VN (number of objects per unit volume) allowed for the assessment of the layer compactness, and as the analyses showed, this value decreased by more than two times after laser treatment. The analysis of the degree of sample coverage by the cermet layer showed that it increased from 70% to 95% after laser treatment, which confirms the treatment’s positive effect on the layer’s quality. This research shows that three-dimensional analysis significantly enriches the information about the geometry of the surface layer, providing data which other research techniques are unable to acquire.Analysis of the geometrical structure of the surface of materials is an issue already widely recognised and included in international standards. The authors present the possibilities of extending the analysis of the coatings’ geometrical structure through X-ray nanotomography imaging, three-dimensional image processing, and stereological methods. Analysis of the state of the art reveals that there are no scientific rapports (indexed by Scopus) on the application X-ray nanotomography for analysis of the geometry of a coating. The presented study shows that this imaging technique can be applied and provide additional information on the quality of the layer. The comparative tests were carried out on samples with a cermet coating before and after laser treatment, including standard tests of the surface geometry and the analysis of three-dimensional images obtained from nanotomography. A set of parameters describing the compactness and thickness distribution of the applied coating is proposed, which facilitates the qualitative assessment of the application process and improvements through the additional processing of technological layers. The obtained results show that although the average thickness values before and after laser treatment did not differ significantly, their distribution on the sample surface was different, as presented in the visualisation. The determined stereological parameter  The properties of the material surface are essential for the exploitation properties of the final elements and determining their durability. Thus, correctly modelling the surface geometry is a crucial issue in surface engineering. The geometry of the material’s surface influences the exploitation properties, which is well known and widely described. The impact of the surface geometry on the tribology properties was described by Atkins , MaldonaApplying a surface layer on the base material is a method for enhancing the properties of the elements and obtaining specifications for the application surface of manufactured components. Enhancement of the metal surface’s exploitative properties on metallic alloys may be obtained by different methods: mechanical, thermo-mechanical, thermal, thermo-chemical, electrochemical and chemical, and physical. Each method of producing the surface layer allows for obtaining a specific type of surface layer with a particular thickness and purpose. The same methods can be carried out using different processes. All those methods can produce both protective coatings and top layers, except for mechanical methods used only for manufacturing top layers. Kovalchenko et al.  proved tIn production, the practice surface layer may be deposed by applying a broad spectrum of technologies, including thermo-chemical surface layer modification processes such as nitriding, physical vapour deposition (PVD), and chemical vapour deposition (CVD), as well as electroplating to improve wear or corrosion resistance. The electro-spark deposition (ESD) method belongs to the group of techniques based on using a concentrated energy stream. It is a process that can reduce component wear, improve the coating’s resistance to corrosion, and extend the exploitation time of the component or tool. B. R. Lazarenko and N. I Lazarenko developed the process that Gould  and ReynThe formation of the anti-wear carbide-ceramic coatings with electrodes made by powder metallurgy methods is effective and low in cost. Super hard coatings can be applied to the cutting edges of tools such as turning knives, cutters, chisels, and taps. Considering the properties of coatings deposed by the ESD method, it can be successfully used on machine elements that operate in extreme conditions, such as intense abrasive wear and impact loads, as proven by the research of Radek et al. ,15.The ecological thread is another advantage, encouraging the use of super hard spark erosion coatings. Holmerg and Erdamir  publisheIn the ESD method, some failures in the coating appear that prevent its broader application in production in more well-recognised areas. Significant imperfections include a high surface roughness and cracks in the layer, because the roughness becomes so high due to the treatment that it limits its use. At the same time, the residual stresses cause cracks in and brittleness of the layer and reduce its quality. The most common defects of this type of coating were identified in several studies conducted by Gould , ReynoldOne of the essential disadvantages of ESD coatings is their high final roughness, and this is crucial when applying coatings to very smooth surfaces. Depending on the discharge energy, surface roughness heights are 2–20 µm. The analyses performed ,17 confiAccording to Radek et al. ,18 and PThe material absorbency depends not only on the wavelength of the laser radiation but also on the method of surface preparation and the temperature of the processed elements, as well as the time of the laser radiation’s impact on the material.Laser treatment eliminates the surface of ESD coating defects such as scratches, delamination, and microcracks. The primary purpose of laser processing of layers is to improve their quality and homogenise their structure and chemical composition ,18,20,21Considering the properties of the coating deposed by the ESD method and modelling the geometry by laser treatment, this type of specimen is a suitable example for analysis with the employment of three-dimensional nanotomography and three-dimensional image processing, as well as analysis techniques that were identified in further research by Gądek-Moszczak et al. ,23.The main research goal was to analyse the possibility of using three-dimensional image data for the quantitative and qualitative description of the surface layer geometry. The indirect goal was to develop an appropriate coating detection method so that the image intended for measurement would reflect the actual structure as accurately as possible. It was equally important to determine a set of parameters that would be sensitive to changes in the spatial geometry of the layer after laser processing, among the many available parameters for the geometric description of objects.A thorough analysis of the literature revealed a lack of scientific papers  on the use of X-ray nanotomography to analyse the geometry of the coatings.Based on the obtained visual data in the form of three-dimensional reconstructions and the results of quantitative analysis, an evaluation of the usefulness of the proposed three-dimensional analysis method for qualitative and quantitative assessment of the surface layer geometry was carried out.The base material used in the tests was carbon steel C45, which showed sufficient corrosion resistance in oxidising atmospheres up to approximately 500 °C. The permissible operating temperature of the C45 steel structure parts depended on the corrosion resistance under the given conditions, the time of exposure to high temperatures, and the size and frequency of its fluctuations. C45 steel is carbon steel from which machine parts are made . This durable steel with high ductility is widely used in industries but is characterised by poor machinability, resulting in high roughness of the surfaces. The widespread use of C45 steel can be found in the machine industry, where it is used for producing, for example, gears, spindles of lathes and drills, connecting rods, piston rods, turbine shafts, shafts, and blades .2O3 aluminium oxide;Single-phase Al3N4;Silicon nitride Si2O3 and Si3N4 with hard carbides, nitrides, and oxides.Multi-phase mixtures of AlTo enhance the properties of the surface layer of the C45 steel specimens, the cermet coating was chosen. The use of ceramic tool materials compared with sintered carbides is small but still shows dynamic growth. According to estimates, about 5% of cutting tool blades are made of this group of materials. The most popular materials for the production of ceramic tool materials include the following:2O3 coating obtained by the electro-spark deposition (ESD) method. The Kielce University of Technology led the process of preparing the samples. For comparative analysis of the geometry of the surface changes, two types of probes of hardened C45 steel with the WC-Co-Al2O3 coating were used. The first set of probes had an WC-Co-Al2O3 layer, no additional treatment, and laser treatment afterward.The research was conducted on the specimens with the WC-CO-AlVoltage (U): 230 V;Capacitor volume (C): 300 μF;Current intensity: (I): 2.2 A;2.Exposition time (T): 2 min/cmThe process of deposition by the ESD method was performed using EIL-8A equipment (Ukrainian production). Due to producer indication as well as the results of previous experiments, the parameters of the ESD process were as follows:Spot diameter (d): 0.7 mm;Power (P): 20 W;Laser beam velocity (v): 250 mm/min;Nozzle-workpiece distance (∆l): 1 mm;Pulse duration (t): 0.4 ms;Pulse repetition frequency (f): 50 Hz;Beam shift jump (S): 0.4 mm;Nitrogen gas yield (Q): 25 L/min.After deposition of the cermet coating to enhance the surface geometry, the second type of analysed sample was treated with Nd via a YAG laser (impulse work), model BLS 720. Laser treatment should result in surface roughness reduction and changes in the shape of the profile irregularities. The purpose of laser compaction is to reduce the porosity of the coating and eliminate defects such as scratches, delamination, and cracks in the coating. After laser treatment, the surface layer is expected to have improved integrity, which strongly impacts the layer’s mechanical and functional properties. Proper adjustment of the laser beam is also an important issue because, for smoothing, a low power density and large-diameter laser beam melts only the tops of the asperities. Laser treatments were conducted with the following parameters:Microstructure analysis is a standard test of quantitative and qualitative analysis of materials, including materials with deposited coatings. A high magnification of microscopy observation allows noting possible defects in the coating. The structure of the tested materials was assessed on specimens made in a plane perpendicular to the applied surface layer, which made it possible to determine the coherence of the layer with the substrate and measure its thickness. The observation was performed on a scanning microscopy Joel type JSM-5400 with a magnification of 1000×.An X-ray diffraction study was performed at AGH University of Science & Technology, a PHILIPS X-Ray Diffractometer PW 1830 utilising the X-ray diffraction technique was applied to determine the coatings’ phase compositions. The Cu anode lamp provided filtered Kα radiation. The voltage supplied to the device amounted to 40 kV, while the current was 30 mA. The measurements were carried out at 2θ from 30° to 60°. The speed of scanning was set to 0.05°/3 s.2, while the horizontal resolution amounted to 1.65 × 1.65 µm2. TalyMap Platinium (ver. 6.2) software was applied to analyse the surfaces’ 3D images. Thus, the geometric surface structures of the layers might have been determined.The tests aimed at obtaining a geometric surface structure and roughness profiles