JP2012118037A - Functional porous body, method for manufacturing the same, and method for evaluating functional porous body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functional porous body with which a content state of a functionality giving component is easily determined by non-destruction even when an element which generates fluorescent X-rays by excitation is not contained in the functionality giving component.SOLUTION: A functional porous body is constituted by making the porous body simultaneously contain a first component as a functionality giving component and a second component as a component for trace, in which the first component and the second component are mutually dissolved, or the second component is dissolved by a solvent simultaneously as the first component, an element which generates fluorescent X-rays by excitation is contained in the second component, the element which is contained in the second component is not contained in the first component, the element in the second component is with the content which can be detected by fluorescent X-ray analysis from the surface of the functional porous body and the second component is contained in the functional porous body.

Description

  The present invention relates to an impregnation technique for impregnating a functional body with a porous material such as a cast product, a sintered product, a plastic molded product, paper, wood, a thermal spray, a stone, a particle board, and an inorganic porous plate, The present invention relates to a functional porous body that can easily evaluate the content of a functional component, a method for producing the same, and a method for evaluating the content of a functional component in such a functional porous material.

  The impregnation processing technique is a technique for combining the above porous body and a functional component, and is applied in a wide range of industries.

  However, since the amount of the functional component to be impregnated is often a very small amount, there is no effective method for measuring the amount of the functional component to be impregnated. In general, the imparted function is evaluated by the impregnation effect by performing nondestructive inspection or sampling destructive inspection.

  In many cases, there is no appearance change or significant weight change before and after the impregnation treatment. In this case, since the presence or absence of the impregnation treatment itself cannot be easily determined, the untreated product causes a serious problem. There is a possibility.

  On the other hand, among the porous bodies, the sintered body, paper, wood, food, and the like have a significant weight change due to the impregnation process, but these pores are often unevenly distributed. However, there is a case in which there is no method for examining the partial impregnation distribution of the function-imparting component for these, including destructive inspection.

  In addition, if there is a possibility that a part that has been impregnated with a functional component has a non-impregnated product in some parts after assembly, the impregnation process can be performed without disassembling. If the presence / absence can be determined, the inspection cost can be greatly reduced, but there is no such method at present.

  In addition, when the content of the functional component is decreased or may decrease due to the secular change of the impregnated member, the cost of destructive inspection after removing the member is increased. There is a need for a technique that enables measurement of the content without work, but there is no such method at present.

  Here, in the technique described in Patent Document 1, before reusing waste wood, in order to determine whether or not a toxic CCA preservative is applied or impregnated on waste wood that is a test object, A method for analyzing the absorption characteristics of reflected light and fluorescence obtained by irradiating ultraviolet rays, visible light, and infrared light to an inspection object, and by radiating these electromagnetic waves is proposed, and the copper element contained in the CCA preservative is fluorescent. It has been suggested that it can be detected by X-rays.

  Patent Document 2 proposes a method for easily determining the presence or absence of application when a flame retardant is applied to a wood surface or the like at a construction site to make it flame retardant. That is, ammonium phosphate, which is the main component of the flame retardant, and calcium hydroxide contained in the detection reagent are chemically reacted to synthesize calcium phosphate, which is a phosphor substrate, and further divalent to trivalent rare earth elements and It is activated by adding a transition metal element to form a phosphor material. And although the specific method is not specified in Patent Document 2, these chemical reactions are performed on the surface of the wood, and then the fluorescent light is emitted by irradiating the test object with ultraviolet light. A method has been proposed in which a fluorescent image is recorded with a digital camera to determine whether or not a flame retardant is applied.

  However, the technique described in Patent Document 1 cannot be applied to a functional component that does not include an element that can be subjected to fluorescent X-ray analysis. There is a possibility of adhering or mixing.

  Further, the technique described in Patent Document 2 can cope with the determination of the presence or absence of adhesion due to the surface treatment of the functional component, but cannot check the impregnated product, and requires a very complicated process. It cannot be performed easily, and it cannot be applied to functional components other than phosphoric acid-based flame retardants, and it cannot be applied to judgments other than coating treatment on the surface. was there.

Japanese Patent No. 3739086 JP 2005-233721 A

  The present invention improves the above-mentioned conventional problems, that is, the functional porous body that can easily determine the content of the functional component-providing component inside the functional porous body, and can also partially determine if necessary. An object of the present invention is to provide a material, a method for producing the same, and a method for evaluating a functional porous material.

