PROCEDURE AND MEANS FOR MEASURING WITH THE AID OF A RADIOSOTOPE SOURCE THE DISTRIBUTION OF FILLERS IN A WEB

Abstract: A procedure and means for non-destructively measuring the distribution of the filler and/or coating materials in the thickness direction of paper or cardboard. Radiation from a radio-isotope source is used to excite in the material component its characteristic x-ray radiation, the intensity of this radiation being observed. Measurements are made on both sides of the paper and the contents of other filler components are also determined by x-ray absorption in order to eliminate the effects of these components disturbing the distribution measurement. The base weight of the paper is measured e.g. by beta radiation absorption. Measurements are made both by measuring the characteristic radiation of the material components excited in the paper with different radiation sources and with the aid of absorption measurements of radiation directly from the source or produced with its aid in transformation targets, thus eliminating the effects of these components.

Description: PROCEDUREANDMEANSFORMEASURING.WITHTHEAIDOFARADIOSOTOPE SOURCETHEDISTRIBUTIONOFFILLERSINAWEB The present invention concerns a procedure for measuring the dis¬ tribution in the thickness direction of filler and/or coating materials of paper, cardboard or equivalent and the contents of said materials without destroying the sample, in said procedure the radiation emitted by an x-ray tube being used to excite in the material component under examination of the object under measure¬ ment its characteristic x-ray radiation, the intensity of this radiation being observed, and in which procedure measurements are carried out on both sides of the specimen under examination and in addition the contents of other filler components are determined by x-ray radiation absorption measurements in order to eliminate the effects of said components interfering with the distribution measurement, and the base weight of the paper is determined by beta radiation absorption measurement or by another equivalent procedure. Furthermore, the present invention concerns a means applying the procedure and novel uses of the procedure and the means. When paper and paper machines are discussed in the following, reference is generally made both to paper and cardboard, and respectively both to paper and cardboard machines. Fillers, which as a rule are mineral substances, are incorporated in the paper primarily for their effect of improving the printing technological properties. Fillers are most commonly used for printing papers. The filler addition improves the opacity, light¬ ness, printer's ink absorption and surface smoothness of the paper. y The fillers influence in a particularly advantageous manner the quality of paper to be glazed. It is known in the art to add filler material in two ways, either by mass filling or by coating. In the former procedure, the filler material is added in the form of suspension to the pulp sludge before the arrival of the sludge on the paper machine, whereby the filler material is admixed to the entire fibre material in the finished paper. In the latter procedure, a suitable glue substance is admixed to the filler material in the aqueous phase, such as starch or casein, whereafter the surface of the paper is brushed with this mixture in a continuous process. The filler materials in paper tend to be non-uniformly distributed in the thickness direction of the paper, causing one-sidedness of the paper. The one-sidedness of paper manufactured on Fourdrinier machines is due to the fact that the fillers are washed out together with the water that is drained, from the lower part of the pulp web into the drainage water, whereby they become enriched in the upper part of the web. As is known in the art, endeavours have been made to reduce the problems of one-sidedness, not only by additives improving the retention, but also by gentle dewatering at the initial draining phase, which requires a longer dewatering time and therefore implies lengthening the wire section or reducing the speed of the paper machine. In machines with a planar wire, the difficulties with the fines and filler distribution manifest themselves when papers for offset printing are manufactured. A high filler and fines content on the top surface of the paper causes dusting, which is a serious detri¬ ment in the offset process. In contrast, papers manufactured on a twin wire machine are considered well appropriate for offset print¬ ing. This is due to the symmetrical shape of the fines distribution and to equal leaching of both surfaces of the web owing to two-sided dewatering. It is in fact generally held that owing to more uniform fines distribution, the printing by offset on paper manufactured on a twin wire machine is more successful than that on paper manu- factured on a Fourdrinier machine. Offset printability has indeed increased in significance because offset printing is increasingly replacing the letterpress printing procedure. On the other hand, the filler content of the surfaces of the paper web cannot always be brought on desired level with a twin wire former, and even when using planar wires only the top side of the web (the side facing away from the wire) is satisfactory as to its filler content. The low filler content of the web surface is par- ticularly problematic in so-called SC gravure papers. Attempts may be made to increase the filler content of the paper surfaces by increasing the filler content of the pulp in the headbox, but even with this expedient no satisfactory condition is achieved because of the above-mentioned poor retention characteristic of the filler and of its enriching in the inner parts of the paper. In addition, when the filler content in the headbox has to be increased, the consistency in the headbox is likely to become excessive so that it impairs the