were conducted at Kielce University of Technology (in the Geometric Measurements Lab.). An optical profilometer called Talysurf CCI was applied. The testing field had an area of 1.65 × 1.65 mmThe three-dimensional imaging technique using X-ray microtomography is an increasingly popular method of examining the micro- and nanostructures of materials in different fields of science, such as material engineering, biomaterials, and biology ,27,28,29Three-dimensional analysis based on images obtained from X-ray nanotomography of the surface layer is not a study that may be performed for all materials.I of the X-ray beam of an intensity I0, which passes through an absorbent with a thickness of x, can be calculated according to Beer’s absorption formula [μ is a linear absorption coefficient.This is limited to a specific combination of the base material and the type of material chosen for the coating. X-ray nanotomography is an imaging technique based on the material’s interaction with an X-ray beam. After passing through the sample, the X-rays are attenuated, and the level of attenuation depends on the thickness of the test object, the atomic number of the sample element, and the beam energy. The absorption  formula :(1)I=I0emµ, which is equal to the ratio of µ to the absorbent density ρ. Materials containing atoms with a high Z atomic number absorb X-ray radiation more efficiently than substances consisting of elements with a low Z value. The mass absorption coefficient of mµ increases with the atomic number as approximately Z3. Taking into account this fact and the impact of the wavelength on absorption, the mass absorption coefficient is defined by the formulac is approximately constant between the different absorption thresholds.In practice, the most frequently used variable is the mass absorption coefficient I, the better the contrast in the images, and the better representation of the individual elements of the structure of the tested sample.The desirability of using X-ray micro or nanotomography to test samples consisting of several components, as is the case with porous materials, composites, or materials with coating systems, can be assessed before the test is performed by estimating the radiation absorption of each of the components. The greater the difference in the value of Images that resulted from X-ray nanotomography were recorded as a set of bitmap images or as a RAW file. They could be used to reconstruct the three-dimensional structure in the material study.2O3 before and after laser melting were subjected to research, providing knowledge about changes in the coating after laser processing microstructure analysis of SEM images with EDS analysis, analysis of the geometry of the surface layer using a profilometer, and analysis of the geometry of the layer on images from computed nanotomography.Samples of C45 with WC-Co-AlBased on the SEM microstructure images, a qualitative and quantitative analysis was performed, considering the measurement of the thickness of the obtained layers or the range of the heat-affected zone (HAZ) after laser treatment. The SEM images presented the cross-section of the specimen , showing2O3 coating with a laser beam homogenised its chemical composition. The technological surface layers (TWP) produced by laser melting did not have microcracks and pores  was also observed. The highest peaks in 2C and Fe3W3C, respectively.The X-ray diffraction tests enabled us to determine the WC-Co-AlIt is considered that surface geometric structure (SGS) parameters significantly determine the characteristics of a given surface. They tend to have a significant impact on several phenomena which occur within the considered layer.2O3 coating before and after laser beam machining (LBM).SGS tests are applied in practice to generate images that properly understand surface characteristics. The following steps are considered if the surface’s geometry features need to be determined: measurements conducted with a selected technique, surface presentation, and its parametric assessment. Sa = 0.74 ÷ 0.82 µm. The Sa parameter is the essential amplitude parameter for the quantitative assessment of the condition of the analysed surface. The laser treatment lowered the Sa parameter of the WC-Co-Al2O3 coating, which proved that we were dealing with laser smoothing (reduction of the height of the tops). The WC-Co-Al2O3 coatings were characterised by the value of the parameter Sa = 3.43 − 3.87 μm, while after laser beam machining, the arithmetic mean of the surface height ranged from 3.79 to 4.11 μm.The C45 carbon steel samples on which the coatings were applied were characterised by the value of the parameter Sa)  decreased by about 8% after laser treatment compared with the coating without this treatment. The measurements show that after the laser treatment, there was a slight decrease in the Sa parameter of the WC-Co-Al2O3 layer. The smaller value of the Sa parameter resulted from the tensile forces acting on the surface and, accordingly, the motion of the liquid metal. As a result, a homogeneous surface profile was obtained after solidification. It was also found that the laser smoothing method allowed for achieving the directivity of the micro-geometry structure at the same time. If pulse laser treatment is applied, it is assumed that the main factor affecting the surface profile after solidification is the pressure of vapour causing the disposal of the material from the central zone and the production of characteristic flashes on the boundary between the melted and unmelted zones.The arithmetic mean of the surface height of the coating (Sq and the following parameters: maximum peak height (Sp), maximum pit height (Sv), and maximum height (Sz).A similar tendency was observed for the mean square surface height Sku and the concentration coefficient of kurtosis Ssk. These parameters are sensitive to the occurrence of local elevations or depressions on the surface, as well as defects . Positive values of the surface asymmetry Ssk (skew) for the WC-Co-Al2O3 coating before and after LBM provided information that we were dealing with a smooth surface without plateau-shaped elevations.Supplementary information on the shape of the surface of the tested samples before and after laser treatment is provided by the amplitude parameters: the skewness coefficient-asymmetry Sku = 4.24 ÷ 7.20 prove that the ordinate distribution for all samples was close to the normal distribution.The obtained values of the surface inclination close to each other and within the range 2O3 coating before and after laser beam machining had a random isotropic structure within the range of Iz = 62.99 ÷ 69.62%.The WC-Co-AlRa parameter for a given coating was calculated from two sizes.The roughness measurement is a standard surface geometry analysis specified in standards PN-EN ISO 4287:1999 and PN-EN ISO 11562:1998. The tests were carried out for the coatings mentioned above in two perpendicular directions. The first measurement was made following the movement of the electrode, while the second measurement was vertical to the scanning stitches. The mean value of the 2O3 coatings were made in the direction perpendicular and parallel to the axis of the paths created with the laser beam. The average roughness value for a given layer was calculated. The Ra for the WC-Co-Al2O3 coating was from 3.12 to 3.35 microns, and after laser irradiation, it was from 2.71 to 2.96 µm. The coated C45 steel samples were roughly Ra = 0.41 − 0.43 µm. Examples of measurement charts of the microgeometry parameters of the tested samples are shown in Measurements of the laser-modified WC-Co-AlThe procedure for quantitative analysis of digital images consists of several stages, from image acquisition to 3D visualisation for the assessment of the image quality and visibility of the tested structures and image preprocessing, which includes geometrical translation and filtering, detection, measurements which provide quantitative results essential for qualitative assessment, and conclusions .I = 170 μA and V = 130 kV. The total acquisition time for one sample was approximately 400 min. Reconstruction of the measurement results in the form of a 3D image was carried out using GE software datosX ver. 2.1.0 with the Feldkamp algorithm for a conical X-ray beam. The final spatial resolution was 1 μm, and the dimensions of the tested samples were 2.2 mm × 3.1 mm × 3.0 mm. The resulting sequence of three-dimensional images of the tested samples was saved as an 8-bit RAW file (8 bits for 1 voxel), which gave 256 shades of grey to represent the specimens. The accuracy of the spatial projection of the generated images was 1 μm.The imaging study verifying the effect of laser treatment on the electro-sparking coating’s geometry was performed with Nanotom 180N nanotomography by GE Sensing & Inspection Technologies Phoenix|X-ray Gmbh. The operating parameters of the X-ray tube during the acquisition were as follows: The visibility of the components was sufficient on the obtained images of the cross-section (stack of images from nanotomography) compare a,b and aImages written by the acquisition system in RAW format were imported to Fiji software, an open-source platform for three-dimensional image reconstruction, visualisation, processing, and analysis .The first stage of assessing the quality of the layer was performed on the three-dimensional visualisation. As shown in Visual assessment of a three-dimensional reconstruction of the specimen with ESD cermet coating after laser treatment confirmed the benefits of laser treatment . The cerApplying automatic algorithms for quantitative analysis of the coating required detection of the layer. Detection is a process of transforming images in greyscale into binary images ,32. It if be a grey value of the voxel located at the point . Suppose the voxel intensity value on the initial image f is lower than the defined threshold value T. In that case, it will be converted on the binary image g into the value zero, and voxels whose intensity values are higher than the set threshold T will be converted into one, as defined in Equation (3):Let This method is very effective for high-contrast images, where the difference between the values corresponding to the object and background are significant.The quality of the obtained images of the base material and cermet coating from X-ray nanotomography was acceptable, and the contrast between the based material and coating was well distinguished. Automatic algorithms performed detection of the analysed coating to ensure the repeatability and objectivity of the detection and further analysis. Due to reducing the number of eventual artefacts in the binary images and improving the detection result, three-dimensional median filtration was performed. Median filtration is one method of ranking filtering which effectively reduces the noise ratio in the images. In this filtration, each voxel is analysed with its neighbourhood. All considered voxel intensity values are ordered into a descending sequence of values. The value in the sequence’s middle becomes the new value of the analysed voxel in the resulting image ,32. The Cermet coating detection was possible by automatic methods chosen based on visual observation of their accuracy in surface layer detection. Among the available algorithms for automating thresholds ,36,37,38For detection of the cermet coating for both types of specimens, an algorithm was chosen which, in this case, gave the best detection result among the other testing methods, such as Li, Otsu, maximum entropy, and Yen, which are available in the Fiji algorithm’s library . The visT divides the image I into two parts: the object and background. The object and background grey probabilities are