KR20150146094A - Method of identifying cements using isotope ratio mass spectrometer - Google Patents

Abstract

A method for identifying cement of the present invention comprises the steps of: (a) pretreating a sample including cement; (b) collecting data of the sample by component analysis and isotope ratio mass spectrometry; and (c) outputting information of the cement included in the sample after determining whether the collected data of the sample is same to preset data of a library. By using the identifying method, it is possible to accurately and rapidly identify which cement is included in an unknown sample.

Description

METHOD OF IDENTIFYING CEMENTS USING ISOTOPE RATIO MASS SPECTROMETER < RTI ID = 0.0 >

The present invention relates to a method of identifying a cement which obtains data on cement using a spectrophotometer for the in-line consumptive mass spectrometry, builds a library, and obtains information on unknown cement through the library.

In general, a mass spectrometer uses a single quadrupole, ion trap or time-of-flight mass spectrometer, but these mass spectrometers can be used for detection But does not provide the sensitivity and precision that can consistently distinguish the small differences in the isotope abundance. However, it is a mass spectrometer developed to precisely measure the isotope ratio (Isotope Ratio).

The Isotope Ratio Mass Spectrometer (IRMS) is one of a variety of mass spectrometers that can accurately measure the relative amounts of isotopes in a given sample.

In recent years, isotope mass spectrometry has been very useful for studying the origin and circulation of materials, and it has been widely used for crimes such as the inclusion of chemically similar components in medicines, explosives, fibers, paints, Research is being actively conducted in various fields such as investigation of authenticity and identification of origin of food, honey, and similar medicines in the investigation field, tracking of the source of oil pollution, monitoring of the atmospheric environment and water circulation, and determination of origin of foods and medicines in the atmosphere.

On the other hand, cement is an adhesive to connect sand or gravel. When it reacts with water, it causes hardening hydration reaction by generating a substance called CSH gel (C ₃ S ₂ H ₈ , Calcium Silicate Hydrate) Is called cement paste. When fine aggregate (sand) is added, it is called mortar, and when coarse aggregate is added, it is called concrete.

The main components of commonly used Portland cement are silica (SiO ₂ ), aluminum oxide (AlO ₃ ), iron oxide (Fe ₂ O ₃ ) and lime (CaO) A clinker is used as a powder and is not added other than gypsum (CaSO ₄ .2H ₂ O).

Limestone and clay are most commonly used in cement raw materials and iron is used to reduce the melting point of raw materials when cement is sintered. Gypsum is used for controlling curing time of cement by 2 ~ 3% use.

On the other hand, the amount of municipal waste generated in Korea is on an increasing trend every year. In particular, 49.1% in 2008 is large enough to occupy construction waste. Construction wastes can be recycled as wood, glass, steel, concrete, aggregate and so on.

However, incineration is more than 2.5 times more expensive than incineration of incineration materials such as wood, glass, etc., and the waste to be incinerated is illegally dumped into the landfill. In addition, small-scale builders are often accused of illegally landing industrial waste such as waste concrete and waste bricks for reasons of cost, or throwing them in the rare places of humanity. It is therefore often necessary to identify where these sources of construction waste are located.

In addition, evidence of various types of cement transferred to people and objects during the crime scene is received, and these cement evidence can be used to enhance the value of the evidence and investigation information during the investigation. The evidence of cement is analyzed by the physical and chemical composition of the cement as well as the identity and the comparative test, so that the information and source of the cement type and the manufacturer are obtained and the origin of the bricks used as the killing and injury tool is checked. And identity with bricks, it becomes possible to use it as a place of crime and as evidence of corruption.

In other words, there is a need for an analysis method to confirm the identity of the illegal construction waste, the source of the cement related goods such as the brick, which is the crime proof item, and the construction site item.

In addition, various kinds of cement which are posed to people and objects during the crime scene can be collected as evidence of crime traces and can be used to raise the value of emotion and evidence as evidence in the investigation process. By measuring the consumption of cement for these cement witnesses, it is possible to identify the origin and type of cement, the manufacturer and source of the cement, identify the manufacturer and source of the cement and bricks used as killer and injuries, By identifying the identity of a brick, it becomes possible to use it as a place of crime and as organic evidence of the body.

There is a need for analytical methods to identify the source of illegal construction waste, cement related items such as bricks, which are crime proof items, and whether they are identical with construction site items.

( ² H / ¹ H), carbon ( ¹³ C / ¹² C), and nitrogen ( ¹⁵ N / ¹⁴ N) in the cement were measured using an isothermal analytical spectrometer (IRMS) ), Oxygen ( ¹⁸ O / ¹⁶ O), carbon monoxide ( ¹³ C ¹⁸ O / ¹² C ¹⁶ O) and sulfur ( ³⁴ S / ³² S) The development of differentiation methods has been required. However, there are cases in which it is difficult to accurately classify the types of cement due to various types of additives and impurities (or organic substances) blended into cement of various types of manufacturers. Therefore, there is a need to study the characteristics of cement materials through the rapid and accurate measurement of isotope consumption in cement and establishment of comparative emotion techniques.

1. Carbon isotope stratigraphy using carbonate cements in the triassic sherwood standstone group: Corrib Field, West of Ireland, Susanne Schmid, Richanr H. Worden, Quentin J. Fisher, Chemical Geology, 225 (2006), 137-155. 2. Discrimination of Korea beef of other origin by stable isotope measurements, Micha Horacek, Ji-Sook Min, Food Chemistry, 121 (2010), 517-520.

