XRF-IDENTIFIABLE BLACK POLYMERS

Abstract

The invention subject of the present application concerns sorting of black plastics.

Claims

1-26. (canceled)

27. A composition comprising carbon black and at least one XRF-identifiable material, the composition being a pigment formulation or a reinforcement formulation, wherein the at least one XRF-identifiable material is present in an amount selected to provide an XRF-identifiable signature indicative of the carbon black or the composition comprising same.

28. The composition according to claim 27, comprising a polymer or a prepolymer.

29. An XRF-identifiable masterbatch composition comprising a homogenous blend of carbon black, at least one XRF-identifiable marker and at least one polymer or prepolymer.

30. The composition according to claim 28, wherein the polymer is a thermoplastic polymer or thermoset polymer.

31. The composition according to claim 30, wherein the polymer is selected from Low-Density Polyethylene (LDPE), Linear Low-Density Polyethylene (LLDPE), High-Density Polyethylene (HDPE), Polypropylene (PP), Polyisoprenes, natural rubber and latex.

32. The composition according to claim 27, wherein the ratio between carbon black and the at least one XRF-identifiable marker is at least 100:1, respectively.

33. A method for providing an XRF-identifiable black polymeric raw material, the method comprising marking a polymeric raw material with an amount of an XRF-identifiable marker and black carbon, the amount of the XRF-identifiable marker defining an electromagnetic radiation signature indicative of the raw material composition and/or production profile (a raw material data).

34. The method according to claim 33, wherein the profile comprises one or more data of manufacture, site of manufacture, composition, and presence or absence of unnatural additives.

35. A method for identifying a black plastic during sorting of plastic materials, the method comprising: irradiating with X-Ray or Gamma-Ray radiation a collection of plastic objects comprising black objects marked with at least one XRF-identifiable marker; detecting an X-Ray or Gamma-Ray signal arriving from the objects in response to the X-Ray or Gamma-Ray radiation applied thereto; and applying spectral processing to the detected radiation signal to obtain data indicative of the presence, absence or any change in the predefined characteristic relating to the black plastic.

36. The method according to claim 35, the method comprising: simultaneously irradiating a plurality of objects with at least one X-ray or Gamma-ray excitation beam having a spatially distributed modulated intensity; wherein the intensity of the beam arriving at each of the objects is different and identifiable and wherein the plurality of objects comprising black objects; detecting a secondary X-ray radiation arriving from the plurality of objects and generating signals indicative of the spatial intensity distribution on the plurality of objects; and identifying which of the plurality of black objects are marked by a marking composition according to the detected spatial intensity distribution.

37. The method according to claim 35, wherein the black objects are formed by marking a black plastic with at least one XRF-identifiable marker.

38. The method according to claim 35, wherein the predefined identifiable characteristic comprises the XRF-identifiable pattern concentration or encryption code.

39. A method of sorting black objects in a recycling process, the method comprising: providing measured data indicative of an electromagnetic radiation signature embedded in a black object; identifying radiation emitted from a material in response to X-Ray or gamma-ray radiation, said radiation having spectral features characteristic of the signature, thereby determining whether the material is a black object.

40. An X-Ray Fluorescence (XRF) method of managing black material recycling process, the method comprising: providing first measured data indicative of one or more first electromagnetic radiation signatures embedded in one or more black plastic object; analyzing the measured data to determine, for each of said one or more black plastic object, a respective plastic material condition data, wherein the respective plastic object condition data is indicative of preceding use of said plastic object; generating first sorting data for each of said one or more black plastic objects, based on the respective plastic material condition; and generating marking data for at least one of said one or more black plastic objects, based on the first sorting data, wherein the marking data includes data indicative of at least one marker to be introduced into each of said one or more plastic objects to provide electromagnetic radiation signal for managing a recycling process said one or more black plastic object, wherein the electromagnetic radiation signals of the measured data comprise X-Ray Fluorescence (XRF) signals; and the data indicative of the at least one marker correspond to the at least one marker responding by XRF response signals to XRF exciting radiation.

41. The method according to claim 40, further comprises utilizing at least one of the black plastic objects condition data and the sorting data of said plastic object and generating and storing certificate data characterizing a current condition of said black plastic object to be sorted.

42. The method according to claim 41, wherein the data indicative of the at least one marker is obtained from a database, storing, for each plastic material reuse type, data indicative of a life cycle of said plastic object in association with matching data about corresponding one or more markers.

43. The method according to claim 41, wherein the data indicative of the at least one marker may comprise data corresponding to (a) a number of a successive life cycle of said plastic material being recycled and (b) a successive product type for reuse of recycled plastic object.

44. The method according to claim 41, the method further comprises providing second measured data indicative of one or more second electromagnetic radiation signals originated by one or more contaminant elements presented in the plastic object after being sorted by introducing said marking therein.

45. The method according to claim 41, the method further comprises providing second measured data indicative of one or more second electromagnetic radiation signals originated by one or more contaminant elements presented in the black plastic object after being sorted by introducing said marking therein and updating the certificate data characterizing the black plastic object.

46. An XRF-identifiable pelletized powder comprising a homogenous blend of carbon black and an amount of at least one XRF-identifiable marker.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0084] In order to better understand the subject matter that is disclosed herein and to exemplify how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

[0085] FIGS. 1A-1C are graphs showing intensity as function of concentration for the different components in marker system A in the carbon black powder before pelletizing.

[0086] FIGS. 2A-2C are graphs showing intensity as function of concentration for the different components in marker system B in the carbon black powder before pelletizing.

[0087] FIGS. 3A-3C are graphs showing intensity as function of concentration for the 3 combinations of marker system A after pelletizing.

[0088] FIGS. 4A-4C Peak intensity as function of concentration for pelletized CB vs. powder CB: Marker system A

[0089] FIGS. 5A-5C are graphs showing B-Parts intensity as function of pelletized CBMarker system.

[0090] FIGS. 6A-6C are graphs showing peak intensity as function of concentration for pelletized CB vs. powder CB: Marker system B.

[0091] FIGS. 7A-7C are graphs showing intensity as function of concentration in CB MB for the different components in marker system A.

[0092] FIGS. 8A-8C are graphs showing intensity as function of concentration in CB MB for the different components in marker system B.

