WO2016003347A1 - Ensemble de normes d'étalonnage et leur utilisation dans un procédé de quantification de biocides dans des peintures antisalissures avec un instrument xrf portable - Google Patents

Ensemble de normes d'étalonnage et leur utilisation dans un procédé de quantification de biocides dans des peintures antisalissures avec un instrument xrf portable Download PDF

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Publication number
WO2016003347A1
WO2016003347A1 PCT/SE2015/000044 SE2015000044W WO2016003347A1 WO 2016003347 A1 WO2016003347 A1 WO 2016003347A1 SE 2015000044 W SE2015000044 W SE 2015000044W WO 2016003347 A1 WO2016003347 A1 WO 2016003347A1
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Prior art keywords
compounds
copper
tin
calibration
zinc
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PCT/SE2015/000044
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English (en)
Inventor
Britta EKLUND
Lennart LUNDGREN
Erik YTREBERG
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Eklund Britta
Lundgren Lennart
Ytreberg Erik
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Application filed by Eklund Britta, Lundgren Lennart, Ytreberg Erik filed Critical Eklund Britta
Priority to EP15815665.3A priority Critical patent/EP3164705A4/fr
Publication of WO2016003347A1 publication Critical patent/WO2016003347A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/32—Paints; Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/36—Measuring spectral distribution of X-rays or of nuclear radiation spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
    • G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
    • G01T1/36—Measuring spectral distribution of X-rays or of nuclear radiation spectrometry
    • G01T1/361—Measuring spectral distribution of X-rays or of nuclear radiation spectrometry with a combination of detectors of different types, e.g. anti-Compton spectrometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/07—Investigating materials by wave or particle radiation secondary emission
    • G01N2223/076—X-ray fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/30—Accessories, mechanical or electrical features
    • G01N2223/303—Accessories, mechanical or electrical features calibrating, standardising
    • G01N2223/3037—Accessories, mechanical or electrical features calibrating, standardising standards (constitution)

Definitions

  • the present invention relates to a set of calibration standards for use in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a portable XRF instrument. Further disclosed is a method for manufacturing the set of calibration standards as well as their use in a method of quantify- ing the concentration of tin, copper and zinc compounds in anti-fouling paints with a portable XRF instrument.
  • TBT-based paints became increasingly popular due to its efficiency in preventing biofouling, and as a result, they were estimated to cover around 70-80% of the world ' s fleet in 2004 (3).
  • adverse effects were reported on several mollusc species.
  • French oyster growers reported shell malformations which rendered their produce worthless (4, 5). This effect was traced back to TBT in the water (6, 4, 7, 5).
  • Other populations of mol- lusk species were shown to be sensitive to extremely low TBT concentrations ( ⁇ 10 ng/L) (8). Due to the negative environmental impact, TBT was restricted for use on leisure boats (less than 25 m in length) in several counties in the late 1980s (e.g. EU Directive (89/677/EEC)), and since 2008 there is a global ban of TBT for all sizes of ships due to the adoption of the AFS-convention by the International Maritime Organization (IMO).
  • EU Directive 89/677/EEC
  • the anti-fouling paint need to be scraped off and analyzed by advanced, chemical analytical methods, such as ICP-SFMS.
  • ICP-SFMS advanced, chemical analytical methods
  • XRF handheld X-ray fluorescence spectroscopy
  • Handheld XRF techniques are practical and effective analytical tools having the advantage to determine environmental samples directly on-site.
  • the advantage with XRF is that the analyses are non-destructible and the analytical time is in order of seconds which compared to chemical analysis reduces the analytical cost substantially.
  • the soil application is calibrated using soil standards, it is not compatible for anti-fouling paint matrixes.
  • the methods for screening compounds in soil samples are not applicable for quantifying compounds in anti-fouling paints due to several reasons, including the fact that there are several layers of paints wherein each layer comprises different compositions of metal containing compounds which gives rise to matrix effects as well as other unwanted effects. Consequently, there is a need to develop an anti-fouling paint quantification method for a handheld XRF instrument which has the ability to quantify tin compounds in anti-fouling paints.
  • the first object of the invention is attained by a method comprising the steps of:
  • step ai Applying increasing amounts of tin compounds to anti-fouling paints both separately and in combination with copper compounds and/or zinc compounds to yield a concentration interval between 0-64 % (weightweight) for each of tin, copper and zinc compounds, wherein said anti-fouling paint to be used in step ai) does not comprise tin, copper and zinc compounds, and
  • step bi Applying increasing amounts of copper compounds to anti- fouling paints both separately and in combination with zinc compounds to yield a concentration interval between 0-64 % (weigh weight) for each of copper and zinc compounds, wherein said anti-fouling paint to be used in step bi) does not comprise tin, copper and zinc compounds, and
  • step ci Applying increasing amounts of zinc compounds to anti- fouling paints to yield a concentration interval between 0-64 % (weight:weight) for zinc compounds, wherein said anti-fouling paint to be used in step ci) does not comprise tin, copper and zinc compounds, and mixing the paints with respective compounds, and
  • the second object of the invention is attained by:
  • Calibration standards for tin compounds comprising a thin film coated by a layer of anti-fouling paint comprising tin compounds both separately or in combination with copper compounds and/or zinc compounds with a concentration interval between 0-64% (weight.weight) for each of tin, copper and zinc compounds
  • b. Calibration standards for copper compounds comprising a thin film coated by a layer of anti-fouling paint comprising copper compounds both separately and in combination with zinc compounds with a concentration interval between 0-64% (weigh weight) for each of copper and zinc compounds
  • a layer of anti-fouling paint comprising zinc compounds with a concentration interval between 0-64% (weigh weight) for each of tin, copper and zinc compounds, and wherein said concentration interval 0-64% represents the concentration (weight:weight) of wet layer of tin, copper and zinc compounds applied to the film in the method for manufacturing said set of calibration standards.