calculated, which are applied in Renyi’s entropy formula. According to Liu et al. [I be an image with objects which are the aim of quantitative analysis. Thus, I will be segmented with L levels. The probability of each grey level distribution is {p(1), p(2), p(3), …, p(L)}. Suppose there is only a single threshold T to divide image I into two parts: the objects A0 = {1, 2, 3, …, t} and the background A1 = {t + 1, t + 2, t + 3, …, L − 1}. The object and background grey probabilities are calculated, where w0(t) is the probability of occurrence A0 and w1(t) is the probability of occurrence A1. The sum of both calculated probabilities is w0(t) + w1(t) = 1. The probabilities w0(t) and w1(t) are defined as follows:The RenyiEntropy algorithm took its name after Alfréd Rényi, who tried to work out the most general definition of information measures that preserve additivity for independent events . Renyi’su et al. , the metRenyi’s entropy of the image background and object is defined in the following equations:The total Renyi’s entropy is defined asT should fulfil Equation (9):Finally, the optimal threshold According to the Renyi’s entropy method of a single threshold, Renyi’s entropy of multiple thresholds may be worked out.Binary images due to minimalisation of the artefacts created by the thresholds and local inhomogeneity of grey level values of coating representations were processed by three-dimensional opening  ,32 throuThree-dimensional analysis of the geometrical structure involves the study of its consistency and thickness. The research was performed in Fiji software, employing the algorithms for three-dimensional analysis and applying stereological parameters to assess the crucial features of the layer ,40,41,42V, which gives the volume of the detected coating. The volume is assessed directly from the number of voxels representing the detected object. The second of the parameters chosen for analysis was the surface area S. The algorithm for measuring the surface area of three-dimensional objects creates a mesh from the detected object in the image and calculates the area of the surface of the mesh. A mesh is a set of triangular faces that defines the shape of an object in 3D graphics [The first parameter chosen for analysis was the total volume graphics ,43.S to the total measured volume V indirectly provides information about the degree of surface development. Analysis of the layer located in the direct location of the core material will give information on the percentage of the area of the steel surface not covered by the coating.The ratio of the surface area N forming the coating, its volume, and the surface area were analysed, and the results are presented in VN for the analysed coating confirmed that the laser treatment of the surface cermet layer deposited by ESD increased its consistency. The VN for the coating after LBM was reduced by more than 70% compared with the sample without the LBM.The number of objects V of the coating after LBM increased, which was an effect of the alloying properties of the laser treatment that caused melting of the cermet layer and the core material, which is a positive phenomenon because it increases the coherence of the coating with the base material.The total volume S is a feature that may be used in this analysis to assess the changes in the surface geometry into a more complex one textured by laser machining. This effect was confirmed by the roughness measurement, where Ra increased from 3.12 to 3.35 µm, and after laser irradiation, it increased from 2.71 to 2.96 µm. The value of the ratio of the area surface and total volume provided information on the complexity of the surface. In general, two objects with the same total volume and different S/V values differ by the complexity of their shapes. One of the commonly used shape factors for two-dimensional objects is the ratio of the perimeter and area of the objects [AA is an area fraction of the sample surface covered by a WC-Co-AL2O3 coating. This is calculated by dividing the total surface area covered by a coating by the total surface area of the sample. As presented in The surface area  objects . ParametThe results of stereological analysis of the three-dimensional images of a coating provide the quantitative description of the coating, which is unique, valuable, and essential for reliable analysis of the influence of the technological process and its adjustment on the quality of the layer.The thickness was measured by applying the algorithm for the model-independent thickness assessment in three-dimensional images . The meaAs a result of the analysis, the value of the minimal, maximal, mean, mode, and standard deviation thickness is provided . The thrThe effect of the laser treatment can be observed on the thickness map. Although the mean value of the thickness was close to the mean value for the sample without the laser treatment see , the thi2O3 coatings consisted mainly of the W2C and WC phases, while after laser beam machining, it mainly consisted of the Fe3W3C and W2C phases.The laser treatment eliminated deposition imperfections  and slightly changed the chemical and phase compositions of the coating. The surface layer of the WC-Co-Al2O3 coatings after laser treatment had lower values by approximately 7% compared with the coatings before this treatment.The parameters of the surface geometric structure of the ESD WC-Co-AlAnalysis of the images from X-ray nanotomography of a cermet coating provided a valuable opportunity to analyse a sample with a coating in a specific volume without the bias of sampling error or resulting from the preparation of the sample for microscopic observation. This additional quantitative information, supported by three-dimensional visualisation, allowed for a more precise assessment of the quality of the applied coating and the impact of a different technological process, such as laser processing of its geometry and not just the surface.Three-dimensional analysis provided additional parameters characterising the coating geometry, including compactness and thickness, which are complementary to other standard research methods.Further tests should include measurements of the internal stresses and tests of the tribological electro-spark coatings before and after laser treatment.


Hamsters are often chosen as companion animals but are also a group of animals frequently subjected to laboratory tests. As there are no scientific publications providing information on the anatomical architecture of the brachial plexus of the Djungarian hamster, this study analyses the structure of this part of the nervous system of this species. It is important to know the details of this structure not only for cognitive reasons, but also due to the increasing clinical significance of rodents, which are often used in scientific research. The study was conducted on 55 specimens. Like in humans, the brachial plexus of the Djungarian hamster has three trunks. The following individual nerves innervating the thoracic limb of the Djungarian hamster: the radial nerve, median nerve, ulnar nerve, musculocutaneous nerve, axillary nerve, suprascapular nerve, thoracodorsal nerve, cranial pectoral nerves, caudal pectoral nerve, lateral thoracic nerve, long thoracic nerve, and subscapular nerves. Similarly to other mammals of this order, the brachial plexus of the Djungarian hamster ranges widely (C5-T1). However, its nerves are formed from different ventral branches of the spinal nerves than in other mammals. Phodopus Campbelli), which is a species of similar size and colour, but it does not change its hair colour for winter (Steinlechner Hydrochaeris hydrochaeris), African crested porcupine (Hystrix cristata), Spix's yellow-toothed cavy , rock cavy (Kerodon rupestris) as well as nutria (Myocastor coypus), and small chinchilla (Chinchilla lanigera) , mole-rats , albino rat  . It is native to Siberia as well as semi-deserts in Kazakhstan . The Djungarian hamster carcasses were obtained from veterinary clinics. The animals had been euthanised  for other medical reasons than neurological disease.The research material was placed in a 10% formaldehyde solution for 72 hours. The examination was based on macroscopic preparation with magnifying equipment. In order to visualise the nerves, the sternum was cut, open and the contents of the thoracic cage cavity were removed. After the nerves had been separated from the muscles of the trunk and pectoral limb, swabs soaked with a 3% hydrogen peroxide solution were used to better visualise the nervous tissue and facilitate further preparation. The names of anatomical structures were standardised according to the Nomina Anatomica Veterinaria , median nerve (n. medianus), ulnar nerve (n. ulnaris), musculocutaneous nerve (n. musculocutaneus), axillary nerve (n. axillaris), and suprascapular nerve (n. suprascapularis). Apart from these, other nerves spread from the plexus, i.e. the thoracodorsal nerve , cranial pectoral nerves , caudal pectoral nerve , lateral thoracic nerve , long thoracic nerve (n. thoracicus longus), and subscapular nerves (nn. subscapulares). The radial nerve is the largest nerve of the brachial plexus. It is mainly made of branches C7-T1. Near the middle of the humerus it goes between the medial head and the long head of the triceps muscle of the forearm. Next, there is a muscle branch for the tensor muscle of the antebrachial fascia and a branch for the medial head of the triceps muscle of the forearm, which is subdivided into a ramus for the rest of the head. There is also a ramus for the distal part of the brachial muscle in this area. Then, the radial nerve passes to the other side of the bone, under the lateral head of the triceps muscle of the forearm, where it splits into two ramus – one for the lateral head of the triceps and the other, which is an extension of the radial nerve. It runs along the cephalic vein in the forearm and innervates the extensor muscles of the wrist and digits with a deep branch, which diverges before crossing the elbow joint. It also innervates the forearm rotator muscles. The radial nerve also has a superficial branch, which extends towards the distal part of the limb. The superficial branch completes the sensory innervation of the forearm with the lateral cutaneous antebrachial nerve . After splitting from the median nerve it branches into the caudal cutaneous antebrachial nerve and goes towards the medial surface of the elbow joint. Before entering the forearm it branches into a ramus to the anconeus muscle. Behind the elbow it innervates the forearm flexors . At the wrist level it branches into the dorsal and palmar branches. The dorsal branch first splits into the abaxial dorsal nerve of the 5th digit and then the common dorsal nerve of the 4th digit, which splits into the proper dorsal nerves of the 4th and 5th digits. The palmar branch innervates the same digits on the palmar side. The musculocutaneous nerve consists of branches C5-C7. Its stronger branch comes from C6 (71%) or C7 (29%). This nerve forms a branch which connects it to the median nerve. When it reaches the proximal attachment of the biceps, it branches into the proximal muscle ramus, which serves the biceps brachii. There are also thin secondary ramus branching from it to the coracobrachialis muscle and the brachial muscle near the proximal attachment of this muscle. The main trunk of the nerve runs under the biceps brachii on the bone and splits into another muscle branch near the distal attachment of the biceps brachii. Below the elbow joint it becomes the medial antebrachial cutaneous nerve. The axillary nerve is formed by branches C5-C7. The major branch forming the nerve can be C7 (64%) or C6 (36%). First, the axillary nerve fibres branch into