formation of the paper. Modern high-speed printing presses impose particularly high re¬ quirements on the printing paper. These requirements are based on trouble-free operation of fast printing presses and on the appear¬ ance of the printing. The imprint is considerably influenced by the symmetry between the sides of the paper and the quality of the surfaces of the paper, which is naturally also influenced by the distribution of the fillers. Heretofore no procedures and means have been in use with which the filler distribution could have been measured even on line either on the paper machine, on the printing press or on the paper coating means. The object of the present invention is therefore to provide a new procedure and means suited, in addition to laboratory measurements, for the uses mentioned and which renders possible the control and adjustment of the manufacturing process on the paper machine on the basis of filler distribution measurements. It is known in the art (e.g. the Finnish Patent No. 40587; inven¬ tors: Juhani uusi and Antti Lehtinen, applicant: Valmet Oy) to excite the characteristic x-ray radiation of the filler material by means of radiations (alfa, beta, gamma or x-ray radiation) pen¬ etrating into various depths in the paper, and in this ways to gain information on the vertical distribution of the filler. The procedure has been described in greater detail in: J. Kuusi, Determination of Content and Distribution of Filler and Coating Materials in Paper Using Radioisotope X-Ray Spectrometry, Paper and Timber No. 4A (1970). As was observed in the paper, variations in relation to each other of the filler contents cause certain effects of which the quantitative elimination is impossible by the procedures described in the paper. This has impeded the introduc¬ tion in practice of the procedures. As regards filler measurements, the state of art Is illustrated in general by the publication of April 1982: Buchnes A., McNelles L.A. , Hewitt J.S., The Application of X-Ray Absorption and Fluorescence Analysis to the Measurement of Paper Additivies, Int. J. Appl. Radiat. Isot. Vol. 33, pp. 285 to 292 (1982), where a fluorescence and absorption technique is used to the purpose of determining the total contents of different fillers, based on the assumption that the fillers are uniformly distributed in the thick¬ ness direction of the paper. In practice, this Is hardly ever the case. It is thus understood that in said publication, and likewise in the references cited, therein and in its author's patent: "On-Line System for Monitoring Sheet Material Additivies", U.S. Patent No. 4,081,676, March 1978, no endeavours whatsoever have been made to determine the important thickness-direction distribution, nor has it even been taken into account as a potential source of error in determination of the total filler content. It should be noted, however, that in the instances described in the paper the influence of said source of error Is minimal. The object of the present invention is to provide a procedure and apparatus by which the thickness-direction filler distribution in the paper and the total filler contents can be determined either in the laboratory or directly on the paper machine (on line) also in the case that the contents of different filler components, e.g. CaC0„, TiO ™ , kaolin, talc or equivalent, are variable. Procedures capable of determining the filler distribution and the total filler content directly on the paper machine are not in use at all. The object of the present invention is to provide an oppor¬ tunity not only for immediate product quality control directly on the machine (on line) , but also an entirely new possibility of controlling the paper manufacturing process, the significance of which is emphasized when endeavours are made to manufacture print- ing paper meeting ever greater quality requirements at lowest material costs. The object of the present invention is to achieve that the distribution can be measured and that it can also be controlled, which opens also a chance to develop the paper machine construction and the total control systems of paper machines. In addition, it is an object of the invention to provide a procedure which is also suitable for quality control of the paper fed into fast modern printing presses, and possibly for the control and/or adjustment of the operation of said printing presses. To achieve the aims presented in the foregoing and those which will become apparent later on, the procedure of the invention is mainly characterized in that the distributions of fillers and equivalent are determined by combined processing of the two following sets of measurements:- - absorption measurements carried out for determining the contents of different filler components with radiation obtained directly from the source or produced with its aid in appropriate transforma- tion targets (as many measurements as there are filler components to be considered separate ones) ; - measurements of the characteristic radiation of the material components excited in the paper with different sources of radia- tion. The means of the invention is in turn mainly characterized in that , VIPO the means comprises a measuring head comprising radiation sources and transfer mechanisms therefor, a radiation transformation plate or plates and transfer mechanism therefor, and a radiation detec¬ tor and a pre-a plifier, and that said measuring head is connected to a measuring apparatus comprising a power source, an amplifier and a counter, processor and display unit. A second embodiment of the means of the invention Is mainly charac¬ terized in that the means comprises a measuring head with an x-ray tube emitting radiation varying in energy during the measuring cycle in a known manner, and radiation detectors and pre-amplifiers, and that said measuring head is connected to a measuring apparatus comprising