  • the above mentioned preferred embodiments of the first and second objects of the invention provide a set of calibration standards comprising calibration standards for tin, copper and zinc compounds.
  • This allows using said set of calibration standards in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints, wherein inter-elemental effects (1) between elements (i.e. metals) of tin, copper and zinc compounds within a paint layer, as well as (2) between elements of tin, copper and zinc compounds between paint layers, can be eliminated by a method for calibration involving the use of said calibration standards.
  • matrix effects within a paint layer, as well as, between paint layers are eliminated.
  • the sample matrix which is used in the method of the preferred embodiment is an anti- fouling paint which originally does not comprise any of tin, copper and zinc compounds to be quantified.
  • a concentration interval between 0-64 % of tin, copper and zinc compounds is applied to the anti-fouling paint in order to simulate the concentration of anti-fouling paints applied to boat hulls.
  • Said concentration interval 0-64% represents the concentration of wet layer of tin, copper and zinc compounds applied to the film in the manufacture of the standards.
  • the mixed paints are applied with a thickness which results in a sample morphology representative of the distribution, uniformity, heterogeneity and surface conditions of the anti-fouling paints applied to boat hulls.
  • said set of calibration standards are representative of the anti-fouling paints to be analyzed on boat hulls.
  • the mixed paint is applied on a thin film (i.e. foil) support (i.e. backing material).
  • the backing material gives mechanical strength and is of a high-purity material which is able to withstand high beam intensities.
  • the continuous background radiation produced by the backing material is as small as possible.
  • the film being thin favors low background radiation.
  • the film is preferably made of plastic material, more preferably polyester or polypropylene.
  • the concentration for each of tin, copper and zinc compounds applied on the film is 0-32 %, more preferably, 0%, 1%, 2%, 4%, 8%, 16% and/or 32%.
  • the set of calibration standards will consequently cover the full range of target compounds and interfering matrix element concentrations, as well as reflect variations in concentrations of tin, copper and zinc compounds to produce a representative calibration model when used in method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument.
  • the highest and lowest concentrations of tin, copper and zinc compounds in the set of the calibration standards will define the calibration range.
  • the paint is applied on a polyester film support.
  • the chemical composition of poly- ester attenuates absorption of the primary X-rays and characteristic radiation emitted by the sample.
  • the degree of attenuation is further controlled by the gauge of the film used; the thinner the gauge, the lower the absorption of x-rays.
  • the inherent high strength of polyester film also permits safe sample handling and retention concurrent with maintaining taut film surfaces to define statistically reproducible target- to-sample distance.
  • the film gauge thickness is preferably 2-10 pm.
  • the film gauge thickness the more negligible are interelement matrix effects.
  • the set of calibration standards will provide a more linear relationship between the fluorescent intensity of tin, copper and zinc compounds in the film and the mass per unit are (i.e. area concentration) of tin, copper and zinc compounds in the film.
  • the film has a gauge of 2.5 pm, 3.6 pm or 6.3 pm. The film with a gauge thickness of 2.5 pm is used for applications requiring reduced absorption of the primary X- rays and characteristic long wavelength, including the "L" spectral lines.
  • the film with a gauge thickness of 3.6 pm is (a general purpose film) for both short- and long-wavelength investigations, and particularly well suited for analyzing samples containing mixtures of both heavy and light elements.
  • the application of a 6.3 pm- gauge film used primarily for short-wavelength, i.e. heavy element determinations, but may be extended to include moderately high concentrations of elements hav- ing long wavelengths.
  • 6.3 pm-gauge film is used since tin, copper and zinc compounds are to be quantified with the said set of calibration standards.
  • the wet layer of paint applied to the film has a thickness of about 10-500 pm, more preferably about 50, 100, 150 and 200 pm. It is important to apply a wet layer of paint with the most optimal thickness since a too thick or thin wet layer of paint can result in a crackled dry layer of paint. Moreover, if the wet layer of paint is too thin, then it can be difficult to use paint with high concentrations of zinc and copper compounds, such as ZnO and CU2O, since these oxides are particulate and therefore do not mix easily in small volumes of paint.
  • the standards are to be used in a method for quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints, wherein the concentration is quantified as amount per area, i.e. pg/cm 2 .
  • the concentration is quantified as amount per area, i.e. pg/cm 2 .