[0093] FIG. 9 is a graph showing red spectrumpeak signal for the three components of marker system B in thick sample containing 0.5 wt % CB MB loading. Blackunmarked sample.

[0094] FIG. 10 is a blue spectrumpeak signal for the three components of marker system B in single foil layer containing 2 wt % CB MB loading. Blackunmarked sample.

DETAILED DESCRIPTION OF EMBODIMENTS

[0095] The present disclosure relates to means and methods for marking/identifying black polymers products and is based on the development of specific markers/identifiable components that utilize X-ray fluorescence (herein: XRF), which enables identification and sorting of black plastics for recycling purposes.

[0096] The specific markings/identifiable components denoted herein XRF detectable/identifiable markers are added (incorporated) during the process of black plastic manufacture.

[0097] As shown in the examples below, the XRF-detectable/identifiable markers remained both stable and active (i.e. detectable) during the entire black plastic manufacturing process. Accordingly, XRF-detectable identifiable markers can be added in each one of the black plastic manufacturing steps, including, inter alia, in a dry blending step, in a pelletizing step, in compounding (i.e. masterbatch production) step, in a blowing step or in an injection molding step. This results in a wide range of XRF-identifiable intermediate products (e.g. powder, pelletized powder or masterbatch) as well as plastic products.

[0098] In accordance with the first of its aspects, the present disclosure provides a XRF-identifiable carbon black powder comprising carbon black and at least one XRF identifiable marker.

[0099] Powder as used herein in reference to the XRF-identifiable carbon black relates to fine, dry particles having a size of at most about 100 nm. Additionally, the particles may refer to a dry blend of at least one carbon black and at least one XRF identifiable marker.

[0100] In accordance with some embodiments, the XRF-identifiable carbon black powder is for use in the preparation of XRF-identifiable carbon black pelletized powder. In accordance with some further embodiments, the XRF-identifiable carbon black powder is subjected to a pelletizing process. In some embodiments, pelletizing the dry blend is by a wet pelletizing process to obtain the XRF-identifiable carbon black pelletized powder.

[0101] As appreciated by those versed in the field, the XRF-identifiable carbon black powder is subjected to pelletizing, for example, in order to coagulate the powder.

[0102] In accordance with some other aspects, the present disclosure provides an XRF-identifiable carbon black pelletized powder comprising a homogenous blend of carbon black and at least one XRF identifiable marker.

[0103] The XRF-identifiable marker in accordance with the present invention is a substance which includes at least one compound or element identifiable by XRF signature, namely, can be identified by XRF analysis (e.g., by an XRF analyzer), XRF analysis, that is analysis of the response X-ray signal, can be carried out by a suitable spectrometer such as XRF analyzer which may operate in uncontrolled environment without vacuum conditions (e.g. energy dispersive XRF analyzer which may be a benchtop, mobile or handheld device).

[0104] In some embodiments, the XRF-identifiable marker is a material having a XRF signature and may be selected in a form which includes one or more elements that are identifiable by XRF.

[0105] In some embodiments, the XRF-identifiable marker is or comprises at least one element of the periodic table of the elements which in response to x-ray or gamma-ray (primary radiation) radiation emits an x-ray signal (secondary radiation) with spectral features (i.e. peaks in a particular energy/wavelength) characteristic of the element (an x-ray response signal as XRF signature). An element having such response signal is considered XRF-sensitive.

[0106] The XRF signature may depend on the marking(s) (material compositions, concentrations, etc.) as well as the surface/structure of the specific product on or in which the markings has been embedded.

[0107] The XRF-identifiable marker may be in the form of salts or may be a material comprising at least one atom.

[0108] In some embodiments, the XRF-identifiable marker is or comprises at least one atom or comprises at least one atom selected from, Si, P, S, Cl, K, Ca, Br, Ti, Fe, V, Cr, Mn, Co, Ni, Ga, As, Fe, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, La and Ce.

[0109] In some embodiments, the XRF-identifiable marker is or comprises at least one metal atom.

[0110] In some other embodiments, the XRF-identifiable marker comprises at least one metal salt or a material comprising at least one metal atom.

[0111] In some embodiments, the XRF-identifiable marker is an atom or comprises at least one atom selected from Mo, Ag, Cr, Ti, Mn, K, Ca, Sc, V, Co, Ni, Zn, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd and In.

[0112] In some embodiments, the XRF-identifiable marker is a material comprising at least one atom selected from Mo, Ag, Cr, Ti, Mn, K, Ca, Sc, V, Co, Ni, Zn, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd and In.

[0113] In some embodiments, the XRF-identifiable marker is at least one atom or comprises at least one atom selected from Mo, Ag, Cr, Ti and Mn.

[0114] In some embodiments, the XRF-identifiable marker is a material comprising at least one atom selected from Mo, Ag, Cr, Ti and Mn.

[0115] In some embodiments, the XRF-identifiable marker is at least one metal atom within a carrier. In some embodiments, the XRF-identifiable marker is at least one metal atom within nanoparticles. In some embodiments, the XRF-identifiable marker is or comprises an Ag atom within nanoparticles.

[0116] In some other embodiments, the XRF-identifiable marker is or comprise at least one non-metal atom. In some other embodiments, the XRF-identifiable marker is or comprise at least one atom of P, Se, Br, S, Cl, I and Si.

[0117] In some embodiments, the XRF-identifiable marker is in the form of at least one of molybdenum disulfide, zinc oxide, manganese stearate, manganic oxide, manganese chloride, zinc diricinoleate, potassium bromide, chromium oxide, sodium bromide, titanium oxide, titanium nitride, ammonium bromide and calcium butyrate.

[0118] In some embodiments, the XRF-identifiable marker is in the form of at least one of zinc oxide, manganese stearate, manganese chloride, potassium bromide, chromium oxide, molybdenum disulfide, sodium bromide, titanium oxide, manganic oxide, titanium nitride, ammonium bromide and calcium butyrate.

[0119] In some embodiments, the XRF-identifiable marker is in the form of at least one, at least two or three of titanium oxide, molybdenum disulfide and silver atom.

[0120] In some embodiments, the XRF-identifiable marker is in the form of at least one, at least two or three of titanium oxide, manganic oxide and chromium oxide.

[0121] As described herein, the XRF-identifiable marker is mixed with a carbon black.