one ramus to the subscapular muscle, innervating it in its caudal part, and another ramus to the teres major muscle. Then, behind the connection with the radial nerve, the fibres may branch into a very thin ramus to the latissimus dorsi muscle  at the point where this muscle contacts the teres major muscle. Then the main trunk of the nerve goes around the brachial joint and enters the lateral surface of the scapula, where it innervates the deltoid muscle and the teres minor muscle. The suprascapular nerve is a strong nerve, which is mainly formed by branch C5. Sometimes it is also formed by a thin ramus of branch C4. It innervates the supraspinatus and infraspinatus muscles. The subscapular nerves are formed by branches C5 and C6 and they serve the median and cranial part of the subscapularis muscle. The lateral thoracic nerve is formed by branches C8 and T1. It goes to the chest wall together with the long thoracic nerve, which is formed by branches C7 and C8. The lateral thoracic nerve serves the cutaneus trunci muscle, whereas the long thoracic nerve serves the serratus ventralis muscle , or, much less frequently, by branches C4-T1 . Rarely, a branch from T2 was attached to the plexus 3,2%)   (Aydin and Karan Chinchilla lanigera), which, according to Gamba et al. , a representative of the same superfamily (Muroidea), in which, according to Greene (Meriones unguiculatus) of the Muridae family is formed by nerves C4-T1 , a representative of the Sciuromorpha family, is composed of four nerves (C5-C8) (Aydin Myocastor coypus) is composed of nerves C6-T1  was composed of nerve branches C4-T1. The brachial plexus of the crested porcupine (Hystrix cristata) is composed of branches C5-T1 (Aydin Sajapus apella) was formed by branches C4-T2. The brachial plexus of the vervet (Chlorocebus pygerythrus), which is also an ape, is composed of branches C5-T2 (Booth Sciurus vulgaris) is composed of two trunks: cranial and caudal  – it was composed of branches C8, T1, and T2. The radial nerve of the capybara is composed of the same branches as that of the Djungarian hamster (C7-T1)  is formed from nerves C6-T1 and the ulnar nerve is formed from C7-T1 . Such a branch was noted by Souza et al. (Alouatta guariba), where the musculocutaneous nerve derived from nerves C5-C6 or C5-C7. Both the musculocutaneous nerve and axillary nerve of the Djungarian hamster derive from the C6 nerve. However, C7 is the common nerve of the Gambian pouched rat (Cricetomys gambianus)  Aydin . RepreseT1 Aydin . RodentsT1 Aydin  found thT2 Booth . There iT2 Booth  examinedT2 Booth , in the al Aydin . There aal Aydin . The braal Aydin . The radal Aydin  also nota et al.  in their


This study aimed to develop and implement a universal method for the quantitative assessment of treatment effectiveness in patients with skin and underlying soft tissue defects of the trunk and extremities. The study involved 242 patients, including 46 patients with upper extremity injuries, 179 with lesions of lower extremity tissues, and 17 patients with defects of the integumentary tissues of the trunk. The greatest treatment effectiveness was observed in patients with upper limb injury: excellent result – 60.0%, good – 33.3%, unsatisfactory – 6.7% of patients. In the group of patients with lower extremity injuries, an excellent result was recorded in 19.6% of cases, good (58.1%), satisfactory (15.1%), and unsatisfactory in 7.2% of patients. In patients with trunk injuries, an excellent treatment result was obtained in 23.5%, good – 35.5%, satisfactory – 23.5%, and unsatisfactory – 17.6%. The universal quantitative method for evaluating treatment effectiveness in patients with various types of damage to the trunk and extremities tissues was proposed. This method makes it possible to objectively determine the level of medical service provided to each patient, which is of great importance in the context of medical service reorganization in the state. Modern injuries are characterized by high-energy action of the traumatic factor and simultaneous damage to several anatomical structures –5. Of thHowever, despite the constantly high level of injuries and their significant variety, there are sporadic data on the algorithm for integumentary tissue recovery and assessment of treatment effectiveness in the literature –14. HoweThe wide variety of techniques using plastic material to close wound defects allows the surgeon to choose a technique that sometimes might not be appropriate. –22. In aAt the same time, inadequate assessment of damaged tissues, as well as an untimely and inadequate attempt to restore them, should be recognized as one of the reasons for unsatisfactory treatment results, which determines the relevance of the topic studied –29.The above issues are important for assessing the results of medical practitioners' activity, especially in the context of the reorganization of the health care delivery system in Ukraine .This study aimed to develop and implement a universal method for the quantitative assessment of the effectiveness of treatment results in patients with skin and underlying soft tissue defects of the trunk and extremities.The study involved the examination and treatment of 242 patients with defects of integumentary tissues (DIT) of the trunk and limbs of mechanical origin, which were divided into 3 groups according to the plan.The first group included patients with lower limb tissues injuries – 179 (74.0%), the second – upper limb – 46 (19.0%), and the third group – injuries of the integumentary tissues in the trunk region – 17 (7.0%).The main factor for including patients in the study was the lack of opportunities for primary wound healing or DIT formation due to secondary healing, namely – a large area of damage, the presence of non-viable tissues in the wound, infection, and consequently, the development of surgical infection and wound surface (WS) formation, which could not be restored by standard surgical methods.Criteria for inclusion in the study were male or female patients over 18, diagnosed with a defect of the skin and underlying soft tissues of the trunk and extremities, who needed to restore the shape and function of the body. The study did not include patients according to the following criteria: age less than 18 years, defects in the region of face and head, ulcerative defects caused by chronic vascular or neurological disease, and which were the result of purulent-inflammatory diseases or malignant skin tumors.The distribution of patients in each group was carried out depending on the area, depth and extent of tissue damage into four types of lesions. Type I lesion (n=44 in three groups) – patients with limited (up to 1% of body surface area) area of damage to the skin and underlying tissues to the deep fascia, type II lesion (n=67 in three groups) – patients with large (more than 1% of surface area) WS and damage of soft tissues below the deep fascia, type III lesion (n=90 in three groups) consisted of patients who received DIT together or due to damage to the osteoarticular apparatus system, type IV lesion (n=41 in three groups) – patients with combined or multiple trauma accompanied by damage to bones, tendons, muscles, great vessels, nerves, partial or complete separation of the limb.Most patients treated were of working age – 137 (56.6%). There were many patients in the groups of late adulthood and old age – 75 (31%), which was due to home injuries. The majority consisted of men – 156 (64.5%). There were 86 (35.5%) women in the study. Characteristics of patients and variants of tissue damage are shown in 2. The wound surface of up to 1% of the patient's body surface area was estimated as limited, and over 1% – was estimated as large.The study groups were homogeneous in terms of the localization criterion and comparable in damage type structure. All patients underwent physical examination, including uninjured limbs and trunk, as a possible donor site. The size of the wound defect was determined in cmFor the examination of patients, along with the examination of related specialists, standardized general clinical laboratory methods  and instrumental research methods  were used.The comprehensive program for examining the damaged area consisted of studying regional macrohemodynamics using ultrasound duplex scanning (USDS).Microhemodynamics assessment was carried out according to the indicators of basal blood circulation in the area of limb injury (perfusion coefficients (K) and degree of its impairment) and on the symmetrical area of a healthy limb.For an individual assessment of the microhemodynamics of the covering tissues in the area of damage, the integral perfusion coefficient (K) was determined as the sum of the coefficients of the average blood flow, the average fluctuation of perfusion, the relative coefficient of variation, the coefficient of the neurogenic tone of microvessels and the coefficient of the myogenic tone of microvessels.Analysis of the reparative capabilities of the skin in the injured area was studied using a complex morphological program, which consisted of several stages.2) was taken to restore the covering tissues. In the final part of the study, flow cytometry was used to detect active keratinocytes in the damage zone and the degree of their activity (Z). Active receptors of keratinocytes to collagen types I and III labeled with CD 44 were detected, and the Z index was calculated based on the constructed logistic regression model.At the first stage of the program, the reparative capabilities of the skin were studied, and keratinocytes were selected and labeled using an enzyme-linked immunosorbent assay kit to quantify CD44. During the operation, a skin sample  of type I, III collagen deposition) was performed on biopsy-surgical material of skin fragments from the peri-wound zone of the defect. Kd was determined – the coefficient of collagen deposition in the skin as the ratio of the median area of type I collagen deposition to the median area of type III collagen deposition. Immunohistochemical determination of collagen type I and III accumulation was performed using monoclonal antibodies Rb a-Hu Collagen I, Clone RAH C11 and Rb a-Hu Collagen III, Clone RAH C33.Depending on the type of injury, the patients underwent surgery, which was divided into two stages. The first stage included primary surgical interventions on the injured area – primary surgical debridement (PSD), dissection and drainage of hematomas, and fasciotomy. The second stage was surgery to prepare the WS for the restoration and direct reconstruction of the DIT.For all types of damage, the share of repair and reconstruction operations (second stage) was: type I lesion – 83.6%, type II lesion – 79.2%, type III lesion – 83.6%, type IV lesion – 74.0% of surgical interventions.Criteria for evaluating immediate and remote results were engraftment of skin grafts and flaps, removal of DIT, restoration of regional hemodynamics and innervation in the area of injury, elimination of trophic disorders and desmogenic contractures, and restoration of movement stereotype.The results of treatment were assessed at the time of discharge using functional scales: DASH upper limb impossibility questionnaire [developed by the Institute for Work & Health in collaboration with the American Academy of Orthopedic Surgeons (AAOS) with the support of the American Association of Plastic and Reconstructive Surgeons (2006)] . The con® for Windows 6.0 . The obtained data were checked for normality of distribution based on the Shapiro–Wilk criterion. In the cases of normal distribution, the arithmetic mean (M) and the standard error of the mean (m) were calculated. The parametric Student's t-test (t) was used to assess the significance of differences between the