  In order to solve the above-described problems, the functional porous body of the present invention contains, as described in claim 1, a first component as a functional component and a second component as a trace component in the porous body at the same time. The first component and the second component are compatible with each other or the second component is dissolved in the solvent simultaneously with the first component, and the second component is excited. The element that generates fluorescent X-rays is contained, the element contained in the second component is not contained in the first component, and the element in the second component is the functional porous body. The functional porous body is characterized in that the second component is contained in the functional porous body in such a content that can be detected by fluorescent X-ray analysis from the surface.

  Moreover, the functional porous body of the present invention is the functional porous body according to claim 1, wherein the element is an element having an atomic number of 13 or more and 92 or less, as described in claim 2. And

  Moreover, the functional porous body of the present invention is the functional porous body according to claim 2, wherein the element is Ag, Al, Ba, Bi, Br, Ca, Ce, It is one selected from Cl, Co, Cr, Cu, Fe, I, K, Mn, Mo, Ni, P, S, Si, Sn, Sr, W, Ti, Zn, and Zr. To do.

  Moreover, the functional porous body of the present invention is the functional porous body according to claim 3, wherein the element is Ag, Bi, Br, Mo, Sn, Sr, W, It is one selected from Zn and Zr.

  The method for producing a functional porous body of the present invention is the functional porous according to claim 5, wherein the porous body contains the first component as the functionality-imparting component and the second component as the trace component simultaneously. The first component and the second component are compatible with each other or the second component is dissolved in a solvent simultaneously with the first component, and the second component is excited by the fluorescent X An element that generates a line, the element contained in the second component is not contained in the first component, and the element in the second component is from the surface of the functional porous body. A method for producing a functional porous body, comprising an impregnation step of incorporating the second component into the porous body at the same time as the first component with a content that can be detected by fluorescent X-ray analysis. is there.

  The functional porous body evaluation method of the present invention is the evaluation method of the impregnation state of the first component of the functional porous body according to claim 1, as described in claim 6, wherein the functionality The impregnation state of the first component into the functional porous body is evaluated by examining the impregnation state of the second component into the functional porous body by fluorescent X-ray analysis from the surface of the porous body. This is a method for evaluating a functional porous body.

  The functional porous body evaluation method of the present invention is the functional porous body evaluation method according to claim 6, in which the first component and the second component are impregnated as described in claim 7. And a pre-analysis step of performing a fluorescent X-ray analysis of the element in the porous body.

  According to the functional porous body of the present invention, even if the element that generates fluorescent X-rays by excitation is not contained in the functional component, it is easy to contain the functional component without destruction. Can be determined.

  According to the functional porous body of the present invention described in claim 2, it is possible to more easily and more reliably determine the containing state of the functional component by using a commercially available fluorescent X-ray analyzer.

  According to the functional porous body of the present invention as set forth in claim 3, it is possible to easily determine the content state of the functionality-imparting component in a non-destructive manner, while using a less toxic and cheaper trace component.

  According to the functional porous body of the present invention described in claim 3, it is possible to easily determine the containing state of the functional component at a deeper position of the functional porous body.

  According to the method for producing a functional porous body of the present invention, even if the element that generates fluorescent X-rays by excitation is not included in the functional component, the non-destructive functional component is contained. A functional porous body whose state can be determined can be produced.

  According to the method for evaluating a functional porous body of the present invention, even if the element that generates fluorescent X-rays by excitation is not included in the functionality-imparting component of the functional porous body, it is nondestructive. The content of the internal functional component can be determined.

  According to the method for evaluating a functional porous body according to claim 7, it is possible to more reliably determine the content state of the functional component.

FIG. 1 is a graph showing the examination results (spacer: filter paper) of the evaluation possibility in the sample depth direction. FIG. 2 is a graph showing the results of examination of the possibility of evaluation in the sample depth direction (spacer: Sugi sugi). FIG. 3 is a graph showing the examination result (spacer: cedar board) of the possibility of evaluation in the sample depth direction. FIG. 4 is a graph showing the examination result (spacer: cedar board) of the evaluation possibility in the sample depth direction. FIG. 5 is a graph showing the examination results of the possibility of evaluation in the sample depth direction (spacer: Sugi sugi impregnated with a function-imparting component). FIG. 6 is a graph showing the examination results of the possibility of evaluation in the sample depth direction (spacer: cedar board impregnated with a function-imparting component). FIG. 7 is a graph showing the examination results (spacer: aluminum plate) of the possibility of evaluation in the sample depth direction. FIG. 8 is a graph showing the results of a comparative test between the direct evaluation of the impregnation state of the functional component and the trace component and the evaluation according to the present invention. FIG. 9 is a graph showing the relationship between the impregnation amount of the function-imparting component and the detection strength of the monitor element by fluorescent X-ray analysis in Example 1. FIG. 10 is a graph showing the relationship between the impregnation amount of the functionality-imparting component and the detection intensity of the monitor element in the fluorescent X-ray analysis in Example 2. FIG. 11 is a graph showing the relationship between the impregnation amount of the function-imparting component and the intensity detected by the fluorescent X-ray analysis of the monitor element in Example 3. FIG. 12 is a graph showing the relationship between the amount of impregnation of wood with an incombustible agent and the calorific value measured by a cone calorimeter.