power sources, amplifiers and a multi-channel counter, processor and display unit using a time axis. The procedure and/or means defined in the foregoing are used, as taught by the invention, e.g. on a paper machine, in on-line measurement for measuring the filler distribution in the thickness direction and the total filler content of paper. In addition, ' the results of measurement that are obtained can be used as feedback signals in the control system of the paper machine in the control of the filler distribution and/or of the total filler content of various filler materials. An advantageous application of the invention is in measurement,- and possibly in the control, of the coating material content and/or coating material distribution in paper or cardboard that is either being coated in an on-line pro¬ cess or has been tested in a separate coating apparatus, in particu¬ lar of its one-sidedness. One potential application of the invention is the quality control of the paper being fed into a printing press and/or governing, and possibly controlling, the operation of the printing press. As has in part become apparent already in the foregoing, the Inven- tive idea is that on both sides of the paper is measured the inten¬ sity of the characteristic x-ray radiation of the filler component exdited with different radiation sources and possibly with differ- C P ent angles of incidence of the exciting radiation, this intensity furnishing information about the shape of the distribution. In addition to this it is possible in this x-ray fluorescence measure¬ ment to determine, to serve as an auxiliary quantity in the pro- cessing of results, the intensity of the exciting radiation scattered back from the paper and which correlates, for instance, with the base weight of the paper. What is significant from the point of view of practical applications is that the contents of various filler components are measured by means of x-ray absorp- tion measurements, making use of the primary radiation emitted by the radiation source and a radiation with desired absorption properties which has been derived from this source or from a source placed on the other side of the paper, with the aid of appropriate transformation targets. The auxiliary quantity is the absorption measurement signal of beta radiation used as routine in measure- 2 ments on paper for determinations of base weight (in g/m ) (fibres plus filler). Based on the results of the absorption measurements, it is possible by calculation to eliminate the effects of the variation of the different filler components' contents on the fluorescence measurements, and in this manner to determine the filler distribution and the contents of different filler compo¬ nents. In the laboratory, the Invention affords a chance for a rapid quality control of the paper, and thereby for the control of the manufacturing parametres with a given lead time. Particularly the filler distribution close to the surface layers of the paper has a remarkable significance for the printability of the paper. More¬ over, a distribution of proper shape gives an opportunity to use filler in abundance, thereby lowering the total material costs. The procedures presently used in laboratories, such as dividing the paper into different layers by the aid of a tearing tape, incineration of layers and ash determination, are slower by one order of magnitude and more inaccurate than the procedure of the present invention. Various embodiment examples of the invention and its physical and OMPI mathematical bakcground are considered in the following in greater detail, reference being made to the figures of the drawing attached, to the details of which the Invention is not confined. Fig. 1 presents a typical filler distribution in paper manufactured on a Fourdrinier machine. Fig. 2 presents mass absorption coefficients of some mineral filler and coating materials of paper and of water and of cellulose for low energy x-ray radiation. Fig. 3 shows the main principle of the fluorescence measurement of the invention. Figs. 4A and 4B present the principle of the fluorescence measure¬ ment of the invention with two different angles of incidence of the exciting radiation and angles of departure of the excited radiation. Fig. 5A presents the distribution of filler components prior to coating the paper, while Fig. 5B presents the same paper after the coating process. Fig. 6A presents the principle of the fluorescence measuring appar- atus of the invention. Fig. 6B illustrates the absorption measurement with x-ray radiation. Fig. 6C presents the principle of the absorption measuring means taking place with beta radiation. Fig. 6D presents an arrangement alternative to Fig. 6C in the absorption measurement taking place with x-rays. A typical filler distribution of paper in its thickness direction x can be seen in Fig. 1. The filler is least in quantity on the wire side. In t"his instance, the maximum is reached slightly above OMPI the centre-point of the paper (marked as 0.5 on the horizontal axis) . The filler content decreases towards the top surface (x - 1) . The attenuation (extinction) of x-ray, gamma and beta radiation in matter can generally be expressed by the expotential formula: 1 = 1 e F\ o where I (1/s) is the intensity of the radiation that has gone 2 through a mass course m (g/cm ), I (1/s) the original intensity of the radiation and p (cm 2/g) is °the absorption coefficient repre¬ senting the extinction capacity of the material. The absorption coefficients for low energy (1 to 10 keV) x-ray and gamma radiation (both are the same kind of electromagnetic radia¬ tion) of materials which are important in view of filler measure¬ ments are set forth in Fig. 2, plotted over energy. In the figure, the energy (in keV) has been plotted on the horizontal axis and 2 the absorption coefficient u (in cm /g) on the vertical axis. With the