[0122] The amounts of the carbon black and the at least one XRF-identifiable marker in the identifiable carbon black may vary depending for example, on the end plastic product. Unless otherwise indicated, the amount of at least one XRF-identifiable marker in the identifiable carbon black or any ration thereof refers to the amount or ratio thereof of the active element in the XRF-identifiable marker. In other words, in cases where the XRF-identifiable marker is provided as a salt, for example, a metal salt, the amount of the XRF-identifiable marker or any ratio thereof is made in reference to the active element, i.e. the metal atom.

[0123] Generally, the lower the ratio between the carbon black and the at least one XRF-identifiable marker, the higher the XRF-identifiable marker loading and hence the detection is improved.

[0124] In some embodiments, the ratio between carbon black and the at least one XRF-identifiable marker in the pelletized product or in a composition of the invention is at least 100:1, respectively, or 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1 or 900:1.

[0125] In some other embodiments, the ratio between carbon black and the at least one XRF marker in the pelletized product is between about 100:1 and about 1000:1, respectively.

[0126] The XRF-identifiable carbon black pelletized powder comprising a homogenous blend of the carbon black and of the at least one XRF identifiable marker can be of any size or shape. For example, the pelletized powder is in a form of pellets with sizes ranging between about 30 and about 200 grains.

[0127] As described herein, the XRF-identifiable carbon black pelletized powder may be in accordance with some embodiments, produced by a pelletizing process.

[0128] In accordance with the present disclosure, the XRF-identifiable carbon black, being for example in the form of pelletized powder, is for use in a compounding process to obtain a masterbatch mixture. In some embodiments, the XRF-identifiable carbon black pelletized powder for use in preparing a masterbatch mixture

[0129] In accordance with some other aspects, the present disclosure provides an XRF-identifiable masterbatch (MB) mixture comprising a homogenous blend including carbon black, at least one XRF identifiable marker and at least one thermoplastic polymer.

[0130] The XRF-identifiable masterbatch (MB) mixture may be produced by using a XRF-identifiable carbon black or alternatively by compounding carbon black, at least one XRF identifiable marker and at least one thermoplastic polymer. In other words, the masterbatch mixture in accordance with the present disclosure may be obtained by either a XRF-identifiable carbon black compounded with at least one thermoplastic polymer formed a-priori or alternatively by compounding the three components individually.

[0131] The amounts of the at least one XRF-identifiable marker in the XRF-identifiable masterbatch mixture may vary. In some embodiments, the marked masterbatch comprises at least 0.05% w/w of the at least one XRF-identifiable marker, at times at least 0.08% w/w, at times at least 0.1% w/w, at times at least 2% w/w, at times at least 3% and at times at least 5% of the at least one XRF-identifiable marker.

[0132] In some embodiments, the marked masterbatch comprises between about 0.05% w/w to about 5% of the at least one XRF-identifiable marker, at times between about 0.1% w/w and about 4% w/w, at times between about 0.5% w/w and about 3% and at times between about 0.5% w/w and about 2% of the at least one XRF-identifiable marker.

[0133] In some embodiments, the XRF-identifiable masterbatch mixture comprising at least about 20%, at times at least about 30%, at times at least about 40% and at times at least about 50% of a thermoplastic polymer. In some embodiments, the XRF-identifiable masterbatch mixture comprising about 40% of a thermoplastic polymer.

[0134] As used herein, the term polymer should be understood as having the general meaning known by those skilled in art. Although not limited to, the polymer utilized according to the invention may be a plastic material. In some embodiments, the polymer is a thermoplastic polymer, i.e., exhibits a property in which a solid or essentially solid material turns upon heating into a hot flowable material and reversibly solidifies when sufficiently cooled. The term also denotes that the material has a temperature or a temperature range at which it becomes a hot flowable material.

[0135] In some embodiments, the polymer is selected from polyolefins, polyamides, polystyrenes, polyesters, polycarbonates, polyethylene terephthalates, polyurethanes, polyamides, polyimides, polyacrylonitriles polyvinyl alcohols and biaxially oriented polymer.

[0136] In some embodiments, the polymer is selected from polyolefins (e.g. high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP)); polyethylene terephthalate (PET); polystyrene (PS); polyvinylchloride (PVC); polyurethane (PU); polyamides (PA); polyacrylonitriles; polyimides; polyvinyl alcohols and biaxially oriented polymer.

[0137] In such embodiments, the polyolefin is selected from polypropylene and polyethylene.

[0138] In some embodiments, the polymer is a polyethylene. In some other embodiments, the polymer is low density polyethylene (LDPE).

[0139] The masterbatch of the present disclosure may be in the form of liquid, particle matter, particles or the like provided that it comprises a homogenous blend of the components. Hence, in accordance with the present disclosure, the XRF-identifiable marker may be incorporated into the at least one polymer (polymeric element) without substantially affecting the physical properties (i.e., optical and mechanical properties) of same polymer free of XRF-identifiable marker.

[0140] When referring to the XRF-identifiable marker being incorporated into the at least one polymer it is to be understood that the polymer and the at least one XRF-identifiable marker are being intimately held together by physical interactions therebetween. It was suggested that this allows the at least one XRF-identifiable marker to be homogenously distributed within the polymer, thereby contributing to the increased XRF signal.

[0141] The masterbatch mixture can include additional components, such as non-polymeric components. In some embodiments, the masterbatch mixture comprises an antioxidant, a UV-stabilizer, a flame retardant, a pigment, a stabilizer and a wetting agent.

[0142] In some embodiments, the masterbatch is in the form of particulate matter comprises particles. In some embodiments, the masterbatch is in the form of pellets. In some embodiments, each particle comprises a blend of at least one XRF-identifiable marker, a carbon black and at least one thermoplastic polymer.

[0143] In accordance with the present disclosure, XRF-identifiable masterbatch mixture can be used for the preparation of an article of manufacture by using for example any manufacture method known in the art. In some embodiments, the XRF-identifiable masterbatch mixture is for use in preparing an article of manufacture.

[0144] Thus, in some other aspects the present disclosure provides an XRF-identifiable article of manufacture comprising a homogenous blend comprising carbon black, at least one XRF identifiable marker and at least one thermoplastic polymer.