  In the functional porous body of the present invention, examples of the porous body serving as a base include a cast product, a sintered product, a plastic molded product, paper, wood, a thermal spray, a stone, a particle board, an inorganic porous plate, and the like. It is done.

  The functional component that is the first component may be an organic substance or an inorganic substance, and is a liquid that improves the porous body or a component that adds a function to the porous body. Or, water, various solvents, a mixed solution thereof, or a third component (such as a complex-type substance or a pH adjuster) for making the first component and / or the second component soluble as described later. A solubilizer (solubilizing agent) that is soluble in a liquid (in the present invention, these are collectively referred to as a “solvent”) can be used. Further, it may be a liquid or a solid that is compatible with the second component to form a uniform solution.

  The porous body by the above-described functional component is, for example, hermeticity, strength, electrical insulation, insect proofing / antiseptic, flame retardancy, pressure resistance, airtightness, electrical insulation, rust prevention, adhesiveness, water repellency. , Lubricity, workability, electromagnetic wave shielding properties, deodorizing properties, aromaticity, sound insulation properties, etc. are improved or imparted.

  The second component may be organic or inorganic, but is a liquid or solid that is compatible with the first component to form a uniform solution, or is dissolved in the solvent together with the first component to form a uniform solution. It must be a liquid or a solid that forms

  The second component contains an element that generates fluorescent X-rays upon excitation, and this element contained in the second component is not contained in the first component, and in the functional porous body. The content of the second component is such that an element that generates fluorescent X-rays by excitation in the second component can be detected from the surface of the functional porous body by fluorescent X-ray analysis. It is necessary.

  Here, in the case of a porous body to be used, particularly a porous body derived from a natural product such as wood or paper, an element that generates fluorescent X-rays may be contained in a trace amount or a considerable amount.

  At this time, depending on the type of the second component, an element that generates fluorescent X-rays by excitation in the second component (hereinafter also referred to as “monitor element”) itself is already in the porous body before the impregnation treatment. Alternatively, a case where a considerable amount is included is assumed.

  In this case, the presence of the monitor element in the second component that is included in the functional porous body by the impregnation treatment, based on the amount of the monitor element present in the porous body before the impregnation treatment. Is an amount detectable by fluorescent X-ray analysis from the surface of the functional porous body, that is, the fluorescent X-ray analysis from the surface of the functional porous body after impregnation with the monitor element in the second component By impregnating the porous material with the second component so that the content can be detected by the method, it is possible to eliminate the influence of the monitor element that was present in the porous material before the impregnation treatment. As described above, the effects of the present invention can be obtained.

  That is, the increase in the functional porous body of the monitor element due to the second component that is included in the functional porous body by the impregnation treatment is determined by fluorescent X-ray analysis from the surface of the functional porous body. The effect of the present invention cannot be obtained by impregnating the porous material with the second component in an amount less than detectable.

  Note that the amount of monitor element already present in the porous body before the impregnation treatment (detection intensity of fluorescent X-ray) is measured so that analysis can be performed easily and / or accurately (this process) Is referred to as “pre-analysis step”), and it is preferable to be able to compare with the amount of monitor element (detection intensity of fluorescent X-rays) in the functional porous material after the impregnation treatment.

  Since the content of monitor elements that can be detected by fluorescent X-ray analysis from the surface of the functional porous material differs depending on the type of monitor element used, the type of porous material used, etc. It is necessary to grasp.

  In general, the increase in the amount of the monitoring element in the porous body due to the impregnation of the second component into the porous body is the content of the monitoring element that can be detected by fluorescent X-ray analysis from the surface of the functional porous body. If it is 2 times or more, determination of the presence or absence of impregnation of the first component into the functional porous body is easy, and if it is 5 times or more, the amount of impregnation of the first component into the functional porous body is preferable. Since determination becomes easy, it is more preferable.

  Here, as the monitor element contained in the second component as the trace component, an element having an atomic number of 13 or more and 92 or less usually provides a fluorescent X-ray having a sufficiently high transition energy, so that surface analysis can be performed. It is possible to analyze not only the functional porous body but also a commercially available analyzer, and it is preferable that the elements are Ag, Al, Ba, Bi, Br, Ca, Ce, Cl, Co, Cr. , Cu, Fe, I, K, Mn, Mo, Ni, P, S, Si, Sn, Sr, W, Ti, Zn, and Zr have low toxicity, and further, monitor elements Is one selected from Ag, Bi, Br, Mo, Sn, Sr, W, Zn, and Zr, the state of impregnation from the surface of the functional porous body to a deep position can be examined.