The object of the present invention is to provide a method of identifying an unknown cement sample in illegal dumping or crime scene, and collecting and classifying the data of the cement sample using the composition analyzing apparatus and the isotope consumption mass spectrometer, And to provide a method of detecting cement which obtains information on an unknown cement sample through the construction of a library containing the cement sample.

The method of detecting cement according to an embodiment of the present invention comprises the steps of: (a) pre-treating a sample containing cement; (b) collecting data on the sample by a component analysis method and an in-process mass spectrometry method; And (c) determining whether the equivalence condition is satisfied between data of the collected sample and data of a library constructed in advance, and outputting cement information included in the sample.

The collected data and the data of the library include isotope content data for each constituent element per unit weight of the sample and isotope consumption data of the sample.

The isotope consumption data includes any one selected from the group consisting of measured value data of the in-house consumption, corrected delta value data of the measured value data, and combinations thereof.

The pretreatment of the step (a) comprises: (a-1) mixing and crushing a sample containing cement to form a powder; And (a-2) passing the powder through a sieve of 200 mesh or less.

Wherein the step (b) comprises the steps of: analyzing constituent elements of the sample as a sample in the gas phase by the component analysis method, and collecting isotope content data for each constituent element per unit weight of the sample; And collecting isotonic consumption data of the sample by the isotope consumption mass spectrometry method.

The gaseous sample may include any one selected from the group consisting of hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide, and combinations thereof.

The method for constructing the library of step (c) comprises the steps of: analyzing constituent elements of the sample while converting the sample into a gas to form a gas phase sample by a component analysis method; and analyzing isotopes Wherein the content data is collected; The isotope consumption of the gas phase sample is analyzed by the isocratic consumption mass spectrometry method, and the isotope consumption data of the sample is collected; And statistical principal component analysis, the collected data is classified and stored in a library, and the sample may be a sample of cement.

Whether or not the equivalence condition of the step (c) is satisfied can be determined by comparing the data of the library, the data of isotope content for each constituent element per unit weight of the sample, the isotope consumption data of the sample, Similarity with; The distributional similarity of the data classified by the statistical principal component analysis using the above content data and the same consumption data as the index component; Or similarity due to a combination of these.

If the data collected in step (b) does not satisfy the equivalence condition with the data in the library of step (c), the collected data may be stored in the library.

The isocratic consumption data is selected from the group consisting of ² H / ¹ H, ¹³ C / ¹² C, ¹⁵ N / ¹⁴ N, ¹⁸ O / ¹⁶ O, ³⁴ S / ³² S, ⁴⁸ Ca / ⁴⁶ Ca, And may include any one of them.

The delta value data can be corrected by the following equation:

[Equation 1]

^a R δ (‰) = ((R ^a / R ^b) _samp - (R ^a / R ^b) _std) / ((R ^a / R ^b) _std) × 1000

Wherein R is any one selected from the group consisting of H, C, N, O, S, CO and Ca, a is the mass number of the heavy isotope of R, b is the mass number of the light isotope of R, (R / R) _samp is the _isotope consumption of the sample, and (R / R) _std is the standard-isocratic consumption of the reference material as defined by the International Atomic Energy Agency (IAEA).

The reference material may include any one selected from the group consisting of IAEA-CH ₆ , IAEA-600 caffeine, urea, and combinations thereof.

The apparatus used for the component analysis may be any one selected from the group consisting of elemental analysis, gas chromatography, liquid chromatography, thermogravimetric analysis, and combinations thereof. . ≪ / RTI >

The collection of the data may be performed three or more times and the average value thereof may be used.

Data of the sample, silica (SiO _2), aluminum oxide (Al ₂ O _3), iron oxide (Fe ₂ O _3), lime (CaO), magnesium oxide (MgO), sulfur trioxide (SO _3), potassium oxide (K ₂ O), MnO ₂ , TiO ₂ , Na ₂ O, P ₂ O ₅ , Na ₂ O ₃ , CaSO ₄ , calcium carbonate (CaCO _3), calcium hydroxide (Ca (OH) _2), for example, Ely mite _{(Ye`elimite, Ca 3 Al 6 O} 12 · CaSO 4), light brown millet ^{(Brown millerite, Ca (AlFe 3} +) 2 O ₅₎ Goto Olivine (Forsterite, Mg ₂ SiO _4), Los tight _{(Rostite, Al (SO 4)} (OH) · 5H 2 O), ettringite _{(ettringite, Ca 6 Al 2 (} SO 4) 3 (OH ) ₁₂ · 26H ₂ O), calcium silicate (3CaO · SiO ₂ ), calcium silicate (2CaO · SiO ₂ ), calcium aluminate (3CaO · Al ₂ O ₃ ) _{(4CaO · Al 2 O 3 ·} Fe 2 O 3) based compound, gypsum _{(CaSO 4 · 2H 2 O)} , oxidizing (calcium magnesium aluminum) silicate (calcium magnesium aluminum silicate oxide), acid Calcium Iron Oxide (Ca ₄ Fe ₉ O ₁₇ ), and combinations thereof.

The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

As used herein, the terms "comprise", "having", and the like are used to specify that there is a stated feature, number, step, component, or combination thereof, Does not preclude the presence or addition of one or more other features, steps, components, or combinations thereof.

As used herein, the singular and plural representations are not to be construed as limiting the number of materials for a particular material, but may refer to one particular material or to a group of specific materials.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

The present invention provides a method of detecting cement, and a method of detecting cement will be described in detail below.