mean values. p<0.05 was taken for a significant minimum probability of differences.Statistical processing of quantitative research results was performed on a personal computer using the analysis package in Microsoft Office Excel 2013 and STATISTICAQuality of life was assessed in the postoperative period among 45 patients (out of 46 patients) with posttraumatic defects of the upper extremity. Patient H., born in 1988, case history Nº. 2182 with a diagnosis of traumatic amputation of the left upper extremity; a large granulating wound of the amputation stump of the left upper extremity (type IV lesion) was not studied to assess functional activity.Thus, the largest number of results, 27 (60.0%), were excellent – primary engraftment of a skin graft or flap and removal of DIT, restoration of 90% of precise and strong types of hand grips, absence of deforming scars and contractures, free functioning of distally located joints .A good result was obtained in 15 (33.3%) patients, and it was characterized by the absence of postoperative complications in the reconstruction area and the restoration of precise and strong hand grips of more than 60%. In some cases (closure of the WS by autodermoplasty), there was a residual deformation that did not affect the functionality of the upper extremity as a whole. Satisfactory results of upper extremity DIT treatment were not noted.3 patients with type IV lesions had an unsatisfactory result – partial necrosis of the flap with repeated surgery, restoration of precise and strong types of hand grips less than 40% of a healthy hand; there was a partial deformation in the projection of large distal joints (wrist), repeated surgical correction was required. However, an aesthetic effect was achieved.The use of a differentiated approach to repair damaged integumentary tissues had excellent results in 60.0% of patients, good results in 33.3%, and unsatisfactory results in 6.7% of patients with DIT of the upper extremity.The functional scale of DASH allowed estimating not only disability but also the efficiency of diagnostic and medical tactics. The effectiveness of treatment outcomes in patients with trauma of the upper extremity is shown in There was a statistically significant decrease in the effectiveness of treatment for type IV lesions compared to type I (p<0.05) due to severe polystructural tissue damage in this group of injured. In contrast, the effectiveness of type I, II and III lesions did not show a statistically significant difference (p>0.05).The average treatment effectiveness indicators in patients, taking into account the type of damage to integumentary tissues, shown in the table, indicate the feasibility of the proposed diagnostic and therapeutic tactics not only for type I lesion  but also other more severe upper extremity tissue lesions.The condition of the injured lower extremity was assessed according to the LEFS functional scale, which reflected the qualitative assessment in the form of a Likert scale, daily activity.We proposed a formula for calculating the symptoms of the LEFS scale for quantitative evaluation of results:where n – number of answers.After using the formula, the resulting figure corresponded to the percentage of disability. We proposed a 4-point scale, which identified 4 options for the results of rehabilitation of patients with damage to integumentary tissues and other anatomical structures of the lower extremity – excellent, good, satisfactory, and unsatisfactory to qualitatively assess the degree of disability of the lower extremity for practical use.The data on treatment effectiveness showed excellent rehabilitation results in 19.6% (35/179) of cases among patients with lower extremity injury of type I, II, and III lesions and was characterized by primary skin engraftment or flap and removal of DIT, restoration of regional hemodynamics and innervation in the area of injury, elimination of trophic disorders and, as a consequence, restoration of structural and functional stereotype.In 2 patients with type II lesions (with consequences of trauma), excellent results were indicated by the absence of desmogenic and arthrogenic contractures, complete absence of pathological scars in the area of injury, and complete restoration of anatomical, functional and aesthetic aspects.In patients with type IV lesions, there was no excellent result due to the severity of injuries.The largest number of results on the restoration of the shape and function of the lower extremity – 58.1% (104/179), in the range of good result.Among the patients with large WS (type II lesion), the number of good results was the largest – 69.6%. This was manifested by the absence of postoperative complications in the reconstruction area with the preservation of the deficit of limb function recovery due to the nature of the traumatic injuries.The treatment results obtained in patients with type III and IV lesions, with the largest number of structural changes in tissues – 57.4% and 58.8%, respectively, attracted attention.Examination of patients after 12–36 months noted the absence of desmogenic and arthrogenic contractures, storage of scars in the area of injury, which did not affect the activity of movements, a slight lack of restoration of anatomical, functional and aesthetic aspects.Satisfactory results were obtained in 15.1% (27/179) of patients – ischemic disorders in the area of postoperative intervention without the need for repeated surgery, preservation of the limb as an organ, or amputation of its distal segments with partial restoration of functional stereotype.In the group with type I lesion – 22.6%; in group II – 8.9%; in III – 17.3% and group IV – 11.8%.During the examination of patients after 1 year or more, the absence of arthrogenic contractures, the presence of desmogenic contractures and pathological scars that required surgical correction, partial restoration of anatomical, functional and aesthetic aspects were noted.Unsatisfactory result – lysis of the graft or necrosis of the complex flap, amputation of the limb due to decompensation of hemodynamics or complete tissue rupture, inability to restore the primary anatomy of the lesion and stereotype of movement, was obtained in 7.2% (13/179) of cases.Amputation of the limb at the thigh level was performed in 4 patients with type IV tissue lesion.For the period of observation, the additional signs of unsatisfactory results  were not detected in 9 patients with complications in the early postoperative period.The average efficiency values of restorative treatment indicated the maximum number of good results obtained in patients with type I, II, and III lesion of the integumentary tissues of the lower extremity due to the mechanical etiopathogenetic factor – 75.0±3.6%, 76.6±1.9%, and 68.6±2.3%, respectively (p>0.05).The result of 58.9±9.4% in patients with type IV lesions  was due to the greatest number of unsatisfactory results of reconstructive interventions associated with severe polystructural damage to the cover, underlying soft tissues, osteoarticular apparatus, great vessels and peripheral nerves of the lower extremity .The quantitative assessment of the parameters of household activity and restored disability on functional scales allowed us to determine the effectiveness of the implemented diagnostic and treatment tactics in all clinical groups affected with DIT extremities, as evidenced by the obtained mean values of treatment efficiency.The results of the restoration of functional activity of patients with DIT of the trunk were evaluated using the functional independence measure by counting the number of points. The patient's integrated index of functional independence (FI) was calculated on a diagnostic scale. The latter reflected the patient's physical and intellectual activity after receiving rehabilitation treatment.An excellent result (23.5%) indicated the absence of postoperative complications and complete recovery of motor function and social activity. Good (35.3%) and satisfactory (23.5%) results indicated a lack of activity in the postoperative period, primarily due to the severity of the spinal injury and damage to the spinal cord. Unsatisfactory results  were obtained in 3 (17.6%) patients – in 1 patient with type III injury FI=30.2%, in 2 patients with injury type IV – FI=29.4% and 27.8%, respectively.All complications resulted from compression-ulcer trophic defects and required repeated reconstructive surgery.The mean values of treatment efficacy of trunk DIT were the highest in patients with type II lesions, compared with the results of FI in patients with type III and IV lesions, which was associated with the severity of damage to integumentary tissues, but this difference was not statistically significant due to the small number of patients (p>0.05) .The mean values of rehabilitative treatment of trunk DIT showed sufficiently high efficiency of the proposed diagnostic and treatment tactics for the fastest recovery of compression and ulcer wound defect, which was the main goal in the group of patients with severe spinal and spinal cord injury for the fastest transition to rehabilitation and improving quality of life in this category of patients.The algorithm of diagnostic and surgical tactics for restoring the damaged tissues of an extremity after an injury is developed  based onThe assessment of the literature and our clinical material convinced us that the earliest possible use of reconstructive surgical technologies from the moment of traumatic injuries is an effective method of treating patients with isolated and multiple injuries of various anatomical structures to restore the shape and function of the body (96.9% of positive result). The use of microsurgical techniques and complex flaps in the acute period of trauma is not always possible and necessary, especially when it comes to severe combined polystructural changes with damage to the great vessels, nerves, bones, and super-large defects of the skin and underlying soft tissues. During such a period, the main task of the surgeon is to close the wound surface quickly to avoid the spread of wound infection and to qualitatively restore the vital structures of the body .The literature describes single studies of the reparative capabilities of the skin, namely the activity of keratinocytes, which are not performed in the context of emergency surgical care –35. The This is confirmed by the data analysis of the quantitative assessment of patient's quality of life included in the study groups. Due to this approach, positive results of restorative treatment were obtained within 3 years of observation in 96.0% of patients with type I lesion, 96.78% with type II, 97.87% with type III and 83.76% with type IV lesion of the integument.The complex algorithm of reconstruction of the damaged integumentary tissues depending on the lesion, type, and anatomical, hemodynamic and morphofunctional features of the injury site is proposed, which makes it possible to decide on the use of the reconstruction method in each case. Due to this approach, a positive reconstruction result was obtained in 96.9% of cases. Furthermore, the proposed universal quantitative method for evaluating the treatment effectiveness in patients with various types of tissues damage to the trunk and extremities makes it possible to objectively determine the level of medical service provided to each patient, which is of great importance in the context of medical service reorganization in the state.Prospects for further research are in the field of assessing the effectiveness of surgical interventions to eliminate various types of defects in integumentary tissues and the choice of a method for reconstructing a particular wound surface based on the analysis of long-term results.