exception of a few discontinuous irregularities, the absorp¬ tion coefficient and therefore also the extinction in the material decreases with decreasing energy. However, some of the discontin¬ uous jumps seen in the figure are of central importance in the embodiments of the invention. If we scrutinize the graph of the absorption coefficient of calcium carbonate (CaCO ) , we find that it descends smoothly throughout the range from 1 to 4 keV, until at 4.04 keV energy its value discontinuously increases to be ten¬ fold and thereafter once more decreases smoothly with increasing energy of the radiation. The physical cause underlying this jump is as follows: in the range under consideration, x-ray and gamma radiation are attenuated in the material in the way that the energy of the radiation quanta transfers totally to electrons in the atoms, such electrons by virtue of the energy imparted to them being flung out from the atom, leaving behind a vacancy in the electron shroud. The energy of the x-ray or gamma quantum has to be higher than the binding energy holding the respective electron to its atom. When the energy of the radiation is lower than the 4.04 keV corresponding to the jump in the graph for CaCO,, the radiation Is not able to detach from the calcium atom the electrons of its inner shell (the K shell) , which are the electrons most strongly bound to the atom. When the energy of the incident radia¬ tion surpasses this limit, its quanta can become absorbed in the substance by detaching electrons from the inner shell, and this exactly gives rise to the discontinuous increment of the absorption coefficient. The higher the atomic number of a substance - in practice usually the heavier it is - the higher is the energy at which is found this K absorption limit, i.e. the absorption limit corresponding to the K shell. Thus, it is shown in Fig. 2 that the K absorption limit, due to titanium, of titanium dioxide (TI0 ? ) is located at the energy of 4.96 keV. In talc and kaolin, the element with the highest atomic number is silicon (Si) , and therefore the absorption coefficient decreases steadily after the absorption limit of silicon at 1.8 keV with increasing energy of the radiation. It is thus understood that when on a substance, for instance on calcium, radiation is directed which has an energy higher than the K absorption limit of calcium, vacancies will form on the inner electron shells of the atoms. When these are filled by electrons falling from outer shells, the substance emits its characteristic K x-ray radiation, the energy of which because of recoil losses is slightly lower than the energy of the absorption limit. The strongest line of the calcium K has energy 3.69 keV, which has also been indicated on the energy axis in Fig. 1. Said characteristic x-ray radiation of each element produced through absorption is utilized in a way known in the art in x-ray fluorescence analyses for determining the chemical composition of the specimens being analyzed. In the present invention, said absorption is utilized towards determining the filler content of the paper's different layers and thus towards determining the filler distribution. In order that the determination of said OMPI distribution could be made free enough of error from the viewpoint of the practical applications, the total contents of the different filler components in the paper must be known. This is found out, in the present invention, by the aid of absorption measurements. If in the absorption measurements the extinction caused by paper containing filler is measured with two radiation energies which are as close as possible to the absorption limit of a given compo¬ nent in the way that one energy is above and the other below the limit, the difference in the extinction caused by the paper will furnish information about the content of this filler component. If the paper contains kaolin, talc, calcium carbonate and titanium oxide as fillers, the difference in the extinction of the 5.9 keV line emitted by the Fe radiation source and of the K line of titanium (4.51 keV) will furnish information primarily about the titanium dioxide content (Fig. 2) , the difference in the extinc¬ tion of the difference of 4.51 keV (Ti K) and 3.69 keV (Ca K) radiations will furnish information primarily about the CaCO- content, and the absolute extinction of the 3.69 keV radiation, primarily about the combined content of talc and kaolin, these latter components having absorption components which at the last- mentioned point are clearly higher than the absorption coefficients of any other components of the paper, as Fig. 2 reveals. For determining the contents of various filler components of paper, it is furthermore necessary to know the base weight of the whole 2 paper, that is, its mass per unit area (in g/m ). This is found by measuring the extinction in the paper of beta radiation e.g. 85 from an r source. This is because the different components of paper cause equal extinction of beta radiation (i.e., of electrons thrown out by nuclei) . The use of beta radiation for determining the base weight of paper is known in the art of paper technology and is altogether routine of its nature. The fluorescence measurement used for the actual determination of the filler distribution is described more closely in the following referring to Fig. 3, in connection of which it shall be assumed 2 that the base weight of the paper specimen 10 is 100 g/m and that It contains, as uniformly distributed filler, 25 % calcium carbnonate. As shown in Fig. 3, the exciting radiation I — in the case under 55 e consideration, 5.9 keV radiation from the Fe source 20 — impinges on the paper specimen 10 under the angle of incidence α and excites in the specimen 10 the characteristic radiation of calcium, of 3.69 keV. The detector 30 measuring this radiation I_ observes the radiation departing under the angle 8 from