The method of detecting cement according to an embodiment of the present invention comprises the steps of: (a) pre-treating a sample containing cement; (b) collecting data on the sample by a component analysis method and an in-process mass spectrometry method; And (c) determining whether or not an equivalence condition is satisfied between data of the collected sample and data of a library constructed in advance, and outputting information of the cement contained in the sample.

Wherein the collected data and the data of the library include data on the isotope content of each constituent element per unit weight of the sample and the same consumption data of the sample, , Delta value data in which the measured value data is corrected, and combinations thereof.

The isotope content data for each constituent element per unit weight of the sample is calculated as the ratio of the height or intensity to the corresponding element appearing on the apparatus and the weight of the sample when each element is analyzed by the composition analyzer Lt; / RTI >

The step (a) may be a step of preprocessing the sample containing cement so as to be suitable for data collection and information analysis performed subsequently. The pretreatment may include (a-1) mixing and crushing a target sample containing cement to form a powder; And (a-2) passing the powder through a sieve of 200 mesh or less.

When the sample is pretreated as described above, since the materials contained in the sample are uniformly distributed and the powder may be taken at any point, the composition of the powder may be the same. Therefore, analysis of constituent elements by the composition analyzer, Can improve the accuracy of the data collected at the < RTI ID = 0.0 >

By passing the powder through a sieve having a size of 200 mesh or less, the constituent components of the sample are uniformly distributed during data collection, thereby ensuring reproducibility of measured data.

Hereinafter, prior to the description of the step of performing the component analysis and the mass analysis, a general analysis method of the isotope consumption mass will be described.

An isotope is an atom with the same atomic number but the same number of protons but different nuclide numbers and different masses. These isotopes are classified as radioactive isotopes and stable isotopes.

There is a delta value (δ) as a way of expressing a stable isotope, expressed as:

R _{Abundance ratio} = amount of heavy isotope / amount of light isotope

? (?) = (R _samp - R _std ) / (R _std ) x 1000

(Where R _samp is the isotope ratio in the sample and R _std is the international standard isotope ratio defined by the International Atomic Energy Agency)

For reference, the standard δ ¹³ C is a blood-di Belem nitro established about ¹³ C; as a (Pee Dee Belemnite PDB), R std (13 C / 12 C) = 0.0112372 the PDB, the actual δ ¹³ C is 0 ‰ .

In order to perform the IRMS, the sample to be measured must be converted to a simple gas such as hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ) and nitrogen (N ₂ ). In this converted hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ) and nitrogen (N ₂ ) gases, isotope consumption of the corresponding element is measured.

For example, in the measurement of carbon isotopes, CO ₂ is determined by mass to charge ratio (m / z) by combining with various forms of ¹² C, ¹³ C, ¹⁶ O, ¹⁷ O and ¹⁸ O, 44, 45 and 46, respectively.

( ² H / ¹ H) for the Vienna Standard Mean Ocean Water (VSMOW), carbon ( ¹³ C / ¹² C) for the Vienna Pee Dee Belemnite), nitrogen ( ¹⁵ N / ¹⁴ N) is the atmospheric nitrogen and oxygen ( ¹⁸ O / ¹⁶ O) is the internationally recognized zero point (VSMOW) 0), and expresses the difference.

Wherein the step (b) comprises the steps of: analyzing constituent elements of the sample as a sample in the gas phase by the component analysis method, and collecting isotope content data for each constituent element per unit weight of the sample; And collecting isotonic consumption data of the sample by the isotope consumption mass spectrometry method.

The component analysis may be performed by analyzing constituent elements of the sample using a component analyzer. In this process, the sample may be converted into a gas to form a gas-phase sample. At this time, The isotope content data for the element may be collected.

The subsequent isotope consumption mass spectrometry may be a step of collecting data on the sample by measuring the isotope consumption for constituent elements of the gaseous sample with an isotope mass spectrometry spectrometer.

In order to perform the isotope consumption mass analysis, it may be preferred that the sample is a gas, and the gas may comprise a simple gas such as hydrogen, carbon monoxide, carbon dioxide, nitrogen, oxygen, or a mixture thereof. In order to measure the consumption of this commodity, if the constituent elements of the compound to be measured are plural, the accuracy or reliability of the committee consumption data may be degraded. .

As such, the step of converting the sample into gas can be performed in the step (b), and the component analyzing apparatus used in the component analyzing method for analyzing the constituent elements of the sample while converting the sample to gas is, for example, elemental analysis, gas chromatography, liquid chromatography, thermogravimetric analysis, or a combination thereof may be applied, and the component analyzing apparatus may be a gas chromatograph And the analysis can be performed.

The process of converting the powdery solid sample into the gas phase using the above-described component analyzer may be generally by combustion. For example, by burning a sample to be measured at a high temperature, the constituent material is converted into a gas such as oxygen, carbon dioxide, or nitrogen, and the constituent elements of the sample are analyzed based on the gas to provide a basis for analyzing the consumed mass .

The data collected in step (b) may include isotope content data for each constituent element per unit weight of the sample, isotonic consumption data for the constituent elements of the sample, corrected delta value data, or both . In addition, such data can be classified using statistical principal component analysis. In this case, even if the amount of data is large and complex, data can be classified simply and clearly.

In addition, the data stored in the library of step (c) may include data on the content of isotopes for each constituent element per unit weight for cements of 1 to 18 varieties of cement samples that may be distributed on the market, The delta value data compensated for it, or both.