  • the wet layer of paint has a thickness of about 00 pm since this thick- ness corresponds approximately to a thickness of a layer of anti-fouling paint on boat hulls of leisure boats.
  • the concentration interval 0-32% of wet layer of tin, copper and zinc compounds applied to the film corresponds to an area concentration of dry tin, copper and zinc compounds of 0-1800 pg/cm 2 Sn, 0-4700 pg/cm 2 Cu and 0-2800 pg/cm 2 Zn.
  • the thickness of the wet layer of tin, copper and zinc compounds applied to the film is 100 pm in this preferred embodiment.
  • the calibration standards for each of tin, copper and zinc compounds comprise a minimum of 7-10 samples.
  • the calibration standards for each of tin, copper and zinc compounds preferably comprise a minimum of 7-10 standards. This generates a linear model for the analytes when interelement matrix effects are significant.
  • the punched out pieces for use as standards are preferably circular, and preferably have a diameter of 25 mm. This allows practical handling and storing of the standards.
  • the method for manufacturing a set of calibration standards for use in in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument comprises the steps of:
  • Preparing calibration standards comprising tin compounds, wherein said concentrations of tin compounds is between 0- 32 %, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and ii. Preparing calibration standards comprising both tin and copper compounds, wherein said concentrations of each of tin and copper compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and
  • Preparing calibration standards comprising copper compounds, wherein said concentrations of copper compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and
  • Preparing calibration standards comprising zinc compounds, wherein said concentrations of zinc compounds is between 0- 32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%.
  • the set of calibration standards for use in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument comprises:
  • Calibration standards comprising tin compounds, wherein said concentrations of tin compounds is between 0-32%, preferably 0%, 1 %, 2%, 4%, 8%, 16% and/or 32%, and ii. Calibration standards comprising both tin and copper compounds, wherein said concentrations of each of tin and copper compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and
  • Calibration standards comprising both tin and zinc compounds, wherein said concentrations of each is between 0- 32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and
  • iv. Calibration standards comprising tin, copper and zinc compounds, wherein said concentrations of each compound is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and
  • concentrations of copper compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and
  • Calibration standards comprising both copper and zinc compounds, wherein said concentrations of each of copper and zinc compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and
  • Calibration standards comprising zinc compounds, wherein said concentrations of zinc compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%.
  • the method for manufacturing a set of calibration standards for use in in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument comprises the steps of:
  • Preparing calibration standards comprising both tin and zinc compounds, wherein the concentration of tin compounds is 4% and the concentration of zinc compounds is 32%
  • Manufacturing calibration standards for copper compounds comprising the steps of: i. Preparing calibration standards comprising 1%, 2%, 4%, 8%, 16% and 32% copper compounds, and
  • Manufacturing calibration standards for zinc compounds comprising the steps of :
  • the set of calibration standards for use in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument comprises:
  • Calibration standards comprising both tin and zinc compounds, wherein the concentration of tin compounds is 4 % and the concentration of zinc compounds is 32 %, and b.
  • Calibration standards for copper compounds comprising:
  • the above disclosed four embodiments for the first and second objects of the invention provide a set of calibration standards which are optimal for use in the third object of the invention, as well as fourth and fifth objects of the invention, i.e.
  • the set of calibration standards includes the relevant range of target compound concentrations to be quantified as well as possible anti-fouling paint matrix element concentrations.
  • the set of calibration standards reflects the variations in concentrations of tin, copper and zinc compounds in order to produce a representative calibration model in the preferred embodiments of the third, fourth and fifth objects of the invention.
  • the set of calibration standards includes several standards for tin, copper and zinc compounds with concentrations near the concentrations of anti-fouling paints applied on boat hulls in order to improve accuracy of the method for calibration disclosed in the third, fourth and fifth objects of the invention.
  • said tin compounds is tin metal, inorganic tin, or one or more organotin compounds.
  • said copper compound is inorganic copper, preferably selected from one or more of CU2O, CuSCN and copper metal (powder).
  • said zinc compounds is inorganic zinc, preferably selected from one or more of zinc metal (powder), ZnO and
  • one or more organotin com- pounds is selected from TBT (tributyltin), TPT (triphenyltin) and DBT (dibutyltin) compounds.
  • said TBT and TPT compounds are selected from one or more of TBTO (tributyltin oxide), Tributyltin hy- dride, Tributyltin adipate, Tributyltin dodecenyl succinate, Tributyltin sulfide, Tributyltin acetate, Tributyltin acrylate, TBT fluoride, Tributyltin methacrylate, Tributyltin resinate, Triphenyltin oxide, Triphenyltin hydride, Triphenyltin hydroxide, Triphenyltin chloride and Triphenyltin acetate.
  • TBTO tributyltin oxide
  • Tributyltin hy- dride Tributyltin adipate
  • Tributyltin dodecenyl succinate Tributyltin sulfide
  • Tributyltin acetate Tributyltin
  • TBT, TPT and DBT compounds have been used in anti-fouling paint and the calibration standards of the tin compounds there- fore comprise one or more of TBT, TPT and DBT compounds. Consequently, the set of calibration standards is representative of the sample matrix on the boat hull.
  • said tin compounds is TBTO.