the surface 11 of the specimen 10. Since the exciting radiation I is attenu- ated as it proceeds in the paper specimen 10, it excites calium radiation more efficiently in the adjacency of the top surface 11 which lies closer to the source 20 than in the adjacency of the lower, or back, surface 12. Since the excited characteristic radia¬ tion of calcium also suffers extinction in the specimen 10 to a given extent, the radiation excited adjacent to the top surface 11 has easier access to the detector 30. Both circumstances just mentioned act in the direction that the greater part of the radiation detected by the detector 30, in the case of homogeneous filler distribution, comes from the top layers of the specimen 10, and therefore the topmost layers of the paper will be emphasized in the information thus obtained. The smaller the angles of Incidence and departure t and S of the radiation, the greater are the differences in path length between the top surface and the lower surface 11 and 12, and the greater is the stress placed on the top surface 11 in the information gained by the detector 30. In this manner, it is possible by varying the angles of incidence and departure α and 6 to change the relative weight factors of different layers in the information that is measured. This is demonstrated by Figs. 4A and 4B and by the following Table 1. -sTi OraMPIr TABLE 1 Angle on incidence of the radiation (α) 80 30 Angle of departure of the radiation (3) 80 30 v Relative intensity Depth IIntensity Intensity of information from differ¬ 0.05 0.93 0.86 ent depths in the paper 0.5 j 0.47 0.22 0.95 I 0.23 0.06 In the above Table 1 is shown the relative intensity of the infor¬ mation received in fluorescence measurements (Ca line; Fe source) at various depths in the specimen when two different pairs of angles of incidence and of departure ,β of the radiation are used. The 2 base weight of the paper is 100 g/m and its CaC0„ content 25 %, assumed in this calculation example to be uniformly distributed in the vertical direction. On the depth scale, the surface has been denoted with the coordinate 0 and the back side of the paper with the value 1, making the coordinate of the centre 0.5. The intensity values calculated in Table 1 reveal that the infor¬ mation is strongly weighted in favour of the top side, in other words, emphasizing that side, on which the measurement is perform¬ ed. On changing the angles of incidence and departure of 80° in Fig. 4B one transfers to the angles α,β of 30° in Fig. 4A, this effect is even considerably strengthened. This is seen when, for instance, the values of the intensities obtained from the centre of the paper (0.5) are mutually compared (0.47 and 0.22). Another way in which the relative weighting of the different layers may be varied is to use for excitation radiation sources with differ¬ ent energies. If in the case just considered the Fe source (5.0 238 keV) is replaced with a Pu source, of which the strongest radia¬ tion components have an energy 12-17 keV, the attenuation of this in the paper is so minimal that excitation will take place more or CMPI less uniformly throughout the thickness dimension of the specimen 10. For the excited radiation I_, of course, the extinction effects are the same, indipendent of what radiation has affected the excitation. If now the distribution of a given filler component in the thick¬ ness direction of the specimen 10 is not uniform but for Instance as shown in Fig. 1, the intensities of the characteristic radiation of calcium measured on different sides of the paper are unequal and their difference reflects the one-sidedness of the distribution. A paper having a distribution substantially as in Fig. 1, with base 2 weight 160 g/m and calcium carbonate content about 20 %, yielded with a Fe source and with angles , β of incidence and departure, averaging 80 , for the ratio between different sides (top side/ wire side): 470/410. On making the angles of Incidence and depar¬ ture smaller, this ratio increased, as could be expected. An 3 effect in the same direction was achieved using a H/Ti source, which emits softer (4.5 keV) radiation than the radiation (5.9 keV) of the Fe source. In the following, the determination of the filler distribution on the basis of the results of measurement shall be considered. The basic distribution as in Fig. 1 can be mathematically repre- 2 sented by a polynominal y = ax + bx + c, where y refers to filler content (vertical axis) and x to the coordinate in the vertical direction of the paper (horizontal axis) . The coefficients a,b and c are found by fitting to a reference distribution. From a paper with reference distribution, the intensities of the characteristic radiation of calcium are determined from both sides of the paper to serye as reference values, and the x-ray absorption of the paper with a suitable source (e.g. Fe 5.9 keV) , and the beta 85 absorption (e.g. Kr source). When now from an unknown specimen belonging to the same paper brand are measured the equivalent quantities, the differences between them and of the quantities measured from the reference paper will OMPI yield the filler distribution of the paper sample that is being measured, by mathematical methods, utilizing the known absorption coefficients of the different components. In the vicinity of the reference distribution, a measurement carried out with merely one pair of angles α, β or with one source already yields a rather reliable estimate on the distribution. The reliability and accuracy can be increased by varying the angles of incidence and of depar¬ ture α, β or by using several sources 20 emitting energy I with different energies. This naturally causes the mathematical pro- cessing to be more complicated. In a case which was studied, for the reference polynominal repre- 2 senting the filler distribution was found y -= -42x + 52. lx + 6.7, the unit of