  The second component (trace component) which is a compound containing such a monitor element may be an organic substance or an inorganic substance, but is compatible with the first component (liquid) uniformly, or The first component (which may be either liquid or solid) must be uniformly dissolved in the solvent in which it is dissolved.

  When water is used as the solvent of the impregnation solution used in the impregnation step described later, various complex-type substances can be used in combination to dissolve the first component and / or the second component.

  When an organic solvent is used as the solvent for the impregnation solution, a uniform solution can be obtained by using, as the second component, an octylic acid metal salt, a metal soap, an acetylacetone metal complex, or a salicylic acid metal salt containing a monitor element. be able to.

  In the case of using a solvent, it is necessary to select a solvent that does not impair the first component and the second component, simultaneously and uniformly, and further does not impair the porous body. A low and / or low molecular weight is preferable because impregnation is facilitated.

The functional porous body of the present invention can be obtained, for example, as follows.
<Preparation of impregnation solution>
First, an impregnation solution is prepared. At this time, a solution in which the second component is dissolved in the first component or a solution having the first component and the second component as solutes using the above-described solvent is prepared.

  Here, the concentration of the first component and the concentration of the second component in the impregnation solution are determined in consideration of the balance between the two. That is, the concentration of the first component is a concentration that can realize the content necessary for imparting functionality, and the concentration of the second component is the concentration of the monitor element in the second component in the functional porous body that is the product. Determine the amount so that the amount is not less than a concentration that can be detected by fluorescent X-ray analysis from other surfaces of the functional porous material and is suitable for fluorescent X-ray analysis. .

<Porous body pretreatment>
If necessary, the porous body is pretreated.
What impairs the function of each component of the above impregnation solution present on the surface or inside of the porous body to be used, dilutes the impregnation solution, blocks the pores of the porous body, occupies the inside of the pores In order to sufficiently remove oil or oil, various washing treatments and heat treatments are carried out alone or in combination.

  In addition, when wood is contained in the porous body, a desired functional porous body is obtained by a process of opening a sealing hole in the porous body by irradiating microwaves or performing a steam treatment. It can be changed to a state suitable for the impregnation treatment.

<Impregnation treatment>
As the impregnation treatment, a commonly performed impregnation treatment is performed alone or in combination.

  Such treatment methods include 1) a vacuum impregnation method, 2) a vacuum heat impregnation method, and 3) heating and cooling utilizing a pressure reducing action generated inside the pores of the porous body by cooling the porous body after heating. Impregnation method, or 4) pressure from the impregnating solution generated when the porous body is immersed in the impregnating solution and from the impregnating solution generated when the porous body is brought into contact with the liquid existing in the pores of the porous body. An immersion method using the principle of movement of components can be mentioned.

  In both of the vacuum impregnation method and the vacuum heating impregnation method, the pressure reduction is performed while immersing the porous body in the impregnation solution (wet vacuum), or the pressure reduction is completed or the impregnation solution is contacted with the porous body while the pressure is reduced. (Driving) is possible, and is determined in consideration of the properties of the impregnation solution and the porous body, the required performance of the functional porous body, the cost, and the like.

<Post-processing>
If necessary, the surface of the obtained functional porous body and the residue inside the pores are removed. At this time, various types of cleaning with water, a cleaning agent, or a solvent, wiping, centrifugation, air blowing, or drying treatment (room temperature, warming) are performed alone or in combination. Depending on the functionality-imparting component used, a heat curing treatment is performed. These treatments are further performed in air or in an atmosphere of an inert gas or a reactive gas as necessary.

<Evaluation of impregnation state>
For the evaluation of the impregnation state, fluorescent X-ray analysis is performed on the surface of the porous body containing the first component and the second component simultaneously as described above under conditions suitable for detection of the monitor element.

<Examples of application fields of the present invention>
Incombustibility or incombustibility of wood is one of the important application fields in the impregnation field.
FIG. 12 is a graph showing the relationship between the amount of impregnation when wood is impregnated with a flame retardant as a functional component and the result of measuring the total calorific value for 20 minutes using a corn calorimeter. is there.

