is that a burned plant material has a peak in the differential volume at a specific pore radius.
As shown in
Next, concerning the adsorbent of burned material of soybean hulls of this embodiment, the gas adsorbent examination was actually done using FT-IR Fourier transform infrared spectrophotometer (MIDAC Inc. I-4001). The burning temperature of soybean hulls was set to 900° C. and the median diameter was also approx. 30 μm. In addition, the examination was done in the following ways at Tomoeshokai Inc. Technology Division Yokohama Institute.
First, three test vessels, three petri dishes on which adsorbent placed in each enclosed vessel is put, and three tripods on which each petri dish is placed were prepared. These were the total volume of 0.11248 (L). The first test vessel was enclosed with approx. 5 (g) of adsorbent of soybean hulls of this embodiment and was sealed. The second test vessel was enclosed with approx. 5 (g) of commercially available activated carbon for comparison and was sealed. The third test vessel was not enclosed with adsorbent, etc. Activated carbon manufactured by Kanto Chemical (model version No. 01085-02) was used as activated carbon for comparison.
This activated carbon for comparison was selected for the following reasons;
In contrast to adsorbent of soybean hulls of this embodiment,
There is a common feature of being a plant-derived burned material which is a burned material of sawdust.
There is a approximation point that the particle size of activated carbon for comparison is about 20 μm, whereas the particle size of adsorbent of soybean hulls of this embodiment is about 30 μm.
On the other hand, there are differences from adsorbent of soybean hulls of this embodiment since the pore radius is in broad with approx. 5 Å-approx. 2500 Å and the average pore radius is approx. 100 Å.
Next, the adsorbent, etc. were dried by heating at 120° C. for about 8 hours flowing nitrogen gas at a flow rate of 1 (L/min) in the 1st and 2nd test vessels. Then, heating was stopped and the temperature was lowered to room temperature (approx. 22° C.), where nitrogen gas is flowed. After the adsorbent of soybean hulls of this embodiment and commercially available activated carbon have returned to room temperature, the pressure of each test vessel was reduced to approx. 40 (cmHgG) or less and a test gas which was collected by a gas syringe was introduced to a concentration of 49950 ppm under the pressure of approx. 0.01 MPaG, then, each test vessel was left for one day under room temperature.
Then, during nitrogen gas was fed in each test vessel at approx. 0.5 (L/min), the test gas concentration discharged from each test vessel was measured using FT-IR Fourier transform infrared spectrophotometer connected to each test vessel.
In this embodiment, carbon dioxide (CO2) gas, carbon monoxide (CO) gas, ethylene (C2H4) gas, and ammonia (NH3) gas were selected as test gas, and the test using each of these gases was carried out. Of course, Each time test gas was changed, the heating and drying process described above were performed. In addition, among these test gases, 4 m gas cell for low concentration measurement was used on the occasion of measurement of ammonia gas and 1 cm gas cell for high concentration measurement was used on the occasion of measurement of other gas.
Table 2 is a table showing the test result of gas adsorption test.
6040 ppm1
As shown in Table 2, when carbon dioxide gas was selected as test gas, the maximum concentration of carbon dioxide gas concerning the 3rd test vessel was the detection result of 43600 (ppm). On the other hand, the maximum concentration of carbon dioxide gas concerning the 1st test vessel was the detection result of 1400 (ppm). This shows that approx. 97% of test gas has been absorbed by the adsorbent of soybean hulls of this embodiment during one day leave after introducing test gas in the 1st test vessel.
On the other hand, the maximum concentration of the carbon dioxide gas concerning the 2nd test vessel was the detection result of 7400 (ppm). This shows that about 83% of test gas has been absorbed by commercially available activated carbon during one day leave after introducing test gas in the 2nd test vessel.
In contrast to the measurement result concerning the 1st test vessel and the 2nd test vessel, there is a adsorption difference of approx. 5.3 times because of a measurement result of 1400 (ppm) and 7400 (ppm) from a concentration standpoint. In addition, the absorption of the carbon dioxide gas by adsorbent of soybean hulls of this embodiment has been phenomenally improved approx. 15%.
Similarly, when the adsorbent of soybean hulls of this embodiment is targeted, ammonia gas is the noteworthy test gas. When ammonia gas was selected as test gas, the maximum concentration of ammonia gas concerning the 1st test vessel was the detection result of 12 (ppm). This shows that approx. 99.8% of test gas has been absorbed by the adsorbent of soybean hulls of this embodiment during one day leave after introducing test gas in the 1st test vessel.
On the other hand, the maximum concentration of ammonia gas concerning the 2nd test vessel was the detection result of 160 (ppm). This shows that approx. 97% of test gas has been absorbed by the adsorbent of commercially available activated carbon during one day neglecting after introducing test gas in the 2nd test vessel.
Therefore, in contrast to the measurement result concerning the 1st test vessel and the measurement result concerning the 2nd test vessel, first of all, it can be found that there is a adsorption difference of approx. 13 times because of a measurement result of 12 (ppm) and 160 (ppm) from a concentration standpoint.