y and of the coefficients a,b and c being the CaC0_ content (in %) . It follows that the CaC0„ according to the refer¬ ence distribution, on the wire surface 12 (x = 0) of the specimen 10, is 6.7 % and on the top surface 11 (x = 1), respectively, is 16.8 %. After the results of measurement for the intensity (I) of the characteristic radiation of calcium (I. is the wire side 12, I_ is the top side 11) and the result of the x-ray absorption measure¬ ment (T) for the paper specimen under exmination have been corrected by applying the reference graph, by the aid of the results of the beta absorption measurements to correspond to the base weight of the reference paper, the changes (Δa,Δb,Δc) of the coefficients of the distribution polynominal for the paper under examination can be calculated from the system of equations calculated from the reference polynominal: ΔI. = 0,6113 • Δa + 1,127 • Δb + 3,344 Δc ΔI 2 ■=-=■ = 1,0403 • Δa + 1,832 • Δb + 2,781 • Δc i 2 ΔT 1 1 ψ- = -j • Δa + - - Δb + 1 • Δc In the system of equations, ΔI,ΔIa and ΔT correspond to the values of the paper specimen 10 under examination and to those measured from the reference paper. In tests that have been carries out, the new coefficients obtained from the system of equations were found to yield distributions in agreement with the distributions determined from the same paper specimens by activation analysis close to the reference distribu¬ tion. It is obvious that a more accurate approximation is attained by a greater number of measurements, but the accuracy afforded by the procedure described in the foregoing is adequate in certain supervision applications. If in the instance we are now considering, to the filler of the paper is added for instance kaolin in addition to calcium carbo¬ nate, as is frequently done Intentionally or inadvertently (reused paper, etc.), the situation is significantly altered in the sense of measuring technology. This is because kaolin attenuates, in fluorescence measurements, both the exciting I and the excited I f radiation (especially the last-mentioned) , and as a result the variations of kaolin content affect to a certain degree the calcium carbonate measurements, even if the content and distri¬ bution of the latter should be constant in the specimen 10. The Influence of kaolin on the results is however calculable and can be eliminated by the aid of the known absorption coefficients, provided that the kaolin content in the specimen 10 is known. This leads to the requirement of measuring technology that in connection with the measurements the contents of kaolin and other potential filler components have to be determined. This is possible by using in the absorption measurements radiation energies suitably selected, as has been described in the foregoing. It may be observed in this connection that of the commonly used fillers, talc and kaolin are materials of which the contents must be determined by the absorp¬ tion technique. Fluorescence measurements do not succeed in normal conditions because in these substances the characteristic x-ray radiation even of the heaviest element, silicon (Si), is so weak that it is excessively attenuated in the specimen 10, in the air' space and in the windows of standard detectors 30. Regarding TiO ? , which is occasionally used, the same methods can be applied as for CaC0„, with the difference of course that the K line (4.51 keV) of titanium is excited and measured. It is thus understood that in complicated cases the determination of the thickness-direction distribution of filler requires several x-ray fluorescence measurements on both sides of the specimen 10 and several absorption measurements. The intensity of the exciting radiation I scattered back from the specimen 10, which correlates with several characteristics of the specimen paper may be used as a kind of control quantity in the measurements. In practical instances, when one is moving quite close to a given reference distribution, adequate accuracy is often achieved with rather few measurements. The printing characteristics of paper can be improved by coating the paper with the same substances that are used also as fillers. In that case the contents of mineral components in the surface layers of the paper increase greatly, as can be seen in the appended Figs. 5A and 5B. Since by the procedure of the invention information is gained about the distribution of the paper's mineral components in the paper and in particular about their content in the surface layers of the paper, it is also possible to determine the amount of coating in the coating layers and the difference in coating between the different sides of the paper by the procedure of the invention without destroying the specimen. If the paper is already coated, the filler distribution of the uncoated bottom paper naturally cannot be elicited any longer. The part 100 isolated with interrupted lines in Figs. 6A,6B,6C and 6D is the measuring head, comprising radiation sources 20 and their transporting mechanisms known in themselves in the art, radiation transformation plates and their transfer mechanisms (not presented in detail), a radiation detector 30 and a pre-amplifier 31. In the laboratory apparatus, the measuring head 100 is, for instance, an enclosed apparatus on the table, into which the paper specimen to be examined is conveyed by a suitable mechanism, this mechanism transporting the paper during one measuring cycle into one or several measuring positions. In an on-line apparatus performing the measurements directly on the paper machine, the paper web passes through a measuring head 100 mounted on a measuring beam. The measuring head may be so con¬ structed that it can be traversed across the paper web. For detector 30 is primarily used a proportional counter. In certain instances, in particular in laboratory measurements, a semiconductor counter may also be used with