Each impregnation amount is around 50 kg / m ³ to the left in the graph, and it is 90 kg / m ³ near at 37 mJ / m ² and around 60 mJ / m ² total calorific value of the measurement results of the vicinity. In these results, since the wood ignited during the measurement, the total calorific value is large and the measurement error is also large. However, with respect to other measurement data, the calorific value is 10 MJ / m ² or less and is stable. If the impregnation amount of this incombustible agent exceeds approximately 300 kg / m ² , it satisfies the standard value of 8 MJ / m ² or less, which is the standard for incombustible materials established by the Ministry of Land, Infrastructure, Transport and Tourism, but it is commensurate with an increase in impregnation amount beyond that. There was no decrease in the calorific value.

Therefore, in this field, the present invention can be applied to quality control if the amount of impregnation can be detected in the range of ± 100 kg / m ³ when the center value of the amount of impregnation is 400 kg / m ^3. Or, if the amount of impregnation can be detected with an accuracy higher than ± 100 kg / m ³ , it is possible to reduce the cost by preventing the occurrence of over-spec products with an amount of impregnation exceeding 400 kg / m ^3. I understand that it is possible.

Examples of the present invention will be specifically described below.
Regarding the detection intensity of fluorescent X-rays, a handy type fluorescent X-ray analyzer commercially available from Rigaku Corporation, Thermo-Fisher Scientific Thermo-Niton (XL3t-900S-M) (hereinafter, “X-ray fluorescence analyzer”) The measurement reference plane was brought into contact with the surface of the sample and set according to the specifications of the instrument according to the monitor element to be measured.

<Basic study (Part 1) Solubleness of second component>
The monitor elements used for studying and confirming the effectiveness of the present invention are the 23 types shown in Table 1 and the 3 types of elements shown in Table 2, and the trace components obtained as compounds having these monitor elements were used. Also shown.

  An aqueous solution was prepared from each of these 26 types of trace components. In this case, when ethylenediaminetetraacetic acid (EDTA) is used as a complex material, “EDTA” is indicated, and when an aqueous solution is used without using ethylenediaminetetraacetic acid, “−” is indicated in Tables 1 and 2. .

  Each of the aqueous solutions prepared above was visually observed, but all were uniformly dissolved without precipitation or partial color change.

  Furthermore, Tables 1 and 2 show the emission lines used in the case of performing X-ray fluorescence analysis with the X-ray fluorescence analyzer used in this specification and the theoretical values of transition energy for each monitor element. Also shown together.

<Second basic study Examination of possibility of evaluation in sample depth direction>
The investigation was conducted to determine how deep the fluorescent X-ray analysis is possible with respect to the thickness of the functional porous material depending on the type of the monitor element. Since the depth that can be measured according to the transition energy of fluorescent X-rays generated from each element by excitation is assumed to be deep, the fluorescent X-ray absorber (spacer) made of three kinds of porous bodies having different thicknesses A cedar board with a thickness of about 2 mm, a cedar tree with a thickness of about 200 μm, and a filter paper with a thickness of about 35 μm were prepared. These three types of spacers are untreated without impregnation.

  Among the trace elements for elements shown in Table 1, 16 types of trace component aqueous solutions excluding trace elements for each element of Mo, Zr, Zn, Br, and Ce (in combination with EDTA as described above) Yes, the same shall apply hereinafter) were immersed in filter paper and dried to prepare test specimens each containing a monitor element.

  On these specimens, one of the above three types of spacers (each of filter paper, warp wood, and board) is stacked one by one of the same type, and each time a stack is made, a fluorescent X-ray analyzer is placed on top of it. X-ray fluorescence analysis was performed.

  Moreover, as a porous body containing the monitor elements of each element of Mo, Zr, and Zn, each of the aqueous solution of the trace component of these three elements is not a filter paper but a cedar wood having a 10 cm square and a thickness of 11 mm. Then, the specimen was fabricated by being immersed by vacuum pressure impregnation.

Regarding the detected intensity of fluorescent X-ray, the same point was measured three times and the average was taken.
FIG. 1 shows the results when filter paper is used as a spacer, FIG. 2 shows the results when cedar trees are used, and FIG. 3 shows the results when cedar boards are used.

  These figures are the results of the test specimens made of two types of porous bodies, filter paper and wood. In both cases, the detected intensity of fluorescent X-rays measured without a spacer is set to 1000, and through the spacer. By relatively indicating the detected intensity of fluorescent X-rays when measured, the effects of the difference in detected intensity scale for each measurement element depending on the type of specimen and the specifications of the fluorescent X-ray analyzer are eliminated. Yes.

  From FIG. 1, it can be seen that when Mg is a monitor element, it is impossible to put out the filter paper at the point of 69 μm overlap. With Al, measurement is possible up to 35 μm. It can be seen that other elements can be measured up to about 100 μm in the filter paper depth direction, and Cl can be analyzed up to a depth of about 150 μm (presence can be confirmed). Further, it was found that these measurable depths are deeper as the transition energy is higher.