[0145] The article of manufacture in accordance with the present disclosure may be any plastic product, for example but not limited to plastic products used in the food industry (e.g. packing or equipment), in agriculture (e.g. tools, buckets or films), cosmetic industry (e.g. bottles) or automobile industry (e.g. tiers).

[0146] The article of manufacture comprises may comprise varying amounts of the at least one XRF identifiable marker, depending, for example on the size, shape of the article. In some embodiments, the article of manufacture comprises at least 2 ppm, at times at least at least 4 ppm, at times at least 8 ppm, at times at least 12 ppm, at times at least 16 ppm, at times at least 20 ppm, at times at least 24 ppm, at times at least 41 ppm, at times at least 50 ppm, at times at least 60 ppm and at times at least 500 ppm of the at least one XRF identifiable marker.

[0147] In some embodiments, the article of manufacture comprises between about 2 ppm and about 500 ppm of the at least one XRF identifiable marker, at times between about 4 ppm and about 60 ppm, at times between about 4 ppm and about 50 ppm, at times between about 8 ppm and about 41 ppm of the at least one XRF identifiable marker.

[0148] As further shown in the examples below, it was possible to differentiate marked black plastic from unmarked black plastic. Specifically, the results show the marking of the present invention using the at least one XRF identifiable marker is effective in a variety of articles of manufacture, including thick samples and thin samples.

[0149] As appreciate, the article of manufacture may be obtained by any method known in the art, including, for example, injection molding or blowing. As also appreciated, the process for the preparation of the article of manufacture comprises diluting a masterbatch mixture, for example, the XRF-identifiable masterbatch mixture of the present disclosure with at least one thermoplastic polymer. The at least one thermoplastic polymer that is added during preparation of the article of manufacture may be the same polymer as in the masterbatch mixture or may be a different polymer. In accordance with some embodiments, the polymer is the masterbatch mixture and the polymer added during preparation of the article of manufacture are at least compatible, at times identical.

[0150] The present disclosure provides in accordance with some aspects, a method of preparing an XRF identifiable article of manufacture, the method comprising: [0151] (i) pelletizing a mixture comprising carbon black and at least one XRF identifiable marker; [0152] (ii) melt blending pellets obtained from said pelletizing, with at least one thermoplastic polymer to form a molten; [0153] (iii) molding the molten to obtain said article of manufacture.

NON-LIMITING EXAMPLES

Materials and Methods

[0154] Samples of bare Carbon Black (CB) Printex 60A powder and black products were initially received for background characterization. Based on the analysis results, two markers system were designed denoted herein as A and B. Each marker system comprised a sequence of three components and tested at three different concentrations, total of 6 samples.

[0155] Marker A comprises MoS.sub.2, Silver NP and TiN and Marker B comprises TiN, Cr.sub.2O.sub.3 and Mn.sub.2O.sub.3.

[0156] Three combinations of each one of marker A and marker B were tested, such that three different combinations at different amounts of the three components in each combination were mixed with CB.

[0157] The following Tables 1 and 2 show details of the marker A and marker B.

TABLE-US-00001 TABLE 1 amounts of the components of marker A and CB Marker (g) CB (g) 1.sup.st combination MoS.sub.2 6.673 1984.156 Silver NP 4.000 1984.156 TiN 5.170 1984.156 2.sup.nd combination MoS.sub.2 10.10 1976.235 Silver NP 6 1976.235 TiN 7.756 1976.235 3.sup.rd combination MoS.sub.2 16.683 1960.391 Silver NP 10.00 1960.391 TiN 12.926 1960.391

TABLE-US-00002 TABLE 2 amounts of the components of marker B and CB Marker (g) CB (g) 1.sup.st combination TiN 5.170 1986.235 Cr.sub.2O.sub.3 5.846 1986.235 Mn.sub.2O.sub.3 5.747 1986.235 2.sup.nd combination TiN 7.756 1974.85 Cr.sub.2O.sub.3 8.769 1974.85 Mn.sub.2O.sub.3 8.621 1974.85 3.sup.rd combination TiN 12.926 1958 Cr.sub.2O.sub.3 14.616 1958 Mn.sub.2O.sub.3 14.368 1958

[0158] When referring to the active element in the marker, as can be seen in Table 3, the first combination in both marker A and marker B included 2000 ppm of each component, the second combination in both marker A and marker B included 3000 ppm of each component and the third combination in both marker A and marker B included 5000 ppm of each component.

TABLE-US-00003 TABLE 3 Various combinations of tested active element in marker A and marker B Marker A MoS.sub.2 Silver NP*, ** TiN CB (ppm)* (ppm) (ppm)* (ppm) Combination # 1 2000 2000 2000 992078 Combination # 2 3000 3000 3000 988117 Combination # 3 5000 5000 5000 980196 Reference 2000 *the active element is Mo, Ag and Ti and the amount provided in ppm correspond to the amount of the active element in the component, **NP-nanoparticles Marker B TiN* Cr.sub.2O.sub.3* Mn.sub.2O.sub.3* CB (ppm) (ppm) (ppm) (ppm) Combination # 4 2000 2000 2000 991618 Combination # 5 3000 3000 3000 987427 Combination # 6 5000 5000 5000 979045 *the active element is Ti, Cr and Mn and the amount provided in ppm correspond to the amount of the active element in the component.

[0159] After finalizing the different loadings (conc.1, conc.2, conc.3 for each marker system), the six markers combinations were mechanically mixed for approx. 5 minutes with CB powder (batch size: 2 kg each) at the amounts detailed in Table 1 and were subjected to a standard pelletizing step. The marked pelletized CB samples were then compounded with low-density polyethylene (LDPE) and loading instructions were sent for each combination to compensate on markers' addition. Table 4 shows the theoretical loading to compensate on markers' addition (originally 40 wt % CB is added) and actual loading which was added experimentally. As can be seen, the actual marked CB loading in all the samples was 40% regardless of the marker system concentration indicating that the markers' loading in the MB is lower than anticipated.