a view to increasing the accuracy. The measuring head 100 is connected to a measuring apparatus 40 comprising a voltage source 41, an amplifier and a counter, proces¬ sor and display unit 42. A control unit 43 connected to the proces¬ sor governs the performing of the measuring cycle and the processing of results. In the laboratory version of the means of the invention, the pro¬ cessor functions may be replaced with manual operations, and the results may also of course be processed manually or using an exter¬ nal computer 50. In fact, the measuring equipment external to the measuring head 100 is standard measuring equipment, and the in- ventive idea proper is associated with the measuring head 100. The extent of the equipment external to the measuring head 100 and of the computer programmes associated therewith is greatly depend¬ ent on the degree of automation and the standard of accuracy aimed at, and on the extent of the measuring range, that is on the number of different paper brands and the variation limits, within each brand, of the quantities which are measured. Fig. 6A illustrates the exciting of the characteristic fluorescence radiation of a filler component (CaCO, or TiC and its measuring on the other side of the paper specimen 10. The radiation emitted by the radiation source 20 excites in the specimen 10 the charac- teristic x-ray radiation of a given element (Ca or Ti) of its filler, part of which is going to the detector 30 and being count¬ ed. The detector 30 differentiates between the different kinds of radiation by their energy with such accuracy that from the measured pulse height distribution the contribution of each radiation compo¬ nent can be elicited by mathematical means. If it is desired to make the measurement with exciting radiations I having different energies, the source of radiation 20 may be exchanged by the aid of a suitable mechanism. If, again, it is desired to employ different angles of incidence and departure α,β of the radiation with reference to the surface of the paper specimen 10, it is possible to move the source 20 laterally and possibly to use appropriate collineators or radiation beam detectors, known in themselves in the art. Since for determining the filler distribution a fluorescence measurement has to be made on both sides of the specimen, in the laboratory version the paper specimen 10 must be turned over, or two measuring heads 100 carrying out measurement on different sides of the specimen 10 have to be used. When measurements are carried out directly on the paper machine, the latter alternative is the only possible. Fig. 6B presents an arrangement by which absorption measurements are carried out with x-ray radiation of different energies. The radiation from the radio isotope source 20 is either scattered by an exchangeable target plate 21 or excites therein radiation appropriate for absorption measurements, this radiation passing partly through the paper specimen 10 into the detector 30. The 5.9 keV Fe), 4.51 keV (Ti K) and 3.69 keV (Ca K) radiation components which were required above in our absorption measurement example are obtained with the aid of a Fe source by means of plastic (scat¬ tering) , titanium or marble target plates 21. In certain instances the absorption measurements, too, may be performed with the aid of the source used in the fluorescence measurements, as shown in Fig. 6C. As shown in Fig. 6C, the radiation that has passed from the source 20 through the specimen 10 is scattered from the backing plate 22 or excites therein radiation appropriate for absorption measure¬ ments, which partly passes through the specimen 10 Into the detector 30. In this instance to the signal being measured is admixed the signal of the radiation excited in the paper specimen 10 by the source 20, this signal reducing the accuracy of measure¬ ment in certain cases. Fig. 6D presents the absorption measurement, associated with the invention, used as routine in the papermaking industry towards base weight measurements and carried out with the aid of a beta radia¬ tion source 23, this measurement furnishing in distribution measure¬ ments according to the invention the auxiliary quantity which is indispensable in the processing of the results of measurement. Detailed refrence distributions which are indispensable for demon¬ strating and proving the practical applicability of the procedure of the present invention may be determined by neutron activation analysis of microtome sections made of paper. The technique is described in: Kuusi, J. and Lehtinen, A.J., "Neutron Activation Analysis of Microtome Cuts in Examination of Paper for Its Filler Distribution", Pulp and Paper Magazine of Canada, 71, No. 3 (1970). The procedure and the means described in the foregoing are suitable to be used either in laboratory measurements or in on-line measure¬ ments on a paper machine. In the last-mentioned use, the results obtained with the measuring apparatus may be used as feedback signals for guiding and/or controlling the papermaking process towards implementing a given desired filler distribution. A poss¬ ible application of the invention is the use of the procedure or of the means in the measurement, and possibly even in the control, of the coating agent content and/or coating distribution either of paper or cardboard to be coated in an on-line process or of paper treated in separate coating means, in particular of its one-sided¬ ness. Of the applications of the invention may further be mentioned the quality control of paper being fed into a printing press, and even the guiding or control of the operation of a printing press to the end of optimizing the printing quality and minimizing the trouble encountered in the operation of the printing press. In the following are presented the claims, different details of the invention being allowed to vary within the inventive idea thereby defined.