  • the set of calibration standards has to be representative of the sample matrix on the boat hull in order to provide accurate results in the method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument. Since, TBTO was the most used organotin compound in anti-fouling paint in the 1960s and 1970s, said calibration standards of organotin compound therefore comprise TBTO.
  • the set of calibration stand- ards comprises calibration standards for TBTO, CU2O and ZnO. This allows using said set of calibration standards in a method for quantifying the concentration of all three of TBTO, CU2O and ZnO in anti-fouling paints.
  • the calibration standards are chemically analyzed for total concentration of Sn, Cu and Zn, wherein the chemically analyzed total concentration of Sn, Cu and Zn and the weight and area of the standards are used to calculate the total concentration per area (i.e. area concentration) expressed as g/cm 2 .
  • said method also comprises the following step d:
  • said further compound is selected from one or more of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, barium and iron compounds.
  • said set of calibration standards also comprises:
  • Calibration standards for a further compound comprising a thin film coated by a dry layer of anti-fouling paint comprising said further compound both separately and in combination with tin, copper and zinc compounds with a concentration interval between 0-64%, preferably 0-32%, for each of further, tin, copper and zinc compounds, wherein said further compound is selected from one or more of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, bar- ium and iron compounds.
  • Mercury, lead, arsenic, cadmium and chromium compounds as well as other toxic compounds have in the past (and maybe in the present) been added to anti-fouling paints.
  • one or more of these compounds are also included in the set of calibration standards so that they can also be quantified in the fourth and fifth objects of the invention.
  • the said second object of the invention is attained by using the above disclosed preferred embodiments of the method for at- taining the first object of the invention.
  • the preferred embodiments of the above mentioned set of calibration standards of the second object of the invention are obtained according to the method according to preferred embodiments of the first object of the invention.
  • This product-by-process embodiment is necessary since it is difficult to define the set of calibration standards without referring to the method for manufacturing said set of calibration standards. This is due to the fact that it is difficult to indicate the amount of dry tin, copper and zinc compounds on the film in pg/cm 2 since the anti-fouling paint can be applied with a thickness of 50, 100, 150 and 200 um.
  • the amount of dry tin, copper and zinc compounds in pg/cm 2 is dependent of the thickness of the paint layer. Consequently, it is difficult to define a preferred embodiment of the second object of the invention without including a product-by-process embodiment in the invention.
  • an object of the invention is to provide a kit for use in quantifying the concentration of tin, copper and zinc compounds in anti- fouling paints with a handheld XRF, comprising the above disclosed preferred embodiments of the first and/or second objects of the invention.
  • the third object of the invention is attained by the following method for calibration with the set of calibration standards described in the above preferred embodiment said method comprising the steps of:
  • the boat hull material is situated underneath the most bottom layer, i.e. most the bottom calibration standard.
  • the scan is performed by aiming the handheld-XRF instrument on the top layer, i.e. the top calibration standard.
  • the use of above disclosed set of calibration standards (of the first and second objects of the invention) in the method for calibration (of the third object of the invention) results in the technical effects and advantages described in the above preferred embodiments of said set of calibration standards.
  • Tin, copper and zinc compounds (such as organotin compounds CU2O and ZnO) have been included in anti-fouling paints in different time periods since the 1960s.
  • Organotin compound based anti-fouling paints were used in the 1960s and 1970s before they were banned in many countries due to serious toxic effects on marine life. Copper and zinc based anti-fouling paints (such as CU2O and ZnO) have been used since then as alternatives. Additionally, the use anti-fouling paints comprising more than one of tin, copper and zinc compounds shouldn't be ruled out. Due to these reasons, a boat hull can comprise several layers of paint wherein each layer comprises either (1) only tin, copper and zinc compounds, or (2) one or more of tin, copper and zinc compounds. Additionally, each layer can comprise varying concentrations of tin, copper and zinc compounds. Since there can be several layers of paint on a boat hull, and that the chemical composition and concentration of the anti-fouling paint varies significantly in each paint layer, the method of calibration according to the preferred embodiment takes these variations into account in order to generate an accurate and precise calibration model.
  • the method for calibration according to the present invention is adapted to be used in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument. Since the boat hull of a leisure boat is covered with several layers of paint, the method for calibration is, as indicated below, designed to include several layers of paint.
  • X-ray measurements are susceptible to variable scattering of the source of X-rays from the boat hull material beneath the anti-fouling paint layers. Although, some XRF analyzers might provide corrections for substrate scattering, the most optimal correction for this scattering is to emulate the scattering in the method for calibration.
  • a piece of boat hull material is placed behind the first layer of calibration standards as indicated above.
  • the piece of boat hull material is preferably non-metallic and does not comprise any layers of anti-fouling material.
  • the piece of boat hull material is made of the same material as a real boat hull material from a leisure boat and has the same thickness, preferably 3 mm - 100 mm, more preferably 5- 50, even more preferably 21 mm.
  • the non-metallic piece of boat hull material is preferably chosen from the group comprising wood, fiberglass, carbon fiber, Kevlar, composite material, gelcoat, composite covered with gelcoat, plastic-based material, Roplene, rubber, polymer, or combinations of said non- metallic materials.