TABLE-US-00004 TABLE 4 CB loading in MB production Theoretical Experimental Loading (%) Actual Loading (%) Marked LDPE Marked LDPE Sample Description CB (wt %) (wt) CB (%) (%) Marker system A - Conc. 1 40.3195 59.685 40.000 60.00 Marker system A - Conc. 2 40.4811 59.519 40.000 60.00 Marker system A - Conc. 3 40.8083 59.197 40.000 60.00 Marker system B - Conc. 1 40.3382 59.668 40.000 60.00 Marker system B - Conc. 2 40.5093 59.497 40.000 60.00 Marker system B - Conc. 3 40.8560 59.140 40.000 60.00 Reference 60.000 40.000 60.00

[0160] When referring to the active element in the marker, the first combination in both marker A and marker B included 806 ppm of each component, the second combination in both marker A and marker B included 1210 ppm of each component and the third combination in both marker A and marker B included 2016 ppm of each component.

[0161] Next, all the above 7 CB MBs were mixed with LDPE resin at 0.5, 1, and 2 wt % and processed to produce 21 injection molded samples+21 foil samples for SMX detection, total 42 samples were produced. The compositions of the samples are shown in the Table below.

TABLE-US-00005 TABLE 5 Final products' composition MB loading in the final product (wt %) Marked CB-MB A - Conc. 1 0.5 1 2 Marked CB-MB A - Conc. 2 0.5 1 2 Marked CB-MB A - Conc. 3 0.5 1 2 Marked CB-MB B - Conc. 1 0.5 1 2 Marked CB-MB B - Conc. 2 0.5 1 2 Marked CB-MB B - Conc. 3 0.5 1 2 Reference (unmarked CB-MB) 0.5 1 2

TABLE-US-00006 TABLE 6 Final products' composition active element in final product (ppm) marker A - Conc. 1 for each component 4 8 16 marker A - Conc. 2 for each component 6 12 24 marker A - Conc. 3 for each component 10 20 41 marker B - Conc. 1 for each component 4 8 16 marker B - Conc. 2 for each component 6 12 24 marker B - Conc. 3 for each component 10 20 41 Reference 0 0 0

Results

Dry Mixing Step

[0162] Bare components at their powder form were mechanically mixed with CB powder for approximately 5 minutes. Each concentration was measured 3 times for homogeneity evaluation. The detection results for the three concentrations of marker system A are shown in Table 7 and FIG. 1.

TABLE-US-00007 TABLE 7 Detection results for the 3 combinations of marker system A Marker System A Component 1 Component 2 Component 3 Average STD R. STD Average STD R. STD Average STD R. STD (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) Conc. 1 383047.3 21886.21 6 141771 19356.16 14 476028.7 34292.45 7 Conc. 2 657588.3 25599.25 4 219447 15451.3 7 894815.7 13221.44 1 Conc. 3 1039791 16149.19 2 353790 17420.78 5 1288623 8265.02 1

[0163] Considering that the bare marker components were mixed with the CB powder for only few minutes, all the three components showed distinguish peaks and all concentrations can be separated from each other. The relative STD (=100*std/average), which is indication for homogeneity, is considerably low for all the three components suggesting good homogeneity of markers' component in the CB powder.

[0164] The detection results for the different components for marker system B are shown in Table 8 and FIG. 2. Same here, each concentration was measured 3 times for homogeneity evaluation.

TABLE-US-00008 TABLE 8 Detection results for the 3 combinations of marker system B Marker System B Component 1 Component 2 Component 3 Average STD r. STD Average STD r. STD Average STD r. STD (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) concentration 1 592443.7 54622.35 9 778458 39045.93 5 517802 20099.81 4 concentration 2 819181.7 19914.93 2 1012437 5011.14 0.5 982201.3 72448.68 7 concentration 3 1398773 64262.25 5 1701970 164035.8 10 1829376 154316.1 8

[0165] All the three components in marker system B showed clear peaks. Same as shown in marker system A, also marker system B presented distinguish peaks in each concentration and all peaks were well separated from each other. However, when comparing the two marker systems, marker system B showed lower relative STD values in all the concentrations, suggesting that marker system B has potentially better distribution in CB powder.

Pelletizing Step

[0166] All components were analyzed after pelletizing to evaluate the quality of dispersion. From each concentration 3 measurements were taken and results for marker system A are shown in Table 9 and FIG. 3. As evident from the results, all components showed relative STD below 10 in all the concentrations, indication of good dispersion quality.

TABLE-US-00009 TABLE 9 Detection results for the 3 combinations of marker system A after pelletizing step Marker System A Component 1 Component 2 Component 3 Average STD R. STD Average STD R. STD Average STD R. STD (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) concentration 1 905317.7 42904 5 304808.3 26090 9 586227.3 14992.95 3 concentration 2 1386094 2295 0.2 461442.3 5185.01 1 899036.7 28666.18 3 concentration 3 2094822 52237 2 645441.7 13170.81 2 1265099 25730 2

[0167] Evaluation of dispersion quality before and after pelletizing was also studied by comparing the components' intensity before pelletizing (powder form) and after pelletizing. The results are plotted in FIG. 4 where dark colors specify components after pelletizing and light colors specify components before pelletizing.

[0168] As shown in FIG. 4, both components 1 and 2 showed higher peak intensity after pelletizing suggesting an improvement in dispersion quality. Component 3 on the other hand did not present increase in peak intensity after pelletizing and it can be assumed that maximum dispersion already reached in the dry mixing step.

[0169] Same as done for marker system A, was repeated for marker system B and all components were analyzed after pelletizing to evaluate the quality of dispersion. From each concentration 3 measurements were taken and results for marker system B re shown Table 10 and FIG. 5. As shown in FIG. 5, all the three components in marker system B presented relative STD below 5 in all the concentrations, lower than the values obtained in marker system A. As the lower the relative standard deviation the better the dispersion quality in CB, it can be concluded that the dispersion quality of marker system B is superior than marker system A. This supports our previous claim that marker system B is more compatible with CB powder.

TABLE-US-00010 TABLE 10 Detection results for the 3 combinations of marker system B after pelletizing step Marker System B Component 1 Component 2 Component 3 Average STD R. STD Average STD R. STD Average STD R. STD (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) concentration 1 616915.3 13568.29 2 895194.7 27058.02 3 1076165 19190.31 2 concentration 2 832225.3 23669.21 3 1256152 33297.48 3 1483002 35585.84 2 concentration 3 1570542 17834.78 1 2179145 2181.62 0.1 2495610 5144.72 0.2

[0170] Evaluation of dispersion quality before and after pelletizing was also studied for marker system B and results are plotted in FIG. 6.