  In FIG. 2, the monitoring elements when using cedar trees as spacers are the measurement results of Cu, Fe, Mn, Cr, Ti, Ca, and K. It can be seen that there is a measurable depth of about 500 μm to 1000 μm for each element of K, Ca, and Ti, about 1500 μm for Cr, about 2000 μm to 2500 μm for Mn and Fe, and about 3000 μm for Cu. The result is that the higher the is, the deeper it is.

  FIG. 3 shows the measurement results of monitor elements of W, Sn, Ag, Mo, Zr, Sr, Bi, and Zn when cedar boards are used as spacers. From this figure, it was found that there is a measurable depth of approximately 5 mm for Sn, approximately 10 mm for Zn, W, and Bi, and approximately 17 mm for Ag, Zr, Sr, and Mo.

  Among these monitor elements, W has the highest transition energy, but the relationship between the transition energy and the measurable depth is not necessarily maintained in FIG. Specifically, the measurement depths of the W, Sn, and Ag monitor elements are out of the order of transition energy. In particular, both W and Sn elements have significantly lower measurable depth ranks in the order of transition energy order. This is thought to be due to the problem of specifications of the fluorescent X-ray analyzer used. From these results, it is understood that it is necessary to carry out a detailed preliminary examination depending on the monitor element to be used.

  Further, for the two elements of Ce and Br, only the evaluation using the cedar board whose result is shown in FIG. 2 as a spacer was performed. The results are shown in FIG.

  From FIG. 4, it is understood that a measurable depth of about 4 mm can be obtained with Ce and about 7 mm with Br.

  In addition, about the three elements shown in Table 2, when the detection test was done without the spacer about the test body dried after impregnating the filter paper with aqueous solution, it was confirmed that these elements are detected.

<Third basic study Examination of effects of intermediary of functional ingredients>
FIG. 5 shows that a functional imparting component is impregnated into a cedar tree using a 46% by weight aqueous solution (a flame retardant) of ammonium borate as a functional component. This is a result of X-ray fluorescence analysis of a test specimen having Zn, Cu, Fe, Mn, Cr, Ti, Ca, or K as each monitor element.

  These eight kinds of elements are obtained by adding Zn having a slightly higher transition energy to the seven elements used in the experiment in FIG. 2 using untreated trees as spacers.

  In the result shown in FIG. 5, the measurable depth is generally shallower than the result shown in FIG. 2 because the absorption effect on the fluorescent X-ray of the spacer is increased by the interposition of the functional component. It is. However, it is possible to detect monitor elements that exist deeper than the surface, and it is confirmed that monitor elements present deeper than the surface can be detected even in wood containing flame retardants. And the possibility of quantitative analysis was confirmed.

  Of the monitor elements, Ti, Ca, and K elements, in this experiment, only one spacer was introduced, the detected value was zero, and the measurable depth was approximately 200 μm. It is confirmed that the measurable depth of other monitor elements is approximately 700 μm for Cr, approximately 800 μm to 1000 μm for Mn and Fe, and approximately 1500 μm for the monitor elements of Cu and Zn.

  FIG. 6 shows a spacer obtained by impregnating a cedar board with a 46% by weight aqueous solution of ammonium borate phosphate as described above so that the weight of the cedar board is 137, and W, Sn, Ag, It is the result of having performed X-ray fluorescence analysis of each monitor element about the test body which respectively contains Mo, Zr, Sr, Bi, or Zn as a trace element.

  From FIG. 6, the measurable depth is about 2 to 3 mm for W and Zn, about 3 to 4 mm for Sn, about 5 mm for Bi, and about 7 to 11 mm for Sr, Zr, Mo, and Ag. It was confirmed.

  In the result shown in FIG. 6, the measurable depth is generally shallower than the result shown in FIG. 3, which is the same as the result of the comparison between FIG. 2 and FIG. This is because the effect of the spacer on the absorption of fluorescent X-rays has been increased by the inclusion of. However, it is possible to detect monitor elements that exist deeper than the surface, and it is confirmed that monitor elements present deeper than the surface can be detected even in wood containing flame retardants. And the possibility of quantitative analysis was confirmed.

<Fourth basic study Study with aluminum spacer>
FIG. 7 shows the measurement results of Mo, Zr, and Sr monitor elements when a 1 mm thick aluminum plate is used as the spacer. In the case of the aluminum layer, it was confirmed that the measurable depth of Sr was approximately 1 mm, that of Zr was approximately 1 mm, and that of Mo was approximately 2 mm. Thus, it was confirmed that it is possible to detect a monitor element existing at a position deeper than the surface even when a metal is present, and the possibility of quantitative analysis was confirmed.