  • Gelcoat is a material used to provide a high-quality finish on the visible surface of a fibre-reinforced composite material. The most common gel- coats are based on epoxy or unsaturated polyester resin chemistry. Gelcoats are modified resins which are applied to moulds in the liquid state. They are cured to- form crosslinked polymers and are subsequently backed with composite polymer matrices, often mixtures of polyester resin and fiberglass or epoxy resin with glass.
  • An example of a material which ca be used as a boat hull material comprises an outer 4 mm layer of gelcoat, a 14 mm porous intermediary layer and an inner 3 mm layer of gelcoat.
  • the calibration curve is based on the adjusted intensity of K a signals, i.e. the intensity rates have been adjusted for air background, peak overlap and elemental interference from other elements in the sample that have peak energies close to the element of interest.
  • Compton normalization is per- formed, i.e. each elements adjusted rate were divided by the scatter produced in the light element (LE) region of the sample.
  • a regression analysis (for each element to be detected) is performed to calculate the slope and the intercept of the calibration curve.
  • the method comprises the steps of:
  • Calibrating with calibration standards comprising the steps of: 1) Scanning each of the calibration standards for tin compounds when placed on a respective piece of a boat hull material, and
  • a scan doesn't have to be made in each of the above disclosed steps 1-5 in the above preferred embodiment.
  • the method comprises the steps of :
  • each of the calibration standards for tin compounds comprising 1%, 16%, 8% and 16% tin compounds on a respective piece of a boat hull material, wherein the resulting single layer of standard is referred to as layer 3, and
  • each of the calibration standard for copper compounds comprising 2%, 2%, 8% and 8% copper compounds on top of the previous standards comprising 1%, 16%, 8% and 16% tin compounds, respectively, wherein the resulting single layer of standard is referred to as layer 2, and
  • each of the calibration standard for copper compounds comprising 2%, 2%, 8% and 8% copper compounds on top of the previous standards comprising 2%, 2%, 8% and 8% copper compounds, respectively, wherein the resulting single layer of standard is referred to as layer 1 , and
  • each of the calibration standards for tin compounds comprising 8%, 4%, 1%, 16% tin compounds on a respective piece of a boat hull material, wherein the resulting single layer of standard is referred to as layer 3, and
  • each of the calibration standard for zinc compounds comprising 2%, 4%, 8% and 16% zinc compounds on top of the previous standards comprising 8%, 4%, 1%, 16% tin compounds, respectively, wherein the resulting single layer of standard is referred to as layer 2, and
  • each of the calibration standard for zinc compounds comprising 2%, 4%, 8% and 16% zinc compounds on top of the previous standards comprising 2%, 4%, 8% and 16% zinc compounds, respectively, wherein the resulting single layer of standard is referred to as layer 1 , and
  • each of the calibration standards for tin compounds comprising 8%, 4%, 1% and 16% tin compounds on a respective piece of a boat hull material, wherein the resulting single layer of standard is referred to as layer 3, and
  • each of the calibration standards for zinc compounds comprising 4%, 2%, 8% and 16% zinc compounds on top of the previous standards comprising 8%, 4%, 1% and 16% tin compounds, respectively, wherein the resulting single layer of standard is referred to as layer 2, and
  • each of the calibration standard for copper compounds comprising 2%, 4% 16% and 18 % copper compounds on top of the previous standards compris- ing 4%, 2%, 8% and 16 % zinc compounds, respectively, wherein the resulting single layer of standard is referred to as layer 1 , and
  • layer 3 30 standard is referred to as layer 3
  • each of the calibration standards for zinc compounds comprising 2%, 4%, 8%, 16% and 32 % zinc compounds on a respective piece of a boat hull material, wherein the resulting single layer of standard is referred to as layer 3, and
  • each of the calibration standard for zinc compounds comprising 2%, 4%, 8%, 16% and 32 % zinc compounds on top of the previous standards comprising 2%, 4%, 8%, 16% and 32 % zinc compounds, respectively, wherein the resulting single layer of standard is referred to as layer 2, and
  • Steps i-xvii in the above preferred embodiment is representative of the variations of paint layers that can be found in boat hulls.
  • this preferred embodiment takes into consideration that boat hulls can have 1-5 layers of anti-fouling paints that each layer can comprise one or more of tin, copper and zinc compounds.
  • Step i represents a boat hull comprising three layers of anti-fouling paint comprising tin compounds in each layer.
  • Step ii represents tin compounds in the paint layer closest to the boat hull and copper compounds in the next two layers of anti-fouling paint.
  • Step iii represents tin compounds in the paint layer closest to the boat hull and zinc compounds in the next two layers of anti-fouling paint.
  • Step iv represents tin compounds in the paint layer closest to the boat hull, zinc compounds in the next layer of anti-fouling paint and copper compounds in the layer after.
  • Step v represents a boat hull coated with a single layer of anti-fouling paint comprising of tin compounds.
  • Step vi represents a boat hull coated with two layers of anti-fouling paint comprising of tin compounds.
  • Step vii represents a boat hull coated with a layer of anti-fouling paint comprising tin and zinc.