[0171] As can be seen, all the three components showed an increase in peak intensity after pelletizing suggesting that this step is essential to achieve high dispersion in CB.

[0172] Summarizing this step, pelletizing increases components detectability and decreases relative STD values, indication that the dispersion of all components in both systems was improved.

Compounding Step

[0173] All pelletized CB were mixed at 40 wt % with 60 wt % LDPE and compounded to produce marked CB MB. The detection results for marked CB MB containing marker system A are shown in Table 11 and FIG. 7. As expected, with decreasing CB loading (from 100 to 40 wt % in MB), the average intensity for all the components decreases, however without major changes in the relative STD supporting again our observation that the resultant dispersion after pelletizing is good.

TABLE-US-00011 TABLE 11 Detection results for the 3 combinations of marker system A after compounding step Marker System A Component 1 Component 2 Component 3 Average STD R. STD Average STD R. STD Average STD R. STD (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) concentration 1 549082.3 11370.6 2 192561.2 3177.8 2 266865.7 4865.38 2 concentration 2 772427.7 11158.84 1 254256.8 3547.7 1 371409 14965.36 4 concentration 3 1357321 47939.58 4 420058.2 20987.2 5 582088.8 38002.7 7

[0174] The detection results for marked CB MB containing marker system B are shown in Table 12 and FIG. 8. Same as observed with marker system A, with decreasing CB loading (from 100 to 40 wt % in MB), the average intensity for all the components of marker system B decreases without major changes in the relative STD.

TABLE-US-00012 TABLE 12 Detection results for the 3 combinations of marker system B after compounding step Marker System B Component 1 Component 2 Component 3 Average STD R. STD Average STD R. STD Average STD R. STD (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) concentration 1 259056.5 8827.74 3 444275.8 15853.8 4 537775.8 19038 4 concentration 2 372197.2 10208.8 3 664725.8 13697 2 789838.5 10944.7 1 concentration 3 757557.5 40202 5 1233133 59312.9 5 1427703 75575.7 5

[0175] In order to measure in percentage, the component's intensity in the MB and assess if they follow the same reduction as the CB (from 100 to 40 wt %), equation 1 was used:

[00001]$\begin{array}{cc}\mathrm{component}\%\mathrm{in}\mathrm{MB}=100*\frac{I_{MB}}{I_P}& \left(1\right)\end{array}$ [0176] where [0177] I.sub.MB is the average intensity of the 3 components in the MB [0178] I.sub.p is the average intensity of the 3 components in the pelletized CB

[0179] The average results are shown in Table 13 for the different concentration of marker system A & B. As can be seen, all the concentrations showed on average 40 wt % components loading in the MB which perfectly aligned with the CB loading in the MB. This again supports the suggestion that the components are homogenously dispersed.

TABLE-US-00013 TABLE 13 Average components loading the CB MB Marker system A Marker system B Average R. STD Average R. STD Conc. (%) (%) Conc. (%) (%) Component 1 1 39 0.02 1 41 0.03 Component 2 2 38 0.01 2 41 0.03 Component 3 3 40 0.01 3 41 0.03

Samples Production Step

Dispersion Quality Analysis

[0180] The average intensity results and relative STD for all the combinations in thick samples are shown in Table 14 and Table 15 for marker system A and B respectively. As expected, all components showed increase in intensity with increasing CB MB loading. Looking at the relative STD values (=dispersion quality), no clear trend was observed with increasing component concentration. In marker system A, component 1 presented good dispersion, component 2 poor dispersion and component 3 medium dispersion in the final product. In marker system B, component 1 showed inferior dispersion (higher relative STD values) compared to components 2 and 3 in concentrations 1 and 2. In concentration 3, all components showed decrease in dispersion quality.

TABLE-US-00014 TABLE 14 Average intensity for all the combinations in Marker system A on thick samples Marker System A Wt % Component 1 Component 2 Component 3 marked Average STD R. STD Average STD R. STD Average STD R. STD CB MB (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) Conc. 1 0.5 88.19 6.22 7% 32.53 16 49% 64.68 9.6 15% 1 118.06 5.32 5% 40.84 12.18 30% 108.8 13.62 13% 2 228.03 27.35 12% 105.1 23.27 22% 208.48 38.97 19% Conc. 2 0.5 98.55 4.52 5% 26.05 10.66 41% 77.56 8.9 11% 1 155.44 17.26 11% 59.11 10.42 18% 164.36 25.95 16% 2 281.23 35.91 13% 137.14 46.99 34% 261.79 21.04 8% Conc. 3 0.5 151.85 18.79 12% 55.3 11.08 20% 131.43 25.04 19% 1 279.94 46.75 17% 113.66 29.03 26% 239.96 55.49 23% 2 605.53 19.22 3% 287.31 24.85 9% 574.63 22.89 4%

TABLE-US-00015 TABLE 15 Average intensity for all the combinations in Marker system B on thick samples Marker System B wt % Component 1 Component 2 Component 3 marked Average STD R. STD Average STD R. STD Average STD R. STD CB MB (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) Conc. 1 0.5 50.23 7.63 15% 105.88 6.6 6% 108.9 4.69 4% 1 109.1 9.21 8% 257.35 17.57 7% 323.63 30.28 9% 2 188.47 16.45 9% 453.47 43.9 10% 574.83 62.86 11% Conc. 2 0.5 73.85 13.73 19% 193.98 14.16 7% 236.09 18.74 8% 1 97.58 13.8 14% 303.46 34.98 12% 377.58 35.05 9% 2 243.35 12.3 5% 749.34 33.34 4% 972.06 33.11 3% Conc. 3 0.5 119.81 21.8 18% 352.68 70.21 20% 467.27 103.14 22% 1 280.42 38.2 14% 737.15 102.56 14% 1026.93 165.24 16% 2 471.23 80.49 17% 1287.5 187.99 15% 1798 227.01 13%

[0181] The average intensity results and relative STD for all the combinations on thin foils was also studied and results are shown in Table 16 and 17 for marker system A and B respectively. For marker system A the analysis was made on 4 foil layers whereas for marker system B on single layer. Same as also shown on thick samples, all components showed increase in intensity with increasing CB MB loading, this was expected as the actual loading of the component increases with increasing CB MB loading. Moreover, with increasing components' concentration no trend was observed in relative STD indicating that the dispersion quality did not change. Same observation given for Marker system A on thick samples is seen on foils where component 1 presented good dispersion, component 2 poor dispersion and component 3 medium dispersion in the final product. In marker system B, component 1 showed inferior dispersion (higher relative STD values) compared to components 2 and 3 in all concentrations. Unlike the thick samples, concentration 3 showed similar dispersion quality to concentration 1 and 2.