Changes in the optical and emission properties were seen after the radiation treatment, and the magnitude of the changes depended on the irradiation source and dose. For all the investigated materials, the absorption coefficients in the 200–550 nm range increase post-irradiation, revealing the formation of defects in the glasses during the irradiation. While the spectroscopic properties of the tellurite glass remain unchanged, a small reduction in the Yb3+ emission intensity was seen after irradiating the phosphate, borosilicate, and germanate glasses, indicating that a reduction of Yb3+ to Yb2+ might occur in these glasses during the radiation treatment. The changes in the optical and spectroscopic properties after proton irradiation are small as they are localized at the surface of the glasses due to the shallow penetration depth of the proton in the glass. Even though the doses are small, the electron irradiation produces larger changes in the optical and spectroscopic properties since the electrons penetrate the entire volume of the glasses. All the changes in the optical and spectroscopic properties of the glasses were successfully reversed after a short heat treatment revealing the reversible nature of the photo-response of the investigated glasses. The radiation effects of electrons and protons on the spectroscopic and optical properties of oxide glasses doped with Yb Especially, the Yb3+ doped silica fibers have found broad acceptance in the industry, defense, life sciences, etc.  units, according to  and [GaO4]− units, respectively [3 and Q2 units.The germanate glass exhibits three main Raman bands at 500 (H), 780 (I), and 860 cmGe or Ga , locatedructures . The banectively ,33. Ther−1 (M). The 450 cm−1 peak is assigned to Te-O-Te link symmetric stretch in TeO4 or TeO3 polyhedra, the band at around 660 cm−1 to Te-O stretch in TeO4, and the band at 770 cm−1 to more distorted TeO4, also sometimes labeled as TeO3+1 [4 and TeO3+1 units [The Raman spectrum of the tellurite glass has three distinguishable bands at 450 (K), 660 (L), and 750 cms TeO3+1 . Thus, t+1 units .3+ are presented in 3+ ions located in a phosphate network [3+ is inserted in a borosilicate network rather than in a phosphate network. The intensity of the shoulder at ~1025 nm increases further when the Yb3+ ions are inserted in the HMO matrices due to the high disorder and the electric field surrounding the Yb3+ ions, as discussed earlier. Indeed, in 3+ ions. This results in the reinforcement of the lowest emission components in parallel to the progressive quenching of the zero-line component.The integrated emission area and the normalized emission band of Yb network . Both thThe investigated glasses were subjected to radiation treatment using electrons and protons. The particle energies, doses, calculated penetration depths, and irradiation times are summarized in No noticeable changes in the surface roughness of the glasses could be seen after both radiation treatments, even for the higher doses. No expansion nor contraction could be detected using a 3D optical profiler. However, all the investigated glasses show a darker shade after the irradiation with electrons, whereas a slight dark coloration was observed after the irradiation with protons. Those changes in the optical properties are clearly shown in 32− (phosphoryl), PO44− (phosphoranyl), or PO22− (phosphinyl), which have been reported to exhibit absorption bands at 210, 240 and 265 nm, respectively [The Ca-  and Sr-phosphate  glasses show similar changes in their optical properties after irradiation, which agree with those reported in ,37. Afteectively . Oxygen ectively . A largeectively . 2, ·O-Si-O·), respectively, and the 325 and 380 nm bands to oxygen-deficient centers  [C, >Si:) ,44,45. B−-O) at 315 nm [4+ into Ti3+ occurring during the radiation treatment, as reported in [The subtracted absorption spectra of the germanate glass after radiation treatment with electrons and protons are shown in t 315 nm . The radorted in ,48.As opposed to the other glasses, the irradiation of tellurite glass leads only to a shift of the absorption edge to a longer wavelength, as depicted in The differences in the optical properties after irradiation are the most distinct for the phosphate and borosilicate glasses indicating that they are the most sensitive glasses to radiation treatment, probably due to the relative lightness of their atoms (see the density of the glasses in 3+ charge transfer (CT) -related absorption bands are a potential source for absorption bands [3+ local environment, such as the defects of interest.Ybon bands ,52, but,on bands ,54,55. FOne should also point out that more defects are formed in the glasses after irradiation with electrons than after irradiation with protons. As explained in , this is3+ absorption and emission bands of the phosphate and tellurite glasses were seen after the radiation treatments, the radiation treatment with electrons had a slight impact on the shape of the absorption and emission bands of the borosilicate and germanate glasses as depicted in 3+ zero-line emission in the germanate glass (3+ 2F7/2 excited state. It is also possible that the sites of the Yb3+ ions change after the radiation treatment.While no noticeable changes in the Ybte glass d. This r3+ emission of the glasses, as illustrated in The irradiation treatment was also found to have an impact on the overall intensity of the Yb3+ emission intensity area is seen after the electron radiation treatment in all glasses, the magnitude of which depends on the dose, while the changes induced by the proton radiation are negligible. The largest decrease in the emission intensity area after irradiation can be seen from the borosilicate and germanate glasses. As for the changes in the optical properties after the radiation treatment, a larger decrease in the Yb3+ emission intensity area is observed after irradiation with electrons than after irradiation with protons. Additionally, a larger decrease in the Yb3+ emission intensity area is observed after irradiation with electrons than after irradiation with protons. The decrease in the emission intensity area can be related to the changes in the Yb3+ absorption properties presented in 3+ and stabilizes the centers that quench the radiative de-excitation of Yb3+ ions partly. Alternatively, photo-ionization of the RE has been observed in [3+ in gamma-irradiated oxyfluorophosphate glass, for example, so, therefore, reduction of Yb3+ to Yb2+ must be considered. A decrease in the intensity of the Yb3+ emission was reported in silica glass [2+. However, no evidence of photo-ionization of the other glass constituents was seen in the absorption spectra in 3+ spectroscopic properties in the tellurite glasses were seen after the radiation treatments, this glass appears to be the most photo-resistant against defect formation of the investigated glasses and so a promising glass for the development of novel Yb3+ doped fiber for radiation environments for example. Except for the tellurite glass, a decrease in the Yberved in  for Sm3+ca glass  and in gca glass  after rag (It is well known that defects can recover over time ,60,61,62g  for 15 m3+ emission intensity area also changes over time and after heat treatment. The heat treatment of the irradiated glasses at their respective Tg for 15 min results in an increase in the Yb3+ emission intensity area to the level of the as-prepared glasses. Similar recovery over time was also reported in irradiated phosphate glasses and silica fiber [As depicted in ca fiber ,60. Recoca fiber  to severca fiber .3+ doped oxide glasses was investigated. The radiation treatments result in the formation of various defects and thus changes in the optical properties of the glasses, but also in the decrease in the Yb3+ emission area and in the alteration of the Yb3+ environment in some glasses, the amplitude of these effects being dependent on the glass compositions and deposited doses. These modifications in the optical and spectroscopic properties are also more pronounced after irradiation with electrons than with protons. The borosilicate and germanate glasses were found to be the most sensitive to radiation treatment, while the tellurite glass appeared to be the least sensitive using either electrons or protons and, therefore, is a good candidate for radiation-resistant laser glasses. As mentioned for other glass systems, the color centers relax over time and can be bleached using a suitable thermal treatment of the glasses at their respective glass transition temperature, indicating that the photo-response of the glasses to irradiation with electrons and protons is a reversible process.In this paper, the effect of radiation treatment using electrons and protons on the optical and spectroscopic properties of a panel of Yb


The removal of dyes with zeolites was performed via two mechanisms: adsorption and photocatalysis. Removal of dyes through adsorption was achieved by studying the Freundlich adsorption isotherms, while photocatalytic removal of dyes was performed under UV irradiation. In both cases, the removal experiments were conducted for 180 min at two temperatures (283 K and 293 K), and dye concentrations were determined spectrophotometrically. Additionally, after photodegradation, mineralization was analyzed as chemical oxygen demand. A computational analysis of the structures of MB and RB was performed to gain a deeper understanding of the obtained results. The computational analysis encompassed density functional theory (DFT) calculations and analysis of two quantum-molecular descriptors addressing the local reactivity of molecules. Experimental results have indicated that the considered zeolites effectively remove both dyes through both mechanisms, especially NH4BETA and NH4ZSM-5, due to the presence of active acidic centers on the outer and inner surfaces of the zeolite. The lowest efficiency of dye removal was achieved in the presence of NaY zeolite, which has a lower SiO2/Al2O3 ratio. A more efficient reduction was completed for RB dye, which agrees with the computationally obtained information about reactivity.This study investigated the potential of zeolites (NH Clean and unpolluted water is an irreplaceable resource that enables life on Earth. Water quality has deteriorated yearly due to rapid economic and industrial progress ,2,3. TheMethylene blue (MB) belongs to the group of xanthene dyes, and rhodamine B (RB) to the group of