<Summary of the above basic study results>
From the above experiments, when using an X-ray fluorescence spectrometer, 18 elements, with the exception of W, Ag, and Sn, among 21 elements shown in Table 1, were measured as the transition energy was higher. The tendency that the possible depth is deep was confirmed. In particular, the transition energy of the Kα1 line of W is the highest among the elements subjected to the fluorescent X-ray analysis, and is more than twice the energy of Sn having the second highest transition energy. Further, when compared with Mo having the highest transition energy among the above 18 kinds of elements, the multiple is about 3.4 times.

  Despite this tendency, the measurable depth of W is significantly shallower than that of the Mo element. The W, Ag, and Sn elements, which are exceptions from the above trend, are the three elements with the highest transition energy among the 23 types of elements shown in Table 1, and are the most difficult to excite the Kα1 line at the same time. Therefore, by using an apparatus having specifications more suitable for fluorescent X-ray analysis of these elements, there is a high possibility that a measurable depth deeper than the above 20 elements can be obtained, and the measurable depth increases. There is a high possibility that the industrial application fields can be expanded from the viewpoint.

  In addition, when a test body having Cr, Fe, and Mn is used as a monitor element to be used in combination with the phosphoric acid aqueous solution of ammonium borate used above, the measurable depth is within a range of several hundred μm to 2 mm. I understood. Similarly, the measurable depth of each monitor element of Zn, Bi, Sr, Ar, Mo, Ag, Sn, and W was about 2 mm to 11 mm.

  Moreover, from the above results, it is suggested that if the atomic number is 13 or more among the monitor elements used, it is possible to detect the monitor element existing at a position deeper than the surface and to perform quantitative analysis. It was.

<Fifth basic study Impregnation state of functional component and trace component>
In the present invention, in order to indirectly determine the impregnation state of the functional component by using fluorescent X-ray analysis of the monitor element in the trace component, these two kinds of components are impregnated at any part impregnated in the porous body. It is necessary that the abundance ratios of the components are not significantly different.

  Here, an experiment was conducted using an impregnation solution (combined with EDTA) in which sodium molybdate was dissolved as a trace component in a 46 wt% ammonium phosphate borate aqueous solution.

  Using this impregnation solution, a cedar board having a length of 800 mm, a width of 100 mm, and a thickness of 45 mm was impregnated by a vacuum pressure impregnation method, and then dried to obtain a sample of a functional porous body.

  The sample was cut seven times on a plane orthogonal to the longitudinal direction so that the width was 5 mm from one end to the other end in the longitudinal direction to obtain 7 sections. Of these, the evaluation pieces 1, 2,.

  The center point of the cut surface close to the end of the six evaluation pieces having a length of 100 mm, a width of 45 mm, and a thickness of 5 mm, and two distances of 2.5 cm from the center point in the width direction of the evaluation piece. About the point, the fluorescent X ray analysis about phosphorus (P) and molybdenum (Mo) was performed using the fluorescent X ray analyzer. In addition, the measurement was performed 3 times each and the average value was calculated | required. The results are shown in FIG.

  The P / Mo values shown in FIG. 8 are the values obtained when the average value of the three points on each of the first to sixth evaluation pieces is 1000, and the average value of the three points on the first plate is 1000. The detection value of phosphorus and the detection value of molybdenum are values obtained by dividing the detection strength of phosphorus by the detection strength of molybdenum.

  From FIG. 8, it can be seen that the ratio between the functional component and the tracing component is kept uniform with respect to the longitudinal direction of the sample, and there is no significant difference in the ratio of the two in the measurement location.

<Example 1>
Cylindrical aluminum sintered body with outer diameter of 25.5mm, inner diameter of 19.1mm, and length of 25.5mm (3 types of porosity: 10%, 15%, 20%, 3 each) is porous As a body, vacuum pressure impregnation treatment using an impregnation solution in which zirconium octylate as a trace component is dissolved in a liquid acrylic functional component (sealing agent) so as to have a weight ratio of 100 to 0.1 Went.

  Next, after sufficiently removing the impregnation solution adhering to the surface of the porous body in the washing step, the functional component and the trace impregnated in the pores of the aluminum sintered body by the immersion hardening step of immersing in warm water The ingredients were immobilized.