  • Step ix represents a boat hull comprising three layers of anti-fouling paint compris- ing copper compounds in each layer.
  • Step x represents a boat hull comprising one to four layers of anti-fouling paint comprising copper compounds in each layer.
  • Step xi represents a boat hull comprising three layers of anti-fouling paint comprising copper and zinc compounds in each layer.
  • Step xii represents a boat hull comprising three layers of anti-fouling paint comprising copper and zinc compounds in the two first layers closest to the boat hull and wherein the third layer comprising only anti-fouling paint without any tin, copper and zinc compounds.
  • Step xiii represents a boat hull coated with a single layer of anti-fouling paint comprising of copper compounds.
  • Step xiv represents a boat hull coated with a single layer of anti-fouling paint comprising of copper and zinc compounds.
  • Step V represents a boat hull comprising three layers of anti-fouling paint com- prising zinc compounds in each layer.
  • Step xvi represents a boat hull comprising one to four layers of anti-fouling paint comprising zinc compounds in each layer.
  • Step xvii represents a boat hull coated with a single layer of anti-fouling paint comprising of zinc compounds.
  • Anti-fouling paints comprising tin compounds such as organotin compounds (such as TBTO) were developed and used in the 1960s and 1970s. It can therefore be assumed that the oldest layers of anti-fouling paint on boat hulls comprise tin compounds such as organotin compounds. Hence, calibration standards for tin compounds are not placed on top of calibration standards of copper and zinc compounds.
  • the said calibration curves are stored in the handheld XRF-instrument.
  • the handheld XRF-instrument can be pre-calibrated by the manufacturer using the method for calibration and set of calibration standards disclosed in the present invention. This consequently allows for instant quantification of real samples, i.e. instant quantification of tin, copper and zinc compounds on boat hulls of leisure boats at the site where said leisure boats are harbored, stored, anchored etc.
  • said piece of boat hull material is of non-metallic material and free of anti-fouling paint.
  • steps a and b optionally comprise the steps of calibrating and providing calibration curves also of further compounds.
  • Said further compound is selected from one or more of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, barium and iron compounds.
  • Mercury, lead, arsenic, cadmium and chromium compounds as well as other toxic compounds have in the past been added to anti-fouling paints.
  • one or more of these compounds are also subjected to the method calibration so that they can also be quantified in the fourth and fifth objects of the invention.
  • the fourth object of the invention relating to the use of the set of calibration standards according to the above mentioned preferred embodiments (of the first and second objects) in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument, is attained by the following steps:
  • a Calibrating according to the third object of the invention
  • b Providing calibration curves of tin, copper and zinc compounds by plotting (log) ⁇ -Compton adjusted intensities of Sn, Cu and Zn and (log) chemically measured concentrations (pg/cm 2 ) of Sn, Cu and Zn in the standards, respectively, and optionally storing said calibration curves in the memory of said XRF-instrument, and
  • the fifth object of the invention relating to a method of quantifying the concentration of tin, copper and zinc compounds in anti- fouling paints with a handheld XRF instrument, by using the set of calibration standards according to the above mentioned preferred embodiments (of the first and second objects), comprising the steps of:
  • a Calibrating according to the third object of the invention
  • b Providing calibration curves of tin, copper and zinc compounds by plotting (log) ⁇ -Compton adjusted intensities of Sn, Cu and Zn and (log) chemically measured concentrations ( g/cm 2 ) of Sn, Cu and Zn in the standards, respectively, and optionally storing said calibration curves in the memory of said XRF-instrument, and
  • the fourth and fifth object of the invention is attained by using preferred embodiments of above mentioned set of calibration standards (of the first and second objects of the invention) and method for calibration (of the third object of the inven- tion). Consequently, the use of the preferred embodiments of the set of calibration standards and method for calibration, in said preferred embodiments of the fourth and fifth objects, results in the technical effects and advantages described in the above mentioned preferred embodiments of the set of calibration standards and method for calibration. Hence, these technical effects and advantages will not be repeated here once again.
  • said calibration curves are stored in the handheld XRF-instrument.
  • steps a-e comprise the steps of calibrating, providing calibration curves, scanning and quantifying also further compounds.
  • Said further compound is selected from one or more of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, barium and iron compounds.
  • Figure 1 Regression (calibration curve) for tin.
  • the X-axis shows the log value of the chemically analyzed concentration of tin while the y-axis displays the log value of Ko-Compton adjusted intensity.
  • Figure 2. Regression (calibration curve) for copper.
  • the X-axis shows the log value of the chemically analyzed concentration of copper while the y-axis displays the log value of ⁇ -Compton adjusted intensity.
  • Figure 3. Regression (calibration curve) for zinc.
  • the X-axis shows the log value of the chemically analyzed concentration of zinc while the y-axis displays the log value of ⁇ -Compton adjusted intensity.
  • the present invention relates to a set of calibration standards for use in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a portable XRF instrument. Further disclosed is a method for manufacturing the set of calibration standards as well as their use in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a portable XRF instrument. While the present invention has been described with reference to the below specific Example 1, which is intended to be illustrative only and not to be limiting of the disclosure, it is noted that changes, additions and/or deletions may be made to the disclosed example without departing from the spirit and scope of the disclosure. The scope of the disclosure is therefore not covered the specific example, but rather by the patent claims.