However, it should be understood that the number of cements that can be included in the library is not limited to the above 18 kinds, but that the information about the cement stored first may be about 18 kinds. In addition to the 18 types, Data on cement produced by the company or illegally distributed cement may be stored.

The isocratic consumption data is selected from the group consisting of ² H / ¹ H, ¹³ C / ¹² C, ¹⁵ N / ¹⁴ N, ¹⁸ O / ¹⁶ O, ³⁴ S / ³² S, ⁴⁸ Ca / ⁴⁶ Ca, It is possible to use any one of the measured values. However, in order to confirm whether or not the operation of the analyzed apparatus is normally performed, Or more, and if it is measured about three times, accuracy and reliability higher than a certain level can be secured. In other words, it may be desirable to measure the consumption of the same member more than three times and use the average value.

The cementitious consumption data may be obtained by measuring the isotopic consumption of the constituent elements of the cement constituent material, and the cement constituting material is, for example, silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ) ₂ O ₃ , CaO, MgO, SO ₃ , K ₂ O, MnO, TiO ₂ , Na ₂ O, (P ₂ O ₅ ), sodium peroxide (Na ₂ O ₃ ), calcium sulfate (CaSO ₄ ), calcium carbonate (CaCO ₃ ), calcium hydroxide (Ca (OH) ₂ ), yeildite Ca ₃ Al ₆ O ₁₂ .CaSO ₄ ), Brown millerite (Ca (AlFe ³⁺ ) ₂ O ₅ ), Forsterite (Mg ₂ SiO ₄ ), Rostite, Al (SO ₄ ) _{(OH) · 5H 2 O)} , ettringite _{(ettringite, Ca 6 Al 2 (} SO 4) 3 (OH) 12 · 26H 2 O), silicon wild ginseng calcium (3CaO · SiO ₂₎ based compound, a silicate of calcium ( 2CaO · SiO ₂₎ type compounds, calcium aluminate (3CaO · Al ₂ O ₃₎ based compounds, aluminate-iron quinoa calcium _{(4CaO · Al 2 O 3 ·} Fe ₂ O ₃ ) compound, gypsum (CaSO ₄ .2H ₂ O), calcium oxide (calcium magnesium aluminum oxide) silicate, calcium iron oxide (Ca ₄ Fe ₉ O ₁₇ ) Mixture, and these constituents may be converted to simple gases to measure isocratic consumption. That is, the isotope consumption of elements such as hydrogen, carbon, oxygen, nitrogen, sulfur, or calcium constituting the materials may be measured.

The delta value data may be corrected by: < EMI ID = 1.0 >

[Equation 1]

^a R δ (‰) = ((R ^a / R ^b) _samp - (R ^a / R ^b) _std) / ((R ^a / R ^b) _std) × 1000

Wherein R is any one selected from the group consisting of H, C, N, O, S, CO and Ca, a is the mass number of the heavy isotope of R, b is the mass number of the light isotope of R, (R / R) _samp is the _isotope consumption of the sample, and (R / R) _std is the standard-isocratic consumption of the reference material as defined by the International Atomic Energy Agency (IAEA).

The reference material may include, but is not limited to, for example, IAEA-CH ₆ , IAEA-600 caffeine, urea, or combinations thereof. , Sulfur, and the like.

The correction can be performed using one standard material, but it is possible to improve the accuracy of the obtained delta value data by using two or more reference materials.

By converting the above consumption data to the delta value data, it is possible to give accuracy and reliability to the consumption data of the same member, minimize errors in analyzing the equipment such as malfunction of the equipment, .

For example, through the above correction, it is possible to check whether there is an instrument analysis error such as a malfunction of a device. The sample consumption is measured three times or more and the calibration curve is drawn using the standard material, R ² ) value is 0.99 or more, it is possible to confirm that there is no correlation between the data obtained by three or more measurements and that the apparatus is operating normally when the reference material does not show a significant difference from the measured value have.

In other words, since in-house consumption of standard substances is internationally recognized, it is possible to obtain more accurate data by ensuring the validity, precision and reproducibility of the equipment when compensating the same consumption measured by using it.

The data collected in step (b) may be a material for securing information on an unknown sample including cement. In step (c), the step of outputting information of cement may include: And a determination is made as to whether the equivalence condition is satisfied between the collected data.

The equivalence condition is the similarity of any data selected from the group consisting of isotope content data for each constituent element per sample unit weight, isotonic consumption data of the sample, and combinations thereof; The distributional similarity of the data classified by the statistical principal component analysis using the above content data and the same consumption data as the index component; Or similarity due to a combination of these factors.

In other words, it is possible to compare the collected data with the data of the library to judge whether or not they are similar. If there is a difficulty in comparing the numerical values and there are overlapping parts, if the judgment is difficult, And the positional similarity of the data in the two-dimensional or three-dimensional graph space can be determined by locating the classified data based on the index data and placing the classified data on the graph. Can be performed.

If the data satisfying the above condition is not found in the library even after the determination of whether or not the equivalence condition is satisfied, the collected data may be stored in the library. This may be a means to at least increase the amount of information in the library even if it fails to output information about the sample.

The method for constructing the library comprises the steps of: analyzing constituent elements of the sample while converting the sample into a gas to form a gas phase sample by a component analysis method; and calculating isotope content data for each constituent element per sample unit weight ; The isotope consumption of the gas phase sample is analyzed by the isocratic consumption mass spectrometry method, and the isotope consumption data of the sample is collected; And statistical principal component analysis, the collected data is sorted and stored in a library, and the sample may be a sample of cement.