thiazine dyes . They arDue to all the aforementioned, numerous physical, chemical, and biological methods have been developed to remove dyes from the water environment ,26,27,28•OH), are generated and may indiscriminately react with many organic compounds by electrophilic addition to the double bond or electron-transfer reaction. The formed intermediates can further react with dissolved molecular oxygen and increase degradation efficiency to less toxic or non-toxic compounds [2, H2O, and inorganic ions, has attracted particular attention [The adsorption efficiency mainly depends on the affinity of the adsorbate to the adsorbent and the specific surface of the adsorbent ,38,39,40ompounds ,45,46,47ttention ,48.4  interconnected by oxygen atoms, is negatively charged, and cations and water molecules are placed in the channels and cavities to achieve electroneutrality [Thanks to their high adsorption capacity, thermal and mechanical stability, and unique and precisely defined crystal structure, zeolites have been widely applied in adsorption, ion exchange, and catalysis. Recently, zeolites have been used in photodegradation processes, often as carriers of photocatalysts ,50,51. Tutrality ,52,53.2/Al2O3 ratio [2/Al2O3 ratio.The properties of zeolites, such as adsorption, ion exchange, etc., are determined by the internal and external surface and by the SiOO3 ratio . The surO3 ratio ,54. SyntThe three-dimensional structure of the BETA zeolite is characterized by two mutually vertically flat channels (0.76 × 0.64 nm) and a sinusoidal channel with a diameter of 0.55 × 0.55 nm. In contrast, the porous structure of ZSM-5 zeolite is characterized by the flat channels of an elliptical cross-section (0.51 × 0.55 nm), which are interspersed with a sinusoidal channel of a circular cross-section (0.54 nm) . Zeolite4BETA, NH4ZSM-5, and NaY zeolite and by photodegradation under the influence of UV radiation in the presence of these zeolites. After photodegradation, the degree of mineralization was analyzed as chemical oxygen demand (COD) to gain a better insight into the photocatalytic process efficiency. Quantum-mechanical calculations within the density functional theory (DFT) approach gave us important insights into the reactivity of MB and RB, which helped us to interpret the obtained results, and explain the difference in degradation efficiency of these two dyes.This study observed the removal efficiency of MB and RB dyes from the aqueous environment by adsorption on NHThe Freundlich isotherm and specific adsorption parameters describe the adsorption suspension of RB-zeolites and MB-zeolites. To establish the most appropriate adsorption equilibrium correlation and the accuracy in parameter prediction of non-linear isotherm models were compared and discussed .c is the equilibrium concentration, and FK and n are specific empirical constants [4BETA, NH4ZSM-5, and NaY zeolite are presented in x/m is the amount of adsorbed substance in equilibrium, eγ is the adsorbate concentration at equilibrium, and oγ is the initial concentration of adsorbate). Adsorption parameters , and according to Giles belong to S4 group, indicating multi-layered physical adsorption. The only exception occurs for the RB-NH4ZSM-5 suspension, at 293 K, where one plateau is registered, which suggests that the adsorption is a monolayer and that, in addition to physical adsorption, chemisorption also occurs.Based on the obtained results regarding the adsorption of RB  and MB  on NH4BEPhysical adsorption results from weak intermolecular interactions, while chemisorption is based on the exchange of valence electrons between the adsorbent and adsorbate. One may not always set the boundary between physisorption and chemisorption. Observing RB and MB’s adsorption on zeolites can provide interesting information about possible interactions with the zeolite surface. The results show that NaY zeolite was the worst adsorbent for RB and MB dye. Obtained results can be explained by the fact that the acidity of the surface was decisive for adsorption, i.e., the presence of Lewis and Brønsted active centers located on the outer and inner zeolite surfaces.2/Al2O3 in NH4BETA and NH4ZSM-5 zeolites indicates the presence of active sites of the acidic character of different strengths, which favor a better interaction with these dyes. The surface of high-silicate zeolites is more homogeneous with an organophilic nature, in contrast to the zeolite surface with a lower content of SiO2/Al2O3, which is more selective for water and other polar molecules [The higher ratio of SiOolecules ,54,58.4BETA zeolite compared to NH4ZSM-5 zeolite can be explained by the larger specific surface area of NH4BETA zeolite, and this is supported by the value of the constant k (4BETA (k = 54.87) and RB-NH4BETA (k = 15.35); this shows a very high affinity between this adsorbent and adsorbates. Based on the value of the constant n . This could mean that the dye molecules, in addition to weak van der Waals interactions, partially bonded to the adsorbent surface even by chemical bonding. The value of the adsorption heat also confirms this for NH4ZSM-5 zeolite, which, although it remained within the limits of physisorption, increased with the temperature increase. RB molecules were probably attached to the active centers of the zeolite by hydrogen bonds via hydrogen atoms from hydroxide groups located on the surface of the zeolite and electronegative nitrogen or oxygen atoms in the dye structure.With the increase in temperature, the adsorption capacity of NH4ZSM-5 zeolite and that the number of adsorbed molecules increases with the increase in temperature (from 53 to 58%). In endothermic reactions, with an increasing temperature, the number of adsorbed species increases because their mobility increases. The total number of adsorbed molecules of RB dye on the NH4BETA zeolite at 293 K amounted to 29%, which indicates that the dye molecules on the NH4BETA zeolite became bonded to the active centers on the outer surface and that the large molecules of RB dye could not reach the inner surface of the zeolite, which is composed of pores and cavities.The calculated value Q  indicate4BETA for MB dye increases with an increasing temperature (I plateau by 23%). In contrast, the adsorption capacity of other zeolites decreases with the increase in temperature, which can also be seen based on the total number of adsorbed MB molecules on the zeolite surface. The highest value of Q is for the MB-NH4ZSM-5 suspension at 283 K, but this value decreased with the temperature increase. Additionally, the number of total adsorbed MB molecules on the surface of the NaY zeolite decreased by 37% with the increased adsorption temperature, indicating that the adsorbate molecules became tied to the active centers by van der Waals forces or dipole bonds. This is also confirmed by the calculated values of adsorption heat (∆adsHm), which decreased with the increase in adsorption temperature.With the increase in reaction temperature, the quantity of adsorbed RB molecules on NaY zeolite decreases, which indicates physical adsorption, and the value of adsorption heat also confirms this. Based on the data presented in 4ZSM-5 zeolite can be explained by the greater possibilities of binding to the outer zeolite surface because at pH > 3, RB dye behaves both as a weak base and as a weak acid. The high degree of MB dye removal in the presence of NH4BETA and NaY zeolites can be explained by the smaller dimensions of the MB molecules, which, in addition to binding to the outer surface, are most probably also bound to the active centers of the inner zeolite surface [When we compare RB and MB dyes, the higher degree of RB removal in the presence of NH surface ,49,59.2 photocatalysts [2 individually. However, one must not ignore the fact that zeolites are crystalline aluminosilicates built from tetrahedra of silicon and aluminum interconnected through oxygen atoms, and it is generally known that porous SiO2 exhibits photocatalytic activity via siloxane bridges, which generate siloxy radicals under the influence of UV radiation (below 390 nm) [When considering the photocatalytic activity of zeolites, many studies focus on zeolites containing framework heteroatoms or a modification of zeolites with oxides or metal ions precisely because of the improvement in photocatalytic capabilities . This isatalysts ,62 or ze 390 nm) ,64 accor4BETA, NH4ZSM-5, and NaY zeolites, under the influence of UV radiation for 180 min, are given in First, the photolysis of RB and MB was examined under UV radiation to see the contribution of adding zeolites to these systems . Slightl2/Al2O3 content, such as NH4BETA and NH4ZSM-5, show a high affinity for removing dyes.One of the critical roles in the process of photocatalytic degradation is played by adsorption, which mainly depends on the affinity of the catalyst for the substrate, the specific surface area of the catalyst, and the nature of the solvent. After adsorption, the photodegradation of adsorbed molecules commences under the influence of radiation. As already mentioned, zeolites with high SiO4ZSM-5 zeolite, then NH4BETA, and finally NaY zeolite. It can be seen in 4ZSM-5 zeolite has the highest ratio of SiO2 and NaY has the lowest.The obtained results of photodegradation of MB and RB dyes under UV radiation  indicate4BETA zeolite. In contrast, in the presence of NH4ZSM-5 and NaY zeolite, there is an insignificant decrease in the degree of degradation, which is probably the effect of the physisorption of the dye molecules on the catalyst surface. In the case of RB dye, the highest efficiency of photodegradation at 293 K was achieved in the presence of NH4BETA zeolite (83.3%). It can be observed that the degree of removal of RB is increased by the increase in temperature reaction, which is most likely the effect of the increased frequency of molecular collisions in the solution.The presence of acid-base centers in the zeolite structure, which have electron donor and electron acceptor properties, prevents the possible recombination of electrons and holes, leading to a higher photodegradation efficiency. The results of the photodegradation of MB dye in the presence of zeolite at 293 K follow the same trend as at 283 K. The increase in temperature did not significantly affect the degree of degradation of MB dye in the presence of NH•OH. The adsorbed dye molecules can be degraded by radical species and mineralized into less toxic products.The photodegradation