TABLE-US-00016 TABLE 16 Average intensity for all the combinations in Marker system A on thin foils Marker System A Wt % Component 1 Component 2 Component 3 marked Average STD R. STD Average STD R. STD Average STD R. STD CB MB (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) Conc. 1 0.5 73.4 9.39 13% 21.73 12.54 58% 13.49 2.04 15% 1 81.09 9.04 11% 22.53 13.14 58% 22.93 1.76 8% 2 113.47 19.58 17% 15.06 4.87 32% 43.45 6.66 15% Conc. 2 0.5 67.49 5.06 8% 18.81 8.73 46% 11.91 2.15 18% 1 92.56 12.1 13% 19.32 6.13 32% 28.22 2.27 8% 2 128.22 18.62 15% 22.39 10.01 45% 53.42 6.27 12% Conc. 3 0.5 100.29 5.22 5% 22.23 11.02 50% 29.84 4.57 15% 1 148.46 17.81 12% 33.97 21.07 62% 59.05 4.59 8% 2 210.84 15.39 7% 34.12 16.97 50% 97.8 9.8 10%

TABLE-US-00017 TABLE 17 Average intensity for all the combinations in Marker system B on thin foils Marker System B Wt % Component 1 Component 2 Component 3 marked Average STD R. STD Average STD R. STD Average STD R. STD CB MB (a.u) (a.u) (%) (a.u) (a.u) (%) (a.u) (a.u) (%) Conc. 1 0.5 6.76 1.62 24% 24.31 2.38 10% 45.9 5.01 11% 1 10.78 2.72 25% 30.02 4.14 14% 56.19 5.35 10% 2 17.35 2.81 16% 44.52 4.37 10% 71.61 4.52 6% Conc. 2 0.5 7.12 1.6 22% 26.85 2.7 10% 48.62 5.98 12% 1 12.07 1.61 13% 33.07 3.12 9% 60.43 2.41 4% 2 21.28 2.82 13% 54.22 3.64 7% 82.36 4.45 5% Conc. 3 0.5 11.88 1.74 15% 33.91 3.49 10% 57.61 6.85 12% 1 21.92 2.14 10% 51.6 4.74 9% 82.04 5.21 6% 2 44.42 3.46 8% 97.63 7.83 8% 137.38 15.05 11%

Separation Between Marked and Unmarked Products

[0182] The aim was to design one marking solution the is capable to distinguish marked from unmarked product for variety of applications that use different CB MB loadings ranging from approx. 0.5 to 2 wt %. Hence, finding the right marker system concentration that is suitable for different CB MB loadings on both thin (foils) and thick (injected) samples was studied.

Thick Samples (Injected Parts)

[0183] The results for thick samples are shown in table 18 and 19 for marker system A and B respectively. The results show that for thick samples, the lowest marker concentration (conc. 1) is sufficient to differentiate marked from unmarked sample in all the different CB MB loadings (0.5, 1 and 2 wt %) with accuracy greater than 95%.

TABLE-US-00018 TABLE 18 Minimum components concentrations needed in marker system A to differentiate marked from unmarked thick sample for different applications Marker system A Components' conc. needed to differentiate 0.5 wt % CB MB 1 wt % CB MB 2 wt % CB MB Injected loading from loading from loading from samples reference Accuracy reference Accuracy reference Accuracy component 1 Conc. 1 >95% Conc. 1 >95% Conc. 1 >95% component 3 Conc. 1 >95% Conc. 1 >95% Conc. 1 >95% *Component 2 was excluded from the analysis due to poor performance

TABLE-US-00019 TABLE 19 Minimum components concentrations needed in marker system B to differentiate marked from unmarked thick sample for different applications Marker System B Components' conc. needed to differentiate 0.5 wt % CB MB 1 wt % CB MB 2 wt % CB MB Injected loading from loading from loading from samples reference Accuracy reference Accuracy reference Accuracy component 1 Conc. 1 >95% Conc. 1 >95% Conc. 1 >95% component 2 Conc. 1 >95% Conc. 1 >95% Conc. 1 >95% component 3 Conc. 1 >95% Conc. 1 >95% Conc. 1 >95%

[0184] To emphasize high separation capability between marked and unmarked sample, the spectrum of marker system B conc.1 at 0.5 wt % CB MB loading is presented in FIG. 9. The black spectrum represents reference sample (unmarked) while the red spectrum represents the marked sample. As can be clearly seen, all three components present good peak repeatability and don't overlap with the reference line.

Thin Samples (25 m Foils)

[0185] Same analysis was conducted on thin films and the results for marker system A are presented in Table 20. From 4 layers onwards (>100 m) good differentiation between marked and unmarked sample is obtained for all the different CB MB loadings (0.5, 1 and 2 wt %) with minimum accuracy of 86%. As expected, at the lowest CB MB loading (0.5 wt %) the maximum marker concentration needed (conc. 3) and with increasing CB MB loading to 1 and 2 wt % the required marker concentration decreases to conc. 2. and conc. 1.

TABLE-US-00020 TABLE 20 Minimum components concentrations needed in marker system A to Marker system A Components' conc. needed to differentiate 0.5 wt % CB MB 1 wt % CB MB 2 wt % CB MB Blown film- loading from loading from loading from 4 layers reference Accuracy reference Accuracy reference Accuracy component 1 Conc. 3 >95% Conc. 3 >95% Conc. 1 >86% component 3 Conc. 3 >95% Conc. 2 >95% Conc. 2 >95% *Component 2 was excluded due to poor performance indicates data missing or illegible when filed

[0186] In marker system B, superior results were obtained. The results in Table 21 show that from 1 layer onwards (>25 m) good differentiation between marked and unmarked sample is obtained for the different CB MB loadings (0.5, 1 and 2 wt %) with minimum accuracy of 80%. The same trend observed in marker system A follows here where at the minimum CB MB loading (0.5 wt %) high marker concentration (conc.3) is required and with increasing CB MB loading (1 and 2 wt %) the required marker concentration decreases (conc2. And conc. 1).