The component analysis method, the in-process mass spectrometry method, the data to be collected, and the method and procedure of calibrating can be performed in substantially the same manner as the above-described method of detecting the cement. That is, a method of constructing a library may be to record information about the cement for identification, while knowing the information such as the source, use, and constituent material of the cement when the library is not constructed for the first time.

In addition, although the cement identification can be performed with priority given to speeding up information output, it is possible to prioritize securing accurate information and a large amount of information in building a library. Therefore, when constructing a library, it may be desirable to use statistical principal component analysis to store the collected data more accurately and granularly.

The method of detecting the cement and the method of constructing the library according to the present invention are based on the composition data of 18 kinds of cement raw materials of the three most widely used domestic three companies (Ssangyong Yang company, Dong Yang cement company, La Paz hola cement company) In order to establish the analytical method that distinguishes each characteristic by obtaining the isotope consumption of the constituent elements of the different cements, the method is provided. However, the type of the cement is not limited to this, Information may also be included.

In addition, if analytical information on the basis of cement is already known or provided, a comparative analysis with cement crime traces will be tried to provide a way to analyze information on the source, origin, and environment of the evidence This information can be confirmed by analyzing the cement and related evidence received as evidence in the field.

The method of detecting cement of the present invention collects and analyzes in-house consumption data on cement samples using a component analyzer for analyzing constituent elements and an isobaric consumption mass spectrometer, By using the library constructed in this way, it is possible to quickly and accurately identify what kind of cement is contained in an unknown sample.

The above method of identification may provide a decisive clue to help the comparison feelings between cement and related evidence received as field evidence.

1 is a schematic diagram showing a method of detecting a cement according to an embodiment of the present invention in a flowchart.
FIG. 2 is a graph showing the results obtained using the carbon isotope consumption data collected by the analysis of the isotope consumption mass.
3A and 3B are graphs showing the results obtained using the oxygen isotope consumption data collected by the analysis of the same consumptive mass. FIG. 3A shows the whole cement sample. FIG. will be.
FIG. 4 is a graph showing the results obtained using the carbon isotope consumption data and the oxygen isotope consumption data collected by the analysis of the same consumption mass.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

FIG. 1 is a flow chart showing the overall procedure for the cementation of the cement using cement and cement-related products and the corrected delta value of the constituent elements of the cement by means of the same method. Referring to FIG. 1, a method of predicting cement is as follows. First, crushed and mixed to homogenize a cement sample, and then subjected to pretreatment to pass through a sieve of 200 mesh or less.

Analyze the constituent elements using a component analyzer (eg, an elemental analyzer, etc.) and collect the isotope content data for each constituent element per unit weight of the sample, while gasifying the sample for isocratic consumption mass analysis .

This gaseous sample is then subjected to isocratic consumption mass spectrometry to collect the isotope consumption of the sample and / or the delta value data for which it has been calibrated, store it in the library together with the data collected by the component analysis, do.

Then, the sample containing the cement to be identified, that is, fragments or traces, is pretreated as described above, and the components are analyzed and mass analyzed in the same manner. The data thus derived are compared with the data of the library And reads out information indicating which cement is contained.

Hereinafter, the method of pretreatment of the cement sample, the analysis of the data obtained by the analysis of the mass consumption of the cement, the method of judging the equivalence condition, and the like will be described by way of examples.

Example  1: Pretreatment of sample

Cement raw materials or blocks of 18 types (12 types of Ssangyong Yang, 3 types of Dongyang Cement and 3 types of LaPaz Halla Cement) produced by three cement manufacturers and sold on the market are crushed and mixed to form a total composition A homogeneous powder was prepared and the powder was passed through a sieve having a size of about 200 mesh or less to control the particle size of the powder, thereby preparing a sample containing cement for the analysis of gas consumption.

The types and uses of the cements produced by the manufacturers are shown in Tables 1 and 2 below.

manufacture company Cement sample number Kinds Ssangyong Yang Company SS-1 Portland cement (1 kind) SS-2 Moderate heat Portland cement (2 kinds) SS-3 Crude Portland cement (3 species) SS-4 Low temperature portland cement (4 kinds) SS-5 Cement SS-6 Cemented steel cement SS-7 Micro cement (MISEM 8000) SS-8 Ultra GrouT Cement (UGC-7000) SS-9 Geocrit (Ground improvement material) SS-10 Expanded Cement (Expander) SS-11 Blast furnace slag cement (slag cement) SS-12 Low heat cement (crude steel cubic balt) Dongyang Cement Company DY-1 One kind of oriental cement DY-2 Three kinds of oriental cement DY-3 Four kinds of oriental cement La Paz Halla Cement Company HR-1 Portland cement HR-2 Low heat cement HR-3 Blast furnace slag cement

division characteristic Usage 1 (usually) - Typical concrete components - For general concrete construction
(Most of domestic production cement) 2 (medium heat) - Maximize long-term strength of 2CaO and SiO ₂ to lower initial hydration heat and increase water resistance in hydration process. - Concrete structure of large volume (dam construction)
- Concrete for road maintenance 3 species (crude steel) - Short-term strength
(Roughly the same as day 3 strength of portland cement at the first day of crude steel cement age) - Urgent construction such as road and underwater construction
- Used to shorten construction period in concrete construction Four (low heat) - 2CaO, SiO ₂ than 2 (medium heat) cement
Increase content - Similar to 2 species
- Large scale mass concrete construction
- Subway-based construction

Example  2: Component analysis and Same-member consumption  Data collection of sample by mass analysis

A model analyzer (model EURO EA 3000 (Euro Vector, USA)) was used as a component analyzer and a model Isoprime (GV Instrument, UK) was used as an in-situ consumption mass spectrometer.