  • a handheld XRF analyzer was used for the purpose to build up an empirical model able to analyze the concentration of Sn, Cu and Zn in anti-fouling paints coated on boat hulls.
  • the XRF analyzer (DELTA-50) was manufactured by Olympus and is powered with a 4W, 50kV x-ray tube, which has the advantage to excite and de- tect heavy elements such as the K-lines of Sn.
  • the analyzer is equipped with a software that enables the setup of own empirical models for quantification of elements in different matrixes.
  • K a net intensity spectral peak were used since this electron transition, i.e. from L-shell to K-shell, is easiest to detect. Compton normalization was used to account for possible matrix effects.
  • the calibration curves were used in our own empirical model and tested in field on boat hulls coated with anti-fouling paints.
  • Empirical model development The standards were analyzed under controlled conditions in the XRF work station by applying the standards on the X-ray tube/detector. To simulate actual field conditions, i.e. boat hulls coated with anti-fouling paints, a plastic piece from a boat hull was allocated behind the standards during the analysis. The standards were scanned with the 50kV beam. Since leisure boats usually have several layer of coatings applied on their hull, the standards were analyzed both individually and together by applying two, three, four or five standards on top of each other (see tables 1-3). The calibration was done on the adjusted intensity of K a signals, i.e.
  • the standards were chemically analyzed for total concentration of Sn, Cu and Zn.
  • the (chemically analyzed) total concentration of Sn, Cu and Zn, the weight and area of the standards allowed us to calculate the total concentration per area, expressed as pg/cm 2 . (see the tables 1-3)
  • the standards were used to examine the relationship between measured Compton adjusted Ka intensities of Sn, Cu and Zn, respectively, and known concentrations of Sn, Cu and Zn in the standards.
  • a regression analysis (for each element) was performed to calculate the slope and the intercept of the calibration curve (see Figures 1-3).
  • a blind test was conducted to assess how well our anti-fouling paint application analysis Sn, Cu and Zn concentration in paint coatings with varying paint thickness/layers correlated.
  • the blind test was conducted by allowing coworkers to apply anti-fouling paints on Mylar films with brushes.
  • the coworkers had five different unlabeled anti-fouling paints (three commercially available containing Cu and Zn and two own-made TBT-paints) to choose between and were instructed to use at least two of them.
  • the aim of the present invention is to develop a XRF model that has the ability to quantify the total concentration of Sn, Cu and Zn on boat hulls.
  • the XRF-result for copper and zinc can be interpreted to arise primarily from copper (I) oxide and zinc (I) oxide, respectively.
  • Tin has to our knowledge, been added to paint formulation as organotin compounds only (primarily TBT). However, organotin compounds can be degraded in several stages and as a final step form non-toxic inorganic Sn.
  • the present invention was used on leisure boats in order to quantify the amount of Sn present on the boats' hull. If Sn was present, the paint was scraped off and collected in clean plastic bottles. In total paint scrapes from 31 boats were collected. The paint flakes were then send to a commercial laboratory (ALS Scandinavia), homogenized and analyzed for total tin and organotin compounds (see "Chemical analysis") in order to determine the proportion of TBT and other organotin compounds on leisure boat hulls.
  • Sample digestion and chemical analyze were performed by a commercial laboratory (ALS Scandinavia).
  • the standards were digested in a solution containing 5mL concentrated HNO3 and 5 mL concentrated HCI on a hotplate for 1 h.
  • the samples were diluted with Milli Q water and analyzed for total Sn, Cu and Zn concentrations by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS).
  • ICP-SFMS inductively coupled plasma-sector field mass spectrometry
  • R 2 0.97 and 0.98, respectively.
  • the LOD and LOQ for Sn were determined to 2.9 and 9.4 pg/cm 2 , respectively.
  • the LOD and LOQ for Cu were determined to 13.3 and 35.9 pg/cm 2 , respectively.
  • Zn the LOD and LOQ were quantified to 23.0 and 73.0 pg/cm 2 , respectively.
  • Example 1 The embodiment in Example 1 is modified by also including calibration standards for further compounds that might be toxic for the environment, such as one or more of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, iron and barium compounds in order to also quantify the concentrations of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, iron and/or barium compounds in anti-fouling paints on boat hulls.
  • organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, iron and/or barium compounds in order to also quantify the concentrations of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, iron and/or barium compounds in anti-fouling paints on boat hulls.
  • the method of quantifying the concentration of tin, copper, zinc in anti-fouling paints with a handheld XRF instrument comprises the steps of: a. Calibrating with calibration standards comprising the steps of:
  • the column “Number of layers” indicates the number of calibration standards placed on the piece of boat hull material; i.e. the number of layers which are scanned by the handheld XRF-instrument.
  • the column "First paint layer” indicates the calibration standard closest to the XRF-instrument, i.e. the handheld XRF instrument is pointed towards the "First paint layer” and a scan is performed.