of MB and RB molecules in the presence of zeolite under UV radiation includes the generation of electron and hole pairs. Electrons in the conduction zone are unstable and pass to adsorbed oxygen molecules, where superoxide radicals are formed, while holes in the valence zone can be captured by the molecules of dye or water, creating 2 and H2O, inorganic ions 4ZSM-5, then NH4BETA, and the lowest degree of mineralization was achieved in the presence of the NaY zeolite. The obtained results of mineralization agree with the results of photodegradation. The mineralization degree is lower than the degree of photodegradation, which indicates the presence of various intermediates, whose mineralization is often slower than the degradation of the initial compound. In the case of MB dye, the degree of mineralization at 293 K is the highest in NH4ZSM-5 zeolite and the lowest in NH4BETA zeolite.Based on the structures of RB and MB dyes, it can be expected that depending on the degree of mineralization, in addition to CO4ZSM-5 zeolite, as well as NH4BETA (283 K), while in the presence of the NaY zeolite, the pH value increases due to the formation of base intermediates.The presence of multiple intermediates is also indicated by the change in the pH value of the solution during the photocatalytic process. As seen in 2 and H2O. The degree of mineralization of RB dye is lower than that of MB dye (except for RB-NH4BETA at 293 K), which is probably a consequence of its forming a more significant number of intermediates. The appearance of a more significant number of intermediates in the case of RB dye is expected, given that the RB molecule is larger than the MB dye.During the decomposition of RB dye, radical species probably first attack nitrogen atoms (N-deethylation process), whereby various intermediates with an aromatic ring are formed. After that, reactive radicals attack carbon atoms, resulting in the cleavage of chromophores and oxidation of intermediates to carboxylic acids, preventing the increase of pH value, as per the results presented in To better understand the experimental results, the influence of the structure of the tested dyes was analyzed. MB and RB are dyes that consist of cation and Cl anion. The starting geometries of MB and RB have been taken from the ChemSpider library and subjected to geometrical optimizations. Since there is a noncovalent interaction between the cation and anion in these cases, we had to apply the dispersion-corrected variant of the B3LYP functional. The geometrically optimized structures of MB and RB are presented in In both cases, the Cl anion was placed near the cations’ positively charged atoms. This means that in the case of the MB, the Cl anion was placed above the sulfur atom, while in the case of the RB, the Cl anion was placed above the nitrogen atom. In the case of the MB, the Cl anion moved significantly to the plane corresponding to the central ring and shifted to interact with the nearby hydrogen atom noncovalently. In the case of the RB, the Cl anion practically remained in the vicinity of the positively charged nitrogen, which disagrees with the finding reported by Delgado and Selsby . Namely,Computational analysis in this work encompassed calculations of the MEP and ALIE quantities, two well-known quantum molecular descriptors describing the local reactivity of the molecules. The MEP descriptor is one of the most frequently calculated quantities to identify molecules’ sites with electron abundance or deficiency. Another popular descriptor for addressing the local reactivity of molecules is the ALIE quantity. MEP is a substantial quantity that reveals which molecular sites are prone to interact with other molecules based on electrostatic interactions. One molecule’s electron-abundant site would react with the electron-deficient site of the other molecule. An equally important but somewhat less frequently applied descriptor is ALIE, which reveals the molecular sites where the lowest amount of energy is required to remove an electron. In other words, this descriptor indicates the molecular sites sensitive to electrophilic attacks. Essentially, both MEP and ALIE descriptors were introduced into practice by Professor Politzer and his coworkers ,68,69,70The analysis of the minimal and maximal values of the MEP descriptor provides a further understanding of the results related to dye removal via adsorption. Namely, the lowest MEP values for both MB and RB dyes are practically the same and are equal to −75.73 kcal/mol and −72.91 kcal/mol, respectively. The similar lowest MEP values are expected since the Cl anion bears the negative charge in both cases. However, there is a huge difference in the maximal MEP values in favor of the RB dye. Namely, the MB dye’s highest MEP value is 34.35 kcal/mol, while the RB dye’s highest MEP value is 56.16 kcal/mol. This discrepancy in the highest MEP values between the MB and RB dyes shows that the RB dye is far more prone to interact with other structures based on electrostatic interactions. Indeed, the adsorption study in this work indicates that the RB dye is removed to a greater extent than the MB, which agrees with the computational results. Conversely, the minimal and maximal ALIE values of MB and RB dyes are very similar, so they are expected to have comparable sensitivity toward electrophilic attacks.3) of MB and RB  were prepared by diluting the basic solutions. Thehe absorption maxima were then determined, and calibration curves were constructed , NH4ZSM-5 , and NaY .The standard dye solutions (0.5–5 mg/dmstructed . SynthetAll zeolites’ specific surfaces (Sp) were determined by the BET method on the Flowsorb II–2300 instrument .−1 and 32 scans to identify the surface acidity of the zeolite . The adsorbent mass was 0.25 g (exact weight ±10−4 g) in contact with 50cm3 of adsorbate solutions of different concentrations (0.5–5 mg/dm3). The results are presented as curves of functional dependence γe., from which the quantity of adsorbed dye on one adsorption monolayer was read, i.e., on the plateau. The amount of adsorbed dye (N) and their total surface (S), as well as the parameter Q, which represents the ratio of the surface of adsorbed molecules and the specific surface of the zeolite, were calculated. The parameters k and n, as well as the adsorption heat (Adsorption experiments of the dyes MB and RB from the aqueous environment on NH3) and RB (1 mg/dm3) under UV radiation was performed in a photochemical cell made of double-walled Pyrex glass in the presence of NH4BETA, NH4ZSM-5, and the NaY zeolite. Into the cell, 20 cm3 of the aqueous solution of dye and 0.1 g of zeolite were weighed (exact weight ±10−4 g), followed by sonification in an ultrasonic bath for 15 min, to achieve a uniform size of the catalyst particles. The photochemical cell was placed on a magnetic stirrer, and the suspension was continuously mixed during the irradiation with a constant oxygen flow. Photodegradation was performed at 283 K and 293 K for 180 min and a high-pressure mercury lamp with a suitable concave mirror was used as a source of UV radiation .Photodegradation of the dyes MB , at a fixed slit width (2 nm), using a 1 cm quartz cell and computer-loaded UV Win 5 data software.The pH value of standard dye solutions was determined using a glass electrode  connected to the pH meter . For monitoring the pH during the degradation, a combined glass electrode  connected to the pH meter was used .6H4COOK as a standard solution, and 2R was 0.995  using a quartz cell  and computer-loaded UV Win 5 data software. Absorbance was recorded on a double-beam T80 + UV-vis Spectrometer. The evolution of absorbance of the digested solution was recorded at 600 nm. The samples were digested at 150 °C for 2 h.The COD was determined according to Standard Method 410.4 declared by EPA, United States Environmental Protection Agency. The calibration curve was obtained using HOOCCas 0.995 . AliquotMolecular DFT calculations on the RB and MB were performed by applying the dispersion corrected version of a B3LYP functional , namely Molecular DFT calculations related to geometrical optimizations and vibrational analysis were performed with an ORCA 5.0.3. package ,77,78,794BETA and NH4ZSM-5 zeolites are very effective adsorbents for these dyes due to acid centers of different strengths responsible for the adsorption, while the NaY zeolite proved to be the least effective. The higher degree of adsorption on the NH4BETA zeolite compared to NH4ZSM-5 can be attributed to a higher specific surface area (about 40% higher). Adsorption of dyes on all zeolites occurs according to the principle of multi-layer physical adsorption, except for the RB dye on NH4ZSM-5, where chemisorption partially occurs. In addition, the high efficiency of removing these organic pollutants was achieved by heterogeneous photocatalysis, where the highest degree of photodegradation of dyes was performed in the presence of a NH4ZSM-5 zeolite (highest SiO2/Al2O3) primarily and secondarily in the presence of a NH4BETA zeolite, probably due to the formation of siloxy radicals. Siloxy radicals with hydroxyl and superoxide radicals contributed to a high degree of dye degradation. Compared to the photodegradation efficiency of dyes, the lower degree of mineralization could be explained by the formation of various decomposition intermediates, which requires a longer irradiation time.Zeolites have a significant place among the most commonly used adsorbents thanks to their specific crystal structure consisting of pores, channels, and cavities of different dimensions, which results in a large internal surface area available for the removal of various organic pollutants, including dyes. The properties of zeolite are determined, among other things, by active centers of different acidity (Lewis and Brønsted type) located on the outer and inner surfaces of the zeolite. Recently, zeolites have increasingly been used as catalysts in photodegradation processes. This study observed the adsorption and photodegradation of the selected organic dyes, MB and RB, in the presence of zeolite material from BEA, MFI, and FAU groups. The characterization of all adsorption suspension s is given through the Freundlich adsorption isotherm, and the corresponding parameters were determined. The results showed that adsorption is still one of the leading methods in wastewater treatment because a high degree of dye removal was achieved under these experimental conditions. NH