In addition, as shown in Table 2, it can be found that the adsorbent using the soybean hulls of this embodiment has a superior gas absorption characteristic as compared with the commercially available activated carbon. For reference, the adsorption difference is approx. 1.03 times from a concentration standpoint and it is negligible in the case of carbon monoxide gas, and the adsorption difference is approx. 1.3 times from a concentration standpoint in the case of ethylene gas.
Incidentally, the adsorption amount per unit weight and contact area are easily computable using the following formula. That is, as an example in the case that test gas is ammonia gas, since the introduced concentration of test gas to the test vessel was 51600 (ppm), the packing amount of test object was 5.0 (g), the enclosed gas amount was 0.113605 (L) and the area of two petri dishes was 26.3917 (cm2), the adsorption amount per unit weight is as follows;
[adsorption amount per unit weight]=[enclosed concentration×(1−maximum gas concentration concerning the 1st test vessel/maximum gas concentration concerning the 3rd test vessel)×enclosed gas amount÷packing amount of test object]
The calculation result of the adsorption amount per unit weight using the above formula was as follows;
[adsorption amount per unit weight]=[51600/1000000×(1−12/6040)×0.113605/5.0]=1.1700 (mL/g)
In addition, the adsorption amount per unit contact area is computable using the following formula;
[adsorption amount per unit contact area]=[enclosed concentration×(1−maximum gas concentration concerning the 1st test vessel/maximum gas concentration concerning the 3rd test vessel)×enclosed gas amount/area of two petri dishes]
The calculation result of the adsorption amount per unit contact area using the above formula was as follows;
[adsorption amount per unit contact area]=51600/1000000×(1−12/6040)×0.113605/26.3917=0.2217 (mL/cm2)
Then, since the test gas came out from each test vessel begins to reach the FT-IR Fourier transform infrared spectrophotometer, gradually, the test gas concentration continued to increase, and the test gas concentration became maximum at about 0.2 (min) as the measurement time in any of the test vessels.
In the case of 3rd test vessel, when measuring time becomes about 1.2 (min), it is observed that almost all of the test gas enclosed in 3rd test vessel was discharged from 3rd test vessel by fed nitrogen gas.
In the case of 2nd test vessel, even if measuring time becomes 2 (min), the test gas concentration is not reduced to 0 (ppm). This means that the adsorption power of carbon dioxide gas by commercially available activated carbon is relatively weak, therefore, a lot of carbon dioxide gas is released from commercially available activated carbon during nitrogen gas is fed to the 2nd test vessel.
In the case of 1st test vessel, when measuring time becomes about 0.8 (min), the test gas concentration is reduced to about 0 (ppm). This means that the adsorption power of carbon dioxide gas by adsorbent of soybean hulls of this embodiment is relatively strong, therefore, carbon dioxide gas is hardly released from adsorbent of soybean hulls of this embodiment during nitrogen gas is fed to the 1st test vessel.
In addition, although it is considerable to be read from
In addition, since the concentration of the test gas concerning the 1st test vessel is not reduced to 0 (ppm) even if measuring time reaches 2.0 (min), the adsorbent of the soybean hulls of this embodiment is understood that adsorption power is strong to carbon dioxide gas rather than carbon monoxide gas.
Furthermore, the confirmation test of oxygen adsorption amount of the adsorbent of this embodiment was done. Specifically, an adsorbent (about 250 g) and an oxygen analyser (OX-01: diaphragm galvanic cell type manufactured by Riken Keiki) were placed in a desiccator and were sealed. In this case, the contact area between the adsorbent and air in the desiccator was approx. 615 cm2, the air volume in the desiccator was approx. 2.5 L.
Although the above adsorbent had been in contact with the atmosphere and had already adsorbed considerable amount of oxygen, the oxygen concentration was decreased by 0.4% after one hour from sealing. The oxygen adsorption amount was 10 mL, the oxygen adsorption amount per unit contact area was 0.016 mL/cm2, and the oxygen adsorption amount per unit weight was 0.04 mL/g after three hours from sealing.
In this embodiment, although gas adsorption was explained as an example, the removal of a toxic substance from liquids such as water containing a toxic substance, like sewage treatment is also possible.
The present invention has applicability in the field of heat conducting sheet, heat conducting board and heat conducting paint, in addition, in the field which adsorbs specific gas from various gases including toxic gases, or removes a toxic substance from a liquid containing a toxic substance.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010-014167 | Jan 2010 | JP | national |
| 2010-053268 | Mar 2010 | JP | national |
| 2010-075350 | Mar 2010 | JP | national |
This is a National Phase Application in the United States of International Patent Application No. PCT/JP2011/051268 filed Jan. 25, 2011, which claims priority on Japanese Patent Application JP 2010-014167, filed Jan. 26, 2010, JP 2010-053268, filed Mar. 10, 2010 and JP 2010-075350, filed Mar. 29, 2010. The entire disclosures of the above patent applications are hereby incorporated by reference.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2011/051268 | 1/25/2011 | WO | 00 | 7/26/2012 |