  For the functional porous material thus prepared, the amount of impregnation of functional components measured by comparing the weight before and after impregnation (each average value of three specimens) and zirconium which is a monitor element by fluorescent X-ray analysis Of X-ray fluorescence detection intensity (in X-ray fluorescence at Kα1) was measured (for one functional porous body, after measuring the central part of the side and 7 mm position from both ends, these measurements were taken) (Each point is an average of the values measured at a total of 27 locations with 3 functional porous bodies manufactured under the same conditions, 2 locations at 3 positions symmetrical about the axis of the cylinder, 9 locations in total) The relationship with is shown in FIG.

  From these data showing a high correlation, it is understood from FIG. 9 that it is possible to measure the content of the function-imparting component with very high accuracy according to the evaluation method of the present invention.

<Example 2>
Similar to Example 1, except that an impregnation solution prepared using strontium salicylate instead of zirconium octylate as a trace component was used.

  With respect to the functional porous body thus prepared, the impregnation amount of the functional component measured by comparing the weight before and after the impregnation, and the fluorescent X-ray (Kα1) of zirconium which is a monitor element by the fluorescent X-ray analysis FIG. 10 shows the relationship with the results obtained when the detection intensity of fluorescent X-rays was measured.

  From FIG. 10, it is understood that according to the evaluation method of the present invention, it is possible to measure the content of the functionality-imparting component with very high accuracy.

<Example 3>
Experiments were conducted using an impregnating solution in which a 46% by weight aqueous solution of ammonium borate phosphate as a component for imparting functionality and sodium molybdate as a component for tracing were dissolved in a weight ratio of 100: 0.6, respectively.

  A plurality of planted cedar boards cut into a rectangular shape with an upper and lower surfaces of 10 cm × 10 cm and a thickness of 12 mm were impregnated with the impregnation solution using a vacuum pressure impregnation method to obtain a functional porous body. At this time, the amount of impregnation was calculated | required by investigating the change of the weight before and after the impregnation when it dried until it became a constant weight at 90 degreeC.

  In the above, four types of functional porous bodies having different impregnation amounts were prepared. With respect to each of these functional porous bodies, a square of 8 cm × 8 cm is drawn inward by 1 cm from each side of the upper and lower surfaces of the plate-like sample, and at intervals of 2 cm in parallel to two orthogonal sides of the square. The detection strength of molybdenum, which is a monitor element, was measured with a fluorescent X-ray analyzer at a total of 50 intersecting points generated when three straight lines were drawn, and the measured values were averaged. The relationship between the impregnation amount of the functional component at this time and the detected strength of molybdenum is shown in FIG.

  From FIG. 11, it is understood that the content of the component for imparting functionality can be measured with very high accuracy from these data showing high correlation according to the evaluation method of the present invention.

Claims (7)

A functional porous body containing a first component as a functional component and a second component as a tracing component in the porous body at the same time,
A) The first component and the second component are compatible with each other or the second component is dissolved in the solvent simultaneously with the first component,
B) The second component contains an element that generates fluorescent X-rays upon excitation,
C) The element contained in the second component is not contained in the first component, and
2) The second component is contained in the functional porous body in such a content that the element in the second component can be detected by fluorescent X-ray analysis from the surface of the functional porous body. A functional porous body characterized by   The functional porous body according to claim 1, wherein the element is an element having an atomic number of 13 or more and 92 or less.   The elements are Ag, Al, Ba, Bi, Br, Ca, Ce, Cl, Co, Cr, Cu, Fe, I, K, Mn, Mo, Ni, P, S, Si, Sn, Sr, W, The functional porous body according to claim 2, wherein the functional porous body is one selected from Ti, Zn, and Zr.   The functional porous body according to claim 3, wherein the element is one selected from Ag, Bi, Br, Mo, Sn, Sr, W, Zn, and Zr. A method for producing a functional porous body, wherein the porous body simultaneously contains a first component as a functional component and a second component as a trace component,
The first component and the second component are compatible with each other or the second component is dissolved in a solvent simultaneously with the first component,
The second component contains an element that generates fluorescent X-rays upon excitation,
The element contained in the second component is not contained in the first component, and
The functional porous body at the same time as the first component and the second component in such a content that the element in the second component can be detected by fluorescent X-ray analysis from the surface of the functional porous body The manufacturing method of the functional porous body characterized by having the impregnation process made to contain in.   The method for evaluating the impregnation state of the first component of the functional porous body according to claim 1, wherein the functional porous body is subjected to X-ray fluorescence analysis from the surface of the functional porous body to the functional porous body. A method for evaluating a functional porous body, wherein the state of impregnation of the first component into the functional porous body is evaluated by examining the impregnation state of two components.   The functional porous material according to claim 5, further comprising a pre-analysis step of performing fluorescent X-ray analysis of the element in the porous material before impregnation with the first component and the second component. Body evaluation method.

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