Samples to be analyzed and standard substances (sucrose, caffeine, urea) defined by the International Atomic Energy Agency were weighed accurately to ㎍ units using a microtiter scale and the samples and standard materials were packaged in capsules (CHNS: Sn capsule, HO : Silver (Ag) capsules) and sealed to prevent leakage. The temperature of the isotope mass spectrometry spectrometer is set at: 1050 ° C. real, oxygen: py-EA IRMS 1400 ° C., and the pressure set at (He, CO ₂ , O ₂ ) Respectively.

In this process, the sample is vaporized into a simple gas, and a simple gas such as hydrogen, carbon monoxide, nitrogen, oxygen, or the like is supplied to the sample. And the isotope consumption of the gasified samples was measured by a mass spectrometer.

Example  3: Construction of library by analysis and classification of collected data

(C_H / W, O_H / W) and isotope consumption data (δ ¹³ C, δ ¹⁸ O) of each sample for each constituent element per unit weight of the sample measured in Example 1, Oxygen, and carbon and oxygen.

At this time, using the isotope consumption data of the reference materials (IAEA-CH ₆ sucrose (-10.4), IAEA-600 caffeine (-27.77), urea (-34.22)) defined by the International Atomic Energy Agency .

The content data (H (Height) / W (Weight)) of the isotope for each constituent element per unit weight of the sample indicates the value of δ ¹³ C or δ ¹⁸ O contained in 1 μg of the sample The formula used was the height or intensity value of the corresponding sample or standard isotope shown on the component analyzer / weight of the test sample (μg).

The H / W average value (R_H / W_ave) of the sample and the H / W (R_H / W_std) value of the standard material were obtained for each constituent element, and the obtained data values are shown in Tables 3 to 5 below.

Standard material IAEA-CH ₆ (-10.4), IAEA-600 caffeine (-27.77), and urea (-34.22) is a measure of whether these data are well measured. The calibration curve (R ² ) was calculated by plotting the calibration curve. The value of the correlation coefficient (R ² ) was 0.99 or more, which was not much different from that of the one using the standard material. This confirms that the device is operating normally.

Data can be more accurate by measuring and calibrating the isotope consumption of two or more reference materials, and it is preferable to continue calibration using a standard material in between. For reference, the selection of a reference material can be selected according to the analytical element (CNHOS), and a standard material close to the value of the sample to be measured is selected.

1) carbon Same-member consumption  Analysis of data

sample δ ¹³ C_ave. (‰) ? ¹³ C_std. (‰) C_H / W_ave. C_H / W_std. SS-1 -3.80 1.15 1.12 0.02 SS-2 -3.87 0.74 0.78 0.02 SS-3 - - - - SS-4 -3.57 1.10 0.80 0.01 SS-5 -19.43 1.35 1.43 0.05 SS-6 -18.26 1.43 0.25 0.00 SS-7 -23.13 0.72 0.84 0.14 SS-8 -6.00 4.27 1.52 0.46 SS-9 -11.32 1.86 0.59 0.02 SS-10 -8.49 1.50 1.70 0.10 SS-11 -4.79 0.96 0.63 0.02 SS-12 -19.87 1.59 2.04 0.36 DY-1 -3.97 1.04 0.82 0.03 DY-2 -20.66 0.70 - - DY-3 -16.14 0.27 - - HR-1 -1.90 1.12 0.93 0.00 HR-2 -12.80 1.02 1.37 0.05 HR-3 -4.12 1.15 0.76 0.01

FIG. 2 shows a graph in which the horizontal axis (x axis) is a delta ¹³ C value (delta value) and the vertical axis (y axis) is C_H / W, based on the data in Table 3 above. In the graph, the horizontal and vertical lines represent the range of the measured data value, and the location where the graphic is located represents the average value.

As shown in Table 3, the δ ¹³ C value of the cement according to the manufacturer varied from -1.90 to -23.13 ‰ (average, -9.69 ‰). The δ ¹³ C values of Ssangyong Yang were -3.80 to -23.13 ‰, and the average was -11.14. The δ ¹³ C values of La Paz Hanla Cement were -1.90 to -12.80 ‰ and the average was -6.27. Thus, it was confirmed that the value of δ ¹³ C has a large variation in distribution, and it is easy to distinguish cement by manufacturer.

By purpose, in the case of SS-12 (low heat), when the δ ¹³ C value was -19.87, C_H / W value is appeared to 2.04, HR-2 (low heat), the δ ¹³ C-values 12.80, and the C_H / W value was 1.37. The δ ¹³ C value of SS-5 (initial velocity) is -19.43 and the C_H / W value is 1.43. The δ ¹³ C value of SS-6 is 5.58 and the C_H / W value is 0.25 Respectively. Referring to FIG. 2, it can be seen that the compartments are clearly divided and thus it is easy to distinguish the above four types of cement.

In Fig. 2, the δ ¹³ C values of the cement samples bound to the circle were overlapped. These cement samples are similar in portland cement and blast furnace slag cement, and blast furnace slag is mixed with Portland cement mixed cement. In the case of expanded cement, it is also possible to confirm that these three cement samples are indistinguishable from the carbon isotope consumption data because they are mixtures of Portland cement. This can be distinguished by using δ ¹⁸ O by other isotope consumption data of cement samples.