  • the layer/standard underneath is referred to as “Second paint layer” and the one layer/standard underneath the "Second paint layer” is referred to as "Third paint layer”.
  • the most bottom layer is in contact with the piece of boat hull material.
  • the % TBTO value in parenthesis rep- resents the concentration wei htwei ht of wet la er of TBTO a lied to the film in the method for manufacturin said set of calibration standards.
  • the column "Scan identity” indicates a scan performed on the a layer of standards; please observe that Scan 1 , 2, 3 etc. in Tables'! -3 is the same scan, i.e. Sn, Cu and Zn are scanned at the same time.
  • the column titled “Zn 9/ ⁇ 2 " discloses the total chemically analyzed area concentration of Zn in the standards that are scanned.
  • the column “I Comp” indicates the detected Compton normalized XRF ⁇ -intensities.
  • the column “Number of layers” indicates the number of calibration standards placed on the piece of boat hull material; i.e. the number of layers which are scanned by the handheld XRF-instrument.
  • the column "First paint layer” indicates the calibration standard closest to the XRF-instrument, i.e. the handheld XRF instrument is pointed towards the "First paint layer” and a scan is performed.
  • the layer/standard underneath is referred to as “Second paint layer” and the one layer/standard underneath the “Second paint layer” is referred to as “Third paint layer” etc.
  • the most bottom layer is in contact with the piece of boat hull material.
  • the % ZnO value in parenthesis re resents the concentration wei htwei ht of wet la er of ZnO a lied to the film in the method for manufacturin said set of calibration standards.
  • the column "Scan identity” indicates a scan performed on the a layer of standards; please observe that Scan 1 , 2, 3 etc. in Tables'! -3 is the same scan, i.e. Sn, Cu and Zn are scanned at the same time.
  • the column titled “Cu pg/cm 2 " discloses the total chemically analyzed area concentration of Cu in the standards that are scanned.
  • the column “I Comp” indicates the detected Compton normalized XRF ⁇ -intensities.
  • the column “Number of layers” indicates the number of calibration standards placed on the piece of boat hull material; i.e. the number of layers which are scanned by the handheld XRF-instrument.
  • the column "First paint layer” indicates the calibration standard closest to the XRF-instrument, i.e. the handheld XRF instrument is pointed towards the "First paint layer” and a scan is performed.
  • the layer/standard underneath is referred to as “Second paint layer” and the one layer/standard underneath the “Second paint layer” is referred to as “Third paint layer” etc.
  • the most bottom layer is in contact with the piece of boat hull material.
  • the % CuO value in parenthesis re resents the concentration wei htwei ht of wet la er of CuO a lied to the film in the method for manufacturin said set of calibration standards.
  • Marine paints the particular case of anti-fouling paints. Prog. Org. Coat. 59, 2-20.

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Abstract

L'invention concerne un ensemble de normes d'étalonnage destinées à être utilisées dans un procédé de quantification de concentration de composés d'étain, de cuivre et de zinc dans des peintures antisalissures avec un instrument XRF portable. L'invention concerne également un procédé de formation de l'ensemble de normes d'étalonnage ainsi que leur utilisation dans un procédé de quantification de concentration de composés d'étain, de cuivre et de zinc dans des peintures antisalissures avec un instrument XRF portable.
PCT/SE2015/000044 2014-07-01 2015-07-01 Ensemble de normes d'étalonnage et leur utilisation dans un procédé de quantification de biocides dans des peintures antisalissures avec un instrument xrf portable WO2016003347A1 (fr)

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EP15815665.3A EP3164705A4 (fr) 2014-07-01 2015-07-01 Ensemble de normes d'étalonnage et leur utilisation dans un procédé de quantification de biocides dans des peintures antisalissures avec un instrument xrf portable

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SE1450814A SE537906C2 (sv) 2014-07-01 2014-07-01 Set of calibration standards and their use in a method of quantifying biocides in anti-fouling paints with a portable xrf instrument

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CN111323282A (zh) * 2020-04-10 2020-06-23 广州海关技术中心 一种含玩具领域限制的17种可迁移元素的油漆粉末标准样品的制备方法
CN111458362A (zh) * 2020-03-18 2020-07-28 广州海关技术中心 一种含玩具领域限制的8种重金属元素的聚乙烯塑料系列标准样品的制备方法
JP2021012054A (ja) * 2019-07-04 2021-02-04 日本電子株式会社 蛍光ｘ線分析装置及びその校正方法

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* Cited by examiner, † Cited by third party
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JP2021012054A (ja) * 2019-07-04 2021-02-04 日本電子株式会社 蛍光ｘ線分析装置及びその校正方法
CN111458362A (zh) * 2020-03-18 2020-07-28 广州海关技术中心 一种含玩具领域限制的8种重金属元素的聚乙烯塑料系列标准样品的制备方法
CN111323282A (zh) * 2020-04-10 2020-06-23 广州海关技术中心 一种含玩具领域限制的17种可迁移元素的油漆粉末标准样品的制备方法
CN111323282B (zh) * 2020-04-10 2022-09-06 广州海关技术中心 一种含玩具领域限制的17种可迁移元素的油漆粉末标准样品的制备方法

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