Claims: Claims 1. A procedure for measuring, without destroying the specimen, the distribution in the thickness direction of the filler and/or coating materials of paper, cardboard or equivalent, wherein by radiation from a radio-isotope source is excited in the material component to be examined, its characteristic x-ray radiation, the intensity of this radiation being observed, and wherein measure¬ ments are made on both sides of the paper under examination and in addition the contents of other filler components are determined by x-ray absorption measurements to the purpose of eliminating the effects of these components disturbing the distribution measure- 2 ment, and the base weight of the paper under exmination (in g/m ) is measured by beta radiation absorption measurement or by another equivalent procedure, characterized in that the distributions of fillers and equivalent are determined by combined processing of the two following sets of measurements:- - absorption measurements carried out for determining the contents of different filler components with radiation obtained directly from the source or produced with its aid in appropriate transforma- tion targets (as many measurements as there are filler components to be considered separate ones) ; - measurements of the characteristic radiation of the material components excited in the paper with different sources of radia- tion. 2. A procedure for according to claim 1, characterized in that the effects exerted on the fluorescence measurements by the variations relative to each other of the different filler components' contents are eliminated by calculation with the aid of the total contents of the different filler components determined by x-ray absorption measurements in such manner that from the fluorescence measure¬ ments the thickness-direction distributions of the different filler components in the paper can be determined. 3. A procedure according to claim 1 or 2, characterized in that for measuring the distributions of different material components are used radiation sources with different energy levels (E) , their energy level (E) being selected so that it is slightly higher than the K absorption limit of the material component to be examined. 4. A procedure according to claim 1,2 or 3, characterized in that measurements are carried out two or more different angles of inci¬ dence (α) of the source radiation. 5. A procedure according to claim 4, characterized in that measure¬ ments are carried out with two or more different angles of departure (β) of the characteristic x-ray radiation excited in the paper specimen or equivalent by the source radiation (I ) . 6. A procedure according to claim4 or 5, characterized in that the angle of incidence (α) of the source radiation has been disposed to equal in its order of magnitude the angle of observation (6) of the excited radiation (I f ) with reference to the paper plane on the same side of the paper. 7. A procedure according to any one of claims 1-6, characterized in that the procedure in addition to x-ray fluorescence measure¬ ments is determined to serve as auxiliary quantity in the proces- sing of results, the intensity of the source radiation scattered back from the paper and which correlates above all with the base weight of the paper. 8. A procedure according to any one of claims 1-7, characterized in that the contents of various filler components or equivalent are measured by x-ray absorption measurements utilizing the primary radiation emitted by the radiation source and radiation with cer¬ tain absorption properties derived from this source or from a source placed on the other side of the paper by a suitable trans- formation target. 9. A procedure according to any one of claims 1-8, used for exam- ining paper in which the filler material is mainly kaolin, talc, calcium carbonate and/or titanium oxide, characterized in that for 55 primary radiation is used 5.9 keV radiation emitted by a Fe radiation source, that the difference encountered between the extinction of the said primary radiation and that of the charac¬ teristic 4.51 keV K line excited in titanium is mainly used towards determining the titanium dioxide content, that the differential absorption observed between said K line of titanium and the 3.69 keV K line of calcium is mainly used towards determining the CaC0_ content, and that the information provided by the absolute attenuation of said Ca-K line is used primarily for determining the combined content of talc and kaolin. 10. A procedure according to any one claims 1-9 characterized in 2 that the base weight (in g/m ) of the paper or equivalent is determined by measuring the attenuation in the object under 85 measurement of beta rays emitted by an Kr source. 11. A means for carrying out a procedure according to any one of claims 1-10, characterized in that the means comprises a measuring head (100), containing radiation sources and transfer mechanisms therefor, a radiation transforming plate or plates and transfer mechanisms therefor, and a radiation detectror (30) and a pre¬ amplifier (31) , and that said measuring head (100) has been connected to a measuring apparatus (40) , a comprising power source (41), an amplifier (42) and a counter, processor and display unit. 12. A means according to claim 10, characterized in .that said measuring apparatus comprises a control unit (43) which controls the carrying out of the measuring cycle and the processing of results. 13. A means according to any one of claims 11 or 12, characterized in that for radiation detector (30) in the measuring head (100) is used a proportional counter or in laboratory measurements requiring particularly high accuracy, a semiconductor counter. 14. A means according to any one of claims 1-13, characterized in that said measuring head has been disposed in conjunction with the paper web travelling on a paper machine to perform on-line measure¬ ment. 15. A means according to claim 14, characterized in that said measuring head (100) has been disposed in conjunction with a trans¬ versal measuring beam In the paper machine to traverse recipro- catingly over the whole width of the paper web or part thereof. 16. A means according to any one of claims 11,12 or 13, charac¬ terized in that the measuring means has been arranged to be a laboratory measuring apparatus by which paper and cardboard samples are examined.. 17. A means according to any one of claims 11-16, characterized in that said measuring apparatus has been connected to a computer (50) in which has been loaded a measurement result-processing and outputting programme. 18. The use of a procedure according to any one of claims 1-9 and/or of a means according to any one of claims 11-17 on a paper machine in on-line measurement for measuring the thickness- direction filler distribution and the total filler content of the paper. 19. A use according to claim 18, characterized in that the results of measurement obtained are used as feedback signals in the control system of a paper machine in controlling the filler distribution and/or the total filler content of different fillers. 20. The use of a procedure according to any one of claims 1-10 and/or of a means according to any one of claims 11-17 in measuring and possibly in controlling the coating material -content and/or the distribution of the coating material, in particular its one- sidedness, either of paper or cardboard to be coated in an on-line process or of paper processed in separate coating means. OMPI IPO 21. The use of a procedure according to any one of claims 1-10 and/or of a means according to any one of claims 11-17 for quality control of the paper to be fed into a printing press and/or guiding and/or controlling the operation of the printing press. OMPI

Inventors: KUUSI JUHANI, KUUSI, JUHANI
Applicants: VALTION TEKNILLINEN, VALTION TEKNILLINEN TUTKIMUSKESKUS
Application year: 1983
Main classification: G01N23
IPC codes: G01N23, G01N33