2) Oxygen Same-member consumption  Analysis of data

sample δ ¹⁸ O_ave. (‰) δ ¹⁸ O_std. (‰) O_H / W_ave. O_H / W_std. SS-1 22.73 1.00 3.28 0.60 SS-2 23.43 0.43 3.38 0.15 SS-3 23.25 0.88 2.90 0.10 SS-4 23.10 0.49 3.00 0.10 SS-5 22.56 1.54 6.93 1.88 SS-6 23.27 0.91 3.17 0.39 SS-7 22.57 1.47 2.02 0.10 SS-8 23.37 1.01 2.62 0.17 SS-9 22.06 0.87 3.82 0.14 SS-10 21.25 1.01 13.56 1.81 SS-11 22.66 1.07 2.34 0.38 SS-12 21.84 0.89 3.10 0.11 DY-1 22.91 0.56 3.37 0.15 DY-2 22.35 0.48 3.22 0.13 DY-3 22.65 0.79 2.70 0.14 HR-1 22.37 0.42 4.00 0.14 HR-2 21.97 1.16 2.95 0.40 HR-3 23.41 0.98 1.97 0.14

FIG. 3A shows a graph based on the data in Table 4, in which the abscissa is the delta ¹⁸ O value (delta value) and the ordinate is O_H / W. In the graph, the horizontal and vertical lines represent the range of the measured data value, and the location where the graphic is located represents the average value.

As shown in Table 4 and FIG. 3A, most δ ¹⁸ O values are about 22.6 ‰, and the δ ¹⁸ O values of the manufacturers are 21.25 (S) of Ssangyang Company, Dong Yang Cement Company and La Paz Hanla Cement Co., SS-5 (swing speed) and SS-10 (swelling agent) for O_H / W value (mean, 3.80) were found to be not significantly different from those of SS- Were different from O_H / W values of other samples, and it was confirmed that these two cement samples could be distinguished. However, except for these two cement samples, the range of change was relatively narrow.

FIG. 3B is a graph showing the scale-up of the delta value and the H / W value of the remaining cement samples except for the two distinguishable cement samples (SS-5 and SS-10) It can be confirmed that it is also possible to distinguish by application such as soil improvement agent (SS-2), low heat generation (SS-12 and HR-2), rough steel (SS-6) and micro (SS-7).

Additionally, the typical chemical composition of Portland cement is _{CaO 60 ~ 67%, SiO 2} 17 ~ 25%, Al 2 O 3 3 ~ 8%, FeO 3 0.5 ~ 6 it contains%, etc., the manufacturer-specific delta Portland cement sample The value (δ ¹⁸ O) was found to be larger than the standard PDB (Pee Dee Belemnite).

3) Carbon and oxygen Same-member consumption  Analysis of data

sample δ ¹³ C_ave. (‰) ? ¹³ C_std. (‰) δ ¹⁸ O (‰) _ ave. δ ¹⁸ O (‰) _ std. SS-1 -3.80 1.15 22.73 1.00 SS-2 -3.87 0.74 23.43 0.43 SS-3 - - 23.25 0.88 SS-4 -3.57 1.10 23.10 0.49 SS-5 -19.43 1.35 22.56 1.54 SS-6 -18.26 1.43 23.27 0.91 SS-7 -23.13 0.72 22.57 1.47 SS-8 -6.00 4.27 23.37 1.01 SS-9 -11.32 1.86 22.06 0.87 SS-10 -8.49 1.50 21.25 1.01 SS-11 -4.79 0.96 22.66 1.07 SS-12 -19.87 1.59 21.84 0.89 DY-1 -3.97 1.04 22.91 0.56 DY-2 -20.66 0.70 22.35 0.48 DY-3 -16.14 0.27 22.65 0.79 HR-1 -1.90 1.12 22.37 0.42 HR-2 -12.80 1.02 21.97 1.16 HR-3 -4.12 1.15 23.41 0.98

Table 5 shows the data of the standard materials of δ ¹³ C and δ ¹⁸ O and the measured values of the samples, respectively, and graphs are shown in FIG. 4, with the X axis being δ ¹⁸ O and the Y axis being δ ¹³ C.

Portland cement and blast furnace slag cement are concentrated on the right side of the graph. It can be seen that the soil improvement agent and the swelling agent are located at similar positions but can be distinguished by the values of δ ¹³ C and δ ¹⁸ O, It was also confirmed that the heat, the hardened steel and the ultra rapid cement can be distinguished by the amounts of δ ¹³ C and δ ¹⁸ O. The micro cement was located on the left side, and it was found that the fluctuation width due to the difference of the amount of δ ¹⁸ O was larger than the amount of δ ¹³ C.

Example  4: Identification of target samples containing cement

Data of the cement samples analyzed according to Examples 2 and 3 were stored and a library was constructed. Then, SS-6, an early-spring steel cement of Ssangyong Yang Co., was assumed to be an unknown cement fragment.

First, the fragments were pulverized and mixed to make the composition uniform, and passed through a 200-mesh sieve to prepare a sample. The unknown samples were analyzed by elemental analyzer, and the samples were gasified. Gas samples were measured three times using the same mass spectrometric spectrometer, and the measured values were used And the same equipment as those of Examples 1 and 2 were used. The results are shown in Table 6 below.