TABLE-US-00021 TABLE 21 Minimum components concentrations needed in marker system B to differentiate marked from unmarked thick sample for different applications Marker system B Components' conc. needed to differentiate 0.5 wt % CB MB 1 wt % CB MB 2 wt % CB MB Blown film - loading from loading from loading from 1 layer reference Accuracy reference Accuracy reference Accuracy component 1 Conc. 3 >95% Conc. 2 >95% Conc. 1 >95% component 2 Conc. 2 > 80% Conc. 2 >86% Conc. 1 >95% Conc. 3 >95% component 3 Conc. 3 >95% Conc. 2 >86% Conc. 1 >95% Conc. 3 >95%

[0187] FIG. 10 plots the spectrum for marker system B conc.1 at 2 wt % CB MB loading to show the separation capability between marked and unmarked film. The black spectrum represents reference sample (unmarked) while the blue spectrum represents the marked sample. As can be clearly seen, all three components present good peak repeatability and do not overlap with the reference line.

Distinction Between the Different CB Loadings

[0188] The ability to separate different CB MB loading was also studied with the goal to show the XRF identifiable marker ability to generate multiple codes by using the same components at different concentrations.

[0189] The ability of marker system A to separate accurately between ref to 0.5 wt %, 0.5 to 1 wt % and 1 to 2 wt % CB MB loading is presented in Table 22. The results show that at conc.1 all MB concentrations can be separated with accuracy >86%. At conc.2 all MB concentrations can be separated with accuracy >95%. Surprisingly, at conc.3 all MB concentrations can be separated with accuracy >68%. From the intensity results of conc. 3, 1 wt % CB MB loading did not present 2 increase in intensity from 0.5% MB. Since this was true for all the components, we believe there might be a weighing error at 1 wt % CB loading. It should be noted that based on 9 measurements at different locations, none of the peaks were overlapping with each other between ref, 0.5, 1 and 2, and the accuracy is based on statistics only.

TABLE-US-00022 TABLE 22 Separation of different CB MB loading as function of marker system concentration for thick samples. % Accuracy between Marker System A Ref-0.5 wt % 0.5-1 wt % 1-2 wt % Injected samples MB MB MB Component 1 Conc. 1 99.7 98 99.7 Component 2 99.7 86 86 Component 1 Conc. 2 99.7 95 95 Component 2 99.7 95 95 Component 1 Conc. 3 99.7 86 99.7 Component 2 99.7 68 99.7

[0190] The ability of marker system B to separate accurately between ref to 0.5 wt %, 0.5 to 1 wt % and 1 to 2 wt % CB MB loading is presented in Table 23. At conc.1 all CB MB concentrations can be separated with accuracy >98%. At conc.2 all MB concentrations can be separated with accuracy >86%. Surprisingly, at conc.3, all MB concentrations can be separated with accuracy >68%. This supports our previous observation in section 6.4.1 that all components showed decrease in dispersion quality (=high relative STD) in concertation 3. Same as noted for marker system A, based on 9 measurements none of the peaks were overlapping with each other between ref, 0.5, 1 and 2, and the accuracy is based on statistics only.

TABLE-US-00023 TABLE 23 Separation of different CB MB loading as function of marker system concentration for thick samples. % Accuracy between Marker System B Ref-0.5 wt % 0.5-1 wt % 1-2 wt % Injected samples MB MB MB Component 1 Conc. 1 99.7 99.7 99.7 Component 2 99.7 99.7 99.7 Component 3 99.7 99.7 98 Component 1 Conc. 2 99.7 95 99.7 Component 2 99.7 95 99.7 Component 3 99.7 95 99.7 Component 1 Conc. 3 99.7 98 68 Component 2 99.7 95 86 Component 3 99.7 99.7 86

Thin Samples (25 m Foils)

[0191] The ability of marker system A to separate accurately between ref to 0.5 wt %, to 1 wt % and 1 to 2 wt % CB MB loading on 4 layers of foils is presented in Table 24. As can be seen from the table below, at conc.3 all MB concentrations can be separated with minimum accuracy of 86%. Component 1 showed increase in accuracy with increasing its concentration, while component 2 showed accuracy of 99.7% in all the concentration. It should be noted that based on 9 measurements at different locations, none of the peaks were overlapping with each other between ref, 0.5, 1 and 2, and the accuracy is based on statistics only.

TABLE-US-00024 TABLE 24 Separation of different CB MB loading as function of marker system concentration for thin samples. % Accuracy between Marker System A Ref-0.5 wt % 0.5-1 wt % 1-2 wt % Thin film - 4 layers MB MB MB Component 1 Conc. 1 38 0 68 Component 2 99.7 99.7 99.7 Component 1 Conc. 2 38 68 68 Component 2 99.7 99.7 99.7 Component 1 Conc. 3 99.7 95 86 Component 2 99.7 99.7 99.7

[0192] The ability of marker system B to separate accurately between ref to 0.5 wt %, to 1 wt % and 1 to 2 wt % CB MB loading on single foil layer is presented in Table Marker system B presents superior results one single foil layer and at conc.3 all MB concentrations can be separated with minimum accuracy of 95%. All components showed increase in accuracy with increasing their concentration. Same as noted for marker system A, based on 9 measurements none of the peaks were overlapping with each other between ref, 0.5, 1 and 2, and the accuracy is based on statistics only.

TABLE-US-00025 TABLE 25 Separation of different CB MB loading as function of marker system concentration for thin samples. % Accuracy between Marker System B Ref-0.5 wt % 0.5-1 wt % 1-2 wt % Thin film - 1 layer MB MB MB Component 1 Conc. 1 38 38 68 Component 2 0 38 86 Component 3 38 38 86 Component 1 Conc. 2 68 86 95 Component 2 38 68 99.7 Component 3 38 68 99.7 Component 1 Conc. 3 99.7 98 99.7 Component 2 95 95 99.7 Component 3 95 95 95