1 time Episode 2 3rd time medium δ ¹³ C -18.77 -17.96 -18.02 -18.25 δ ¹⁸ O 23.19 23.29 23.33 23.27

3A, 3B and 4, which are data stored in the library, it can be confirmed that the unknown sample, which is the subject of the test, is the irregular steel cement of Ssangyong Company, SS-6.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

Claims (13)

(a) preprocessing a sample containing cement;
(b) collecting data on the sample by a component analysis method and an in-process mass spectrometry method; And
(c) determining whether the equivalence condition is satisfied between the data of the collected sample and the data of the library constructed in advance, and outputting the information of the cement contained in the sample,
Wherein the collected data and the data of the library include data on isotope content for each constituent element per unit weight of the sample and isotope consumption data of the sample,
Wherein the isotope consumption data comprises any one selected from the group consisting of measured value data of the in-house consumption, delta value data corrected for the measured value data, and combinations thereof. The method according to claim 1,
The pretreatment of the step (a) comprises: (a-1) mixing and crushing a sample containing cement to form a powder; And (a-2) passing the powder through a sieve of 200 mesh or less. The method according to claim 1,
Wherein the step (b) comprises the steps of: analyzing constituent elements of the sample as a sample in the gas phase by the component analysis method, and collecting isotope content data for each constituent element per unit weight of the sample; And
And the step of collecting the isoterm consumption data of the sample by the isocratic consumption mass spectrometry method. The method of claim 3,
Wherein the gaseous sample comprises any one selected from the group consisting of hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide, and combinations thereof. The method according to claim 1,
The method of constructing the library of step (c)
A constituent element of the sample is analyzed while a sample is converted into a gas to form a gas phase sample by the component analysis method and the isotope content data for each constituent element is collected per sample unit weight;
The isotope consumption of the gas phase sample is analyzed by the isocratic consumption mass spectrometry method, and the isotope consumption data of the sample is collected; And
Wherein the collected data is sorted and stored in a library by statistical principal component analysis,
Wherein the sample is a sample of cement. The method according to claim 1,
Whether or not the equivalence condition of step (c) is satisfied is determined by comparing the data of the library,
Similarity to any one selected from the group consisting of isotope content data for each constituent element per sample unit weight, isotope consumption data of a sample, and combinations thereof;
The distributional similarity of the data classified by the statistical principal component analysis using the above content data and the same consumption data as the index component; or
And the similarity due to the combination thereof. The method according to claim 1,
Wherein the collected data is stored in a library if the data collected in step (b) does not satisfy an equivalence condition with data in the library of step (c). The method according to claim 1,
The isocratic consumption data is selected from the group consisting of ² H / ¹ H, ¹³ C / ¹² C, ¹⁵ N / ¹⁴ N, ¹⁸ O / ¹⁶ O, ³⁴ S / ³² S, ⁴⁸ Ca / ⁴⁶ Ca, The method comprising the steps of: The method according to claim 1,
Wherein the delta value data is corrected by the following equation (1): " (1) "
[Equation 1]
^a R δ (‰) = ((R ^a / R ^b) _samp - (R ^a / R ^b) _std) / ((R ^a / R ^b) _std) × 1000
Wherein R is any one selected from the group consisting of H, C, N, O, S, CO and Ca, a is the mass number of the heavy isotope of R, b is the mass number of the light isotope of R, (R / R) _samp is the _isotope consumption of the sample, and (R / R) _std is the standard-isocratic consumption of the reference material as defined by the International Atomic Energy Agency (IAEA). 9. The method of claim 8,
Wherein the reference material comprises any one selected from the group consisting of IAEA-CH ₆ , IAEA-600 caffeine, urea, and combinations thereof. The method according to claim 1,
The apparatus used for the component analysis may be any one selected from the group consisting of elemental analysis, gas chromatography, liquid chromatography, thermogravimetric analysis, and combinations thereof. The method comprising the steps of: The method according to claim 1,
Wherein said data collection is measured at least three times and the average value is used. The method according to claim 1,
Data of the sample, silica (SiO _2), aluminum oxide (Al ₂ O _3), iron oxide (Fe ₂ O _3), lime (CaO), magnesium oxide (MgO), sulfur trioxide (SO _3), potassium oxide (K ₂ O), MnO ₂ , TiO ₂ , Na ₂ O, P ₂ O ₅ , Na ₂ O ₃ , CaSO ₄ , Calcium carbonate (CaCO ₃ ), calcium hydroxide (Ca (OH) ₂ ), yeelite (Ca ₃ Al ₆ O ₁₂ .CaSO ₄ ), brown millerite, Ca (AlFe ³⁺ ) ₂ O ₅₎ Goto Olivine (Forsterite, Mg ₂ SiO _4), Los tight _{(Rostite, Al (SO 4)} (OH) · 5H 2 O), ettringite _{(ettringite, Ca 6 Al 2 (} SO 4) 3 (OH ) ₁₂ · 26H ₂ O), calcium silicate (3CaO · SiO ₂ ), calcium silicate (2CaO · SiO ₂ ), calcium aluminate (3CaO · Al ₂ O ₃ ) _{(4CaO · Al 2 O 3 ·} Fe 2 O 3) based compound, gypsum _{(CaSO 4 · 2H 2 O)} , oxidizing (calcium magnesium aluminum) silicate (calcium magnesium aluminum silicate oxide), acid Calcium ferrous (Iron Oxide Calcium, Ca ₄ O ₁₇ Fe ₉₎ and the forensic methods of the cement comprises the data for one of the components selected from the group consisting of.

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